DESC:FIELD
The present disclosure relates to a copolymer composition and adhesives made therefrom.
DEFINITIONS
As used in the present disclosure, the following terms are generally intended to have the meaning as set forth below, except to the extent that the context in which they are used to indicates otherwise.
Lap-shear strength: The term “lap-shear strength” refers to the ability of an adhesive to resist forces in the plane of the bonded surfaces.
D3 performance: The term “D3 performance” refers to the ability of an adhesive to resist frequent short-term exposure to running or condensed water and/or to heavy exposure to high humidity in interior applications. European Standard classifies thermoplastic resin based wood adhesives for non-structural applications into durability classes D3 as per standard EN 204 that adhesive must provide minimum values of 2 N/mm2 adhesive strength for thin bond-lines on a wood substrate after 7 days exposure in standard atmosphere followed by 4 days exposure in cold water at (20 ±5)°C.
Boiling water resistance: The term “boiling water resistance” refers to the ability of an adhesive to resist a minimum 6 hours of exposure to boiling water, which means the wood panel must not be detached after 6 hours of exposure.
Back Titration: The term “back titration” refers to a titration method. In this method the concentration of an unknown component is determined by reacting with a known amount of excess reagent.
BACKGROUND
The background information herein below relates to the present disclosure but is not necessarily prior art.
The use of homopolymer or copolymer of vinyl acetate-based adhesive has been known since long, due to their various advantages such as suitable rheology, good adhesion to cellulose substrates, setting speed, high cohesion of the polymer film, and the like. Conventionally, the copolymers of vinyl ester comprise self-crosslinking comonomer units with N-methylol or N-methylol ether functions to improve their strength.
The conventional homopolymer or copolymer of vinyl acetate-based adhesive has poor applicability at low temperature and high temperature. Further, the conventional homopolymer or copolymer of vinyl acetate has poor elongation and water resistance. Furthermore, the conventional vinyl acetate-based homopolymer or copolymer prepared by pre or post crosslinking route, has better water resistance, however, they have very less shelf life due to continuous viscosity pick up with time. This was generally may be due to use of pre or post addition of cross-linkers.
Conventionally, the characteristics of high-range water-resistant vinyl acetate copolymers were usually obtained by inserting a self-crosslinking comonomer alone or mixtures of two or more compounds. Further, the conventional copolymers also used either organic crosslinkers (such as glyoxal, glutaraldehyde, citric acid, tartaric acid, and the like) or inorganic crosslinkers also known as acidic metal salts (such as A1C13, AlNO3, borates, and the like) in combination with the self-crosslinking comonomer. All the above conventional compositions had good water-resistant property, however, they showed a lower stability over time due to continuous viscosity pick up.
Therefore, there is felt a need to develop a copolymer composition and adhesives made therefrom which obviates the drawbacks mentioned herein above or to at least provides an alternative solution.
OBJECTS
Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows.
An object of the present disclosure is to ameliorate one or more problems of the background or to at least provide a useful alternative.
Another object of the present disclosure is to provide a copolymer composition.
Yet another object of the present disclosure is to provide a copolymer composition that is highly stable and has a long shelf life.
Still another object of the present disclosure is to provide a copolymer composition that is resistant to both cold water and boiling water along with good balance of elongation and tensile strength.
Yet another object of the present disclosure is to provide a copolymer composition that has applicability at both low and high temperature.
Still another object of the present disclosure is to provide adhesives made from the copolymer composition.
Other objects and advantages of the present disclosure will be more apparent from the following description, which is not intended to limit the scope of the present disclosure.
SUMMARY
In an aspect, copolymer composition comprising a reaction product of a vinyl monomer, capped polyurethane, a polyvinyl alcohol grafted epoxy compound, at least one first catalyst, at least one second catalyst, additives, and demineralized water.
In an embodiment of the present disclosure, the additives comprise at least one defoamer, at least one buffer solution, at least one stabilizer, and at least one initiator.
In an embodiment of the present disclosure, the vinyl monomer is at least one selected from the group consisting of vinyl acetate, vinyl decanoate, vinyl trimethoxy silane, vinyl neodecanoate, vinyl ester of versatic acid 10, vinyl ester of 2-ethyl hexanoic acid, vinyl-terminated polydimethylsiloxane, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated ethylene-siloxane, monovinyl-terminated polydimethylsiloxane, vinylmethylsiloxane terpolymers, vinylalkoxysiloxane homopolymer, methacryloxypropyl polydimethylsiloxanes, (methacryloxypropyl)methylsiloxane-dimethylsiloxane, and 4-(vinyloxy)butyl benzoate.
In an embodiment of the present disclosure, the epoxy compound is at least one selected from the group consisting of diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of bisphenol-AP, diglycidyl ether of bisphenol-C, diglycidyl ether of bisphenol-E, diglycidyl ether of bisphenol-S, and diglycidal ether of hexa hydroxyphtalic anhydride (HHPA).
In an embodiment of the present disclosure, the first catalyst is at least one selected from the group consisting of dibutyl tin dilaurate, dibutyltin diacetate, dimethyltin dioleate, dibutyltin dimaleate, dioctyltin dilaurate, tertiary butyl hydroperoxide, hydrogen peroxide, tert-Butyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate.
In an embodiment of the present disclosure, the second catalyst is at least one selected from the group consisting of tertiary butyl hydroperoxide, sodium formaldehyde sulfoxylate, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, tert-Butyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate.
In an embodiment of the present disclosure, the defoamer is organo-silicon polymers selected from polysiloxne containing polyglycol, and polyether siloxane copolymer.
In an embodiment of the present disclosure, the buffer solution is selected from the group consisting of ammonia buffer, sodium bicarbonate buffer and sodium acetate buffer.
In an embodiment of the present disclosure, the stabilizer is selected from the group consisting of a first stabilizer and a second stabilizer, wherein the first stabilizer is selected from the group consisting of sodium, potassium, or ammonium salts of fatty acids; C12 - C16 alkyl sulfates selected from ammonium persulfate, sodium dodecyl sulfate (SDS), sodium lauryl sulfate (SLS), nonionic surfactants selected from the group consisting of poly(ethylene oxide) cellulose and hydroxyethyl cellulose, and wherein the in can stabilizer is selected from the group consisting of polyvinyl alcohol and a mixture of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.
In an embodiment of the present disclosure, the initiator is selected from the group consisting of ammonium persulfate, potassium persulfate, sodium persulfate and sodium metabisulfite.
In an embodiment of the present disclosure, at least one end of the capped polyurethane is capped with a capping agent; wherein the capping agent is at least one selected from the group consisting of alcohol, and hydroxyl-acrylate component.
In an embodiment of the present disclosure, the hydroxyl-acrylate component is at least one selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N-hydroxyethyl acrylamide, N-(2-hydroxypropyl)methacrylamide, 3-phenoxy-2-hydroxypropyl methacrylate, glycerol methacrylate and polyethyleneglycol monomethacrylate.
In an embodiment of the present disclosure, the alcohol is at least one selected from the group consisting of isopropyl alcohol, isobutyl alcohol, iso-octyl alcohol, and benzyl alcohol.
In an embodiment of the present disclosure, the backbone of the capped polyurethane is modified by at least one modifier selected from the group consisting of epoxy component, and siloxane component.
In an embodiment of the present disclosure, the epoxy component is at least one selected from the group consisting of diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of bisphenol-AP, diglycidyl ether of bisphenol-C, diglycidyl ether of bisphenol-E and diglycidyl ether of bisphenol-S
In an embodiment of the present disclosure, the siloxane component is at least one selected from silanol functional phenyl-propyl polysiloxane, silanol functional phenyl polysiloxane, silanol functional methyl polysiloxane, dihydroxypolydimethylsiloxane, dihydroxypolydiethylsiloxane and amino silane compounds; wherein i) wherein the amino silanes are selected from 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-methyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-triethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride.
In an embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is in the range of 1:5 to 1:95.
In an embodiment of the present disclosure, the first catalyst is present in an amount in the range of 0.01 mass% to 1 mass%, the second catalyst is present in an amount in the range of 0.01 mass% to 0.1 mass%, the additives are present in an amount in the range 2 mass% to 8 mass%, and the demineralized water is present in an amount in the range of 30 mass% to 50 mass%, wherein the mass% are with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the capped polyurethane is present in an amount in the range of 0.1 mass% to 6 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the vinyl monomer is present in an amount in the range of 40 mass% to 65 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the polyvinyl alcohol is present in an amount in the range of 1 mass% to 10 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the epoxy compound is present in an amount in the range of 0.1 mass% to 2 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the defoamer is present in an amount in the range of 0.02 mass% to 0.2 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the buffer solution is present in an amount in the range of 0.02 mass % to 0.2 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the stabilizer is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the initiator is present in an amount in the range of 2 mass% to 6 mass% with respect to the total mass of the copolymer composition.
In a second aspect, the present disclosure relates to a process for the preparation of a copolymer composition. The process comprises the following steps:
i. obtaining a capped polyurethane;
ii. separately, dissolving predetermined amount of polyvinyl alcohol in a predetermined amount of demineralized water in a reactor at a first predetermined temperature under stirring for a first predetermined time period followed by cooling to a temperature in the range of 60 °C to 75 °C to obtain a first mixture;
iii. adding a predetermined amount of an epoxy compound and a first catalyst to the first mixture at a temperature in the range of 60 °C to 75 °C for a time period in the range of 1 hour to 3 hours to obtain a second mixture comprising polyvinyl alcohol grafted epoxy compound;
iv. separately, mixing a predetermined amount of at least one vinyl monomer with a predetermined amount of the capped polyurethane to obtain a third mixture;
v. mixing first portions of a buffer solution, a defoamer, the third mixture and a predetermined amount of a first stabilizer with the second mixture, followed by adding a first portion of an initiator at a second predetermined temperature under stirring for a second predetermined time period to obtain a fourth mixture;
vi. gradually adding second portions of the third mixture in the fourth mixture for a time period in the range of 5 hours to 7 hours followed by simultaneous addition of second portion of the initiator over a third predetermined time period at a temperature in range of 50 °C to 70 °C to obtain a fifth mixture;
vii. adding a predetermined amount of a second catalyst to the fifth mixture at a third predetermined temperature under stirring for a time period in the range of 20 minutes to 40 minutes to obtain a slurry; and
viii. cooling the slurry to a fourth predetermined temperature followed by mixing second portions of the defoamer, the buffer solution and a predetermined amount of the second stabilizer to the slurry at a fourth predetermined temperature under stirring for a fourth predetermined time period to obtain the copolymer composition.
In an embodiment of the present disclosure, the predetermined amount of the demineralized water is in the range of 30 mass% to 50 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the predetermined amount of polyvinyl alcohol is in an amount in the range of 1 mass% to 10 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the epoxy compound is at least one selected from the group consisting of diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of bisphenol-AP, diglycidyl ether of bisphenol-C, diglycidyl ether of bisphenol-E, diglycidyl ether of bisphenol-S, and diglycidal ether of hexahydrophthalic anhydride (HHPA).
In an embodiment of the present disclosure, the predetermined amount of the epoxy compound is in the range of 0.1 mass% to 2 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the first catalyst is at least one selected from the group consisting of tertiary butyl hydroperoxide, hydrogen peroxide, tert-Butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tertiary butyl hydroperoxide, hydrogen peroxide, tert-Butyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate.
In an embodiment of the present disclosure, the predetermined amount of the first catalyst is in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the predetermined amount of the vinyl monomer in an amount in is in the range of 40 mass% to 65 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the predetermined amount of the capped polyurethane is in an amount in the range of 0.1 mass % to 6 mass% with respect to total mass of the copolymer composition.
In an embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is in the range of 1:5 to 1:95.
In an embodiment of the present disclosure, the buffer solution is at least one selected from the group consisting of ammonia, sodium bicarbonate, and sodium acetate.
In an embodiment of the present disclosure, the first portion of the buffer solution is in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the defoamer is organo-silicon polymer selected from polysiloxane containing polyglycol, and polyether siloxane copolymer.
In an embodiment of the present disclosure, the first portion of the defoamer is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the first stabilizer is selected from the group consisting of sodium, potassium, or ammonium salts of fatty acids; C12 - C16 alkyl sulfates selected from ammonium persulfate, sodium dodecyl sulfate (SDS), sodium lauryl sulfate (SLS), nonionic stabilizer selected from the group consisting of poly(ethylene oxide) cellulose and hydroxyethyl cellulose.
In an embodiment of the present disclosure, the predetermined amount of the first stabilizer is in the range of 1 mass% to 2 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the first portion of the third mixture is in the range of 3 mass% to 8 mass% with respect to the total mass of the third mixture.
In an embodiment of the present disclosure, the initiator is at least one selected from the group consisting of ammonium persulfate, potassium persulfate, sodium persulfate, and sodium metabisulfite.
In an embodiment of the present disclosure, the first portion of the initiator is in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of copolymer composition.
In an embodiment of the present disclosure, the second portion of the initiator is in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the second portion of the third mixture is in an amount in the range of 92 mass% to 97 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the second catalyst is at least one selected from the group consisting of tertiary butyl hydroperoxide, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, tert-Butyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate.
In an embodiment of the present disclosure, the predetermined amount of the second catalyst is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the second portion of the defoamer is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the second portion of the buffer solution is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the second stabilizer is at least one selected from 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4- isothiazolin-3-one.
In an embodiment of the present disclosure, the predetermined amount of the second stabilizer is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the first predetermined temperature is in the range of 85 °C to 95 °C; the first predetermined time period is in the range of 3 hours to 7 hours; the second predetermined temperature is in the range of 50 °C to 70 °C; the second predetermined time period is in the range of 10 minutes to 30 minutes; the third predetermined temperature is in the range of 50 °C to 70 °C; the third predetermined time period is in the range of 30 minutes to 90 minutes; the fourth predetermined temperature is in the range of 25 °C to 45 °C; and the fourth predetermined time period is in the range of 10 minutes to 30 minutes.
In a third aspect, the present disclosure relates to an adhesive composition. The adhesive composition comprises a polyvinyl alcohol, a copolymer composition, a third stabilizer, demineralized water, a cosolvent, and optionally an acrylic emulsion.
In an embodiment of the present disclosure, the third stabilizer is at least one selected from the group consisting of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.
In an embodiment of the present disclosure, the acrylic emulsion is at least one selected from the group consisting of polyacrylic emulsion, styrene-acrylic emulsion, polyacrylamide-acrylic emulsion, wax-acrylic emulsion, and vinyl acetate monomer (VAM) – acrylic emulsion.
In an embodiment of the present disclosure, the cosolvent is at least one selected from the group consisting of butyl carbitol, methyl carbitol, butyl acetate, texanol, butyl carbitol acetate, ethyl carbitol acetate, hexyl carbitol, and propyl cellosolve.
In an embodiment of the present disclosure, the polyvinyl alcohol is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the copolymer composition is present in an amount in an amount in the range of 80 mass% to 90 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the third stabilizer is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the demineralized water is in an amount in the range of 6 mass% to10 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the acrylic emulsion is present in an amount in the range of 1 mass% to 5 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the cosolvent is present in an amount in the range of 2 mass% to 5 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the adhesive composition is characterized by having a lap shear strength in the range of 10.5 MPa to 13 MPa; viscosity at 30 °C in the range of 90 poise to 150 poise; D3 durability lap shear strength in the range of 2 MPa to 2.5 MPa; and drying time at 5 °C in the range of 40 hours to 100 hours.
In a fourth aspect the present disclosure, relates to a process for the preparation of an adhesive composition. The process comprising the following steps:
i) charging predetermined amounts of poly vinyl alcohol and demineralized water in a reactor under stirring at a temperature in the range of 80 °C to 100 °C for a time period in the range of 1 hour to 3 hours followed by cooling at a temperature in the range of 50 °C to 70 °C to obtain a resultant mixture; and
ii) mixing predetermined amounts of the copolymer composition, the third stabilizer, the cosolvent, and optionally the acrylic emulsion to the resultant mixture under stirring at a temperature in the range of 30 °C to 45 °C for a time period in the range of 30 minutes to 90 minutes to obtain the adhesive composition.
DETAILED DESCRIPTION
The present disclosure relates to a copolymer composition and adhesives made therefrom.
Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.
The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms "a,” "an," and "the" may be intended to include the plural forms as well, unless the context clearly suggests otherwise. The terms "comprises," "comprising," “including,” and “having,” are open ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, modules, units and/or components, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the method and process of the present disclosure is not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed elements.
The terms first, second, third, etc., should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.
The use of homopolymer or copolymer of vinyl acetate-based adhesive has been known since long, due to their various advantages such as suitable rheology, good adhesion to cellulose substrates, setting speed, high cohesion of the polymer film, and the like. Conventionally, the copolymers of vinyl ester comprise self-crosslinking comonomer units with N-methylol or N-methylol ether functions to improve their strength.
The conventional homopolymer or copolymer of vinyl acetate-based adhesive has poor applicability at low temperature and high temperature. Further, the conventional homopolymer or copolymer of vinyl acetate has poor elongation and water resistance. Furthermore, the conventional vinyl acetate-based homopolymer or copolymer prepared by pre or post crosslinking route, has better water resistance, however, they have very less shelf life due to continuous viscosity pick up with time. This was generally may be due to use of pre or post addition of cross-linkers.
Conventionally, the characteristics of high-range water-resistant vinyl acetate copolymers were usually obtained by inserting a self-crosslinking comonomer alone or mixtures of two or more compounds. Further, the conventional copolymers also used either organic crosslinkers (such as glyoxal, glutaraldehyde, citric acid, tartaric acid, and the like) or inorganic crosslinkers also known as acidic metal salts (such as A1C13, AlNO3, borates, and the like) in combination with the self-crosslinking comonomer. All the above conventional compositions had good water-resistant property, however, they showed a lower stability over time due to continuous viscosity pick up.
The present disclosure provides a copolymer composition and adhesives made therefrom.
In a first aspect, the present disclosure provides a copolymer composition. The copolymer composition is a reaction product of a vinyl monomer, capped polyurethane, a polyvinyl alcohol grafted epoxy compound, at least one first catalyst, at least one second catalyst, additives, and demineralized water.
In an embodiment of the present disclosure, the additives comprise at least one defoamer, at least one buffer solution, at least one stabilizer, and at least one initiator.
In an embodiment of the present disclosure, the vinyl monomer is at least one selected from the group consisting of vinyl acetate, vinyl decanoate, vinyl trimethoxy silane, vinyl neodecanoate, vinyl ester of versatic acid 10, vinyl ester of 2-ethyl hexanoic acid, vinyl-terminated polydimethylsiloxane, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated ethylene-siloxane, monovinyl-terminated polydimethylsiloxane, vinylmethylsiloxane terpolymers, vinylalkoxysiloxane homopolymer, methacryloxypropyl polydimethylsiloxanes, (methacryloxypropyl)methylsiloxane-dimethylsiloxane, and 4-(vinyloxy)butyl benzoate. In an exemplary embodiment of the present disclosure, the vinyl monomer is a mixture of vinyl acetate, vinyl decanoate, and vinyl trimethoxy silane. In an exemplary embodiment of the present disclosure, the vinyl monomer is a mixture of vinyl acetate, vinyl decanoate, and vinyl trimethoxy silane.
In an embodiment of the present disclosure, the epoxy compound is at least one selected from the group consisting of diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of bisphenol-AP, diglycidyl ether of bisphenol-C, diglycidyl ether of bisphenol-E, diglycidyl ether of bisphenol-S, and diglycidal ether of HHPA. In an exemplary embodiment of the present disclosure, the epoxy compound is diglycidyl ether of bisphenol-A.
In an embodiment of the present disclosure, the first catalyst is selected from the group consisting of dibutyl tin dilaurate, dibutyltin diacetate, dimethyltin dioleate, dibutyltin dimaleate and dioctyltin dilaurate. In an exemplary embodiment of the present disclosure, the first catalyst is dibutyl tin dilaurate.
In an embodiment of the present disclosure, the second catalyst is selected from the group consisting of ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, tert-butyl peroxy-2-ethyl hexanoate, and tert-butyl hydroperoxide. In an exemplary embodiment of the present disclosure, the second catalyst is a mixture of sodium formaldehyde sulfoxylate and tert-butyl hydroperoxide.
In an embodiment of the present disclosure, the defoamer is organo-silicon polymersselected from polysiloxne containing polyglycol, and polyether siloxane copolymer. In an exemplary embodiment of the present disclosure, the defoamer is polyether siloxane copolymer.
In an embodiment of the present disclosure, the buffer solution is selected from the group consisting of ammonia buffer, sodium bicarbonate buffer, and sodium acetate buffer. In an exemplary embodiment of the present disclosure, the buffer solution is sodium bicarbonate buffer.
In an embodiment of the present disclosure, the stabilizer is selected from the group consisting of a first stabilizer and a second stabilizer.
In an embodiment of the present disclosure, the first stabilizer is selected from the group consisting of sodium, potassium, or ammonium salts of fatty acids; C12 - C16 alkyl sulfates selected from ammonium persulfate, sodium dodecyl sulfate (SDS), sodium lauryl sulfate (SLS), nonionic surfactants selected from the group consisting of poly(ethylene oxide) cellulose and hydroxyethyl cellulose. In an exemplary embodiment of the present disclosure, the first stabilizer is sodium lauryl sulphate and nonionic alcohol ethoxylate.
In an embodiment of the present disclosure, the second stabilizer is selected from the group consisting of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one. In an exemplary embodiment of the present disclosure, the second stabilizer is a mixture of chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.
In an embodiment of the present disclosure, the initiator is selected from the group consisting of ammonium persulfate, potassium persulfate, sodium persulfate, and sodium metabisulfite. In an exemplary embodiment of the present disclosure, the initiator is a mixture of ammonium persulfate and sodium metabisulfite.
In an embodiment of the present disclosure, at least one end of the capped polyurethane is capped with a capping agent.
In an embodiment of the present disclosure, the capping agent is at least one selected from the group consisting of alcohol, and hydroxyl-acrylate component. In an exemplary embodiment of the present disclosure, the capping agent is hydroxyl-acrylate component.
In an embodiment of the present disclosure, the hydroxyl-acrylate component is at least one selected from diisocyanatehydroxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N-hydroxyethyl acrylamide, N-(2-hydroxypropyl)methacrylamide, 3-phenoxy-2-hydroxypropyl methacrylate, glycerol methacrylate and polyethyleneglycol monomethacrylate. In a first exemplary embodiment of the present disclosure, the hydroxyl-acrylate component is hydroxypropyl acrylate. In a second exemplary embodiment of the present disclosure, the hydroxyl-acrylate component is hydroxyethyl methacrylate. In a third exemplary embodiment of the present disclosure, the hydroxyl-acrylate component is polyethyleneglycol monomethacrylate. In a fourth exemplary embodiment of the present disclosure, the hydroxyl-acrylate component is N-Hydroxyethyl acrylamide. In a fifth exemplary embodiment of the present disclosure, the hydroxyl-acrylate component is N-(2-Hydroxypropyl) methacrylamide.
In an embodiment of the present disclosure, the alcohol is at least one selected from the group consisting of isopropyl alcohol, isobutyl alcohol, iso-octyl alcohol, and benzyl alcohol. In a first exemplary embodiment of the present disclosure, the alcohol is isopropyl alcohol. In a second exemplary embodiment of the present disclosure, the alcohol is isobutyl alcohol. In a third exemplary embodiment of the present disclosure, the alcohol is isooctyl alcohol. In a fourth exemplary embodiment of the present disclosure, the alcohol is benzyl alcohol.
In an embodiment of the present disclosure, the backbone of the capped polyurethane is modified by at least one modifier selected from the group consisting of epoxy component, and siloxane component. In an exemplary embodiment of the present disclosure, the modifier is an epoxy component. In another exemplary embodiment of the present disclosure, the modifier is a siloxane component.
In an embodiment of the present disclosure, the epoxy component is at least one selected from the group consisting of diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of bisphenol-AP, diglycidyl ether of bisphenol-C, diglycidyl ether of bisphenol-E and diglycidyl ether of bisphenol-S. In an exemplary embodiment of the present disclosure, the epoxy component is diglycidyl ether of bisphenol-A.
In an embodiment of the present disclosure, the siloxane component is selected from silanol functional phenyl-propyl polysiloxane, silanol functional phenyl polysiloxane, silanol functional methyl polysiloxane, dihydroxypolydimethylsiloxane, dihydroxypolydiethylsiloxane, and amino silanes. In an embodiment of the present disclosure, the amino silanes are selected from 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-methyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-triethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride. In an exemplary embodiment of the present disclosure, the siloxane component is silanol functional phenyl-propyl polysiloxane.
In an embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is in the range of 1:5 to 1:95. In a first exemplary embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is 1:94.4. In a second exemplary embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is 1:23.1. In a third exemplary embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is 1:9.25. In a fourth exemplary embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is 1:23.6. In a fifth exemplary embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is 1:23.1.
In an embodiment of the present disclosure, the first catalyst is present in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the first catalyst is present in an amount of 0.01 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the second catalyst is present in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the second catalyst is present in an amount of 0.05 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the additives are present in an amount in the range 2 mass% to 8 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the additives are present in an amount of 6.4 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the demineralized water is present in an amount in the range of 30 mass% to 50 mass% with respect to the total mass of the copolymer composition. In a first exemplary embodiment of the present disclosure, the demineralized water is present in an amount of 40.75 mass%; wherein the mass% are with respect to the total mass of the copolymer composition. In a second exemplary embodiment of the present disclosure, the demineralized water is present in an amount of 39.18 mass%; wherein the mass% are with respect to the total mass of the copolymer composition. In a third exemplary embodiment of the present disclosure, the demineralized water is present in an amount of 36.13 mass%; wherein the mass% are with respect to the total mass of the copolymer composition. In a fourth exemplary embodiment of the present disclosure, the demineralized water is present in an amount of 38.18 mass%; wherein the mass% are with respect to the total mass of the copolymer composition. In a fifth exemplary embodiment of the present disclosure, the demineralized water is present in an amount of 39.08 mass%; wherein the mass% are with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the capped polyurethane is present in an amount in the range of 0.1 mass% to 6 mass% with respect to the total mass% of the copolymer composition. In a first exemplary embodiment of the present disclosure, the capped polyurethane is present in an amount of 0.5 mass% with respect to the total mass of the copolymer composition. In a second exemplary embodiment of the present disclosure, the capped polyurethane is present in an amount of 2 mass% with respect to the total mass of the copolymer composition. In a third exemplary embodiment of the present disclosure, the capped polyurethane is present in an amount of 5 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the vinyl monomer is present in an amount in the range of 40 mass% to 65 mass% with respect to the total mass of the copolymer composition. In a first exemplary embodiment of the present disclosure, the predetermined amount of the vinyl monomer is 47.2 mass% with respect to the total mass of the copolymer composition. In a second exemplary embodiment of the present disclosure, the predetermined amount of the vinyl monomer is 46.2 mass% with respect to the total mass of the copolymer composition. In a third exemplary embodiment of the present disclosure, the predetermined amount of the vinyl monomer is 46.2 mass% with respect to the total mass of the copolymer composition. In a fourth exemplary embodiment of the present disclosure, the predetermined amount of the vinyl monomer is 47.2 mass% with respect to the total mass of the copolymer composition. In a fifth exemplary embodiment of the present disclosure, the predetermined amount of the vinyl monomer is 46.3 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the polyvinyl alcohol is present in an amount in the range of 1 mass% to 10 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the polyvinyl alcohol is present in an amount of 4 mass% with respect to the total mass of the copolymer composition. In another exemplary embodiment of the present disclosure, the polyvinyl alcohol is present in an amount of 5 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the epoxy compound is present in an amount in the range of 0.1 mass% to 2 mass% with respect to the total mass% of the copolymer composition. In an exemplary embodiment of the present disclosure, the epoxy compound is present in an amount in the range of 1 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the defoamer is present in an amount in the range of 0.02 mass% to 0.2 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the defoamer is present in an amount in the range of 0.1 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the buffer solution is present in an amount in the range of 0.02 mass % to 0.2 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the buffer solution is present in an amount in the range of 0.1 mass% with respect to the total mass of the copolymer composition. In another exemplary embodiment of the present disclosure, the buffer solution is present in an amount in the range of 0.07 mass% with respect to the total mass of the copolymer composition
In an embodiment of the present disclosure, the stabilizer is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the stabilizer is present in an amount in the range of 1.54 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the initiator is present in an amount in the range of 2 mass% to 6 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the initiator is present in an amount in the range of 4.7 mass% with respect to the total mass of the copolymer composition. In another exemplary embodiment of the present disclosure, the initiator is present in an amount in the range of 4.8 mass% with respect to the total mass of the copolymer composition.
In a second aspect the present disclosure, provides a process for the preparation of a copolymer composition. The process comprises the following steps.
i) obtaining a capped polyurethane;
ii) separately, dissolving predetermined amount of polyvinyl alcohol in a predetermined amount of demineralized water in a reactor at a first predetermined temperature under stirring for a first predetermined time period followed by cooling to a temperature in the range of 60 °C to 75 °C to obtain a first mixture;
iii) adding a predetermined amount of an epoxy compound and a first catalyst in the first mixture at a temperature in the range of 60 °C to 75 °C for a time period in the range of 1 hour to 3 hours to obtain a second mixture comprising polyvinyl alcohol grafted epoxy compound;
iv) separately, mixing a predetermined amount of at least one vinyl monomer with a predetermined amount of the capped polyurethane to obtain a third mixture;
v) mixing first portions of a buffer solution, a defoamer, the third mixture and a predetermined amount of a first stabilizer with the second mixture, followed by adding a first portion of an initiator at a second predetermined temperature under stirring for a second predetermined time period to obtain a fourth mixture;
vi) gradually adding second portions of the third mixture in the fourth mixture for a time period in the range of 5 hours to 7 hours followed by simultaneous addition of second portion of the initiator over a third predetermined time period at a temperature in range of 50 °C to 70 °C to obtain a fifth mixture;
vii) adding a predetermined amount of a second catalyst to the fifth mixture at a third predetermined temperature under stirring for a time period in the range of 20 minutes to 40 minutes to obtain a slurry; and
viii) cooling the slurry at a fourth predetermined temperature followed by mixing second portions of the defoamer, the buffer solution and a predetermined amount of the second stabilizer to the slurry at the fourth predetermined temperature under stirring for a fourth predetermined time period to obtain the copolymer composition.
The process is described in detail below.
In a first step, the capped polyurethane is obtained.
In an embodiment of the present disclosure, the capped polyurethane is obtained by mixing and reacting a predetermined amount of a polyol with a predetermined amount of a diisocyanate monomer in a predetermined ratio, in the presence of a predetermined amount of a capping agent, optionally, a predetermined amount of a modifier and optionally, a predetermined amount of a third catalyst, under stirring at a speed in the range of 60 rpm to 100 rpm at a temperature in a range of 50 °C to 100 °C.
In an embodiment of the present disclosure, polyol is at least one selected from the group consisting of polypropylene glycol, polyether polyol, polycarbonate polyol, polyester polyol, poly(tetramethylene ether) glycol.
In an embodiment of the present disclosure, the predetermined amount of the polyol is in the range of 50 mass% to 80 mass% with respect to the total mass of the capped polyurethane.
In an embodiment of the present disclosure, the diisocyanate monomer is at least one selected from the group consisting of an isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated toluene diisocyanate, toluene diisocyanate, hydrogenated diphenylmethane diisocyanate, and diphenylmethane diisocyanate.

In an embodiment of the present disclosure, the predetermined amount of the diisocyanate monomer is in the range of 10 mass% to 25 mass% with respect to the total mass of the capped polyurethane.

In an embodiment of the present disclosure, a predetermined mole ratio of the polyol to the diisocyanate is in the range of 1:1.1 to 1: 2.5.

In an embodiment of the present disclosure, the capping agent is at least one selected from alcohol, and hydroxyl-acrylate component. In an exemplary embodiment of the present disclosure, the capping agent is hydroxyl-acrylate component. In an another embodiment of the present disclosure, the capping agent is alcohol.
In an embodiment of the present disclosure, the hydroxyl-acrylate component is selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N-hydroxyethyl acrylamide, N-(2-hydroxypropyl) methacrylamide, 3-phenoxy-2-hydroxypropyl methacrylate, glycerol methacrylate, and polyethyleneglycol monomethacrylate.
In an embodiment of the present disclosure, the predetermined amount of the hydroxyl-acrylate component is present in an amount in the range of 2 mass% to 13 mass% with respect to the mass of the capped polyurethane.
In an embodiment of the present disclosure, the alcohol is selected from the group consisting of isopropyl alcohol, isobutyl alcohol, iso-octyl alcohol, and benzyl alcohol. In an exemplary embodiment of the present disclosure, the alcohol is isopropyl alcohol. In another exemplary embodiment of the present disclosure, the alcohol is isobutyl alcohol. In still another exemplary embodiment of the present disclosure, the alcohol is iso-octyl alcohol. In yet another exemplary embodiment of the present disclosure, the alcohol is benzyl alcohol.
In an embodiment of the present disclosure, the backbone of the capped polyurethane is modified by at least one modifier selected from the group consisting of epoxy component, and siloxane component. In an exemplary embodiment of the present disclosure, the modifier is an epoxy component. In another exemplary embodiment of the present disclosure, the modifier is a siloxane component.
In an embodiment of the present disclosure, the epoxy component is selected from the group consisting of diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of bisphenol-AP, diglycidyl ether of bisphenol-C, diglycidyl ether of bisphenol-E and diglycidyl ether of bisphenol-S.
In an embodiment of the present disclosure, the siloxane component is selected from silanol functional phenyl-propyl polysiloxane, silanol functional phenyl polysiloxane, silanol functional methyl polysiloxane, dihydroxypolydimethylsiloxane, dihydroxypolydiethylsiloxane, and amino silane. In an embodiment of the present disclosure, the amino silanes are selected from 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-methyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-triethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride.`
In an embodiment of the present disclosure, the predetermined amount of the capping agent is in the range of 5 mass% to 25 mass% with respect to the mass of the capped polyurethane.
In an embodiment of the present disclosure, the modifier is selected from the group consisting of bisphenol-A epoxy, diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of bisphenol-AP, diglycidyl ether of bisphenol-C, diglycidyl ether of bisphenol-E, diglycidyl ether of bisphenol-S, silanol functional phenyl-propyl polysiloxane, silanol functional phenyl polysiloxane, silanol functional methyl polysiloxane, dihydroxypolydimethylsiloxane, dihydroxypolydiethylsiloxane and amino silane compounds. In an exemplary embodiment of the present disclosure, the modifier is bisphenol-A epoxy.
In an embodiment of the present disclosure, alcohol is a water compatible hydroxyl terminated alcohol.
In an embodiment of the present disclosure, the alcohol is in the range of 3 mass% to 12 mass% with respect to the total mass of the capped polyurethane.
In an embodiment of the present disclosure, the third catalyst is selected from the group consisting of di(n butyl) tin dilaurate, dibutyltin diacetate, dimethyltin dioleate, dibutyltin dimaleate and dioctyltin dilaurate. In an exemplary embodiment of the present disclosure, the third catalyst is di(n butyl) tin dilaurate.
In an embodiment of the present disclosure, the predetermined amount of the third catalyst is in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the capped polyurethane. In an exemplary embodiment of the present disclosure, the predetermined amount of the third catalyst is 0.03 mass% with respect to the total mass of the capped polyurethane.
In a second step, separately, a predetermined amount of polyvinyl alcohol is dissolved in a predetermined amount of demineralized water in a reactor at a first predetermined temperature under stirring for a first predetermined time period followed by cooling to a temperature in the range of 60 °C to 75 °C to obtain a first mixture.
In an embodiment of the present disclosure, the predetermined amount of the demineralized water is in the range of 30 mass% to 50 mass% with respect to the total mass of the copolymer composition. In a first exemplary embodiment of the present disclosure, the predetermined amount of the demineralized water is 40.75 mass% with respect to the total mass of the copolymer composition. In a second exemplary embodiment of the present disclosure, the predetermined amount of the demineralized water is 39.18 mass% with respect to the total mass of the copolymer composition. In a third exemplary embodiment of the present disclosure, the predetermined amount of the demineralized water is 36.13 mass% with respect to the total mass of the copolymer composition. In a fourth exemplary embodiment of the present disclosure, the predetermined amount of the demineralized water is 38.18 mass% with respect to the total mass of the copolymer composition. In a fifth exemplary embodiment of the present disclosure, the predetermined amount of the demineralized water is 39.08 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the predetermined amount of polyvinyl alcohol is in an amount in the range of 1 mass% to 10 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the predetermined amount of polyvinyl alcohol is 4 mass% with respect to the total mass of the copolymer composition. In another exemplary embodiment of the present disclosure, the predetermined amount of polyvinyl alcohol is 5 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the first predetermined temperature is in the range of 85 °C to 95 °C. In an exemplary embodiment of the present disclosure, the first predetermined temperature is 90°C.

In an embodiment of the present disclosure, the first predetermined time period is in the range of 3 hours to 7 hours. In an exemplary embodiment of the present disclosure, the first predetermined time period is 5 hours.
In a third step, a predetermined amount of an epoxy compound and a first catalyst is added in the first mixture at a temperature in the range of 60 °C to 75 °C for a time period in the range of 1 hour to 3 hours to obtain a second mixture comprising polyvinyl alcohol grafted epoxy compound.
In an embodiment of the present disclosure, the epoxy compound is selected from the group consisting of diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of bisphenol-AP, diglycidyl ether of bisphenol-C, diglycidyl ether of bisphenol-E, diglycidyl ether of bisphenol-S, and diglycidal ether of hexahydrophthalic anhydride (HHPA). In an exemplary embodiment of the present disclosure, the epoxy compound is diglycidyl ether of bisphenol-A.
In an embodiment of the present disclosure, the predetermined amount of the epoxy compound is in the range of 0.1 mass% to 2 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the predetermined amount of the epoxy compound is 1 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the first catalyst is at least one selected from the group consisting of dibutyl tin dilaurate, dibutyltin diacetate, dimethyltin dioleate, dibutyltin dimaleate, and dioctyltin dilaurate, andtertiary butyl hydroperoxide, hydrogen peroxide, tert-Butyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate. In an exemplary embodiment of the present disclosure, the first catalyst is tertiary butyl hydroperoxide.
In an embodiment of the present disclosure, the predetermined amount of the first catalyst is in the range of 0.01 mass% to 0.1 mass% with respect to the mass of with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the first catalyst is 0.01 mass% with respect to the mass of with respect to the total mass of the copolymer composition.
In an exemplary embodiment of the present disclosure, 1 mass% of an epoxy compound and 0.01 mass% of first catalyst is added to the first mixture at a temperature of 70 °C for a time period of 2 hours to obtain a second mixture comprising polyvinyl alcohol grafted epoxy compound.
In a fourth step, separately, a predetermined amount of at least one vinyl monomer is mixed with a predetermined amount of the capped polyurethane to obtain a third mixture.
In an embodiment of the present disclosure, the vinyl monomer is at least one selected from vinyl acetate, vinyl decanoate, vinyl trimethoxy silane, vinyl neodecanoate, vinyl ester of versatic acid 10, vinyl ester of 2-ethyl hexanoic acid, vinyl-terminated polydimethylsiloxane, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated ethylene-siloxane, monovinyl-terminated polydimethylsiloxane, vinylmethylsiloxane terpolymers, vinylalkoxysiloxane homopolymer, methacryloxypropyl polydimethylsiloxanes, (methacryloxypropyl)methylsiloxane-dimethylsiloxane, and 4-(vinyloxy)butyl benzoate. In an exemplary embodiment of the present disclosure, the vinyl monomer is a mixture of vinyl acetate, vinyl decanoate, and vinyl trimethoxy silane.
In an embodiment of the present disclosure, the predetermined amount of the vinyl monomer is in the range of 40 mass% to 65 mass% with respect to the total mass of the copolymer composition. In a first exemplary embodiment of the present disclosure, the predetermined amount of the vinyl monomer is 47.2 mass% with respect to the total mass of the copolymer composition. In a second exemplary embodiment of the present disclosure, the predetermined amount of the vinyl monomer is 46.2 mass% with respect to the total mass of the copolymer composition. In a third exemplary embodiment of the present disclosure, the predetermined amount of the vinyl monomer is 46.25 mass% with respect to the total mass of the copolymer composition. In a fourth exemplary embodiment of the present disclosure, the predetermined amount of the vinyl monomer is 47.2 mass% with respect to the total mass of the copolymer composition. In a fifth exemplary embodiment of the present disclosure, the predetermined amount of the vinyl monomer is 47.2 mass% with respect to the total mass of the copolymer composition.
In a first exemplary embodiment of the present disclosure, vinyl acetate is present in an amount of 45 mass%, vinyl decanoate is present in an amount of 2 mass%, and vinyl trimethoxy silane is present in an amount of 0.2 mass%. In a second exemplary embodiment of the present disclosure, vinyl acetate is present in an amount of 44 mass%, vinyl decanoate is present in an amount of 2 mass%, and vinyl trimethoxy silane is present in an amount of 0.2 mass%. In a third exemplary embodiment of the present disclosure, vinyl acetate is present in an amount of 44 mass%, vinyl decanoate is present in an amount of 2 mass%, and vinyl trimethoxy silane is present in an amount of 0.25 mass%. In a fourth exemplary embodiment of the present disclosure, vinyl acetate is present in an amount of 44 mass%, vinyl decanoate is present in an amount of 2 mass%, and vinyl trimethoxy silane is present in an amount of 0.2 mass%. In a fifth exemplary embodiment of the present disclosure, vinyl acetate is present in an amount of 44 mass%, vinyl decanoate is present in an amount of 2 mass%, and vinyl trimethoxy silane is present in an amount of 0.3 mass%; wherein the mass % is with respect to total mass of the copolymer composition.
In an embodiment of the present disclosure, the predetermined amount of the capped polyurethane is in an amount in the range of 0.1 mass % to 6 mass% with respect to total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the predetermined amount of the capped polyurethane is in an amount of 0.5 mass% with respect to the total mass of the copolymer composition. In another exemplary embodiment of the present disclosure, the predetermined amount of the capped polyurethane is in an amount of 2 mass% with respect to the total mass of the copolymer composition. In still another exemplary embodiment of the present disclosure, the predetermined amount of the capped polyurethane is in an amount of 5 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is in the range of 1:5 to 1:95. In first exemplary embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is 1:94.4. In a second exemplary embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is 1:23.1. In a third exemplary embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is 1:9.25. In a fourth exemplary embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is 1:23.6. In a fifth exemplary embodiment of the present disclosure, the mass ratio of the capped polyurethane to the vinyl monomer is 1:23.15.
In a fifth step, the first portions of a buffer solution, a defoamer, the third mixture, and a predetermined amount of a first stabilizer are mixed with the second mixture, followed by adding a first portion of an initiator at a second predetermined temperature and stirring for a second predetermined time period to obtain a fourth mixture.
In an embodiment of the present disclosure, the buffer solution is at least one selected from the group consisting of ammonia, sodium bicarbonate, and sodium acetate. In an exemplary embodiment of the present disclosure, the buffer solution is sodium bicarbonate.
In an embodiment of the present disclosure, the first portion of the buffer is in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the first portion of the buffer is 0.08 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the defoamer is a organo-silicon polymer selected from the group consisting of polysiloxane containing polyglycol, and polyether siloxane copolymer. In an exemplary embodiment of the present disclosure, the defoamer is polyether siloxane copolymer.
In an exemplary embodiment of the present disclosure, the first portion of the defoamer is in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the first portion of the defoamer is 0.05 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the first stabilizer is selected from the group consisting of sodium, potassium, or ammonium salts of fatty acids; C12 - C16 alkyl sulfates selected from ammonium persulfate, sodium dodecyl sulfate (SDS), sodium lauryl sulfate (SLS); nonionic stabilizer selected from the group consisting of poly(ethylene oxide) cellulose and hydroxyethyl cellulose. In an exemplary embodiment of the present disclosure, the first stabilizer is a mixture of sodium lauryl sulfate and ammonium persulfate.
In an embodiment of the present disclosure, the predetermined amount of the first stabilizer is in the range of 1 mass% to 2 mass% with respect to the total mass of the copolymer composition. In an embodiment of the present disclosure, the predetermined amount of the first stabilizer is 1.5 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the first portion of the third mixture is in the range of 3 mass% to 8 mass% with respect to the total mass of the third mixture. In an exemplary embodiment of the present disclosure, the first portion amount of the third mixture is 5 mass% with respect to the total mass of the third mixture.
In an embodiment of the present disclosure, the initiator is at least one selected from the group consisting of ammonium persulfate, potassium persulfate, sodium persulfate, and sodium metabisulfite. In an exemplary embodiment of the present disclosure, the initiator is a mixture of ammonium persulfate and sodium metabisulfite.
In an embodiment of the present disclosure, the first portion of the initiator is in the range of 1 mass% to 3 mass% with respect to the total mass of copolymer composition. In an exemplary embodiment of the present disclosure, the first portion of the initiator is 2.2 mass% with respect to the total mass of copolymer composition.
In an embodiment of the present disclosure, the second predetermined temperature is in the range of 50 °C to 70 °C. In an exemplary embodiment of the present disclosure, the second predetermined temperature is 60°C.

In an embodiment of the present disclosure, the second predetermined time period is in the range of 10 minutes to 30 minutes. In an embodiment of the present disclosure, the second predetermined time period is 15 minutes.

In a sixth step, gradually second portions of the third mixture are added to the fourth mixture for a time period in the range of 5 hours to 7 hours followed by simultaneous addition of second portion of the initiator over a third predetermined time period at a temperature in the range of 50 °C to 70 °C to obtain a fifth mixture.

In an embodiment of the present disclosure, the second portion of the initiator is in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the copolymer composition. In an embodiment of the present disclosure, the second portion of the initiator is 2.5 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the second portion of the third mixture is in an amount in the range of 92 mass% to 97 mass% with respect to the total mass of the third mixture. In an exemplary embodiment of the present disclosure, the second portion of the third mixture is 95 mass% with respect to the total mass of the third mixture.
In the seventh step, a predetermined amount of a second catalyst is added to the fifth mixture at a third predetermined temperature under stirring for a time period in the range of 20 minutes to 40 minutes to obtain a slurry.
In an embodiment of the present disclosure, the second catalyst is at least one selected from the group consisting of tertiary butyl hydroperoxide, sodium formaldehyde sulfoxylate , ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, tert-Butyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate. In an exemplary embodiment of the present disclosure, the second catalyst is tert-butyl hydro peroxide.
In an embodiment of the present disclosure, the predetermined amount of the second catalyst is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the predetermined amount of the second catalyst is 0.05 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the third predetermined temperature is in the range of 50 °C to 70 °C. In an exemplary embodiment of the present disclosure, the third predetermined temperature is 60 °C.

In an embodiment of the present disclosure, the third predetermined time period is in the range of 30 minutes to 90 minutes. In an embodiment of the present disclosure, the third predetermined time period is 60 minutes.
In a final step, the slurry is cooled to a fourth predetermined temperature followed by mixing second portions of the defoamer, the buffer solution, and a predetermined amount of the second stabilizer to the slurry at the fourth predetermined temperature under stirring for a fourth predetermined time period to obtain the copolymer composition.
In an embodiment of the present disclosure, the second portion of the defoamer is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the second portion of the defoamer is in 0.05 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the second portion of the buffer is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the second portion of the buffer is in an amount of 0.02 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the second stabilizer is at least one selected from 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4- isothiazolin-3-one. In an exemplary embodiment of the present disclosure, the second stabilizer is a mixture of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one.
In an embodiment of the present disclosure, the predetermined amount of the second stabilizer is in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition. In an exemplary embodiment of the present disclosure, the predetermined amount of the second stabilizer is 0.04 mass% with respect to the total mass of the copolymer composition.
In an embodiment of the present disclosure, the fourth predetermined temperature is in the range of 25 °C to 45 °C. In an exemplary embodiment of the present disclosure, the fourth predetermined temperature is 40 °C.
In an embodiment of the present disclosure, the fourth predetermined time period is in the range of 10 minutes to 30 minutes. In an exemplary embodiment of the present disclosure, the fourth predetermined time period is 15 minutes.
In a third aspect, the present disclosure provides an adhesive composition. The adhesive composition comprises a polyvinyl alcohol, the copolymer composition, a third stabilizer, demineralized water, a cosolvent, and optionally an acrylic emulsion.
In an embodiment of the present disclosure, the third stabilizer is selected from the group consisting of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one. In an exemplary embodiment of the present disclosure, the third stabilizer is 5-chloro-2-methyl-4- isothiazolin-3-one.
In an embodiment of the present disclosure, the acrylic emulsion is selected from the group consisting of polyacrylic emulsion, styrene-acrylic emulsion, polyacrylamide-acrylic emulsion, wax-acrylic emulsion, vinyl acetate monomer (VAM) – acrylic emulsion. In an exemplary embodiment of the present disclosure, the acrylic emulsion is polyacrylamide-acrylic emulsion.

In an embodiment of the present disclosure acrylic emulsion is prepared by the charging 0.01 mass% to 0.1 mass% of anionic surfactant, 0.1 mass% to 0.5 mass% of buffer, and 20 mass% to 25 mass% of de-mineralized water into a reactor fitted with a three necked lid and heating at a temperature in the range of 60°C to 100 °C to obtain a heated mixture. Separately, a pre-emulsion reactor is filled with 0.1 mass% to 1 mass% of anionic surfactant, 0.1 mass% to 0.5 mass% of non-ionic surfactant dissolved in 10 mass% to 20 mass% of de-mineralized water, 0.1 mass% to 0.5 mass% of methacrylamide, 15 mass% to 25 mass% of methyl methacrylate, 20 mass% to 30 mass% butyl acrylate, 0.1 mass% to 1 mass% of acrylic acid monomers and stirred at a speed of100 rpm to300 rpm to obtain a milky white pre-emulsion. 1 mass% to 7% of the so obtained milky white pre-emulsion and 1.5 mass% to 2.5 mass% of potassium per sulphate solution (7 % active) are added into the heated mixture followed by adding (once, the exotherm was observed indicating the start of the reaction) the remaining milky white pre-emulsion for a time period of 220 minutes to 260 minutes, by maintaining a temperature in the range of 60 °C to 100 °C to obtain a first intermediate emulsion. 0.01 mass% to 0.1 mass% of sodium formaldehyde sulphoxylate (SFS) in 0.01 mass% to 0.1 mass% of de-mineralized water is mixed in the first intermediate pre-emulsion followed by adding a mixture of 0.01 mass% to 0.08 mass% of tert-butylhydroperoxide dissolved in 0.1 mass% to 0.8 mass% of de-mineralized water for a time period in the range of 1 hour to 3 hours to obtain a second intermediate preemulsion. The second intermediate pre-emulsion is cooled at a temperature below 30°C followed by adding 0.1 mass% to 0.3 mass% preservative dissolved in 3 mass% to 5 mass% of water to obtain the acrylic emulsion.

In an exemplary embodiment of the present disclosure acrylic emulsion is prepared by the following process steps: charging 0.05 mass% of disodium ethoxylated alcohol [C10-C12] half ester of sulfosuccinic acid (anionic surfactant), 0.2 mass% of sodium bicarbonate solution (buffer solution), and 23 mass% of de-mineralized water into a reactor fitted with a three necked lid and heating at 80 °C to obtain a heated mixture. Separately, a pre-emulsion reactor is filled with 0.8 mass% of disodium ethoxylated alcohol [C10-C12] half ester of sulfosuccinic acid (anionic surfactant), 0.3 mass% of alcohol ethoxylate with 41 - ethylene oxide (non-ionic surfactant) dissolved in 18.5 mass% of de-mineralized water, 0.5 mass% of methacrylamide, 22 mass% of methyl methacrylate, 26 mass% butyl acrylate, 0.8 mass% of acrylic acid monomers and stirred at a speed 200rpm to obtain a milky white pre-emulsion. 5% of the so obtained milky white pre-emulsion and 2.25 mass% of potassium per sulphate solution (7 % active) is added into the heated mixture followed by adding (once, the exotherm was observed indicating the start of the reaction) the remaining milky white pre-emulsion for a period of 240 minutes, by maintaining a temperature in the range of 80 °C to obtain a first intermediate emulsion. 0.05 mass% of sodium formaldehyde sulphoxylate (SFS) in 0.5 mass% of de-mineralized water is mixed in the first intermediate pre-emulsion followed by the adding a mixture of 0.05 mass% of tert-butylhydroperoxide dissolved in 0.5 mass% of de-mineralized water for a time period of 2 hours to obtain a second intermediate preemulsion. The second intermediate pre-emulsion is cooled to a temperature below 30°C followed by adding 0.2 mass% 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one (preservative) dissolved in 4.3 mass% of water to obtain the acrylamide acrylic emulsion.
In an embodiment of the present disclosure, the cosolvent is selected from the group consisting of butyl carbitol, methyl carbitol, butyl acetate, texanol, butyl carbitol acetate, ethyl carbitol acetate, hexyl carbitol, and propyl cellosolve. In an exemplary embodiment of the present disclosure, the cosolvent is butyl carbitol acetate.
In an embodiment of the present disclosure, the polyvinyl alcohol is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the polyvinyl alcohol is present in an amount of 2 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the copolymer composition is present in an amount in an amount in the range of 80 mass% to 90 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the copolymer composition is present in an amount of 85 mass% with respect to the total mass of the adhesive composition. In another exemplary embodiment of the present disclosure, the copolymer composition is present in an amount of 83 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the third stabilizer is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the third stabilizer is present in an amount of 1 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the acrylic emulsion is present in an amount in the range of 1 mass% to 5 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the acrylic emulsion is present in an amount of 2 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the cosolvent is present in an amount in the range of 2 mass% to 5 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the cosolvent is present in an amount of 4 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the demineralized water is present in an amount in the range of 6 mass% to 10 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the demineralized water is present in an amount of 8 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the adhesive composition is characterized by having:
• lap shear strength in the range of 10.5 MPa to 13 MPa;
• viscosity at 30 °C in the range of 90 poise to 150 poise;
• D3 durability lap shear strength in the range of 2 MPa to 2.5 MPa; and
• drying time at 5 °C in the range of 40 hours to 100 hours.
In a first exemplary embodiment of the present disclosure, the adhesive composition is characterized by having:
• lap shear strength of 10.6 MPa;
• viscosity at 30 °C of 130 poise;
• D3 durability lap shear strength of 2.1 MPa; and
• drying time at 5 °C of 96 hours.
In a second exemplary embodiment of the present disclosure, the adhesive composition is characterized by having:
• lap shear strength of 11 MPa;
• viscosity at 30 °C of 140 poise;
• D3 durability lap shear strength of 2.12 MPa; and
• drying time at 5 °C of 72 hours.
In a third exemplary embodiment of the present disclosure, the adhesive composition is characterized by having:
• lap shear strength of 12.6 MPa;
• viscosity at 30 °C of 135 poise;
• D3 durability lap shear strength of 2.2 MPa; and
• drying time at 5 °C of 96 hours.
In a fourth exemplary embodiment of the present disclosure, the adhesive composition is characterized by having:
• lap shear strength of 12.7 MPa;
• viscosity at 30 °C of 135 poise;
• D3 durability lap shear strength of 2.3 MPa; and
• drying time at 5 °C of 48 hours.
In a fourth aspect, the present disclosure provides a process for the preparation of an adhesive composition. The process comprises the following steps:
i) charging predetermined amounts of a polyvinyl alcohol and demineralized water in a reactor under stirring at a temperature in the range of 80 °C to 100 °C for a time period in the range of 1 hour to 3 hours followed by cooling at a temperature in the range of 50 °C to 70 °C to obtain a resultant mixture; and
ii) mixing predetermined amounts of the copolymer composition, the third stabilizer, optionally the cosolvent and the acrlylic emulsion to the resultant mixture under stirring at a temperature in the range of 30 °C to 45 °C for a time period in the range of 60 minutes to 90 minutes to obtain the adhesive composition.
The process is described in detail below.
In a first step of preparing the adhesive composition, a predetermined amounts of a poly vinyl alcohol and demineralized water are charged in a reactor under stirring at a temperature in the range of 80 °C to 100 °C for a time period in the range of 1 hour to 3 hours followed by cooling at a temperature in the range of 50 °C to 70 °C to obtain a resultant mixture.
In an embodiment of the present disclosure, the polyvinyl alcohol is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the polyvinyl alcohol is present in an amount of 2 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the demineralized water is in an amount in the range of 6 mass% to 10 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the demineralized water is in an amount 8 mass% with respect to the total mass of the adhesive composition.
In an exemplary embodiment of the present disclosure, a 2 mass% of a poly vinyl alcohol and 8 mass% of demineralized water are charged in a reactor under stirring at a temperature of 90 °C for a time period of 2 hours followed by cooling at a temperature of 60 °C to obtain a resultant mixture.
In a last step of preparing the adhesive composition, predetermined amounts of the copolymer composition, the third stabilizer, a cosolvent, and optionally an acrylic emulsion are mixed in the resultant mixture to obtain the adhesive composition.
In an embodiment of the present disclosure, the copolymer composition is present in an amount in an amount in the range of 80 mass% to 90 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the copolymer composition is present in an amount of 85 mass% with respect to the total mass of the adhesive composition. In another exemplary embodiment of the present disclosure, the copolymer composition is present in an amount of 83 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the third stabilizer is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the third stabilizer is present in an amount of 1 mass% with respect to the total mass of the adhesive composition.
In an embodiment of the present disclosure, the acrylic emulsion is present in an amount in the range of 1 mass% to 5 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the acrylic emulsion is present in an amount of 2 mass% with respect to the total mass of the adhesive composition.
In an exemplary embodiment of the present disclosure, the predetermined amounts of the copolymer composition, the third stabilizer, optionally the cosolvent, and the acrlylic emulsion are mixed with the resultant mixture under stirring at a temperature of 30 °C for a time period of 60 minutes to obtain the adhesive composition.
In an embodiment of the present disclosure, the cosolvent is present in an amount in the range of 2 mass% to 5 mass% with respect to the total mass of the adhesive composition. In an exemplary embodiment of the present disclosure, the cosolvent is present in an amount of 4 mass% with respect to the total mass of the adhesive composition.
The foregoing description of the embodiments has been provided for purposes of illustration and not intended to limit the scope of the present disclosure. Individual components of a particular embodiment are generally not limited to that particular embodiment but are interchangeable. Such variations are not to be regarded as a departure from the present disclosure, and all such modifications are considered to be within the scope of the present disclosure.
The present disclosure is further described in light of the following experiments which are set forth for illustration purpose only and not to be construed for limiting the scope of the disclosure. The following experiments can be scaled up to industrial/commercial scale and the results obtained can be extrapolated to industrial scale.
Experimental details:
Experiment 1A: Synthesis of the capped polyurethane (CPU) in accordance with the present disclosure
72 kg of polypropylene glycol (polyols) was charged in a reactor fitted with stirrer, reflux condenser, nitrogen inlet, and a thermocouple followed by passing nitrogen gas with a constant flow to obtain a charged reactor. 16.10 kg of isophorone diisocyanate was slowly added in the charged reactor under stirring at 80 rpm for 40 minutes to obtain a first mixture.
0.03 kg of di(n-butyl) tin dilaurate (third catalyst) was added to the first mixture and the temperature was raised slowly up to 100 °C followed by maintaining the same temperature till a second mixture desired % NCO was obtained. After the desired % NCO was obtained, the temperature was reduced to 50 °C. The desired % NCO was calculated based on the diamine back titration which are standard methods.
4.69 kg of hydroxyethyl methacrylate was added slowly to the second mixture over a time period of 40 minutes to obtain a first mass. After the complete addition of hydroxyethyl methacrylate, the temperature was maintained at 50 °C for 2 hours to obtain a second mass.
7.18 kg of isopropyl alcohol (IPA) was added slowly to the second mass over a time period of 40 minutes followed by maintaining the temperature at 50 °C for 2 hours and cooling down to 40 °C to obtain the capped polyurethane (CPU-1).
Experiment 1B: Synthesis of the capped polyurethane (CPU) in accordance with the present disclosure
Capped polyurethanes CPU-2 to CPU-17 were prepared in the same manner as CPU-1 except the compositions was varied. The specific amount (mass%) of the CPU compositions is tabulated in Table-1.
Table-1: Compositions of capped polyurethane (CPU) of different backbones.

Ingredients Weight (kg)
CPU-1 CPU-2 CPU-3 CPU-4 CPU-5 CPU-6 CPU-7 CPU-8 CPU-9 CPU-10 CPU-11 CPU-12 CPU-13 CPU-14 CPU-15 CPU-16 CPU-17
Polyol-1000 (Polypropylene glycol) -- 25 26 -- 19 15 18 -- 23 -- -- 18 -- -- -- -- --
Polyol-2000
(Polypropylene glycol) 72 40.97 -- 75.08 52.12 50.67 -- 72 42.52 67.46 73.59 -- 74.23 75.23 71 71 71
Polyol-2000
(Polyester Polyol) -- -- 45.18 -- -- -- 54.05 -- -- -- 53.70 -- -- -- -- --
Isophorone diisocyanate 16.10 20.22 16.58 -- -- -- -- 16.01 19.68 -- -- -- -- 16.12 16.16 16.10
Hexamethylene diisocyanate -- -- -- 12.63 15.16 -- -- -- -- 11.35 12.38 12.48 12.65 -- -- --
diphenylmethane diisocyanate -- -- -- -- -- 21.51 16.81 -- -- -- -- 16.76 -- -- -- -- --
Di(n-butyl) tin dilaurate 0.03 0.03 0.03 -- -- -- -- 0.03 0.03 -- -- -- -- -- 0.03 0.03 0.03
Hydroxypropyl acrylate -- -- -- -- -- -- -- 4.69 -- -- -- -- -- -- -- --
Hydroxyethyl methacrylate 4.69 5.92 4.85 4.89 5.86 5.25 4.1 7 -- -- -- -- -- 4.68 4.66 4.69
Polyethylene
glycol Monomethacrylate -- -- -- -- -- -- -- -- -- 11.8 -- -- -- -- -- -- --
N-
Hydroxyethyl acrylamide -- -- -- -- -- -- -- -- -- -- 4.24 -- 4.27 4.33 -- -- --
N-(2-Hydroxypropyl) methacrylamide -- -- -- -- -- -- -- -- -- -- 4.5 -- -- -- -- --
Isopropyl alcohol 7.28 7.86 7.36 6.68 7.86 7.57 6.59 7.27 7.79 -- -- -- -- -- 7.07 7.15 --
Isobutyl alcohol -- -- -- -- -- -- -- -- -- -- -- -- -- 7.79 -- -- --
Isooctyl alcohol -- -- -- -- -- -- -- -- -- 9.45 9.79 7.04 -- -- -- -- --
Benzyl alcohol -- -- -- -- -- -- -- -- -- -- -- -- 9.1 -- -- -- --
Bisphenol A epoxy (modifier) -- -- -- -- -- -- -- -- -- -- -- -- -- -- 1.1 -- --
silanol functional phenyl-propyl polysiloxane (modifier) -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- 1 --
Aminosilane (modifier) -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- -- 8.18
Total 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

Experiment-2: Process for the preparation of copolymer composition in accordance with the present disclosure.
Experiment 2a:
4 kg of polyvinyl alcohol and 40.75 kg of demineralized water were charged into a reactor fitted with a stirrer, thermocouple, and reflux condenser and stirred at 90 °C for 5 hours followed by cooling to 70 °C to obtain a first mixture
1 kg of bisphenol A epoxy (epoxy compound) and 0.01 kg tertiary butyl hydroperoxide (first catalyst) were charged into the first mixture at a temperature of 80°C for a time period of 2 hours to obtain a second mixture comprising polyvinyl alcohol grafted epoxy compound.
Separately, 0.5 kg of caped polyurethane (CPU-1), 45 kg of vinyl acetate, 2 kg of vinyl decanoate, 0.2 kg of vinyl trimethoxy silane were mixed to obtain a third mixture.
0.08 kg of a sodium bicarbonate buffer solution, 0.05 kg of polyether siloxane copolymer (defoamer), 1 kg of a sodium lauryl sulphate, 0.5 kg of a nonionic alcohol ethoxylate and a first portion of the third mixture (5% of third mixture) were added to the second mixture in the reactor as a seed followed by adding 1.1 kg of 4.5 % solution of ammonium persulfate and 1.1 kg of sodium metabisulfite at 60 °C for 15 minutes to obtain a fourth mixture.
To the fourth mixture, second portion (95%) of the third mixture was added slowly for 6 hours to the fourth mixture followed by adding 1.25 kg of 2 % solution of ammonium persulfate and 1.25 kg of 2% sodium metabisulfite for 1 hour at 60 °C to obtain a fifth mixture.
0.05 kg of a solution of sodium formaldehyde sulfoxylate and 0.05 kg of a solution of tert-butyl hydro peroxide (second catalysts) were added to the fifth mixture at 60 °C under stirring at 90 rpm for 30 minutes to obtain a slurry.
The slurry was cooled to 40 °C followed by mixing 0.04 kg of a mixture of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one (second stabilizer), 0.05 kg of polyether siloxane copolymer (Defoamer) and 0.02 kg of ammonia buffer solution under stirring at 90 rpm at 35°C for a time period of 15 minutes and filtered to obtain the copolymer composition.
Experiment 2b to 2e:
Experiments 2b to 2e are performed in a similar manner as experiment 2a except the proportion of the ingredients are varied. The specific amount for each of the components are provided in Table-2.
Table-2: Copolymer composition in accordance with the present disclosure.
Ingredients
(kg) Experiment 2a Experiment 2b Experiment 2c Experiment 2d Experiment 2e
Polyvinyl alcohol
(PVA) 4 5 5 5 5
Demineralized water 40.75 39.18 36.13 38.18 39.08
bisphenol A epoxy
(epoxy compound) 1 1 1 1 1
tertiary butyl hydroperoxide (First catalyst) 0.01 0.01 0.01 0.01 0.01
Capped polyurethane 0.5
(CPU-1) 2
(CPU-1) 5
(CPU-1) 2
(CPU-1) 2
(CPU-2)
vinyl acetate
(vinyl monomer) 45 44 44 44 44
vinyl decanoate (vinyl monomer) 2 2 2 3 2
vinyl trimethoxy silane
(vinyl monomer) 0.2 0.2 0.25 0.2 0.3
First portion of buffer solution
(sodium bicarbonate buffer solution) 0.08 0.05 0.05 0.05 0.05
First portion of polyether siloxane copolymer (defoamer) 0.05 0.05 0.05 0.05 0.05
first stabilizer
(sodium lauryl sulphate) 1 1 1 1 1
first stabilizer (nonionic alcohol ethoxylate) 0.5 0.5 0.5 0.5 0.5
First portion of initiator
(ammonium persulfate) 1.1 1.1 1.1 1.1 1.1
First portion of initiator
(sodium metabisulfite) 1.1 1.1 1.1 1.1 1.1
Second portion of initiator (2 % solution of ammonium persulfate and sodium metabisulfite) 1.25 1.3 1.3 1.3 1.3
1.25 1.3 1.3 1.3 1.3
sodium formaldehyde sulfoxylate
(second catalyst) 0.05 0.05 0.05 0.05 0.05
tert-butyl hydro peroxide
(second catalyst) 0.05 0.05 0.05 0.05 0.05
Mixture of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one
(second stabilizer) 0.02 0.02 0.02 0.02 0.02
0.02 0.02 0.02 0.02 0.02
Second portion of polyether siloxane copolymer (Defoamer) 0.05 0.05 0.05 0.05 0.05
Second portion of ammonia Buffer solution 0.02 0.02 0.02 0.02 0.02
Total 100 100 100 100 100

Comparative Experiment: Synthesis of the copolymer composition without the use of CPU and epoxy.
5 kg of polyvinyl alcohol and 38 kg of demineralized water were charged into a reactor fitted with a stirrer, thermocouple, and reflux condenser and stirred at 90 °C for 5 hours followed by cooling to 60 °C to obtain a first mixture.
Separately, 45 kg of vinyl acetate, 2 kg of vinyl decanoate, and 0.2 kg of vinyl trimethoxy silane were mixed to obtain a second mixture.
0.05 kg of a sodium bicarbonate buffer solution and a first portion (5 %) of the second mixture were added to the first mixture in the reactor as a seed followed by adding 1.1 kg of 4.5 % solution of ammonium persulfate and 1.1 kg of sodium metabisulfite at 60 °C for 15 minutes to obtain a third mixture.
To the third mixture,second portion (95%) of the second mixture was added slowly for 6 hours to the third mixture followed by adding of 1.3 kg of 2 % solution of ammonium persulfate and 1.3 kg of 2% solution of sodium metabisulfite for 1 hour at 60 °C to obtain a fourth mixture.
0.05 kg each of a solution of sodium formaldehyde sulfoxylate and tert-butyl hydro peroxide (second catalysts) were added to the fourth mixture at 60 °C under stirring for 30 minutes to obtain a slurry.
The slurry was cooled to 40 °C followed by mixing 0.04 kg of a mixture of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, 0.05 kg of polyether siloxane copolymer (Defoamer) and 0.02 kg of ammonia buffer solution under stirring at 90 rpm at 40 °C for a time period of 15 minutes and filtered to obtain the copolymer composition.
Experiment-3: Preparation of acrylic emulsion in accordance with the present disclosure.
0.05 kg of disodium ethoxylated alcohol [C10-C12] half ester of sulfosuccinic acid (anionic surfactant), 0.2 kg of sodium carbonate solution (buffer solution) and 23 kg of de-mineralized water were charged into a reactor fitted with a three necked lid and heated to 80°C to obtain a heated mixture.
Separately, a pre-emulsion reactor was filled with 0.8 kg of disodium ethoxylated alcohol [C10-C12] half ester of sulfosuccinic acid (anionic surfactant), 0.3 kg of alcohol ethoxylate with 41 - ethylene oxide (non-ionic surfactant) dissolved in 18.5 kg of de-mineralized water, 0.5 kg of methacrylamide, 22 kg of methyl methacrylate, 26 kg butyl acrylate 0.8 kg acrylic acid monomers and stirred at a speed of 200 rpm to obtain a milky white pre-emulsion.
5% of the milky white pre-emulsion and 2.25 kg of potassium per sulphate solution (7 % active) was added into the heated mixture followed by adding (once, the exotherm was observed indicating the start of reaction) the remaining milky white pre-emulsion were added for a period of 240 minutes, by maintaining a temperature at 80 °C to obtain a first intermediate emulsion.
0.05 kg of sodium formaldehyde sulphoxylate (SFS) in 0.5 kg of de-mineralized water was mixed into the first intermediate pre-emulsion followed by the addition of mixture of 0.05 kg of tert-butylhydroperoxide dissolved in 0.5 kg of de-mineralized water for two hours to obtain a second intermediate preemulsion. The second intermediate pre-emulsion was cooled to a temperature below 30°C followed by adding 0.2 kg preservative dissolved in 4.3 kg of water was added to obtain the acrylamide acrylic emulsion.
Experiment no 4: Preparation of adhesive composition using the copolymer and acrylic emulsion prepared in accordance with the present disclosure.
Experiment no 4a:
2 kg of polyvinyl alcohol and 8 kg of demineralized water were charged into a reactor fitted with stirrer and thermocouple followed by stirring at 90 rpm at 90 °C for 2 hours and cooling to 60 °C to obtain a resultant mixture.
To the resultant mixture, 85 kg of copolymer composition of experiment 2a, 1 kg of 5-chloro-2-methyl-4- isothiazolin-3-one (third stabilizer), and 4 kg of butyl carbitol acetate (cosolvent) was mixed to the resultant mixture under stirring at 50 rpm at 30 °C for 60 minutes to obtain the adhesive composition.
Experiment no 4b:
2 kg of polyvinyl alcohol and 8 kg of demineralized water were charged into a reactor fitted with stirrer and thermocouple followed by stirring at 90 rpm at 90 °C for 2 hours and cooling to 60 °C to obtain a resultant mixture.
To the resultant mixture, 83 kg of copolymer composition of experiment 2a, 1 kg of 5-chloro-2-methyl-4- isothiazolin-3-one (third stabilizer), 4 kg of butyl carbitol acetate (cosolvent) and 2 kg of acrylamide acrylic emulsion (acrylic emulsion) obtained in experiment 3 was mixed to the resultant mixture under stirring at 50 rpm at 30 °C for 60 minutes to obtain the adhesive composition.
Experiment no 4c to 4e:
Experiments 4c to 4e were performed in the same manner as experiment 4a except the proportion of copolymer composition, third stabilizer, cosolvent, and the acrylic emulsion was varied. The composition of experiments 4a to 4e is summarized in Table 3.
Table 3: Adhesive composition of experiments 4a to 4e.
Experiment No Polyvinyl alcohol
(mass%) Demineralized water
(mass%) Copolymer composition
(mass%) Third stabilizer
(mass%) Cosolvent
(mass%) Acrylic emulsion
(mass%)
4a 2 8 85
(experiment 2a) 1 4 --
4b 2 8 83
(experiment 2a) 1 4 2
4c 2 8 85
(experiment 2b) 1 4 --
4d 2 8 83
(experiment 2b) 1 4 2
4e
(comparative) 2 8 83
(comparative experiment) 1 4 2

Experiment-5: Performance evaluation of the adhesive composition comprising the copolymer composition prepared in accordance with the present disclosure.
The adhesive composition of the present disclosure was evaluated for the properties such as viscosity, accelerated stability, and mechanical/performance properties such as lap-shear strength, boiling water resistance and drying at cold temperature.
As per European standards BS EN-204, the prepared adhesive compositions (experiments 4a to 4e) were tested for their D3 performance in adhesive composition. The adhesive compositions prepared in accordance with the present disclosure were applied to the wood specimens and dried for 7 days at standard ambient conditions (temperature of 25 °C to 35 °C). After 7 days, specimens were immersed in cold water for 4 days and tested the lap shear strength. The results are presented in Table-4.
Table 4. Physical and performance properties of adhesive composition
Experiment Viscosity at 30 °C (Poise) Stability at 55 °C
for 3 months Lap shear strength (MPa) Boiling water resistance for 8 hours D3 durability lap shear strength
= 2 (MPa) Drying time in cold temp at around 5° C
4a 130 Stable 10.60 No detachment 2.1 96 Hours
4b 140 Stable 11.00 No detachment 2.12 72 Hours
4c 135 Stable 12.60 No detachment 2.2 96 Hours
4d 135 Stable 12.70 No detachment 2.3 48 Hours
4e
(comparative) 180 Unstable 10.1 Detachment 1.3 144 Hours

From Table 4, it is observed that the adhesive compositions optionally comprising acrylic emulsion as tackifier of the present disclosure is stable at 55 °C for 3 months which indicates that the copolymer composition and adhesive of the present disclosure has a minimum twelve-month of shelf life.
Further, the copolymer-based adhesive of the present disclosure is found to have excellent cold water (passes D3 durability test) and boiling water resistance and increased mechanical properties (lap shear strength in the range of 10 MPa to 12.7 MPa). In general, polyvinyl acetate adhesive (comparative experiment) at and around 5° C dried in a minimum 7 days whereas adhesive made in accordance with the present disclosure dried within 48 hours.
The adhesive prepared in accordance with the present disclosure was applied on a film forming Teflon mold and peeled off after drying to obtain a film. The film was subjected for the evaluation of tensile strength and the elongation properties. The film of the adhesive composition prepared with copolymer composition of the present disclosure is found to have enhanced properties such as elongation and tensile strength while exhibiting excellent water resistance without using any additional cross-linkers.
Furthermore, from Table 4, it can be inferred that the copolymer composition of the present disclosure has faster handling strength as it passes D3 durability test which indicates that the copolymer composition when coated on a substrate, the coating dries within 30-45 minutes and the substrate is ready to handle in 30-45 minutes for further purpose. Also, this adhesive composition is efficient work even at low temperatures of 3 °C (colder climate). Moreover, it was confirmed that the D3 durability lap shear strength is greater than 2 Mpa.
Still further, it can be inferred that the adhesive composition of the present disclosure is stable at 55 °C for 3 months, whereas the adhesive of the comparative experiment is unstable due to the increased viscosity pick up. Even further, it is observed that the viscosity of the present disclosure is less compared to the viscosity of the comparative experiment due to the presence of polyvinyl alcohol grafted epoxy compound and capped polyurethane combination. The desired viscosity of the adhesive composition should be in the range of 90 poise to 150 poise which can be applied with ease, whereas the adhesive with viscosity of below 90 poise and above 150 poise are difficult to be applied on the substrate. From the table 4 it is confirmed that the viscosity of the adhesive of the present disclosure is within the desired range.
TECHNICAL ADVANCEMENTS
The present disclosure described herein above has several technical advantages including, but not limited to, the realization of an adhesive composition comprising the copolymer composition that:
• has stable viscosity with a minimum twelve-month shelf life;
• has excellent cold water and boiling water resistance;
• has increased mechanical properties such as lap shear strength;
• has balance in properties of lap shear strength with excellent water resistance;
• circumvents the use of any additional cross-linkers; and
• has quick drying ability even in cold climate conditions as well as applicable in hot and humid climate conditions;
and a process for the preparation of an adhesive composition that;
• is simple and economical.
Throughout this specification, the word “comprise”, or variations such as “comprises” or “comprising, will be understood to imply the inclusion of a stated element, integer or step,” or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the invention to achieve one or more of the desired objects or results. While certain embodiments of the inventions have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Variations or modifications to the composition of this invention, within the scope of the invention, may occur to those skilled in the art upon reviewing the disclosure herein. Such variations or modifications are well within the spirit of this invention.
The numerical values given for various physical parameters, dimensions and quantities are only approximate values and it is envisaged that the values higher than the numerical value assigned to the physical parameters, dimensions and quantities fall within the scope of the invention unless there is a statement in the specification to the contrary.
While considerable emphasis has been placed herein on the specific features of the preferred embodiment, it will be appreciated that many additional features can be added and that many changes can be made in the preferred embodiment without departing from the principles of the disclosure. These and other changes in the preferred embodiment of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation. ,CLAIMS:WE CLAIM:
1. A copolymer composition is a reaction product of:
a. a vinyl monomer;
b. a capped polyurethane;
c. a polyvinyl alcohol grafted epoxy compound;
d. at least one first catalyst;
e. at least one second catalyst;
f. additives; and
g. demineralized water.
2. The composition as claimed in claim 1, wherein said additives comprises:
i) at least one defoamer;
ii) at least one buffer solution;
iii) at least one stabilizer; and
iv) at least one initiator.
3. The composition as claimed in claim 1, wherein said vinyl monomer is at least one selected from the group consisting of vinyl acetate, vinyl decanoate, vinyl trimethoxy silane, vinyl neodecanoate, vinyl ester of versatic acid 10, vinyl ester of 2-ethyl hexanoic acid, vinyl-terminated polydimethylsiloxane, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated ethylene-siloxane, monovinyl-terminated polydimethylsiloxane, vinylmethylsiloxane terpolymers, vinylalkoxysiloxane homopolymer, methacryloxypropyl polydimethylsiloxanes, (methacryloxypropyl)methylsiloxane-dimethylsiloxane, and 4-(vinyloxy)butyl benzoate.
4. The composition as claimed in claim 1, wherein:
i) said epoxy compound is at least one selected from the group consisting of diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of bisphenol-AP, diglycidyl ether of bisphenol-C, diglycidyl ether of bisphenol-E, diglycidyl ether of bisphenol-S, and diglycidal ether of hexa hydroxyphtalic anhydride (HHPA);
ii) said first catalyst is at least one selected from the group consisting of dibutyl tin dilaurate, dibutyltin diacetate, dimethyltin dioleate, dibutyltin dimaleate, dioctyltin dilaurate, tertiary butyl hydroperoxide, hydrogen peroxide, tert-Butyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate; and
iii) said second catalyst is at least one selected from the group consisting of tertiary butyl hydroperoxide, sodium formaldehyde sulfoxylate, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, tert-Butyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate..
5. The composition as claimed in claim 2, wherein:
(i) said defoamer is organo-silicon polymers selected from polysiloxane containing polyglycol, and polyether siloxane copolymer;
(ii) said buffer solution is selected from the group consisting of ammonia buffer, sodium bicarbonate buffer, and sodium acetate buffer;
(iii) said stabilizer is selected from the group consisting of a first stabilizer and a second stabilizer, wherein said first stabilizer is selected from the group consisting of sodium, potassium, or ammonium salts of fatty acids; C12 - C16 alkyl sulfates selected from ammonium persulfate, sodium dodecyl sulfate (SDS), sodium lauryl sulfate (SLS), nonionic surfactants selected from the group consisting of poly(ethylene oxide) cellulose and hydroxyethyl cellulose, and wherein said second stabilizer is selected from the group consisting of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one; and
(iv) said initiator is selected from the group consisting of ammonium persulfate, potassium persulfate, sodium persulfate and sodium metabisulfite.
6. The composition as claimed in claim 1, wherein at least one end of said capped polyurethane is capped with a capping agent; wherein said capping agent is at least one selected from the group consisting of alcohol, and hydroxyl-acrylate component.
7. The composition as claimed in claim 6, wherein
i) said hydroxyl-acrylate component is at least one selected from diisocyanatehydroxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, N-hydroxyethyl acrylamide, N-(2-hydroxypropyl)methacrylamide, 3-phenoxy-2-hydroxypropyl methacrylate, glycerol methacrylate and polyethyleneglycol monomethacrylate; and
ii) said alcohol is at least one selected from the group consisting of isopropyl alcohol, isobutyl alcohol, iso-octyl alcohol, and benzyl alcohol.
8. The composition as claimed in claim 1, wherein a backbone of said capped polyurethane is modified by at least one modifier selected from the group consisting of epoxy component, and siloxane component.
9. The composition as claimed in claim 8, wherein:
i) said epoxy component is at least one selected from the group consisting of diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of bisphenol-AP, diglycidyl ether of bisphenol-C, diglycidyl ether of bisphenol-E and diglycidyl ether of bisphenol-S; and
ii) said siloxane component is at least one selected from silanol functional phenyl-propyl polysiloxane, silanol functional phenyl polysiloxane, silanol functional methyl polysiloxane, dihydroxypolydimethylsiloxane, dihydroxypolydiethylsiloxane, and amino silane compounds;wherein said amino silanes are selected from 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-methyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyl-triethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride.
10. The composition as claimed in claim 1, wherein a mass ratio of said capped polyurethane to said vinyl monomer is in the range of 1:5 to 1:95.
11. The composition as claimed in claim 1, wherein
i) said first catalyst is present in an amount in the range of 0.01 mass% to 0.1 mass%;
ii) said second catalyst is present in an amount in the range of 0.01 mass% to 0.1 mass%;
iii) said additives are present in an amount in the range of 2 mass% to 8 mass%; and
iv) said demineralized water is present in an amount in the range of 30 mass% to 50 mass%;
wherein said mass% are with respect to the total mass of said copolymer composition.
12. The composition as claimed in claim 1, wherein
i) said capped polyurethane is present in an amount in the range of 0.1 mass% to 6 mass%;
ii) said vinyl monomer is present in an amount in the range of 40 mass% to 65 mass%;
iii) said polyvinyl alcohol is present in an amount in the range of 1 mass% to 10 mass%; and
iv) said epoxy compound is present in an amount in the range of 0.1 mass% to 2 mass%;
wherein said mass% are with respect to the total mass of said copolymer composition.
13. The composition as claimed in claim 2, wherein:
i) said defoamer is present in an amount in the range of 0.02 mass% to 0.2 mass%;
ii) said buffer solution is present in an amount in the range of 0.02 mass % to 0.2 mass%;
iii) said stabilizer is present in an amount in the range of 1 mass% to 3 mass%; and
iv) said initiator is present in an amount in the range of 2 mass% to 6 mass%;
wherein said mass% are with respect to the total mass of said copolymer composition.
14. A process for the preparation of a copolymer composition, said process comprising the following steps:
i) obtaining a capped polyurethane;
ii) separately, dissolving a predetermined amount of polyvinyl alcohol in a predetermined amount of demineralized water in a reactor at a first predetermined temperature under stirring for a first predetermined time period followed by cooling to a temperature in the range of 60 °C to 75 °C to obtain a first mixture;
iii) adding a predetermined amount of an epoxy compound and a first catalyst to said first mixture at a temperature in the range of 60 °C to 75 °C for a time period in the range of 1 hour to 3 hours to obtain a second mixture comprising polyvinyl alcohol grafted epoxy compound;
iv) separately, mixing a predetermined amount of at least one vinyl monomer with a predetermined amount of said capped polyurethane to obtain a third mixture;
v) mixing first portions of a buffer solution, a defoamer, said third mixture and a predetermined amount of a first stabilizer with said second mixture, followed by adding a first portion of an initiator at a second predetermined temperature under stirring for a second predetermined time period to obtain a fourth mixture;
vi) gradually adding second portions of said third mixture in said fourth mixture for a time period in the range of 5 hours to 7 hours followed by simultaneous addition of second portion of said initiator over a third predetermined time period at a temperature in range of 50 °C to 70 °C to obtain a fifth mixture;
vii) adding a predetermined amount of a second catalyst to said fifth mixture at a third predetermined temperature under stirring for a time period in the range of 20 minutes to 40 minutes to obtain a slurry; and
viii) cooling said slurry to a fourth predetermined temperature followed by mixing second portions of said defoamer, said buffer solution, and a predetermined amount of the second stabilizer to said slurry at said fourth predetermined temperature under stirring for a fourth predetermined time period to obtain said copolymer composition.
15. The process as claimed in claim 14, wherein:
(a) said predetermined amount of demineralized water is in the range of 30 mass% to 50 mass% with respect to the total mass of the copolymer composition;
(b) said predetermined amount of polyvinyl alcohol is in an amount in the range of 1 mass% to 10 mass% with respect to the total mass of the copolymer composition;
(c) said epoxy compound is at least one selected from the group consisting of diglycidyl ether of bisphenol-A, diglycidyl ether of bisphenol-F, diglycidyl ether of bisphenol-AP, diglycidyl ether of bisphenol-C, diglycidyl ether of bisphenol-E, diglycidyl ether of bisphenol-S, and diglycidal ether of hexahydrophthalic anhydride (HHPA);
(d) said predetermined amount of the epoxy compound is in the range of 0.1 mass% to 2 mass% with respect to the total mass of the copolymer composition;
(e) said first catalyst is at least one selected from the group consisting of dibutyl tin dilaurate, dibutyltin diacetate, dimethyltin dioleate, dibutyltin dimaleate, and dioctyltin dilaurate, andtertiary butyl hydroperoxide, hydrogen peroxide, tert-Butyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate;
(f) said predetermined amount of said first catalyst is in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition;
(g) said predetermined amount of said vinyl monomer is in an amount in the range of 40 mass% to 65 mass% with respect to the total mass of the copolymer composition; and
(h) said predetermined amount of the capped polyurethane is in an amount in the range of 0.1 mass % to 6 mass% with respect to the total mass of the copolymer composition.
16. The process as claimed in claim 14, wherein a mass ratio of said capped polyurethane to said vinyl monomer is in the range of 1:5 to 1:95.
17. The process as claimed in claim 14, wherein:
i) said buffer is at least one selected from the group consisting of ammonia, sodium bicarbonate, and sodium acetate;
ii) said first portion of buffer solution is in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of said copolymer composition;
iii) said defoamer is a organo-silicon polymer selected from the group consisting of polysiloxane containing polyglycol, and polyether siloxane copolymer;
iv) said first portion of said defoamer is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of said copolymer composition;
v) said first stabilizer is selected from the group consisting of sodium, potassium, or ammonium salts of fatty acids; C12 - C16 alkyl sulfates selected from ammonium persulfate, sodium dodecyl sulfate (SDS), sodium lauryl sulfate (SLS), nonionic stabilizer selected from the group consisting of poly(ethylene oxide) cellulose and hydroxyethyl cellulose;
vi) said predetermined amount of said first stabilizer is in the range of 1 mass% to 2 mass% with respect to the total mass of the copolymer composition;
vii) said first portion of said third mixture is in the range of 3 mass% to 8 mass% with respect to the total mass of the third mixture;
viii) said initiator is at least one selected from the group consisting of ammonium persulfate, potassium persulfate, sodium persulfate and sodium metabisulfite; and
ix) said first portion of said initiator is in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the copolymer composition.
18. The process as claimed in claim 14, wherein:
i) said second portion of said initiator is in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the copolymer composition;
ii) said second portion of said third mixture is in an amount in the range of 92 mass% to 97 mass% with respect to the total mass of the said third mixture;
iii) said second catalyst is at least one selected from the group consisting of tertiary butyl hydroperoxide, sodium formaldehyde sulfoxylate , ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, tert-Butyl peroxy-2-ethylhexanoate, and tert-butyl peroxy-2-ethylhexanoate;
iv) said predetermined amount of said second catalyst is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition;
v) said second portion of defoamer is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition;
vi) said second portion of buffer solution is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition;
vii) said second stabilizer is at least one selected from 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one; and
viii) said predetermined amount of said second stabilizer is in an amount in the range of 0.01 mass% to 0.1 mass% with respect to the total mass of the copolymer composition.
19. The process as claimed in claim 14, wherein:
i) said first predetermined temperature is in the range of 85 °C to 95 °C;
ii) said first predetermined time period is in the range of 3 hours to 7 hours;
iii) said second predetermined temperature is in the range of 50 °C to 70 °C;
iv) said second predetermined time period is in the range of 10 minutes to 30 minutes;
v) said third predetermined temperature is in the range of 50 °C to 70 °C;
vi) said third predetermined time period is in the range of 30 minutes to 90 minutes;
vii) said fourth predetermined temperature is in the range of 25 °C to 45 °C; and
viii) said fourth predetermined time period is in the range of 10 minutes to 30 minutes.
20. The process as claimed in claim 14, wherein said vinyl monomer is at least one selected from vinyl acetate, vinyl decanoate, vinyl trimethoxy silane, vinyl neodecanoate, vinyl ester of versatic acid 10, vinyl ester of 2-ethyl hexanoic acid, vinyl-terminated polydimethylsiloxane, vinyl-terminated polyphenylmethylsiloxane, vinyl-terminated ethylene-siloxane, monovinyl-terminated polydimethylsiloxane, vinylmethylsiloxane terpolymers, vinylalkoxysiloxane homopolymer, methacryloxypropyl polydimethylsiloxanes, (methacryloxypropyl)methylsiloxane-dimethylsiloxane, and 4-(vinyloxy)butyl benzoate.
21. An adhesive composition comprising:
i) a polyvinyl alcohol;
ii) a copolymer composition as claimed in claim 1;
iii) a third stabilizer;
iv) demineralized water;
v) a cosolvent; and
vi) optionally an acrylic emulsion.
22. The composition as claimed in claim 21, wherein:
i) said third stabilizer is at least one selected from the group consisting of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one;
ii) said acrylic emulsion is at least one selected from the group consisting of polyacrylic emulsion, styrene-acrylic emulsion, polyacrylamide-acrylic emulsion, wax-acrylic emulsion, and vinyl acetate monomer (VAM) – acrylic emulsion; and
iii) said cosolvent is at least one selected from the group consisting of butyl carbitol, methyl carbitol, butyl acetate, texanol, butyl carbitol acetate, ethyl carbitol acetate, hexyl carbitol, and propyl cellosolve.
23. The composition as claimed in claim 21, wherein:
i) said polyvinyl alcohol is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the adhesive composition;
ii) said copolymer composition is present in an amount in an amount in the range of 80 mass% to 90 mass% with respect to the total mass of the adhesive composition;
iii) said third stabilizer is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the adhesive composition;
iv) said demineralized water is in an amount in the range of 6 mass% to10 mass% with respect to the total mass of the adhesive composition;
v) said acrylic emulsion is present in an amount in the range of 1 mass% to 5 mass% with respect to the total mass of the adhesive composition; and
vi) said cosolvent is present in an amount in the range of 2 mass% to 5 mass% with respect to the total mass of the adhesive composition.
24. The composition as claimed in claim 21, wherein said composition is characterized by having:
• lap shear strength in the range of 10.5 MPa to 13 MPa;
• viscosity at 30 °C in the range of 90 poise to 150 poise;
• D3 durability lap shear strength in the range of 2 MPa to 2.5 MPa; and
• drying time at 5 °C in the range of 40 hours to 100 hours.
25. A process for the preparation of an adhesive composition as claimed in claim 21, said process comprising the following steps:
i) charging predetermined amounts of a poly vinyl alcohol and demineralized water in a reactor under stirring at a temperature in the range of 80 °C to 100 °C for a time period in the range of 1 hour to 3 hours followed by cooling to a temperature in the range of 50 °C to 70 °C to obtain a resultant mixture; and
ii) mixing predetermined amounts of said copolymer composition, said third stabilizer, said cosolvent and optionally said acrlylic emulsion to said resultant mixture under stirring at a temperature in the range of 30 °C to 45 °C for a time period in the range of 30 minutes to 90 minutes to obtain said adhesive composition.
26. The process as claimed in claim 25, wherein:
i) said polyvinyl alcohol is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the adhesive composition;
ii) said demineralized water is present in an amount in the range of 6 mass% to 10 mass% with respect to the total mass of the adhesive composition;
iii) said copolymer composition is present in an amount in the range of 80 mass% to 90 mass% with respect to the total mass of the adhesive composition;
iv) said third stabilizer is present in an amount in the range of 1 mass% to 3 mass% with respect to the total mass of the adhesive composition;
v) said acrylic emulsion is present in an amount in the range of 2 mass% to 5 mass% with respect to the total mass of the adhesive composition; and
vi) said cosolvent is present in an amount in the range of 2 mass% to 5 mass% with respect to the total mass of the adhesive composition.

Dated this 24th day of November, 2023

_______________________________
MOHAN RAJKUMAR DEWAN, IN/PA – 25
of R.K.DEWAN & CO.
Authorized Agent of Applicant