Title of Invention: Method for producing conjugated diene-based polymer
technical field
[One]
Cross-Citation with Related Applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0119589 on September 27, 2019, and all contents disclosed in the literature of the Korean patent application are incorporated as a part of this specification.
[3]
technical field
[4]
The present invention relates to a method for producing a conjugated diene-based polymer, specifically, a conjugated diene-based polymer in which a saponified dimer acid is used in the polymerization initiation step, and a monomer and an emulsifier are divided and added three or more times after the polymerization reaction is started. It relates to a manufacturing method of
background
[5]
Acrylonitrile-butadiene-styrene (ABS) copolymer resin has relatively good physical properties such as moldability and gloss as well as mechanical strength such as impact resistance, so electrical parts, electronic parts, office equipment, or automobiles It is widely used in parts, etc.
[6]
ABS resin prepared by emulsion polymerization has the advantage of exhibiting a relatively good balance of physical properties and having excellent gloss. Therefore, ABS resin is mainly produced by emulsion polymerization rather than bulk polymerization. ABS resin produced by emulsion polymerization is mixed with a styrene-acrylonitrile (SAN) copolymer to maximize the characteristics of the SAN resin composition to diversify products and create high added value.
[7]
On the other hand, the gloss or clarity of the ABS resin is not only affected by the particle diameter size and particle distribution of the dispersed rubber polymer, but also the polybutadiene latex (PBL) and the emulsifier remaining after polymerization of ABS, residual monomers, oligomers, It is affected by the gas generated from the surface of the resin by impurities such as heat stabilizer and SAN. In particular, the gas generated on the surface of the resin during the high-temperature injection process affects the roughness of the surface and greatly reduces the gloss or clarity of the resin, and is known as a factor limiting the quality improvement of the resin.
[8]
[9]
Prior art literature
[10]
(Patent Document 1) KR 10-1279267 B1
[11]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[12]
The present invention is to solve the problems of the prior art, it is included in a thermoplastic resin to improve impact strength and surface sharpness, and to provide a method for producing a conjugated diene-based polymer that can reduce the amount of gas generated during injection aim to
[13]
Another object of the present invention is to provide a method for producing a graft copolymer including the conjugated diene-based polymer and a thermoplastic resin composition including the graft copolymer.
means of solving the problem
[14]
In order to solve the above problems, the present invention provides a step of initiating a polymerization reaction by batching 30 to 50 parts by weight of 100 parts by weight of a conjugated diene-based monomer, 0.1 to 5 parts by weight of a saponified dimer acid, and a polymerization initiator into a reactor ( S1), the step of dividing the remaining conjugated diene-based monomer and the emulsifier over three or more times according to the polymerization conversion after the start of the polymerization reaction (S2), and terminating the polymerization reaction at a polymerization conversion rate of 90 to 99% (S3) It provides a method for producing a conjugated diene-based polymer comprising a.
[15]
In addition, in the present invention, in the method for producing the conjugated diene-based polymer, the step S2 is a step of adding a conjugated diene-based monomer and an emulsifier at a polymerization conversion rate of 20 to 35% (S2-1), a polymerization conversion rate of 45 to 60% at the time point Preparation of a conjugated diene-based polymer comprising the step of introducing a conjugated diene-based monomer and an emulsifier (S2-2) and adding a conjugated diene-based monomer and an emulsifier at a polymerization conversion rate of 70 to 80% (S2-3) provide a way
Effects of the Invention
[16]
When using the method for producing the conjugated diene-based polymer provided by the present invention, the impact strength and surface clarity of the thermoplastic resin including the conjugated diene-based polymer prepared by increasing the standard deviation of the particle diameter of the prepared conjugated diene-based polymer can be improved. And, it is possible to reduce the amount of gas generated in the injection process of the thermoplastic resin.
Modes for carrying out the invention
[17]
Hereinafter, the present invention will be described in more detail.
[18]
The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of ​​the present invention.
[19]
[20]
The conjugated diene-based monomer of the present invention may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and piperylene, of which 1,3-butadiene may be preferable.
[21]
[22]
The aromatic vinyl monomer of the present invention may be at least one selected from the group consisting of styrene, α-methyl styrene, α-ethyl styrene, and p-methyl styrene, among which styrene is preferable.
[23]
[24]
In the present invention, the vinyl cyan-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile and α-chloroacrylonitrile, of which acrylonitrile This is preferable.
[25]
[26]
In the present invention, "derived unit" refers to a unit derived from the compound, and specifically, may refer to a substituent in which the compound itself or some atoms of the compound are removed.
[27]
[28]
In the present invention, the average particle diameter and standard deviation of the particle diameter of the conjugated diene-based polymer can be measured through a particle size analyzer manufactured by Nicomp, and specifically measured by diluting a polymer sample to be measured, and the average particle diameter and standard deviation of the intensity Wt can be read and measured.
[29]
[30]
Method for producing conjugated diene-based polymer
[31]
The present invention provides a step (S1) of starting a polymerization reaction by adding 30 to 50 parts by weight of 100 parts by weight of a conjugated diene-based monomer, 0.1 to 5 parts by weight of a saponified dimer acid, and a polymerization initiator to a reactor (S1), polymerization after the polymerization reaction is started Preparation of a conjugated diene-based polymer comprising the step (S2) of dividing the remaining conjugated diene-based monomer and the emulsifier over three or more times according to the conversion rate and terminating the polymerization reaction at a polymerization conversion rate of 90 to 99% (S3) provide a way
[32]
[33]
1) polymerization initiation step
[34]
The method for producing a conjugated diene-based polymer provided by the present invention is to initiate a polymerization reaction by collectively injecting 30 to 50 parts by weight, a saponified dimer acid, and a polymerization initiator in a reactor among 100 parts by weight of a conjugated diene-based monomer to be polymerized. includes steps.
[35]
[36]
The conjugated diene-based monomer added in this step may be 30 to 50 parts by weight, preferably 35 to 45 parts by weight, based on 100 parts by weight, which is the total amount of the conjugated diene-based monomer to be polymerized. When the conjugated diene-based monomer is added in the above-described range in the polymerization initiation step, the particle size standard deviation of the finally prepared conjugated diene-based polymer may be wide.
[37]
[38]
In this step, a saponified dimer acid and a polymerization initiator are added together with a conjugated diene-based monomer. In the present invention, the saponified dimer acid serves as an emulsifier. The dimer acid may be at least one selected from compounds represented by the following Chemical Formulas 1 to 6:
[39]
[Formula 1]
[40]

[41]
[Formula 2]
[42]

[43]
[Formula 3]
[44]

[45]
[Formula 4]
[46]

[47]
[Formula 5]
[48]

[49]
[Formula 6]
[50]
.
[51]
[52]
The saponified product refers to a metal salt of a carboxylic acid group produced by saponification of an acid, and may be, for example, an alkali metal salt or an alkaline earth metal salt, and specifically may be a sodium salt, a potassium salt, a magnesium salt, or a calcium salt.
[53]
[54]
The polymerization initiator serves to initiate a polymerization reaction, and may be one or more of a water-soluble polymerization initiator, and a mixture of an oil-soluble polymerization initiator and an oxidation-reduction catalyst, and it is particularly preferable to use a combination thereof.
[55]
Specifically, the water-soluble polymerization initiator may be at least one selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate, and the oil-soluble polymerization initiator is cumene hydroperoxide, diisopropyl benzene hydroperoxide, It may be at least one selected from the group consisting of azobis isobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, and benzoyl peroxide, and the oxidation-reduction catalyst is sodium formaldehyde sulfoxylate, It may be at least one selected from the group consisting of sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrole phosphate, and sodium sulfite. When the polymerization initiators listed above are used, initiation of the polymerization reaction can be carried out smoothly.
[56]
[57]
The polymerization initiator may be added in an amount of 0.01 to 1 parts by weight, preferably 0.01 to 0.5 parts by weight, based on 100 parts by weight of the conjugated diene-based monomer. When the polymerization initiator is used less than this, polymerization initiation may not be performed smoothly, and when used in more than this, the physical properties of the finally prepared conjugated diene-based polymer may be adversely affected.
[58]
[59]
2) polymerization reaction step
[60]
In the method for producing a conjugated diene-based polymer provided by the present invention, a polymerization reaction is performed by dividingly adding the remaining conjugated diene-based monomers and an emulsifier after the polymerization reaction is started.
[61]
[62]
In this step, out of 100 parts by weight of the conjugated diene-based monomer to be polymerized, the remaining monomers except for the monomer introduced in the polymerization initiation step are added, and the monomer and the emulsifier are dividedly added over three or more times. The order of the divided input may be 3 or more, preferably 3 to 5 times. Especially preferably, it may be 3 or 4 times. In case of divided input in a smaller order than this, uniform polymerization of the monomer may not be achieved, and in case of divided input in a higher order than this, process operation may be difficult. Split input at this stage The reference point of time may be polymerization conversion.
[63]
[64]
The amount of the conjugated diene-based monomer divided in this step may be less than or equal to the amount of the conjugated diene-based monomer introduced immediately before. For example, when 30 parts by weight of the conjugated diene-based monomer is added at the start of polymerization, the amount of the first dividedly added conjugated diene-based monomer during the polymerization reaction may be less than or equal to 30 parts by weight, specifically 25 It may be a part by weight, and the amount of the secondly dividedly added conjugated diene-based monomer may be less than or equal to 25 parts by weight, for example, 15 parts by weight. By controlling the amount of the conjugated diene-based monomer input in this way, the reaction time can be made equal to the existing one while maintaining the wide particle distribution of the polymer produced, and through this, the impact strength of the finally produced polymer is excellent, Polymers can be produced with good productivity.
[65]
[66]
In addition, this step S2 is specifically the step of adding the conjugated diene-based monomer and the emulsifier at the time of the polymerization conversion rate of 20 to 35% (S2-1), the step of adding the conjugated diene-based monomer and the emulsifier at the time of the polymerization conversion rate of 45 to 60% (S2-2) and a step (S2-3) of adding a conjugated diene-based monomer and an emulsifier at a polymerization conversion rate of 70 to 80% (S2-3).
[67]
In addition, in step S2-1, 20 to 30 parts by weight of a conjugated diene-based monomer is added, in step S2-2, 15 to 25 parts by weight of a conjugated diene-based monomer is added, and in step S2-3, 10 to 30 parts by weight of a conjugated diene-based monomer is added. 20 parts by weight is added, and the total amount of the conjugated diene-based monomer added in steps S2-1 to S2-3 may be 70 parts by weight or less, and the amount of the conjugated diene-based monomer added in steps S2-1 to S2-3 may satisfy Equation 1 below:
[68]
[Equation 1]
[69]
M1≥M2≥M3
[70]
In the formula, M1, M2, and M3 are the amounts of the conjugated diene-based monomer input in steps S2-1, S2-2 and S2-3, respectively.
[71]
[72]
For example, in step S2-1, 25 parts by weight of a conjugated diene-based monomer is added at a polymerization conversion rate of 20 to 35%, and in step S2-2, 20 parts by weight of a conjugated diene-based monomer is added at a polymerization conversion rate of 45 to 60%, In step S2-3, 15 parts by weight of a conjugated diene-based monomer is added at a polymerization conversion of 70 to 80%, and more specifically, in step S2-1, 25 parts by weight of a conjugated diene-based monomer is added at a polymerization conversion of 30%, and , In step S2-2, 20 parts by weight of the conjugated diene-based monomer is added at a polymerization conversion rate of 50%, and in step S2-3, 15 parts by weight of the conjugated diene-based monomer is added at a polymerization conversion rate of 70%.
[73]
[74]
When step S2 includes steps S2-1, S2-2, and S2-3 as described above, the polymerization reaction may be smooth, and the prepared conjugated diene-based polymer may have better impact strength.
[75]
[76]
In the present invention, the polymerization conversion rate is obtained by measuring the weight of 1.5 g of the prepared conjugated diene-based polymer in a hot air dryer at 150 ° C. there is.
[77]
[Equation 1]
[78]
Polymerization conversion (%) = total solid content (TSC) X (weight of monomer and auxiliary material added) / 100- (weight of auxiliary material added other than monomer)
[79]
[80]
In Equation 1, the auxiliary material includes all of the remaining components except for the monomer among the materials input to the polymerization reaction, and for example, an initiator or an emulsifier may correspond to the auxiliary material.
[81]
[82]
The emulsifier input in step S2 may be at least one selected from the group consisting of saponified rosin acid, saponified fatty acid, saponified dimer acid and saponified oleic acid, and the emulsifier may be divided and added like the conjugated diene-based monomer. can
[83]
[84]
Meanwhile, the molecular weight regulator may be further added in steps S1 and S2, and the total amount of the molecular weight regulator input in steps S1 and S2 may be less than 1 part by weight based on 100 parts by weight of the conjugated diene-based monomer. When the total amount of the added molecular weight regulator is greater than this, the balance of physical properties of the prepared conjugated diene-based polymer may be deteriorated.
[85]
[86]
The molecular weight modifier is α-methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, carbon tetrachloride, methylene chloride, methylene bromide, tetraethyl thiuram disulfide, dipentamethylene thiuram It may be at least one selected from the group consisting of disulfide, and diisopropylxanthogen disulfide.
[87]
[88]
3) Closing phase
[89]
The method for producing a conjugated diene-based polymer of the present invention includes a step (S3) of terminating the polymerization reaction at a polymerization conversion rate of 90 to 99%. A final conjugated diene-based polymer is prepared through this step, and the average particle diameter of the conjugated diene-based polymer prepared through the production method of the present invention may be 1000 to 2000 Å, preferably 1000 to 1500 Å.
[90]
[91]
The conjugated diene-based polymer obtained in this step may be enlarged through the step (S4) of thickening by adding a coagulant, or a coagulant and an auxiliary coagulant after completion of the polymerization reaction, and the average particle diameter of the enlarged conjugated diene-based polymer is 2500 to 4000 Å , preferably 2500 to 3500 Å.
[92]
[93]
When the average particle diameter of the conjugated diene-based polymer and the enlarged conjugated diene-based polymer is within the above-described range, physical properties including impact strength of the polymer may be excellent.
[94]
[95]
As the coagulant that can be used in this step, an acidic coagulant may be used, and specifically, sulfuric acid, acetic acid, MgSO 4 , CaCl 2 or Al 2(SO 4) 3 may be used, and the auxiliary coagulant is sodium alginate or sodium silicate. A sodium-assisted coagulant or a polymer-based polymer coagulant can be used.
[96]
[97]
Method for preparing graft copolymer
[98]
The present invention provides a method for preparing a graft copolymer by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to the conjugated diene-based polymer prepared by the above preparation method.
[99]
The graft copolymer may include a conjugated diene-based polymer in an amount of 40 to 70% by weight, an aromatic vinylic monomer in an amount of 15 to 35% by weight, and a vinyl cyanide monomer in an amount of 5 to 25% by weight. When the components of the graft copolymer are within the above-mentioned ranges, the chemical resistance and processability of the graft copolymer may be excellent.
[100]
The graft copolymer may be prepared by mixing an aromatic vinyl-based monomer and a vinyl cyanide-based monomer with a conjugated diene-based polymer, adding an emulsifier and an initiator, and performing graft polymerization. The emulsifier and the initiator may be the same as those described above in the method for preparing the conjugated diene-based polymer.
[101]
[102]
Thermoplastic resin composition
[103]
The present invention provides a thermoplastic resin composition comprising a graft copolymer prepared by the above-described method for preparing the graft copolymer and a copolymer including units derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyanide-based monomer.
[104]
[105]
Specifically, the copolymer including the aromatic vinyl-based monomer-derived unit and the vinyl cyan-based monomer-derived unit may be a styrene-acrylonitrile copolymer. The content of the graft copolymer in the thermoplastic resin composition may be 10 to 50% by weight.
[106]
[107]
The thermoplastic resin composition may be extruded and injected to manufacture a molded article, and the molded article may be used for various purposes such as electric parts, electronic parts, and automobile parts.
[108]
[109]
Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only illustrative of the present invention and are not intended to limit the scope of the present invention.
[110]
[111]
Example 1
[112]
90 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 35 parts by weight of 1,3-butadiene as a conjugated diene-based monomer, and a dimer that is a mixture of one or more of the compounds represented by Formulas 1 to 6 as an emulsifier 0.8 parts by weight of acid saponification, 0.25 parts by weight of potassium carbonate as electrolyte, 0.044 parts by weight of potassium hydroxide, 0.25 parts by weight of t-dodecyl mercaptan as molecular weight regulator, 0.04 parts by weight of t-butyl hydroperoxide as reaction initiator, dextrose 0.02 parts by weight, 0.0015 parts by weight of sodium pyrrole phosphate, and 0.0007 parts by weight of ferrous sulfate were added, and the temperature was raised to 55° C. to initiate a polymerization reaction.
[113]
After the polymerization reaction is started, when the polymerization conversion is 30%, 25 parts by weight of 1,3-butadiene, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.05 parts by weight of potassium persulfate, and 0.15 parts by weight of dimer acid saponification as an emulsifier A weight part was added, and the temperature was raised to 78°C and maintained, followed by polymerization for 6 hours.
[114]
Next, at the time of polymerization conversion of 50%, 25 parts by weight of 1,3-butadiene, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.15 parts by weight of dimer acid saponification, 0.05 parts by weight of potassium carbonate, and 0.01 parts by weight of potassium hydroxide parts were sequentially added, and then 15 parts by weight of 1,3-butadiene, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.15 parts by weight of saponified dimer acid, 0.05 parts by weight of potassium carbonate and hydroxide at the time of polymerization conversion of 70% By sequentially adding 0.01 parts by weight of potassium, the polymerization conversion rate was 95%, and the reaction was completed.
[115]
The average particle diameter of the prepared polybutadiene was 1280 Å, and the standard deviation of the particle diameter was 350 Å. An enlarged polybutadiene was obtained by adding 0.8 parts by weight of acetic acid to the prepared polybutadiene, and the average particle diameter of the enlarged polybutadiene was 3270 Å, and the standard deviation of the particle diameter was 920 Å.
[116]
[117]
Example 2
[118]
An enlarged polybutadiene was obtained by adding 0.3 parts by weight of sodium alginate and 0.6 parts by weight of acetic acid to the polybutadiene prepared in Example 1..
[119]
The average particle diameter of the enlarged polybutadiene was 3230 Å, and the standard deviation of the particle diameter was 992 Å.
[120]
[121]
Example 3
[122]
90 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 30 parts by weight of 1,3-butadiene as a conjugated diene-based monomer, and a dimer that is a mixture of one or more of the compounds represented by Formulas 1 to 6 as an emulsifier 0.75 parts by weight of acid saponification, 0.25 parts by weight of potassium carbonate as electrolyte, 0.044 parts by weight of potassium hydroxide, 0.25 parts by weight of t-dodecyl mercaptan as molecular weight regulator, 0.04 parts by weight of t-butyl hydroperoxide as reaction initiator, dextrose 0.02 parts by weight, 0.0015 parts by weight of sodium pyrrole phosphate, and 0.0007 parts by weight of ferrous sulfate were added, and the temperature was raised to 55° C. to initiate a polymerization reaction.
[123]
After the polymerization reaction is started, when the polymerization conversion is 25%, 25 parts by weight of 1,3-butadiene, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.05 parts by weight of potassium persulfate, and 0.1 parts by weight of dimer acid saponification as an emulsifier A weight part was added, and the temperature was raised to 78°C and maintained, followed by polymerization for 6 hours.
[124]
Next, at the time of polymerization conversion of 35%, 15 parts by weight of 1,3-butadiene, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.1 parts by weight of dimer acid saponification, 0.05 parts by weight of potassium carbonate, and 0.01 parts by weight of potassium hydroxide parts were sequentially added, and 15 parts by weight of 1,3-butadiene and 0.1 parts by weight of saponified dimer acid were added at the time of polymerization conversion of 50%.
[125]
Then, at the polymerization conversion rate of 70%, 15 parts by weight of 1,3-butadiene, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.15 parts by weight of dimer acid saponification, 0.05 parts by weight of potassium carbonate and 0.01 parts by weight of potassium hydroxide sequentially The reaction was completed at a polymerization conversion rate of 95%.
[126]
The average particle diameter of the prepared polybutadiene was 1260 Å, and the standard deviation of the particle diameter was 282 Å. An enlarged polybutadiene was obtained by adding 0.3 parts by weight of sodium alginate and 0.7 parts by weight of acetic acid to the prepared polybutadiene, and the average particle diameter of the enlarged polybutadiene was 3290 Å, and the standard deviation of the particle diameter was 870 Å.
[127]
[128]
Comparative Example 1
[129]
75 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 90 parts by weight of 1,3-butadiene as a monomer, 3 parts by weight of saponified dimer as an emulsifier, 0.1 parts by weight of potassium carbonate as an electrolyte, t as a molecular weight regulator - 0.1 parts by weight of dodecyl mercaptan, 0.15 parts by weight of t-butyl hydroperoxide as a reaction initiator, 0.06 parts by weight of dextrose, 0.005 parts by weight of sodium pyrrole phosphate, and 0.0025 parts by weight of ferrous sulfate are administered in batches, and the temperature is raised to 55° C. and reacted to a polymerization conversion of 30 to 40%.
[130]
Thereafter, 0.3 parts by weight of potassium persulfate was added in batches, the temperature was raised to 72° C., and 10 parts by weight of the remaining 1,3-butadiene was added at a polymerization conversion rate of 60 to 70% for polymerization reaction, and the polymerization conversion rate was 95. % to complete the reaction. The average particle diameter of the prepared polybutadiene was 1220 Å, and the standard deviation of the particle diameter was 210 Å. 1.5 parts by weight of acetic acid was added to the prepared polybutadiene to enlarge, and the average particle diameter of the enlarged polybutadiene was 3290 Å, and the standard deviation of the particle diameter was 690 Å.
[131]
[132]
Comparative Example 2
[133]
An enlarged polybutadiene was obtained by adding 0.3 parts by weight of sodium alginate and 1.32 parts by weight of acetic acid to the polybutadiene prepared in Comparative Example 1.
[134]
The average particle diameter of the enlarged polybutadiene was 3230 Å, and the standard deviation of the particle diameter was 823 Å.
[135]
[136]
Comparative Example 3
[137]
90 parts by weight of ion-exchanged water in a nitrogen-substituted polymerization reactor (autoclave), 50 parts by weight of 1,3-butadiene as a conjugated diene-based monomer, and a dimer that is a mixture of one or more of the compounds represented by Formulas 1 to 6 as an emulsifier 1.1 parts by weight of acid saponification, 0.27 parts by weight of potassium carbonate as electrolyte, 0.06 parts by weight of potassium hydroxide, 0.25 parts by weight of t-dodecyl mercaptan as molecular weight regulator, 0.04 parts by weight of t-butyl hydroperoxide as reaction initiator, dextrose 0.02 parts by weight, 0.0015 parts by weight of sodium pyrrole phosphate, and 0.0007 parts by weight of ferrous sulfate were added, and the temperature was raised to 55° C. to initiate a polymerization reaction.
[138]
After the polymerization reaction is started, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.05 parts by weight of potassium persulfate and 0.15 parts by weight of a dimer acid saponified product as an emulsifier are added at a time when the polymerization conversion is 40%, and the temperature is set to 78° C. The temperature was raised to and maintained for polymerization reaction for 6 hours.
[139]
Next, at the time of polymerization conversion of 50%, 35 parts by weight of 1,3-butadiene, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.15 parts by weight of dimer acid saponification, 0.05 parts by weight of potassium carbonate, and 0.01 parts by weight of potassium hydroxide parts were sequentially added, and then 15 parts by weight of 1,3-butadiene, 0.1 parts by weight of t-dodecyl mercaptan as a molecular weight regulator, 0.15 parts by weight of saponified dimer acid, 0.05 parts by weight of potassium carbonate and hydroxide at the time of polymerization conversion of 70% 0.01 parts by weight of potassium was sequentially added to complete the reaction at a polymerization conversion rate of 95%.
[140]
The average particle diameter of the prepared polybutadiene was 1235 Å, and the standard deviation of the particle diameter was 242 Å. An enlarged polybutadiene was obtained by adding 0.3 parts by weight of sodium alginate and 1.1 parts by weight of acetic acid to the prepared polybutadiene, and the average particle diameter of the enlarged polybutadiene was 3225 Å, and the standard deviation of the particle diameter was 835 Å.
[141]
[142]
ASBS DP and Injection Specimen Manufacturing
[143]
12 parts by weight of acrylonitrile, 28 parts by weight of styrene, 20 parts by weight of ion-exchanged water, dimer acid mixed in a separate mixing device with 60 parts by weight of polybutadiene and 1000 parts by weight of ion-exchanged water prepared in Examples and Comparative Examples A mixed solution consisting of 0.4 parts by weight of saponification and 0.35 parts by weight of t-dodecyl mercaptan, 0.12 parts by weight of t-butyl hydroperoxide, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrrole phosphate, and 0.002 parts by weight of ferrous sulfate at 70° C. was continuously added for 3 hours.
[144]
After the input was completed, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrrole phosphate, 0.001 parts by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide were added in batches, and the temperature was raised to 80° C. over 1 hour. After completion of the reaction, an acrylonitrile-butadiene-styrene (ABS) graft copolymer was prepared.
[145]
0.8 to 2 parts by weight of MgSO 4 was added to the prepared ABS graft copolymer and agglomerated, washed and dried to obtain ABS powder (DP), 27 parts by weight of the obtained ABS powder and SAN (styrene-acrylonitrile, Mw = 120,000, acrylonitrile content 27%) 73 parts by weight were mixed to obtain a thermoplastic resin composition. The obtained thermoplastic resin composition was extruded and injected to obtain an injection specimen.
[146]
[147]
Example 4 and Comparative Example 4
[148]
In the process of preparing the injection specimen of Example 1, instead of 60 parts by weight of a single polybutadiene, the polybutadiene and the enlarged polybutadiene of Example 1 were mixed 1:2, and 1.2 parts by weight of MgSO 4 The graft copolymer and injection A specimen was prepared, which was referred to as Example 4.
[149]
Also, in the same manner, in the manufacturing process of the injection specimen of Comparative Example 1, instead of 60 parts by weight of a single polybutadiene, the polybutadiene and the enlarged polybutadiene of Comparative Example 1 were mixed 1:2, and 2 parts by weight of MgSO 4 was used to graft air. Coalesced and injection specimens were prepared, and this was referred to as Comparative Example 4.
[150]
[151]
Average particle diameter and particle diameter standard deviation of polybutadiene and enlarged polybutadiene prepared in Examples and Comparative Examples, conversion to polybutadiene (PBL) and conversion to ABS graft copolymer, and injection specimens in each case 4 parts by weight of MgSO is summarized in Table 1 below.
[152]
[153]
[Table 1]
Average Particle Size (Å) Particle Size Standard Deviation (Å) PBL Conversion Rate ABS Conversion Rate MgSO4 Input Parts by Weight
Example 1 Polybutadiene 1280 350 95.0 95.3 0.7
Hypertrophic polybutadiene 3270 920 95.7 1
Example 2 Hypertrophic polybutadiene 3230 992 95 0.8
Example 3 Polybutadiene 1260 282 95.1 95.8 0.7
Hypertrophic polybutadiene 3290 870 95.5 0.8
Comparative Example 1 Polybutadiene 1220 210 95.2 96.1 2
Hypertrophic polybutadiene 3290 690 95.7 2
Comparative Example 2 Hypertrophic polybutadiene 3230 823 94.9 1.7
Comparative Example 3 Polybutadiene 1235 242 95.3 95.2 1.45
Hypertrophic polybutadiene 3225 835 95.0 1.45
[154]
[155]
Experimental Example 1. Confirmation of physical properties of injection specimens
[156]
For the injection specimens prepared in Examples and Comparative Examples, physical properties were measured using the following method.
[157]
[158]
* Izod impact strength (IMP, kgfcm/cm): According to ASTM D256, 1/8 inch and 1/4 inch thick pellet specimens were notched and measured.
[159]
* Sharpness (reflection haze): Using a polished specimen, the sharpness was measured by adding gloss values ​​between 17 to 19° and 21 to 23° according to standard measurement ASTM E430. The lower the sharpness value measured by this method, the better the sharpness of the injection specimen.
[160]
[161]
The measured physical properties are summarized in Table 2 below.
[162]
[163]
[Table 2]
Polybutadiene Type 1/4 inch IMP 1/8 inch IMP Clarity
Example 1 Polybutadiene 5.2 6.7 0.8
Hypertrophic polybutadiene 23.1 23.4 1.8
Example 2 Hypertrophic polybutadiene 23.5 24.3 1.4
Example 3 Polybutadiene 3.8 5.7 1.0
Hypertrophic polybutadiene 22.7 23.3 1.4
Example 4 Polybutadiene / Hypertrophic Polybutadiene 18.2 18.3 0.9
Comparative Example 1 Polybutadiene 3.2 5.0 1.7
Hypertrophic polybutadiene 21.8 22.7 2.7
Comparative Example 2 Hypertrophic polybutadiene 22.3 23.0 2.3
Comparative Example 3 Polybutadiene 3.6 5.2 1.4
Hypertrophic polybutadiene 22.2 22.9 2.2
Comparative Example 4 Polybutadiene/Enlarged Polybutadiene 16.1 15.0 1.6
[164]
[165]
From the above results, it was confirmed that the injection specimen prepared from the thermoplastic resin including the conjugated diene-based polymer prepared by the method of the present invention exhibited more excellent impact strength and sharpness.
[166]
[167]
Experimental Example 2. Confirmation of the amount of coagulated product during polymerization and acetic acid coagulation
[168]
After measuring the weight of the coagulated material produced in the reaction tank of Examples and Comparative Examples, the weight of the total polymer and the weight of the monomer, and calculating the content of the solid coagulated material of the conjugated diene-based polymer using Equation 2 below, it is shown in Table 3 it was
[169]
[Equation 2]
[170]
Coagulant content = Weight of coagulated product inside the reactor (g) / Total polymer weight and monomer weight (100 g)
[171]
[172]
[Table 3]
Polybutadiene type Small-diameter production Coagulation amount Large-diameter coagulation amount
Example 1 Polybutadiene 0.02 -
Hypertrophic polybutadiene - 0.043
Example 2 Hypertrophic Polybutadiene - 0.045
Example 3 Polybutadiene 0.0175 -
Hypertrophic polybutadiene - 0.04
Example 4 Polybutadiene / Hypertrophic Polybutadiene - 0.023
Comparative Example 1 Polybutadiene 0.018 -
Hypertrophic polybutadiene - 0.041
Comparative Example 2 Hypertrophic polybutadiene - 0.045
Comparative Example 3 Polybutadiene 0.021 -
Hypertrophic polybutadiene - 0.037
Comparative Example 4 Polybutadiene / Hypertrophic Polybutadiene - 0.021
[173]
[174]
From the above results, it was confirmed that when the manufacturing method according to the embodiment of the present invention was used, the coagulation was generated at a level similar to the method of the comparative example.
[175]
[176]
Experimental Example 3. Confirmation of gas generation during injection
[177]
The total amount of volatile organic compounds (VOCs) generated for 1 hour at 250° C. for 1 g of the graft copolymer prepared in Examples and Comparative Examples was analyzed using HS-GC/MSD, and the results are shown in Table 4 below was described as
[178]
[179]
[Table 4]
Polybutadiene Type Gas Generation (ppm)
Example 1 Polybutadiene 1170
Hypertrophic Polybutadiene 1590
Example 2 Hypertrophic Polybutadiene 1260
Example 3 Polybutadiene 1210
Hypertrophic Polybutadiene 1520
Example 4 Polybutadiene / Hypertrophic Polybutadiene 1620
Comparative Example 1 Polybutadiene 1930
Hypertrophic Polybutadiene 2580
Comparative Example 2 Hypertrophic polybutadiene 2310
Comparative Example 3 Polybutadiene 1727
Hypertrophic Polybutadiene 1840
Comparative Example 4 Polybutadiene / Hypertrophic Polybutadiene 2490
[180]
[181]
From the above results, it was confirmed that when the manufacturing method according to the embodiment of the present invention is used, the amount of gas generated during injection is small compared to the case where the conventional method or the method of the comparative example is used, so that the injection specimen can have a uniform surface.
[182]
[183]
Experimental Example 4. Confirmation of residual Mg content in ABS powder
[184]
The Mg content remaining in the ABS powders prepared in Examples and Comparative Examples was confirmed using an analysis of the mineral content through ICP Mass, and the results are shown in Table 5 below.
[185]
[186]
[Table 5]
Polybutadiene type Residual Mg content (ppm)
Example 1 Polybutadiene 550
Hypertrophic Polybutadiene 690
Example 2 Hypertrophic Polybutadiene 632
Example 3 Polybutadiene 572
Hypertrophic Polybutadiene 659
Example 4 Polybutadiene / Hypertrophic Polybutadiene 780
Comparative Example 1 Polybutadiene 1320
Hypertrophic Polybutadiene 1370
Comparative Example 2 Hypertrophic polybutadiene 1150
Comparative Example 3 Polybutadiene 843
Hypertrophic Polybutadiene 865
Comparative Example 4 Polybutadiene/Enlarged Polybutadiene 1220
[187]
[188]
From the above results, it was confirmed that the amount of residual Mg was small when using the manufacturing method of Examples of the present invention, so that the physical properties of the conjugated diene-based polymer could be excellent.
Claims
[Claim 1]
30 to 50 parts by weight of 100 parts by weight of the conjugated diene-based monomer, 0.1 to 5 parts by weight of a saponified dimer acid, and a polymerization initiator are collectively added to a reactor to initiate a polymerization reaction (S1); After initiation of the polymerization reaction, the remaining conjugated diene-based monomer and the emulsifier are dividedly added three or more times according to the polymerization conversion (S2); And terminating the polymerization reaction at a polymerization conversion rate of 90 to 99% (S3); Method for producing a conjugated diene-based polymer comprising a.
[Claim 2]
The method of claim 1, wherein in step S2, the remaining conjugated diene-based monomer and the emulsifier are dividedly added three or four times.
[Claim 3]
The method of claim 1, wherein the amount of the conjugated diene-based monomer divided in step S2 is less than or equal to the amount of the conjugated diene-based monomer added immediately before.
[Claim 4]
According to claim 1, wherein the step S2 comprises the steps of adding a conjugated diene-based monomer and an emulsifier at a polymerization conversion rate of 20 to 35% (S2-1); adding a conjugated diene-based monomer and an emulsifier at a polymerization conversion rate of 45 to 60% (S2-2); and adding a conjugated diene-based monomer and an emulsifier at a polymerization conversion rate of 70 to 80% (S2-3).
[Claim 5]
The method according to claim 4, wherein in step S2-1, 20 to 30 parts by weight of the conjugated diene-based monomer is added, in step S2-2, 15 to 25 parts by weight of the conjugated diene-based monomer is added, and in step S2-3, the conjugated diene is added. 10 to 20 parts by weight of the system monomer is added, and the total amount of the conjugated diene-based monomer added in steps S2-1 to S2-3 is 70 parts by weight or less.
[Claim 6]
[Claim 5] The method for producing a conjugated diene-based polymer according to claim 4, wherein the amount of the conjugated diene-based monomer added in steps S2-1 to S2-3 satisfies the following formula 1: [Formula 1] M1≥M2≥M3 In the formula, M1, M2 and M3 are the amounts of the conjugated diene-based monomer input in steps S2-1, S2-2 and S2-3, respectively.
[Claim 7]
The method of claim 1, wherein the dimer acid is at least one selected from compounds represented by the following Chemical Formulas 1 to 6: [Formula 1] [Formula 2] [Formula 3] [Formula 4] [Formula 5] [Formula 6] .
[Claim 8]
The method of claim 1, wherein the polymerization initiator is at least one of a water-soluble polymerization initiator, and a mixture of a fat-soluble polymerization initiator and an oxidation-reduction catalyst.
[Claim 9]
The method of claim 8, wherein the water-soluble polymerization initiator is at least one selected from the group consisting of potassium persulfate, sodium persulfate and ammonium persulfate, and the oil-soluble polymerization initiator is cumene hydroperoxide, diisopropyl benzene hydroper Oxide, azobis isobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, and at least one selected from the group consisting of benzoyl peroxide, the oxidation-reduction-based catalyst is sodium formaldehyde sulfoxylate , sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrole phosphate, a method for producing at least one conjugated diene-based polymer selected from the group consisting of sodium sulfite.
[Claim 10]
The method of claim 1, wherein the polymerization initiator is added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the conjugated diene-based monomer.
[Claim 11]
The conjugated diene according to claim 1, wherein the molecular weight modifier is further added in steps S1 and S2, and the total amount of the molecular weight modifier added in steps S1 and S2 is less than 1 part by weight based on 100 parts by weight of the conjugated diene-based monomer. Method for producing a polymer-based polymer.
[Claim 12]
The method of claim 1, wherein the emulsifier is at least one selected from the group consisting of saponified rosin acid, saponified fatty acid, saponified dimer acid, and saponified oleic acid.
[Claim 13]
The method of claim 1, wherein the conjugated diene-based polymer has an average particle diameter of 1000 to 2000 Å.
[Claim 14]
The method of claim 1, further comprising a step (S4) of adding a coagulant or a coagulant and an auxiliary coagulant after completion of the polymerization reaction to increase the size (S4), wherein the average particle diameter of the conjugated diene-based polymer is 2500 to 4000 Å. manufacturing method.
[Claim 15]
15. A method for producing a graft copolymer by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer to the conjugated diene-based polymer prepared by the method of any one of claims 1 to 14.
[Claim 16]
A graft copolymer prepared by the method of claim 15; and a copolymer including a unit derived from an aromatic vinyl-based monomer and a unit derived from a vinyl cyan-based monomer.