CA1271294A - Vinyl aromatic/terpene/phenol/terpolymers - Google Patents

Abstract

VINYL AROMATIC/TERPENE/PHENOL TERPOLYMERS
Abstract of Disclosure Disclosed is a process for making terpolymers having a Ring and Ball softening point of 69°C to 130°C prepared from a vinyl-substituted aromatic hydrocarbon, a monoterpene hydrocarbon and a phenol. The terpolymers are useful as tackifiers in adhesive compositions.

Description

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This invention relates to a process for making novel ter-polymers that are particularly adapted for use as tackifiers in adhesive compositions.
European patent application 75,771 discloses a ?rocess in which (1) an alkylated phenol is reacted with a terpene, or

(2) a phenol is reacted with a terpene and the reaction prod-uct is alkylated, e.g., with styrene. The product is used as a stabilizer for polymers. The general formula for the phenol used in the reaction is given as HO OH OH

~t R 3 , n R 2 1~ where R can contain a terpene group or an alkyl, cyclohe~yl or cyclohexenyl group or a group derived from divinylbenzene or diisopropenylbenzene (emphasis added), Rl, R2 and R3 are H, alkyl, cycloalkyl or aralkyl, and n is a whole number from 0 to 20.
lS In the process of the European patent application, the vinyl-substituted aromatic component, if one is present, and the terpene component are never present simultaneously in the reaction mixture. Therefore it is not possible to have a structure in which the terpene component is linked to a vinyl-substituted aromatic component.
It would be desirable to develop a process in which the vinyl-substituted aromatic component and the terpene component . .

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could be linked to each other as well as to the phenol compo-nent, that would produce vinyl-substituted aromatic/terpene/
phenol terpolymers suitable for use as tackifiers in adhesive compositions.
According to the invention, a process for preparing a polymeric product from a phenol, a terpene, and a vinyl-substituted aromatic component, is characterized in that the monomers in a mixture comprising, by weight, (l) from about 12% to about ~5~ of a vinyl-substituted aromatic hydrocarbon having the general formula ~, R" ~ Cl-CH2 where R' is hydrogen or -CH3 and R" is hydrogen, a -CH=CH2 group or a l-10 C alkyl group, (2) from about 5% to about 75 of at least one monoterpene hydrocarbon, and (3) from about 0.75~ to about 50~ of at least one phenol, are simultaneously polymerized in a solvent and in the presence of a catalyst to produce a vinyl-substituted aromatic/terpene/phenol terpolymer having a Ring and Ball softening point of from about ~9C to about 130C, the percentages of components (1), (2) and (3) being such as to total 100~.
All parts and percentages are by weight unless otherwise indicated.
In the process of the invention, all o~ the components are present at the same time in the reaction mixture, so the terpolymers are formed by the simultaneous polymerization of the vinyl-substituted aeomatic component, the monoterpene com-ponent, and the phenol component, and the phenol is an inte-gral part of the polymer chain. The coupling between the three components will be random and no specific structure can be written.

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-3-The sites on the phenol that are available for reaction with the vinyl-substituted aromatic component and the mono-terpene component include the -OH group, and any unsubstituted carbon atoms in positions ortho and para to the -OH group. ' S For instance, in phenol itself there are four reactive sites where coupling with the other two components of the monomer charge can occur.
There are several suitable procedures for carrying out the process of the invention. In one procedure, the three-monomer blend and the catalyst are added with agitation to the solvent in the reaction vessel via separate inlets. The temperature is controlled by an external cooling bath. In this procedure sufficient catalyst is added to initiate the reaction.
l; In another procedure, solvent and all monomers are ini-tially present in the reaction vessel. Reaction is initiated by the intermittent addition of small ~luantities of catalyst until an exotherm results of magnitude such that it must be controlled by the external cooling bath.
Another procedure may be used when the monomer charge contains 20~ by weight or more of the phenol component. This procedure involves the formation of a complex of the phenol component and the BF3 catalyst in the solvent, followed by slow addition of a solution of the vinyl- substituted aromatic component and the monoterpene component to the solution of the BF3/phenol complex. The re~uirement for at least 20~ by weight of the phenol component in the monomer charge is to ensure that at least about 0.75~ of phenol is present in the mixture until the addition of the other two monomers is com-pleted.
In any of the procedures, after the reaction is complete, the catalyst is neutralized by reacting it with a~ueous caus-tic or lime. The product is then isolated a~ter removing sol-vent and any other volatiles.
The reaction temperature is from about -1~C to about +65C, preferably from about 0C to about +50C.

- ~, Suitable catalysts include BF3, 3C13, and complexes of BF3 with, for example, water, ethyl alcohol, ~3PO4, phenol or ether. BF3 is preferred.
The solvent used is one that is inert under the polymeri-zation conditions and includes aliphatic or preferably aromat-ic hydrocarbons such as toluene or xylene, or blends of aro-matic hydrocarbons such as Exxon Aromatic 100.
The vinyl-substituted aromatic hydrocarbons (l) for use in the process of the invention have the general formula ~ CH2 where R' is hydrogen or -CH3 and R" is hydrogen, a -CH=CH2 group or a 1-10 C alkyl group. Suitable vinyl-substituted aromatic hydrocarbons include, but are not limited to, sty-rene, alpha-methylstyrene, para-methylstyrene, vinyl-toluene, tert-butylstyrene, alpha-p-dimethylstyrene, and divinyl-benzene. Styrene is preferred. Mixtures of two or morevinyl-substituted aromatic hydrocarbons can be used as com-ponent (1) if desired. The vinyl-substituted aromatic hydro-carbon is used in an amount of from about 123 to about 95~ by weight, preferably erom about 21~ to about 77~ by weight, based on the total monomer charge.
Monoterpene hydrocarbons (2) for use in the proc~ss of the invention include, but are not limited to, alpha-pinene, beta-pinene, dipentene, limonene and camphene. Alpha-pinene is preferred~ Mixtures of two or more monoterpene hydro-carbons can be used as component (2) if desired. The mono-terpene hydrocarbon is used in an amount of from about 5~ to about 75% by weight, preferably from about 19~ to about 65~, based on the total monomer charge.
The phenols (3) for use in the process of the invention have at least one unsubstituted C atom in the positions ortho or para to the -OH group and include, but are not limited to, rr~

phenol and alkyl-sustituted phenols such as para-nonylphenol, meta-cresol, ortho-cresol and bisphenol A. Phenol is pre-ferred. ~ixtures of two or more phenols can be used as compo-nent (3) if desired. The phenol is used in an amount of from about 0.75~ to about 50% by weight, preferably from about 3 to about 40% by weight, based on the total monomer charge.
Also, according to the invention, a polymeric product made from a phenol, a terpene, and a vinyl-substituted aromat-ic component, is characterized in that it is a vinyl-substituted aromatic/terpene/phenol terpolymeric tackifierhaving a Ring and 8all softening point of from about 69C to about 130C, suitable for use in adhesive compositions, the polymeric product being produced by the simultaneous polymeri-zation of (l) from about 12% to about 95% of a vinyl-lS substituted aromatic hydrocarbon having the general formula R " ~ 2 where R' is hydrogen or -CH3 and R" is hydrogen, a -CE~=CH2 group or a l-lO C alkyl group, (2) from about 53 to about 753 of a monoterpene hydrocarbon and (3) from about 0.75~ to about 50% of a phenol.
The terpolymers prepared in accordance with this inven-tion are light in color (Gardner~l to 5). Their resistance to color-darkening in air at elevated temperatures may be im-proved by the addition of small amounts of antioxidants such as dilauryl thiodipropionate or distearyl thiodipropionate.
The terpolymers made according to the process of the in-vention have a Ring and Ball softening point of about 69C
to about 130C, and are particularly suitable for use as tackifiers in adhesive compositions. Since low molecular weight products are normally more soluble in any given adhe-sive composition than a high molecular weight ~ ~e ~td~<

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product, a low molecular weight product is desirable, the weight average molecular weight of the terpolymers is prefer-ably from about 500 to about 2000, The compatibility of the terpolymer with the adhesive composition in which it is to be used can be controlled by ad-justing the ratio of the three components of the monomer charge. For example, if the adhesive composition is predomi-nantly aromatic in nature, a larger proportion of the vinyl-substituted aromatic component will be used. If the adhesive composition is predominantly aliphatic in nature, a larger proportion of the terpene component will be used.
The compatibility can be further controlled by varying processing conditions such as reaction time, reaction tempera-ture and the type of catalyst used. These processing condi-tions influence the molecular weight of the terpolymer productand its softening point.
One type of adhesive composition in which the terpolymers can be used is a solvent-based pressure-sensitive adhesive.
Such an adhesive may be prepared using the terpolymers made according to the process of the invention and an elastomeric polymer such as natural rubber, styrene-butadiene (SBR), styrene-isoprene-styrene (SIS), and styrene-butadiene multi-block copolymers. The terpolymer and the elastomer are dis-solved in a solvent such as toluene. An antioxidant such as tetrakis[methylene- (3,5-di-tert-butyl-4-hydroxyhydro-cinnamate)]methane (Irganox 101 ~ Ciba 5eigy) and other stabilizers may be included in the composition if desired.
Another type of adhesive composition in which the ter-polymers can be used is a hot melt pressure-sensitive adhe-sive. Such adhesives may be prepared, for example, by dis-solving the terpolymer, an elastomer such as those mentioned in the preceding paragraph, and an antioxidant in a naphthenic plasticizer at an elevated temperature.
Still another type of adhesive composition in which the terpolymers can be used is a nonpressure-sensitive hot melt adhesive. The components of such an adhesive composition are ~ Tr~

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hot-blended and may be, for example, the terpolymec, a wax such as paraffin, and an elastomer such as an ethylene/vinyl acetate copolymer.
In any of these adhesive compositions the weight ratio o~
terpolymer to elastomer is determined by the use for which the composition is intended.
The terpolymers of this invention may also be used as viscosity modifiers ~or coating compositions and as modifiers for printing inks. As hindered phenolic materials, the ter-polymers may also be useful as oxidative stabilizers for otherpolymers.
The following examples are illustrative of the invention and are not intended to limit its scope in any way.

Exam~le 1 l; A one-liter, three-neck reaction vessel is equipped with a mechanical stirrer, thermometer well, addition funnel, inlet tube to feed catalyst beneath the liquid surface and provision for dry nitrogen blanketing, The reaction vessel is charged with 270 g dry aromatic solvent and flushed with dry nitrogen while cooling as the contents are brought to 0C by means of an external dry ice/isopropanol cooling bath. A mi%ture of 120 g dry styrene and 180 g dry alpha- pinene is blended with 30 g pure phenol dissolved in 30 g aromatic solvent to orm a monomer solution. The monomer solution is added to the reac-tion vessel at 0C over a period of 36 minutes while simul-taneously adding 4.3 g gaseous BF3 catalyst. Catalyst addi-tion is continued another 14 minutes until 6.0 g total BF3 is added~ The reaction mixture is heated to 40C and stir-ring-is continued for one hour. The catalyst is removed by neutralizing with 110 ml of hot caustic solution ~ollowed by three hot water washes. The aqueous phase is separated and discarded. The organic phase is heated under nitrogen while removing solvent and finally sparged with superheated steam at 225C to isolate the terpolymer product. The resulting terpolymer has a Ring and Ball softening point of 106C and ~J 1 ' .

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lB Gardne ~color of 4+ and is obtained in 92~ yield.
The aromatic solvent used in Examples 1-13 is a recycled blend of var ious aromatic compounds, the main components o~
which are para- and meta-xylene (10.6~), para- and meta-S ethyltoluene (13~8~), mesitylene (7.0~), pseudocumene (9.5~),hemimellitene (7.2%), and higher boiling components (13.6~).

Example 2 A one-liter, three-neck reaction vessel is equipped with a mechanical stirrer, thermometer well, provision for dry ni-trogen blanketing and an adjustable inlet tube to feed cata-lyst ~eneath the liquid surface. The reaction vessel is charged with 180 g dry styrene, 120 9 dry alpha-methylstyrene, 30 g dry alpha-pinene, 313 9 dry aromatic solvent blend, and 15 g phenol. Under nitrogen, the temperature is adjusted to 0C by means of an external dry ice/isopropanol bath.
Gaseous BF3 (0.48 g) is then introduced intermittently over a period of lS minutes~ A strong exotherm results which is controlled at 0 to +5C. After this exotherm subsides, BF3 addition is continued until 0.86 g total BF3 is added to the reaction vessel. The reaction mixture is then heated to 40 C. After 1 hour, excess lime is added to neutrali~e the catalyst. The temperature is raised to 100C and lime and neutralization products are ~emoved by ~iltration. The terpolymer is isolated by heating under nitrogen and ~inally 2S sparging at 225C with superheated steam. A terpolymer with a Ring and Bal.l softening point o~ 119C and Gardne ~color l+ is obtained in 91.4~ yield.

Example_3 The reaction apparatus is the same as the one described in Example 1. The reaction vessel is charged with 300 g dry aromatic solvent, flushed with dry nitrogen, and the contents cooled to 0C. A solution of 30 g phenol in 120 g dry styrene and 180 g dry beta-pinene is added dropwise to the reaction vessel at 0C over 35 minutes while simultaneously ~ T~

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adding 4.2 g gaseous BF3. The reaction nixture is allo~1ed to warm to 20C over a 1 hour period and the catalyst is then neutralized with excess lime. The temperature is raised to 100C~ After filtration, the organic phase is heated 5 under nitrogen and finally sparged with steam at 225C. A
t terpolymer with a Ring and Ball softening point of 102C
B and a Gardner~kcolor of 5- is obtained in 89.43 yield.

Example 4 The reaction apparatus is the same as the one described 10 in Example 1. The reaction vessel is charged with 150 g dry aromatic solvent, flushed with dry nitrogen and the contents cooled to 0C. A solution of 15 g phenol in 210 g dry sty-rene with 90 g dry dipentene and 150 g dry aromatic solvent is added dropwise to the reactor at 0C over a 1 hour period 15 while simultaneously adding 7.2 g gaseous BF3 catalyst. The reaction mixture is allowed to warm to +15C while stirring for an additional hour, and the catalyst is then neutralized with excess lime. The temperature is raised to 100C. Lime and neutralization products are removed by filtration. The 20 organic phase is heated under nitrogen and finally sparged with steam at 250C. A terpolymer with a Ring and sall softening point o 110C and a Gardner~color of 3+ is ob-tained in 91.5~ yiel~.

Example 5 The reaction apparatus is the same as the one described in Example 1. Dry aromatic solvent (277 g) is placed in the reaction vessel. After flushing with dry nitrogen, the con-tents of the vessel are stirred and cooled at 0C while a solution of 15 g phenol in 210 g dry styrene and 90 g dry 30 alpha-pinene is added over a period of 34 minutes. During onomer addition, 4.1 g gaseous 3F3 is also continuously added to the reaction medium. The mixture is heated to 40C
and held at this te~perature for 1 hour. Lime is u~ed for neutralization of the catalyst. The terpolymer product is e ,/,~j 7~

isolated by filtration, ~ollowed by distillation of solvent under nitrogen and finally steam sparging at 260C. A ter-polymer with a Ring and 8all softening point of 97C and a Gardner~color of l is obtained in 92.0~ yield.

Example 6 The reaction apparatus is the same as the one described in Example 2. The reaction vessel is charged with 172.8 g dry styrene, 57.6 g dry alpha-pinene, 4,8 9 divinylbenzene, 9.& g phenol and 360 9 dry aromatic solvent. The contents are cooled to 0C under nitrogen and 0.86 g gaseous BF3 is introduced intermittently over a period of 28 minutes, A con-trolled (0 to +2C) strong exotherm lasting for 20 minutes results, After the exotherm subsides, BF3 addition is con-tinued until l.l g total catalyst are added, Stirring is con-tinued at 0C for 30 minutes. Neutralization of the cata-lyst with excess lime is followed by ~iltration at 100C.
The organic phase is heated under nitrogen to remove solvent and finally sparged with steam at 245C. A terpolymer with a Ring and Ball softening point of 116C and a Gardner color of l- is obtained in 95.4~ yield.

Example 1 The reaction apparatus is the same as the one described in Example 1. Dry aromatic solvent ~300 9) is charged to the reaction vessel and the contents are brought to 0C under nitrogen. A blend of 15 9 phenol in 210 9 dry vinyltoluene and 90 g dry alpha-pinene is added with agitation at 0C
over a period of l/2 hour, During this time 3.6 9 gaseous ~F3 catalyst is also continuously added to the reactor.
The temperature is allowed to increase to 20C during the next hour and the catalyst is then neutralized with excess lime. After heating to 100C and filtering, the organic phase is stripped of solvent under nitrogen and steam sparged at 250 C. A terpolymer having a Ring and Ball softening point of 110C and a Gardne ~color of 1 is obtained in 91,73 yield.

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Example 8 The reaction apparatus and general procedure are the same as those described in Example 1. To the reaction vessel containing 284.5 9 aromatic solvent maintained at 0C is added a solution of 192 g styrene, 108 g alpha-pinene and 18 9 phenol over a 1/2 hour period while 3.8 g BF3 is also added, After an additional hour of reaction at 40C, the catalyst is neutralized. A terpolyme~with a Ring and Ball ,lB softening point of g7C and a Gardner~ color of 3- is isolated in 97.6% yield.

Example 9 The reaction apparatus is the same as the one described in Example 1. A solution of 180 g styrene, 120 g ~lpha-pinene, and 30 g para-nonyl phenol is added to a reaction vessel containing 300 9 dry aromatic solvent and maintained at 25C for one hour. 3F3 (8.4 g) is also passed into the reaction mixture. After one additional hour at 25C, the catalyst is neutralized. A terpolymer with a Ring and Ball softening point of 80 C and Gardne~color of 1~ is isolated in 85.6~6 yield.

Example 10 The reaction apparatus is the sarne as the one described in Example 1~ BF3 catalyst is passed into a reaction ves-sel containing 300 g dry aromatic solvent maintained at 25C. A solution of 180 g styrene, L20 g alpha-pinene and 30 g ortho-cresol is added over a one hour period. After an additional hour of reaction time, the catalyst is neutralized.
A terpolymer with a F<ing and Ball softening point of 85C
is obtained in 84.1% yield.

Example 11 The reaction apparatus is the same as the one described in Example 2. The reaction vessel i5 charged with L80 g sty rene, 120 g alpha-pinene, 30 g bisphenol A and 400 9 aromatic 9~

solvent and the contents are brought to 40C. BF3 (2.~ g) is added over a two hour period during which time the bis-phenol A gradually dissolves in the reaction medium. After an additional 20 minute induction period, a strong exotherm results. When this exotherm subsides, the reaction is contin-ued another 1.5 hours at 40C. The catalyst is then neu-B tralized A terpolymer with a softening point of 90C andGardne color of 3+ is isolated in 84.1% yield.

Exam~le 12 The reaction apparatus and general procedure are the same as those described in Example 1. To a reaction vessel containing 300 9 aromatic solvent maintained at 0C is added a solution of 180 9 dry styrene, 120 g alpha-methylstyrene, 15 g alpha-pinene and 2.5 9 phenol over a l/2 hour period while simultaneously adding 3.8 g BF3. After an additional hour at 403C, the catalyst is neutralized. A
terpolymer having a Ring and Ball softening point of 69C
and a Gardner~color of 1 is isolated in 93.8~ yield.

Example 13 The reaction apparatus is the same as the one described in Example 1. The reaction vessel is charged with 63 9 of phenol dissolved in 300 9 aromatic solvent. ~t 25C, 1.5 g BF3 is passed into the reaction vessel to ~orm a soluble complex with the phenol. ',~hile maintaining a reaction temper-25 ature of 25C, a solution of 63 g styrene and 174 g alpha-pinene is added to the stirred reaction vessel over a 3.3 hour period. After an additional 0.5 hr, the catalyst is neutral-ized. A terpolymer~having a Ring and Ball softening point of 129C and a Gardne ~ olor of 4+ is isolated in 87.4~ yield.

Exam~le 14 Solvent-based pressure sensitive adhesive compositions are prepared by the following procedure.
40 Parts by weight of terpolymer prepared according to ~p ~
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Example 1 are mixed in a glass jar with ~0 parts by weight of B a milled natural rubber (Pale Crepe~containing 1~ by weight p,p'-dioctyldlphenylamine) and 0.3 parts by weight antioxidant (Irganox 1010, Ciba Geigy) in 733 parts toluene by tumbling for 3 to 4 days. This procedure is repeated for two addition-al samples using weight ratios of terpolymer to rubber of 50:50 and 60:40. The adhesives are cast as a l.O mil film on a Myla ~substrate, air dried and finally oven dried at 60-70C for 5 minutes. Once cool, release paper is applied to the adhesives and they are stored at 22C and 50% relative humidity. Adhesive testing is performed after storage for 24 hours. The Pressure Sensitive Tape Council (PSTC) tests used and the test results are given below.
Terpolymer:Elastomer40:60 50:50 60:~0 Ratio Peel Strength (oz/in) 28 53 101 (PSTC-l) Quick Stick (oz/in) 20 33 68 (PSTC-5) Rolling 3all Tack (cm)1.9 6.1 25 (PSTC-6) Shear Adhesion (min)2015 1210 300 (PSTC-7) Example 15 A solvent-based peessure sensitive adhesive is prepared by the following procedure.
40 Parts by weight of the terpolymer prepared according to Example 5, 60 parts b~weight of a styrene-butadiene elas-tomer (Ameripol S~R 1011 ~ B. F. Goodrich Co.) and 0.3 parts by weight antioxidant (Irganox 1010~ Ciba Geigy) are dissolved in 900 parts toluene by tumbling for 3 to 4 days. The adhe-sive is cast as a 1.0 mil film on a Mylar~substrate, air dried and finally oven dried at 60-70C for 5 minutes. When cool, release paper is applied to the adhesive and it is stored at 22C and 50~ relative humidity. Adhesive testing is per-3~

formed after storage for 24 hours with the following results:
Peel Strength 6L oz/in 2uick Stick 32 oz/in Rolling Ball Tack 4.1 cm 5 Shear Adhesion 2614 minutes Example 16 A hot melt pressure-sensitive adhesive is prepa~ed by the following procedure.
60 Parts by weight of the terpolymer prepared according to Example 8 are mixed, while blanketed with nitrogen, with B 20 parts plasticizing oil (Shellflex 311 ~ and 0.5 part anti-oxidant (Irganox 1010~ Ciba Geigy) and heated to 175C. 40 Parts by weight of a butadiene-styrene multiblock copolymer (Stereon 840 ~ Firestone Co.) are added and mixing is contin-ued until homogeneity is attained. The adhesive is cast as a 1 mil film on a ~ylar substrate at 350F. Once cool, re-lease paper is applied to the adhesive film and it is stored at 22C and 50~ relative humidity. Adhesive testing is per-formed after storage for 24 hours with the following results:
Peel Strength 73 oz/in Quick Stick 55 oz/in Rolling Ball Tack 30 cm Example 17 The terpolymers of this invention can also be used in nonpressure-sensitive hot melt adhesive compositions. 70 Parts by weight of paraffin wax (Chevron~155 ~ 105 parts by weight ethylene/vinyl acetate ~Elvax 220, Du Pont Co.), 175 parts by weight of the terpolymers shown in the Table and antioxidant are heated and stirred under nitrogen until homo-geneous. Cloud point data and heat aging data for the hotmelt adhesive compositions are given in the Table.
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Claims (14)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for preparing a polymeric product from a phenol, a terpene, and a vinyl-substituted aromatic component, characterized in that the monomers in a mixture comprising, by weight, (1) from about 12% to about 95% of a vinyl-substituted aromatic hydrocarbon having the general formula where R' is hydrogen or -CH3 and R" is hydrogen, a -CH=CH2 group or a 1-10 C alkyl group, (2) from about 5% to about 75% of a monoterpene hydrocarbon, and (3) from about 0.75% to about 50% of a phenol, are simultaneously polymerized in a solvent and in the presence of a catalyst to produce a vinyl-substituted aromatic/terpene/phenol terpolymer having a Ring and Ball softening point of from about 69°C to about 130°C, the percentages of components (1), (2) and (3) being such as to total 100%.

2. A process for prepaxing a polymeric product as claimed in claim 1, further characterized in that the vinyl-substituted aromatic hydrocarbon (1) is styrene.

3. A process for preparing a polymeric product as claimed in claim 1 or 2, further characterized in that the monoterpene hydrocarbon (2) is alpha-pinene.

4. A process for preparing a polymeric product as claimed in claim 1 or 2, further characterized in that the phenol (3) is phenol.

5. A process for preparing a polymeric product as claimed in claim 1 further characterized in that the vinyl-substituted aromatic hydrocarbon (1) is styrene, the monoterpene hydrocarbon (2) is alpha-pinene and the phenol (3) is phenol.

6. A process for preparing a polymeric product as claimed in claim 1, further characterized in that the catalyst is BF3.

7. A process for prepariny a polymeric product as claimed in claim 1, further characterized in that the reaction is carried out at a temperature of from ahout -15°C to about +65°C.

8. A polymeric product made from a phenol, a terpene, and a vinyl-substituted aromatic component, characterized in that it is a vinyl-substituted aromatic/terpene/phenol terpolymeric tackifier having a Ring and Ball softening point of from about 69°C to about 130°C, for use in adhesive compositions, the polymeric product being produced by the simultaneous polymerization of (1) a vinyl-substituted aromatic hydrocarbon, (2) a monoterpene hydrocarbon, and (3) a phenol.

9. A polymeric product as claimed in claim 8, further characterized in that polymeric product is produced by the simultaneous polymerization of (1) from ahout 12% to about 95% of the vinyl-substituted aromatic hydrocarbon, (2) from about 5% to about 75% of the monoterpene hydrocarbon, and from about 0.75% to about 50% of the phenol.

10. A polymeric product as claimed in claim 8 or 9, further characterized in that the vinyl-substituted aromatic hydrocarbon (1) has the general formula where R' is hydrogen or -CH3 and R" is hydrogen, a -CH=CH2 group or a 1-10 C alkyl group.

11. A polymeric product as claimed in clalm 8, further characterized in that the vinyl-substituted aromatic hydrocarbon (1) is styrene.

12. A polymeric product as claimed in claim 8, further characterized in that the monoterpene hydrocarbon (2) is alpha-pinene.

13. A polymeric product as claimed in claim 8, further characterized in that the phenol (3) is phenol.

14. A polymeric product as claimed in claim 8, further characterized in that the vinyl substituted aromatic hydrocarbon (1) is styrene, the monoterpene hydrocarbon (2) is alpha-pinene and the phenol (3) is phenol.