FORM 2


THE PATENT ACT, 1970 (39 OF 1970)
COMPLETE SPECIFICATION (See Section 10)
1. "A PROCESS FOR THE MODIFICATION OF THE ROSIN MODIFIED PHENOLIC RESINS WITH ISOCYANATES USEFUL AS THE REINFORCING AGENTS FOR RUBBERS."
2. (a) Dr. Ghatge Nanasaheb Dattajirao
(Principal Investigator & The Consultant) And
(b) Mr. Ghatge Shivraj Nanasaheb (The Partner),
Indian Adhesives & Glues,
Speciality Chemicals Division, 7, Vishrambag Co-operative Housing Society, Senapati Bapat Road, Pune 411016, India, Nationality - Indian.
(c) Dr. Kadam Shivajirao Shripati (The Consultant),
Bharati Vidyapeeth's,
Poona College of Pharmacy, Pune 411038, India, Nationality - Indian.
And
(d) Dr. Shinde Babanrao Mahadeo (The Consultant), Division of Polymer Chemistry, National Chemical Laboratory, Pune 411008, India, Nationality - Indian.
The following specification (particularly) N/A
The nature of the invention and the manner in which it is to be N/A performed
3. "A PROCESS FOR THE MODIFICATION OF THE ROSIN MODIFIED PHENOLIC RESINS WITH ISOCYANATES USEFUL AS THE REINFORCING AGENTS FOR RUBBERS."

Rosin is a complex mixture1 of mutually soluble, naturally occurring high molecular weight organic compounds containing free acidic groups and conjugated reactive double bonds. This mixture contains major constituents: (i) abietic acid, and (ii) levopimaric acid. It is a clear pale yellow to dark amber thermoplastic resinous solid mass, which is isolated from pine trees.
The carboxylic acid group is responsible for the overall chemical reactivity of the rosin. Esterification of the carboxylic acid with alcohols yields a thermoplastic resinous esters1,2. In addition to the reactivity as a carboxylic acid, other equally important reactions are attributed to conjugated double bonds of the rosin. Oxidation can occur at these double bonds and can cause the rosin to darken and finally becomes brittle, less soluble in organic solvents. It can be stabilized by physical and chemical processes involving hydrogenation, dehydrogenation, polymerization, etc. These stablization treatments cause aromatization of the double bonds to eliminate unsaturation, thus rendering the rosin much less susceptible to oxidation. Rosin processed in this manner is termed as 'MODIFIED ROSIN.'
Other commercially important reactions involving conjugated double bonds of the rosin are those with dibasic acids like fumaric acid and maleic acid/anhydride by Diel's Alder Mechaism.3'4 Martin5 reported that the addition of one phenol dialcohol per one mole of rosin molecules resulted in the formation of a 'ROSIN MODIFIED PHENOLIC RESINS.' It was pointed out that the methylol groups of phenol dialcohols can react with the rosin at its conjugated double bonds forming a cyclic ring structures, in which phenolic hydroxyl groups are involved.
Rosin and its esters find application as a plasticizer for many polymeric materials including rubbers. Rosin acids form the major part of pine tars, which are used as softners for rubbers. The important use of rosin namely in the manufacture of styrene butadiene rubber was reported by Guthbertson.6 The presence of the rosin acids in styrene-butadiene rubber also contributes to the tack for tyre building, improves hysteresis properties, tensile strength, tear strength, tear resistance and enhances the reinforcement of the rubbers with carbon blacks.

Thus, it was decided to synthesize the rosin resins for the reinforcement of natural and synthetic rubbers. The modifications of phenolic dialcohols with rosin were carried out in our earlier Indian Patent7. In the present investigations, the extension of this invention was continued to modify the rosin modified phenolic resins with mono-or diisocyanate for the preparation of isocyanate modified rosin resins for the reinforcements of rubbers.
It was assumed that me double bonds in cardanol may react widi me conjugated double bonds of rosin to give the cardanol modified rosin resins. The most interesting characteristic property of these resins is that these resinous products can be crushed to form crystalline powder and on keeping even at room temperature aggregate to form an original united solid mass. These resinous end products are useful in the preparation of adhesive tapes.
Further, these cardanol modified rosin resins were then reacted with mono- or diisocyanate to obtain isocyanate modified rosin resins. These resinous end products were found to be useful in the preparation of adhesive tapes. The utility of these modified rosin resins was tested for usefulness in adhesive tapes in a rubber products manufacturing company in Pune.
EXAMPLES:
[1] Preparation of Cardanol Dialcohols (CDA) from the reaction of Cardanol with formaldehyde:
The phenolic dialcohols were prepared from the reaction of cardanol / m-cresol / phenol with formaldehyde using similar experimental procedure as reported in Indian Patent7.
[2] Preparation of Resol Resin from the reaction of Cardanol with Formaldehyde:
The phenolic resol resins were prepared from the reaction of cardanol / m-cresol/phenol with formaldehyde using similar experimental procedure as reported in Indian Patent .

[3] Preparation of Resol from the reaction of Cardanol and m-Cresol with Formaldehyde:
The phenolic resol resins were prepared from the reaction of cardanol and m-cresol with formaldehyde using similar experimental procedure as reported in Indian Patent7.
[4] Preparation of Resol from the reaction of Cardanol and Phenol with Formaldehyde:
The phenolic resol resins were prepared from the reaction of cardanol and phenol with formaldehyde using similar experimental procedure as reported in Indian Patent7.
[5] Modification of Cardanol Dialcohols using Rosin:
The modification of cardanol dialcohols with rosin were carried out using similar experimental procedure as reported in Indian Patent7 and is tabulated in Table-1.
[6] Modification of Resol-Resins using Rosin:
The modifications of resol resins with rosin were carried out using similar experimental procedure as reported in Indian Patent7 and are tabulated in Table-2.
[7] Modification of Rosin Modified Phenolic Resins with Monoisocyanate:
A mixture of equimolar quantity of rosin modified phenolic resin ('x' g.) and monoisocyanate ('y' g) was made by heating at 70-90°C for 1 hour in nitrogen atmosphere in a 500 ml three necked round bottomed flask equipped with a mechanical stirrer, thermowell, reflux condenser and a nitrogen gas inlet tube. It was then heated to 120° -30°C for the specific period till it gave a clear solubility in white spirit (1:1).
The resinous end products thus obtained, were found to be brittle, dark brown-red colored transparent solids having lower softening points than that of rosin

modified phenolic resins and are tabulated in Table-3, and the reaction scheme is given in Scheme-1.
Modification of Rosin Modified Phenolic Resins with Diisocyanate:
A mixture of equimolar quantity of rosin modified phenolic resin ('a' g) and diisocyanate ('b' g) was made by heating the reaction mixture in a suitable so/vent medium (tofuene or xylene) at 70-90° C for 1 hr. in a nitrogen atmosphere in a 500 ml. three necked round bottomed flask, equipped with a mechanical stirrer, thermowell, reflux condenser and a nitrogen gas inlet tube. It was then heated to 120-130°C for the specific period till it gave a clear solubility in white spirit (1:1 ratio).
The resinous end products thus obtained were found to be sticky, dark-brown-red colored transparent solids having lower softening points than that of rosin modified cardanol resins and are tabulated in Table-4, and the reaction scheme is given in Scheme-7.
Modification of Rosin with Cardanol:
Rosin (lOOg, 0.33 mole) was melted at 120°-30°C in a round bottomed three necked flask, equipped with a mechanical stirrer, thermowell, nitrogen gas inlet tube and reflux condenser. Cardanol ('y' g) was added to the rosin at 120-30°C and the heating was continued for further 3 hrs. It was then heated at 150-60°C for a specific period till it gave a clear solubility in white spirit (1:1 ratio). These end products were found to be transparent sticky solids having lower softening points than that of the rosin; and are tabulated in Table-5, and the reaction scheme is given in Scheme-1.
Modification of Rosin Modified Cardanol with Isocyanates:
A mixture of equimolar quantity of rosin modified cardanol resin ('a' g) and isocyanate ('b' g) made by heating the reaction mixture in a solvent medium (toluene or xylene) at 70-90°C for 1 hr. in a nitrogen atmosphere in a 500 ml. three necked round bottomed flask, equipped with a mechanical stirrer,

thermowell, reflux condenser and a nitrogen gas inlet tube. It was then heated to 120-30°C for a specific period till it gave a clear solubility in white spirit (1:1 ratio). The resinous end products thus obtained were found to be sticky, dark brown-red coloured transparent solids having lower softening points than that of rosin modified cardanol resins. Scheme-2A & 2B represents the modifications of cardanol with rosin and then with isocyanates.

REFERENCES:
1. H.I. Enos, G.C. Harris and G.W. Hedrick, "Encyclopedia of Chemical Technology," Vol. 17,475-508 (1968).
2. H.F. Payne, Organic Coating Technology, Vol. 1, 156-61 (1954).
3. L. Ruzika, P.J. Ankersmit and B. Frank, Hev. Chem. Act. 15,12789 (1932).
4. R.V. Lawrence and O.S. Eckhardt, U.S. Pat. 2,628,226 (Feb. 10,1953).
5. S.R.W. Martin, "Synthetic Resin Chemistry," Chapman and Hall Ltd., London (1951).
6. G.R.. Guthberston, W.S. Coe and J.L. Brady, Ind. Eng. Chem., 38,945 (1946).
7. N.D. Ghatge, S.N. Ghatge, S.S. Kadam and B.M. Shinde; Indian Patent Appln. No.309/MUM/2001 (April 2,2001).

INDIAN ADHESIVES AND GLUES , PUNE
APPLICATION NO

TOTAL PAGES . 3
THIS PAGE 1 OF 3

ISOCYANATE BLOCKED ROSIN MODIFIED RESOL RESINS ( RESIN-III)

ROSIN MODIFIED RESOL RESINS (RESIN-I)

SCHEME 1 : SYNTHESIS OF ROSIN MODIFIED RESOL PRODUCTS
APPLICANT (S) : (Dr.GHATGE ND.) (Mr.GHATGE S.N.) (Dr.KADAM S-S-) AND (Dr. SHINDE B.M.)


INDIAN ADHESIVES AND GLUES , PUNE
APPLICATION NO

TOTAL PAGES 3
THIS PAGE 2 OF 3

ROSIN MODIFIED CARDANOL PRODUCT

SCHEME 2A.: SYNTHESIS OF ROSIN MODIFIED CARDANOL PRODUCTS.
APPLICANT(S): (Dr.GHATGE N.D.) (Mr.GHATGE S.N.) (Dr.KADAM S.S.) AND (Dr.SHINDE B.M.)


INDIAN ADHESIVES AND GLUES , PUNE TOTAL PAGES 3
APPLICATION NO. THIS PAGE . 3 OF 3

CARDANOL OR PHENYL
3-PENTA DECENYL PHENOL ISOCYANATE

SCHEME 2B : SYNTHESIS OF ROSIN MODIFIED ISOCYANATE BLOCKED CARDANOL PRODUCTS.
APPLICANT(S). (Dr.GHATGEN.D.) (Mr.GHATGE S.N) (Dr.KADAM S.S.) AND (Dr. SHINDE B.M.)


Table-l: Rosin Modified Phenolic Resins* using Cardanol Dialcohols

Sr. No. Name of the Resin Parts of Cardanol
Dialcohols per 100
parts of Rosin
g- Softening Point
°C Acid Value
mg of
KOH/g Nature of the Resin
1. Rosin 60-65 175-80 Pale yellow crystalline solid
2. Resin-I 18.0 70-75 150-52 Brown red colored crystalline transparent solid
3. Resin-II 36.0 75-80 128-30 —do—
4. Resin-III 54.0 80-85 118-20 —do—
5. Resin-IV 72.0 85-90 110-12 —do—
6. Resin-V 108.0 90-95 90-95 —do—
7. Resin-Vl 144.0 100-105 74-75 —do—
♦Solubility: Soluble in most of organic solvents like white spirit, acetone, ethyl acetate, butyl alcohol, benzenen toluene, xylene, carbon tetra chloride, chloroform, dimethyl formamide (DMF), dimethyl acetamide (DMAC), dimethyl sulphoxide (DMSO) etc.

Table-2: Rosin Modified Phenolic Resins* using Cardanol Resole Resins

Sr. No. Name of the Resin Parte of Cardanol Resole Resins per 100 parts of Rosin
g- Softening
Point
°C Acid Value mg of KOH/g Nature of the Resin
1. Rosin-VII 10.0 75-80 155-58 Brown red colored crystalline transparent solid
2. Resin-VIII 20.0 80-85 142-45 —do~
3. Resin-IX 50.0 100-105 128-30 ~do-
4. Resin-X 80.0 110-15 118-20 —do—
5. Resin-XI 100.0 115-20 110-13 —do—
6. Resin-XII 120.0 120-25 88-90 —do—
7. Resin-XlII 150.0 130-35 76-78 —do—
♦Solubility: Soluble in most of organic solvents like white spirit, acetone, ethyl acetate, butyl alcohol, benzenen toluene, xylene, carbon tetra chloride, chloroform, dimethyl formamide (DMF), dimethyl acetamide (DMAC), dimethyl sulphoxide (DMSO) etc.

Table-3: Modifications of Rosin Modified Phenolic Resins* with Phenolic Isocyanate (Ph-NCO)

Sr.
No. Name of the Resin Parts of Cardanol
Dialcohols (CDA) per
100 parts of Rosin
g- Parts of Ph-NCO
per 100 parts of
the Resin Softening
Point
°C Acid Value mgofKOH/g Nature of the Resin
1. Rosin 60-65 175-80 Pale yellow crystalline solid
2. ResinM-I" 18.0 6.0 65-70 150-55 Brown red coloured crystalline solid
3. ResinM-II 36.0 12.0 70-75 125-30 -do-
4. ResinM-III 54.0 18.0 75-80 115-20 -do-
5. ResinM-IV 72.0 24.0 80-85 105-10 -do-
6. ResinM-V 108.0 36.0 85-90- 90-95 -do-
7. ResinM-VI 144.0 48.0 100-05 70-75 -do-
*Solubilitv: Soluble in most of the organic solvents like white spirit, acetone, ethyl acetate, butyl alcohol, benzene, toluene, xylene, carbon tetrachloride, chloroform, dimethyl formamide (DMF), dimethyl acetamide (DMAC), dimethyl sulphoxide (DMSO) etc.

**

Ph-NCO has been used in equimolar quantities for modification of Resin-1 to Resin-VI.

Table-4: Modifications of Rosin Modified Phenolic Resins* with Tolylene Diisocyanate (TDI)

Sr. No. Name of the Resin Parts of Cardanol
Dialcohols (CDA) per
100 parts of Rosin
g- Parts of TDI per
100 parts of the
Resin**
g- Softening
Point
°C Acid Value mgofKOH/g Nature of the Resin
1. Rosin 60-65 175-80 Pale yellow crystalline solid
2. Resin-MD-I 18.0 6.0 75-80 150-55 Brown red coloured crystalline solid
3. Resin-MD-II 36.0 8.70 80-85 125-30 -do-
4. Resin-MD-HI 54.0 13.55 85-90 115-20 -do-
5. Resin-MD-IV 72.0 17.40 90-95 90-95 -do-
6. Resin-MD-V 108.0 26.10 90-95 90-95 -do-
7. Resin-MD-VI 144.0 38.80 105-10 70-75 -do-
♦Solubility: Soluble in most of the organic solvents like white spirit, acetone, ethyl acetate, butyl alcohol, benzene, toluene, xylene, carbon tetrachloride, chloroform, dimethyl formamide (DMF), dimethyl acetamide (DMAC), dimethyl sulphoxide (DMSO) etc.

**

TDI (Tolylene Diisocyanate) has been used in equimolar quantities for modification of Resin-I to Resin-VI.

Table-5: Characteristic Properties of Rosin Modified Phenolic (Cardanol) Resins*

Sr. No. Name of the Resin Parts of Cardanol per 100 parts of Rosin** Softening
Point
°C Acid Value mg ofKOH/g Nature of the Resin
1. Rosin ... 60-70 175-78 Amber/Pale yellow coloured amorphous solid
2. Resin-CR-I 10.0 60-65 155-157 Pale yellow coloured sticky solid
3. Resin-CR-II 20.0 60-65 155-57 -do-
4. Resin-CR-III 30.0 55-60 140-48 -do-
5. Resin-CR-IV 40.0 45-50 120-23 -do-
6. Resin-CR-V 50.0 45-50 112-15 -do-
7. Resin-CR-VI 60.0 35-40 105-07 Brownish coloured Viscous liquid
♦Solubility: Soluble in most of the organic solvents like white spirit, acetone, ethyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), butyl alcohol, benzene, toluene, xylene, carbon tetrachloride, chloroform, dimethyl formamide (DMF), dimethyl acetamide (DMAC), dimethyl sulphoxide (DMSO) etc.
** Cardanol dimethyl acetamide (DMAC), dimethyl sulphoxide (DMSO) etc. has been used in parts per 100
parts of the rosin to obtain Resin-CR-I to Resin-CR-VI.

We claim:
(i) A process for making modifications of phenolic resol resins with rosin to obtain rosin modified phenolic resins for the reinforcement of rubbers such as natural rubber, styrene butadiene rubber (SBR), nitrile rubber, neoprene, polyisoprene, etc.
(ii) Further, a process for making modifications of these rosin modified phenolic resins with isocyanates was carried out and were then utilized these final resinous end products for the reinforcement of natural as well as synthetic rubbers.
(iii) Caradnol has been used to modify rosin and thereafter reaction of the final product with isocyanate was carried out to obtain isocyanate modified cardanol-rosin resins for use as tackifying agents for rubbers as well as in making adhesive tapes.
(iv) Commercially available isocyanates (aliphatic as well as aromatic) used in the present study were: butyl isocyanate (Bu-NCO), phenyl isocyanate (Ph-NCO), tolyene diisocyanate (TDI), 4,4-methylene diphenyl diisocyanate (MDI) hexamethyl diisocyanate (HDI), isophorone diisocyanate (TPDI), etc.


Dated this 6th of August 2002
(a) DR. GHATGE NANASAHEB DATTAJIRAO
(b) MR. GHATGE SHIVRAJ NANASAHEB
(c) DR. KADAM SHIVAJIRAO SHRIPATI
(d) DR. SHINDE BABANRAO MAHADEO

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