Vinyl aromatic/terpene/phenol/terpolymers

Abstract: 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: This invention relates to a process for making novel terpolymers that are particularly adapted for use as tackifiers in adhesive compositions. European patent application 75,771 discloses a process in which (1) an alkylated phenol is reacted with a terpene, or (2) a phenol is reacted with a terpene and the reaction product 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 where R can contain a terpene group or an alkyl, cyclohexyl or cyclohexenyl group or a group derived from divinylbenzene or diisopropenylbenzene (emphasis added); R¹, R² and R³ are H, alkyl, cycloalkyl or aralkyl; and n is a whole number from 0 to 20. EP-0 209 956 A1 relates to hydrogenated hydrocarbon resins that are the hydrogenation products of a resinous hydrocarbon polymer based on one or more polymerizable monomers containing one or more vinyl groups and a phenolic monomer. The non-aromatic polymerizable monomer preferably is a diolefinic hydrocarbon, a terpenic hydrocarbon and/or a mixture consisting of diolefinic and terpenic hydrocarbons, in particular dicyclopentadiene and/or pentdiene. EP-0 210 706 A1 relates to a resinous copolymer composition based on a vinyl aromatic hydrocarbon monomer and at least one other hydrocarbon monomer having a copolymerizable unsaturation. The copolymer composition comprises at least 5 % by weight of paramethylstyrene, in an amount that is at least equal to any amount of metamethylstyrene units present in said copolymer composition. In the process of EP-A-75771, 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 for the preparation of a polymeric product, for use as tackifiers in adhesive composition having a specific softening point and thus an appropriate compatibility to different adhesive composition in which the vinyl-substituted aromatic component and the terpene component could be linked to each other as well as to the phenol component, that would produce vinyl-substituted aromatic/terpene/phenol terpolymers. According to the invention a process for preparing a polymeric product according to claim 1 is provided. All parts and percentages are by weight unless otherwise indicated. In the process of the invention, all of 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 aromatic component, the monoterpene component, and the phenol component, and the phenol is an integral part of the polymer chain. The coupling between the three components will be random and no specific structure can be written. The sites on the phenol that are available for reaction with the vinyl-substituted aromatic component and the monoterpene component include the -OH group, and any unsubstituted carbon atoms in positions ortho and para to the -OH group. 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. In another procedure, solvent and all monomers are initially present in the reaction vessel. Reaction is initiated by the intermittent addition of small quantities 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 requirement 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 completed. In any of the procedures, after the reaction is complete, the catalyst is neutralized by reacting it with aqueous caustic or lime. The product is then isolated after removing solvent and any other volatiles. The preferred reaction temperature is from -15°C to + 65°C, preferably from 0°C to + 50°C. Suitable catalysts include BF₃, BCl₃, and complexes of BF₃ with, for example, water, ethyl alcohol, H₃PO₄, phenol or ether. BF₃ is preferred. The solvent used is one that is inert under the polymerization conditions and includes aliphatic or preferably aromatic hydrocarbons such as toluene or xylene, or blends of aromatic hydrocarbons such as Exxon® Aromatic 100. The vinyl-substituted aromatic hydrocarbons (1) for use in the process of the invention have the general formula 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, styrene, alpha-methylstyrene. paramethylstyrene, vinyl-toluene, tert-butylstyrene, alpha-p-dimethylstyrene, and divinylbenzene. Styrene is preferred. Mixtures of two or more vinyl-substituted aromatic hydrocarbons can be used as component (1) if desired. The vinyl-substituted aromatic hydrocarbon is used in an amount of from 12% to 95% by weight. preferably from 21% to 77% by weight, based on the total monomer charge. Monoterpene hydrocarbons (2) for use in the process of the invention are limited to, alpha-pinene, beta-pinene, dipentene, limonene and camphene. Alpha-pinene is preferred. Mixtures of two or more monoterpene hydrocarbons can be used as component (2) if desired. The monoterpene hydrocarbon is used in an amount of from 5% to 75% by weight, preferably from 19% to 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, phenol and alkyl-sustituted phenols such as para-nonylphenol, meta-cresol, ortho-cresol and bisphenol A. Phenol is preferred. Mixtures of two or more phenols can be used as component (3) if desired. The phenol is used in an amount of from 0.75% to 50% by weight, preferably from 3% to 40% by weight, based on the total monomer charge. Also, according to the invention, a polymeric product (terpolymeric tackifier) made from a phenol, a terpene, and a vinyl-substituted aromatic component. is provided having a Ring and Ball softening point of from 69°C to 130°C, suitable for use in adhesive compositions, the polymeric product being produced by the simultaneous polymerization as mentioned above. The terpolymers prepared in accordance with this invention are light in color (Gardner 1 to 5). Their resistance to color-darkening in air at elevated temperatures may be improved by the addition of small amounts of antioxidants such as dilauryl thiodipropionate or distearyl thiodipropionate. Since low molecular weight products are normally more soluble in any given adhesive composition than a high molecular weight product, a low molecular weight product is desirable; the weight average molecular weight of the terpolymers is preferably 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 adjusting the ratio of the three components of the monomer charge. For example, if the adhesive composition is predominantly 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 temperature and the type of catalyst used. These processing conditions influence the molecular weight of the terpolymer product and 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 multiblock copolymers. The terpolymer and the elastomer are dissolved in a solvent such as toluene. An antioxidant such as tetrakis[methylene- (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane (Irganox® 1010) and other stabilizers may be included in the composition if desired. Another type of adhesive composition in which the terpolymers can be used is a hot melt pressure-sensitive adhesive. Such adhesives may be prepared, for example, by dissolving 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 hot-blended and may be, for example, the terpolymer, a wax such as paraffin, and an elastomer such as an ethylene/vinyl acetate copolymer. In any of these adhesive compositions the weight ratio of 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 for coating compositions and as modifiers for printing inks. As hindered phenolic materials, the terpolymers may also be useful as oxidative stabilizers for other polymers. The following examples are illustrative of the invention. Example 1 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 0°C by means of an external dry ice/isopropanol cooling bath. A mixture 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 form a monomer solution. The monomer solution is added to the reaction vessel at 0°C over a period of 36 minutes while simultaneousy adding 4.3 g gaseous BF₃ catalyst. Catalyst addition is continued another 14 minutes until 6.0 g total BF₃ is added. The reaction mixture is heated to 40°C and stirring is continued for one hour. The catalyst is removed by neutralizing with 110 ml of hot caustic solution followed 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 225°C to isolate the terpolymer product. The resulting terpolymer has a Ring and Ball softening point of 106°C and Gardner color of + 4 and is obtained in 92% yield. The aromatic solvent used in Examples 1-13 is a recycled blend of various aromatic compounds. the main components of which are para- and meta-xylene (10.6%), para- and meta-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 nitrogen blanketing and an adjustable inlet tube to feed catalyst beneath the liquid surface. The reaction vessel is charged with 180 g dry styrene, 120 g dry alpha-methylstyrene, 30 g dry alpha-pinene, 313 g dry aromatic solvent blend, and 15 g phenol. Under nitrogen, the temperature is adjusted to 0°C by means of an external dry ice/isopropanol bath. Gaseous BF₃ (0.48 g) is then introduced intermittently over a period of 15 minutes. A strong exotherm results which is controlled at 0°C to + 5°C. 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 neutralize the catalyst. The temperature is raised to 100°C and lime and neutralization products are removed by filtration. The terpolymer is isolated by heating under nitrogen and finally sparging at 225°C with superheated steam. A terpolymer with a Ring and Ball softening point of 119°C and Gardner color 1 + 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 0°C. 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 0°C over 35 minutes while simultaneously adding 4.2 g gaseous BF₃. The reaction mixture is allowed to warm to 20°C over a 1 hour period and the catalyst is then neutralized with excess lime. The temperature is raised to 100°C. After filtration, the organic phase is heated under nitrogen and finally sparged with steam at 225°C. A terpolymer with a Ring and Ball softening point of 102°C and a Gardner color of 5- is obtained in 89.4% yield. Example 4 The reaction apparatus is the same as the one described in Example 1. The reaction vessel is charged with 150 g dry aromatic solvent, flushed with dry nitrogen and the contents cooled to 0°C. A solution of 15 g phenol in 210 g dry styrene with 90 g dry dipentene and 150 g dry aromatic solvent is added dropwise to the reactor at 0°C over a 1 hour period while simultaneously adding 7.2 g gaseous BF₃ catalyst. The reaction mixture is allowed to warm to + 15°C while stirring for an additional hour, and the catalyst is then neutralized with excess lime. The temperature is raised to 100°C. Lime and neutralization products are removed by filtration. The organic phase is heated under nitrogen and finally sparged with steam at 250°C. A terpolymer with a Ring and Ball softening point of 110°C and a Gardner color of 3 + is obtained in 91.5% yield. 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 contents of the vessel are stirred and cooled at 0°C while a solution of 15 g phenol in 210 g dry styrene and 90 g dry alpha-pinene is added over a period of 34 minutes. During monomer addition, 4.1 g gaseous BF₃ is also continuously added to the reaction medium. The mixture is heated to 40°C and held at this temperature for 1 hour. Lime is used for neutralization of the catalyst. The terpolymer product is isolated by filtration, followed by distillation of solvent under nitrogen and finally steam sparging at 260°C. A terpolymer with a Ring and Ball softening point of 97°C and a Gardner color of 1 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 g divinylbenzene, 9.6 g phenol and 360 g dry aromatic solvent. The contents are cooled to 0°C under nitrogen and 0.86 g gaseous BF₃ is introduced intermittently over a period of 28 minutes. A controlled (0 to + 2° C) strong exotherm lasting for 20 minutes results. After the exotherm subsides, BF₃ addition is continued until 1.1 g total catalyst are added. Stirring is continued at 0°C for 30 minutes. Neutralization of the catalyst with excess lime is followed by filtration at 100°C. The organic phase is heated under nitrogen to remove solvent and finally sparged with steam at 245°C. A terpolymer with a Ring and Ball softening point of 116° C and a Gardner color of 1 - is obtained in 95.4% yield. Example 7 The reaction apparatus is the same as the one described in Example 1. Dry aromatic solvent (300 g) is charged to the reaction vessel and the contents are brought to 0°C under nitrogen. A blend of 15 g phenol in 210 g dry vinyltoluene and 90 g dry alpha-pinene is added with agitation at 0°C over a period of 1/2 hour. During this time 3.6 g gaseous BF₃ catalyst is also continuously added to the reactor. The temperature is allowed to increase to 20°C during the next hour and the catalyst is then neutralized with excess lime. After heating to 100°C 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 110°C and a Gardner color of 1 is obtained in 91.7% yield. Example 8 The reaction apparatus and general procedure are the same as those described in Example 1. To the reaction vessel containing 284.5 g aromatic solvent maintained at 0°C is added a solution of 192 g styrene, 108 g alpha-pinene and 18 g phenol over a 1/2 hour period while 3.8 g BF₃ is also added. After an additional hour of reaction at 40°C, the catalyst is neutralized. A terpolymer with a Ring and Ball softening point of 97°C 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 alpha-pinene, and 30 g para-nonylphenol is added to a reaction vessel containing 300 g dry aromatic solvent and maintained at 25°C for one hour. BF₃ (8.4 g) is also passed into the reaction mixture. After one additional hour at 25°C, the catalyst is neutralized. A terpolymer with a Ring and Ball softening point of 80°C and Gardner color of 1 + is isolated in 85.6% yield. Example 10 The reaction apparatus is the same as the one described in Example 1. BF₃ catalyst is passed into a reaction vessel containing 300 g dry aromatic solvent maintained at 25°C. A solution of 180 g styrene, 120 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 Ring and Ball softening point of 85°C is obtained in 84.1% yield. Example 11 The reaction apparatus is the same as the one described in Example 2. The reaction vessel is charged with 180 g styrene, 120 g alpha-pinene, 30 g bisphenol A and 400 g aromatic solvent and the contents are brought to 4° C. BF₃ (2.6 g) is added over a two hour period during which time the bisphenol 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 continued another 1.5 hours at 40°C. The catalyst is then neutralized. A terpolymer with a softening point of 90°C and Gardner color of 3+ is isolated in 84.1% yield. Example 12 The reaction apparatus and general procedure are the same as those described in Example 1. To a reaction vessel containing 300 g aromatic solvent maintained at 0°C is added a solution of 180 g dry styrene, 120 g alpha-methylstyrene, 15 g alpha-pinene and 2.5 g phenol over a 1/2 hour period while simultaneously adding 3.8 g BF₃. After an additional hour at 40°C, the catalyst is neutralized. A terpolymer having a Ring and Ball softening point of 69°C 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 g of phenol dissolved in 300 g aromatic solvent. At 25°C, 1.5 g BF₃ is passed into the reaction vessel to form a soluble complex with the phenol. While maintaining a reaction temperature of 25°C, 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 neutralized. A terpolymer having a Ring and Ball softening point of 129°C and a Gardner color of 4+ is isolated in 87.4% yield. Example 14 Solvent-based pressure sensitive adhesive compositions are prepared by the following procedure. 40 Parts by weight of terpolymer prepared according to Example 1 are mixed in a glass jar with 60 parts by weight of a milled natural rubber (Pale Crepe containing 1% by weight p,p′-dioctyldiphenylamine) and 0.3 parts by weight antioxidant (Irganox® 1010) in 733 parts toluene by tumbling for 3 to 4 days. This procedure is repeated for two additional samples using weight ratios of terpolymer to rubber of 50:50 and 60:40. The adhesives are cast as a 2.54 x 10⁻³cm (1.0 mil) film on a Mylar® substrate, air dried and finally over dried at 60-70°C for 5 minutes. Once cool, release paper is applied to the adhesives and they are stored at 22°C 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. Example 15 A solvent-based pressure-sensitive adhesive is prepared by the following procedure. 40 Parts by weight of the terpolymer prepared according to Example 5, 60 parts by weight of styrene-butadiene elastomer (Ameripol® SBR 1011) and 0.3 parts by weight antioxidant (Irganox® 1010) are dissolved in 900 parts toluene by tumbling for 3 to 4 days. The adhesive is cast as a 2.54 x 10⁻³cm (1.0 mil) film on a Mylar® substrate, air dried and finally oven dried at 60-70°C for 5 minutes. When cool, release paper is applied to the adhesive and it is stored at 22°C and 50% relative humidity. Adhesive testing is performed after storage for 24 hours with the following results: Example 16 A hot melt pressure-sensitive adhesive is prepared by the following procedure. 60 Parts by weight of the terpolymer prepared according to Example 8 are mixed, while blanketed with nitrogen, with 20 pats plasticizing oil (Shellflex® 371) and 0.5 part antioxidant (Irganox® 1010) and heated to 175°C. 40 Parts by weight of a butadiene-styrene multibock copolymer (Stereon® 840A) are added and mixing is continued until homogeneity is attained. The adhesive is cast as a 2.54 x 10⁻³cm (1 mil) film on a Mylar® substrate at 177° C (350° F). Once cool, release paper is applied to the adhesive film and it is stored at 22°C and 50% relative humidity. Adhesive testing is performed after storage for 24 hours with the following results: 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), 175 parts by weight of the terpolymers shown in the Table and antioxidant are heated and stirred under nitrogen until homogeneous. Cloud point data and heat aging data for the hot melt adhesive compositions are given in the Table.

Claims: A process for preparing a polymeric product having a Ring and Ball softening point of from 69°C to 130°C from a phenol, a terpene, and a vinyl-substituted aromatic component, characterized in simultaneously polymerizing the monomers in a mixture comprising, by weight, (1) from 12 % to 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 5 % to 75 % of a monoterpene hydrocarbon selected from alpha-pinene, beta-pinene, dipentene, limonene and camphene, and (3) from 0.75 % to 50 % of a phenol, the percentages of components (1), (2) and (3) being such as to total 100 % in a solvent and in the presence of a catalyst. A process as claimed in claim 1, further characterized in that the vinyl-substituted aromatic hydrocarbon (1) is styrene. A process as claimed in claim 1 or 2, characterized in that the monoterpene hydrocarbon (2) is alpha-pinene. A process as claimed in claim 1, 2 or 3 characterized in that the phenol (3) is phenol. A process as claimed in any of the preceding claims, characterized in that the catalyst is BF₃. A process as claimed in any of the preceding claims, characterized in that the reaction is carried out at a temperature of from -15°C to + 65°C. A polymeric product having a Ring and Ball softening point of 69°C to 130°C made from a phenol, a terpene, and a vinyl-substituted aromatic component, characterized by the simultaneous polymerization of (1) from 12 % to 95 % of the 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 5 % to 75 % of a monoterpene hydrocarbon selected from alpha-pinene, beta-pinene, dipentene, limonene and camphene, and (3) from 0.75 % to 50 % of the phenol, the percentages of components (1), (2) and (3) being such as to total 100 % in a solvent and in the presence of a catalyst. A polymeric product as claimed in claim 7, characterized in that the vinyl-substituted aromatic hydrocarbon (1) is styrene. A polymeric product as claimed in claim 7, characterized in that the monoterpene hydrocarbon (2) is alpha-pinene. A polymeric product as claimed in claim 7, characterized in that the phenol (3) is phenol.

Inventors: DAUGHENBAUGH NORMAN EDWARD JR, DAUGHENBAUGH, NORMAN EDWARD, JR.
Applicants: HERCULES INC, HERCULES INCORPORATED
Application year: 1987
Main classification: C08G61
IPC codes: C08F36, C08F32, C08L9, C08L23, C08F212, C08L7, C08F210, C08L91, C08F12, C09J165, C08G61, C08F236, C08F232