Blends of styrene-butadiene diblock and styrene-butadiene-styrene tri-block interpolymers can be used in a variety of applications. In an adhesive composition, the diblock polymer provides tack strength, while the triblock polymer provides the composition with its elastomeric properties.

One process for preparing such composition is to physically blend indepen- dently prepared triblock and the diblock copolymers. However, such a process requires a large blending capacity and is therefore undesired.

Moreover, separate preparation of the diblock and triblock polymers makes control of the final composition of the mixture extremely difficult. Better adhesive properties generally result from having identical molecular weights of the styrene blocks in the diblock and triblock polymers, and blending makes achieving an optimal ratio of component polymers difficult.

Another method of forming diblock/triblock compositions involves partial coupling of live diblock species. Suitable coupling agents include reactive halogen compounds such as, for example, dimethyl dichlorosilane, SiCl4, CH2Br2, PCI3, and divinyl benzene. This method can achieve matching of the molecular weights of the styrene blocks in the diblock and triblock polymers, if a solvent in which the polystyrene is completely soluble is used. If the polystyrene is insoluble in the solvent (for example, hexane), the polystyrene maximum molecular weight is limited. For acceptable adhesive properties, exceeding this maximum molecular weight is desirable.

Yet another method of forming diblock/triblock compositions is to use a multiple catalyst charge and staggered addition of monomers with deactivation of a portion of the growing polymer chains before or during sub- sequent monomer charge (s). For example, a high diblock TPE can be formed

by allowing Li to initiate styrene polymerization, addition of further catalyst/ initiator and butadiene, and a further charge of styrene. The resulting compositions exhibit poor adhesion to stainless steel and polypropylene and have low cohesive tensile strength, however.

SUMMARY OF THE INVENTION Briefly, the present invention provides a process of forming a composition which includes a diblock copolymer and a triblock interpolymer is provided. The process includes polymerizing a first type of monomer in a suitable solvent in the presence of a first anionic catalyst (or initiator) system then adding a second type of monomer and allowing copolymeri- zation with the first type of monomer to form a living diblock copolymer. A chain transfer agent is added in sufficient amount to terminate only a portion of the living diblock copolymer to form the diblock copolymer and to form a second anionic catalyst (or initiator) system capable of catalyzing polymeri- zation of the second type of monomer. A second portion of the second type of monomer is added and allowed to copolymerize with the living diblock copolymer and to be initiated by the second anionic catalyst (or initiator) system. A second portion of the first type of monomer is added to form the triblock interpolymer.

In other aspects, the invention provides a polymer composition and an adhesive composition which include this polymer composition.

The following definitions apply hereinthroughout unless a contrary intention is expressly indicated: "interpolymer"means a polymer that includes mer units derived from two or more different types of monomer; "living polymer"means a macromolecule that is prepared by anionic polymerization and has active terminals (e. g., lithium ion terminals) which enable it to undergo further polymerization or to be terminated through a suitable terminating process; and

"functional terminating agent"means a compound that includes a functional group (i. e., a group other than H) selected to add functionality to polymers with which they react.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS A triblock/diblock polymer blend is particularly suited to use in an adhesive composition. The polymer blend preferably includes a styrene- butadiene-styrene elastomer and a styrene-butadiene diblock copolymer.

These are preferably formed in a single reactor from multiple charges of vinyl aromatic (e. g., styrene) and conjugated diene (e. g., butadiene) monomers, using an anionic catalyst (or initiator) system. A chain transfer agent, such as hexamethylene imine (HMI) or other cyclic or secondary amine, is added partway through the process. The chain transfer agent functions both to terminate the diblock and to initiate the formation of another polymer chain. The process is carried out in a suitable solvent, which may be cyclic or aliphatic.

In one embodiment, the process includes the sequential steps of: (1) polymerizing a vinyl aromatic monomer or compound, A, in an inert hydrocarbon solvent such as cyclohexane in the presence of a suitable anionic catalyst (or initiator) system until substantially complete conversion to a living polymer; (2) adding a conjugated diene, B, and allowing it to copolymerize with the living polymer until substantially complete conversion; (3) terminating a portion of the living polymer chains with a chain transfer agent; (4) adding a second portion of a conjugated diene, B', and allowing it to polymerize until substantially complete conversion; (5) adding a second portion of a vinyl aromatic compound, A', and allowing it to polymerize until substantially complete conversion; and (6) quenching the living polymer chains by adding at least one of a functional terminating agent and a protic terminating agent.

("Substantially complete conversion"means that the polymerization is allowed to proceed until at least 90%, more preferably at least 95%, and most preferably at least 98%, of the initially charged monomer has been polymerized. As a result, the blocks are relatively free of monomer (s) other than the one (s) just charged.) A protic terminator removes residual catalyst or initiator (Li, in the case of an organolithium catalyst) from the polymers formed and thereby prevents further reaction. Where both a functional terminating agent and a protic terminating agent are used, the protic terminating agent is preferably used after the functional terminating agent.

After the polymerization has been terminated, the product can be isolated, e. g., by drum drying, steam stripping, or flash evaporation.

The process just shown results in a block copolymer composition that includes a triblock interpolymer of the general formula A1-B,-B2-A2 and two diblock copolymers of the general formula A1-B1 and B 2-A2, which may be the same or different, where: A, represents a poly (vinyl aromatic) block formed in step 1; B, represents a poly (conjugated diene) block formed in step 2; B2 represents a poly (conjugated diene) block formed in step 4; A2 represents a poly (vinyl aromatic) block formed in step 5; Ai and A2 may be formed from the same or different vinyl aromatic compounds; and B, and B2 may be formed from the same or different conjugated dienes.

The A1-B1-B2-A2 interpolymer is termed a triblock because the B1 and B2 blocks are both formed from conjugated dienes and thus function as a single conjugated diene midblock, even though the B, and B2 portions of the block may be formed from different conjugated dienes.

The above described process may be illustrated by the following reaction scheme, where A represents a vinyl aromatic monomer, B repre- sents a conjugated diene, Li represents an anionic catalyst or initiator, C-H

represents a chain transfer agent, T-X represents a terminating agent such as a protic and/or functional terminating agent, and X represents a functional group or hydrogen on the interpolymer derived from a terminating agent.

Step Add Products 1 A + Li Ai-Li 2 B A1-B1-Li 3 C-H A1-B1-Li +A1-B1H +C-Li (newcatalyst) 4 B A1-B1-B2-Li + A1-B1H + B2-Li 5 A A1-B1-B2-A2-Li + A1-B1H + B2-A2-Li 6 T-X A1-B1-B2-A2X + A1-B1H + B2-A2X In this reaction scheme, only a portion (about 15 to 80% by weight, preferably about 50% by weight) of the diblock polymer chains are terminated with the chain transfer agent while the remainder of the chains are terminated by the protic and/or functional terminating agent (replacing the positively charged Li with H or functional group) in step 6.

The conjugated diene block B1B2, i. e., the conjugated diene midblock of the triblock, is larger than either of the two butadiene blocks B1 and Bs in the two diblock copolymers.

The vinyl aromatic blocks, A,, in the diblock and triblock are substantially identical, as are the two A2 blocks. Specifically, the ratio of the molar weights of the two blocks is preferably from about 0.9 to 1.1, more preferably from about 0.095 to 1.05, and most preferably is about equal to 1.

Optionally, by using appropriate amounts of the same monomer, the A, and A2 blocks can be substantially identical to each other.

The vinyl aromatic compound can be any one or more of, for example, styrene, a-methyl styrene, p-methyl styrene, p-tert-butyl styrene, 1,3-dimethyl styrene, vinyl toluene, and vinyl naphthalene, of which styrene is preferred. For example, Ai and A2 may be derived from randomly copoly- merized styrene and a-methyl styrene, although both such blocks preferably are homopolymer blocks.

The conjugated diene is preferably one or more C4-C8 conjugated dienes such as, e. g., 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, or mixtures thereof, of which 1,3-butadiene and/or isoprene are preferred. For example, both B blocks may be derived from randomly copolymerized butadiene and isoprene, or one or more blocks can be derived from each of butadiene and isoprene, although both B blocks are preferably homopolymer blocks.

Polymerization occurs in a suitable solvent, such as an inert hydrocarbon. Examples of suitable hydrocarbon solvents include linear or branched hydrocarbons such as n-hexane, octane, and isopentane; cyclic aliphatic hydrocarbons, such as cyclohexane, cycloheptane, and cyclope- tane; alone or in a combination of two or more such solvents. Hexane and mixtures of cyclohexane and hexane are particularly preferred.

The functional terminating agent, if used, is selected so as to impart desirable properties to the resultant interpolymer composition. The interpolymer composition particularly is suited for use as an adhesive, alone or with other components of an adhesive composition. For these uses, functional groups which add desirable adhesive properties are selected.

The properties are chosen dependent on the specific end use. For example, one functional group may improve peel adhesion to stainless steel, while another to polypropylene or polyethylene. (In this respect, terminating agents which provide hydroxyl functional groups improve adherence to polyethylene and polypropylene.) On addition of the functional terminator to the interpolymer composition, the living polymer anions on the diblock and triblock interpolymers are provided with a functional group which, after treatment with a protic terminating agent, results in the desired functional group.

Exemplary functional terminators are shown in Table 1, accompanied by the functional group provided in the diblock and triblock polymers.

Table 1 Functional Terminator Functional Group 1. Monofunctional epoxy compounds, Hydroxyl,-OH such as cyclohexene oxide 2. Alkoxysilanes such as tetraethoxy-Alkoxysilane,-Si (OAlk) 3 silane Si (OEt) 4 such as ethoxysilane 3. Imines, particularly condensation Amine,-NH (R) products of benzaldehydes and amines such as Schiff Bases, e. g., Dimethyl- aminobenzilidene butylamine 4. C02 Carboxyl,-COOH

The protic terminating agent can be one or more active hydrogen compounds such as water (e. g., as steam), alcohols, phenols, and carboxylic acids. Examples include boric acid in water, methanol, ethanol, isopropanol, and ethyl hexanoic acid. The protic terminator may be used as the only terminating agent, i. e., all living ends of the copolymers are replaced with H. Alternatively, the functional terminating agent may be added in a sufficient quantity (i. e., less than a stoichiometric amount) to terminate only a portion of the interpolymer chains. For example, 25%, 50%, or 80% of the polymer chains can be terminated with the functional group in step 6, with the remainder being protically terminated in a subse- quent step (not shown). In this way, the percentage of functionally termi- nated interpolymer chains can be selected to provide optimal properties of the composition according to its intended use.

The process yields a living polymer (i. e., one having a reactive end group) after steps 1-5. The reactive end group is typically a negatively charged end group which forms an ionic bond or other ionic association with a positively charged species, such as a metal cation. A variety of polymeri- zation catalysts (or initiators) are suited to use in steps 1-5, and forming a living polymer. Preferred catalysts (or initiators) are organic alkali metal compounds, particularly organolithium catalysts. The organolithium catalyst

may be any organolithium compound which acts as an initiator in polymerizetion having the general formula RLi, where R is selected from alkyls, cycloalkyls, alkenyls, aryls, and aralkyl having from 1 to about 20 carbon atoms. Exemplary R groups include n-butyl, s-butyl, methyl, ethyl, isopropyl, cyclohexyl, allyl, vinyl, phenyl, benzyl, and the like. Suitable organic compounds of lithium include organolithium or lithium salts of an organic acid, such as alkyl lithium compounds, lithium salts of alcohols, lithium salts of glycol ethers, lithium salts of alcohols, phenols, thioalcohols, and thiophenols, lithium salts of dialkylaminoethanol, lithium salts of secon- dary amines, lithium salts of cyclic imines, and the like. A preferred class of organolithium compounds is the alkyl lithium compounds, wherein the alkyl group may be a linear alkyl compound or a cycloalkyl group. Preferred organic compounds of lithium include one or more C2-C, alkyllithiums such as methyl lithium, ethyl lithium, n-propyl lithium, n-butyl lithium, sec-butyl lithium, isoamyllithium, and the like. Preferred alkyl lithium compounds are n-butyl lithium and sec-butyl lithium, with sec-butyl lithium being particularly preferred. The anionic catalyst (or initiator) may be a combination of two or more of such compounds.

The chain transfer agent is one which is capable of both terminating a living polymer, to prevent further polymerization, and of forming a new catalyst/initiator which catalyzes the polymerization of further additions of monomers. Suitable chain transfer agents are cyclic amines such as imines, tertiary amines, and secondary amines. For example, the chain transfer agent may be an alkyl, dialkyi, cycloalkyl or a dicycloalkyl amine having the general formula R'R2NH or a cyclic amine having the general formula In these formulas, R1 and R2 independently are an alkyl, cycloalkyl or aralkyl having from 1 to about 20 carbon atoms, and R3 is a divalent alkylen,

bicycloalkane, substituted alkylen, oxy-or N-alkylamino-alkylene group having from 1 to about 12 carbon atoms. Exemplary R'and R2 groups include methyl, ethyl, butyl, octyl, cyclohexyl, 3-phenyl-1-propyl, isobutyl, and the like. Exemplary R3 groups include trimethylene, tetramethylene, hexamethylene, oxydietheylene, N-alkylazadiethylene, and the like.

Exemplary chain transfer agents include pyrrolidine ; piperidine; 3- methylpiperdine ; piperazine; 4-alkylpiperazine ; 4-propylpiperazine ; perhy- droazepine; 3,3,5-trimethylhexahydroazepine; HMI ; 1-azacyclooctane ; aza- cyclotridecane, also known as dodecamethyleneimine ; azacycloheptadec- ane, also known as hexadecamethyleneimine ; 1-azacycloheptadec-9-ene ; 1-azacycloheptadec-8-ene ; and bicyclic such as perhydroisoquinoline, perhydroindole, 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane; and the like.

Other useful examples of chain transfer agents are those that contain alkyl, cycloalkyl, aryl and aralkyl substituents of the cyclic and bicyclic amines, including, but not limited to 2- (2-ethylhexyl) pyrrolidine ; 3- (2- propyl) pyrrolidine ; 3,5-bis (2-ethylhexyl) piperidine; 4-phenylpiperidine ; 7- decyl-1-azacyclotridecane ; 3,3-dimethyl-1-azacyclotetradecane; 4-dodecyl- 1-azacyclooctane ; 4-(2-phenylbutyl)-1-azacyclooctane ; 3-ethyl-5-cyclohexyl- 1-azacycloheptane ; 4-hexyl-1-azacycloheptane ; 9-isoamyl-1-azacyclohepta- decane; 2-methyl-1-azacycloheptadec-9-ene ; 3-isobutyl-1-azacylodo- decane; 2-methyl-7-t-butyl-1-azacylododecane ; 5-nonyl-azacyclodecane ; 8- (4'-methyl phenyl)-5-pentyl-3-azabicyclo [5. 4.0] undecane; 1-butyl-6-azabi- cyclo [3.2.1] octane; 8-ethyl-3-azabicyclo [3.2.1] octane; 1-propyl-3-azabi- cyclo [3.2.2]-nonane; 3- (t-butyl)-7-azabicyclo [4.3.0] nonane; 1,5,5-trimethyl-3- azabicyclo [4. 4.0] decane; and the like.

Preferred chain transfer agents are cyclic amines such as HMI and piperidine, with HMI being particularly preferred. The chain transfer agent may be a combination of two or more chain transfer agents.

If desired, the polymerization may be carried out in the presence of a polar modifier, such as a Lewis base, e. g., THF. Examples of other polar compounds are ethers, such as dimethyl ether, diethyl ether, diphenyl ether,

dibenzyl ether, and anisole ; amines, such as trimethylamine, triethylamine, pyridine, and tetramethyl ethylene diamine; thioethers, such as thiophene; and polyethers such as 1,2-dimethoxy ethane, glyme, and diglyme.

The polymerization reactions may be carried out at equal or different temperatures within the range of from about-10° to 150°C, preferably 10° to 110°C. The reaction pressure is not critical but should be sufficient to maintain the reaction mixture in the liquid phase. In step 1 of the reaction scheme, a reactor capable of mixing and heating or cooling is charged with a solvent, such as cyclohexane, the first monomer, such as styrene, and sufficient organolithium catalyst (such as an organolithium catalyst) to gen- erate poly (vinyl aromatic) blocks of a desired molecular weight, preferably 6,000 to 22,000 weight average molecular weight (Mw). A polar modifier, such as THF, is optionally added at this stage to improve uniformity of polymer chain length and/or allow a lower reaction temperature. The styrene may be pre-blended with a portion of the solvent to aid mixing.

The reactor then can be heated to an appropriate temperature, preferably about 20° to 65°C. Once the monomers have been (substantially) polymerized, the mixture is preferably cooled and, in step 2, the second monomer (e. g., butadiene) is charged. As with the styrene, the butadiene may be pre-blended with solvent. The temperature is then raised to about 55° to 100°C and the polymerization allowed to proceed until substantially all the butadiene has polymerized onto the living styrene polymers.

In step 3, a chain transfer agent is added in a sufficient amount to protically or otherwise terminate at least a portion of the living AB polymer.

A new catalyst is formed from the chain transfer agent and the living end group split from the living AB polymer, e. g., a N-lithio salt of HMI in the case of an alkyl lithium catalyst and a HMI chain transfer agent. This catalyst functions as a living catalyst and is able to catalyze the formation of new polymers as further additions of monomers are made (steps 4 and 5).

In step 4, a further amount of B (e. g., butadiene) is added and the reactor is heated to an appropriate temperature, preferably about 55° to

100°C. The polymerization is allowed to proceed until substantially all the butadiene has polymerized, either with the living styrene-butadiene inter- polymers or with the newly formed living catalyst. No further addition of catalyst is needed in step 4.

In step 5, a further addition of A is made to complete the triblock and diblock copolymers. No further addition of catalyst is needed in step 5, unless it is desired to continue the reaction scheme to form a mixture of diblock, triblock, and tetrablock (or more) interpolymers. Further monomer additions can be performed, if desired, to produce multiblock polymers, with or without additional charges of catalyst. For diblock/triblock compositions, however, the reaction is preferably quenched in step 6 by addition of a term- inator at this stage to terminate the diblock and triblock interpolymers.

Further steps may be included, such as the addition of an antioxidant or stabilizer to the composition. Exemplary stabilizers or antioxidants include high molecular weight hindered phenols, such as S-and P- containing phenols. Representative hindered phenols include 1,3,5- trimethyl, 2,4-tris (3,5-di-tertbutyl-4-hydroxybenzyl) benzene; pentaerythrityl tetrakis-3-tris (3,5-di-tertbutyl-4-hydroxybenzyl) propionate, and the like.

In an alternative embodiment, partial functional termination is used in combination with further additions of monomers. A functional terminator, such as cyclohexene oxide, can be added to the polymerization mixture after step 5. Additional charge (s) of one or more of the monomers is then added to the polymerization mixture. This provides a mixture of di-and tri- block functionally or protically terminated interpolymers, together with multi- block polymers which may be longer than the di-and triblock interpolymers (depending on whether additional catalyst charges are added) and may be functionally or protically terminated.

As indicated above, the process is not limited to diblock and triblock compositions. The process can be extended, between steps 2 and 3 or 4-5, to add further charges of one or more monomers.

The vinyl aromatic content of the triblock and diblock copolymers may vary over a wide range. For adhesive formulations, the vinyl aromatic content preferably does not exceed 55% (by wt.) based on the total weight of the block copolymer. More particularly, the vinyl aromatic content of both diblock and triblock copolymers is preferably from 10 to 50% (by wt.), more preferably from 12 to 40% (by wt.), and most preferably from 14 to 35% (by wt.), although higher or lower vinyl aromatic content may be desirable for some applications.

The Mw of the vinyl aromatic blocks is not bound to specific values, but may suitably be from 5,000 to 30,000, preferably 12,000 to 21,000. The butadiene blocks Bi, B2 have a preferred Mw of 17,000 to 43,000. The apparent Mw of the triblock copolymer may suitably be from 50,000 to 400,000, preferably 60,000 to 120, 000. Molecular weights, throughout the specification, are as measured by GPC using polystyrene standards.

In another embodiment, a similar process is used to form a block copolymer composition including block copolymers in a solvent such as a linear hydrocarbon, e. g., hexane, or a mixture of solvents, such as a hexane/cyclohexane mixture, in which the poly (vinyl aromatic) blocks are insoluble or poorly soluble. Here, a small amount of a poly (conjugated diene) such as polybutadiene is formed first. This acts as a dispersant for the poly (vinyl aromatic) block formed in the second step. The reaction scheme thus may proceed as follows, using the same letters as above to represent the various components and using the letter b to represent a small amount of conjugated diene or conjugated diene polymer block :

Step Add Products 1a b + Li b-Li 1b A + Li b-A1-Li + A1-Li 2 B b-A1-B1-Li + A1-B1-Li 3 C-H bAi-Bi-Li + bAi-BiH + Ai-Bi-Li + Ai-Bi-H + C-Li (new catalyst) 4 B bA1-B1-B2-Li + bA1-B1H +A1-B1-B2-Li + A1-B1-H + B2-Li 5 A bAi-Bi-B2-A2-Li + bAi-BiH + Ai-Bi-B2-A2-Li + Ai-Bi-H + B2-A2- Li 6 T-X bAi-Bi-B2-A2X + bA1-B1H + A1-B1-B2-A2X + A1-B1-H + B2-A2X + TLi (inactive) Steps 2-6 are essentially the same as previously described. Step 1, however, now includes two steps-step 1a resulting in the formation of a small amount of poly (conjugated diene) and step 1 b adding the same ingredients as step 1 of the prior embodiment to form a poly (vinyl aromatic) block. Only a small amount of poly (conjugated diene) is needed to disperse the poly (vinyl aromatic). Thus, step 1a in this embodiment includes adding only a small amount of conjugated diene, preferably less than about 10%, more preferably around 5% of the total conjugated diene and a portion of the catalyst, preferably about one third of the total catalyst charge, to gener- ate a small amount of b-Li, e. g., polybutadiene of relatively low molecular weight. Preferably, the Mw of the polybutadiene is about 4500.

The polybutadiene is generated in a sufficient amount to disperse the vinyl aromatic monomer A added in step 1 b. Preferably, sufficient vinyl aromatic monomer and enough catalyst are added in step 1b to ensure that the styrene blocks of the resulting copolymers are of equivalent molecular weight. Because of the small amount of b-Li generated in step 1 a, step 1 b results in the formation of a small amount of b-A1-Li and a larger amount of Ai-Li, e. g., polystyrene.

Step 2 results in the formation of a small amount of b-A1-B1-Li and a larger amount of A1-B1-Li, corresponding to the amounts of b-A1-Li and Ai-Li produced in step 1b. Step 3 results in formation of small amounts of bA1-B1- Li and bAi-BiH and larger amounts of A1-B1-Li and A1-B1-H. As a result, the

final mixture formed in step 6 is primarily formed from the triblock A1-B1-B2- A2X, and the two blocks, A1-B1-H, and B2-A2X, with only small amounts of bA1-B1-B2-A2 X and bA1-B1H. Thus, the overall properties of the copolymer composition are primarily dependent on the A,-Bi-B2-A2X, Ai-BiH, and B2-A2X copolymers. Additionally, while bA1-B1H and bA1-B1-B2-A2X are actually tri-and tetra-block copolymers, respectively, they tend to function as di-and tri-blocks, respectively, because of the small amount of b present.

As in the prior embodiment, step 6 involves protically and/or functionally terminating the living copolymers, stopping further reaction.

The A1-B1H and B2-A2X can be substantially the same (i. e, derived from the same monomers, of similar molecular weight, and similarly termi- nated), or different either in monomer composition, average molecular weight, or termination (H or X).

The present invention also relates to a block copolymer composition that includes (1) a triblock interpolymer B1-A1-A2-B2 having two different or equal polymer end blocks B1 and B2 derived from conjugated diene (s) and one polymer midblock A1-A2 derived from vinyl aromatic monomer (s); and (2) a diblock polymer A2-B2 having one polymer block A2 derived from vinyl aromatic monomer and one polymer block B2 derived from conjugated diene.

The process for forming the composition is the same as that described above, except in that conjugated diene is charged in place of vinyl aromatic monomer, and vice versa.

The compositions of the present invention are suited for use in adhesive compositions, asphalt compositions, and a variety of other uses.

To form an adhesive composition, the diblock/triblock composition may be combined with a variety of tackifying resins, plasticizing oils, waxes, stabi- lizers, and the like. Exemplary tackifying resins include hydrocarbon resins, synthetic polyterpenes, rosin esters, natural terpenes, and the like. Exam- ples include natural and modified rosins such as gum rosin, wood rosin, hydrogenated rosin; glycerol and pentaerythrol esters of natural and modi- fied rosins; copolymers and terpolymers of natural terpenes, e. g., styrene/

terpene; polyterpene resins; phenolic-modified terpene resins and hydrog- enated derivatives thereof; aliphatic petroleum hydrocarbon resins having a Ball and Ring softening point of from about 70° to 135°C ; aromatic petro- leum hydrocarbon resins and hydrogenated derivatives thereof ; and alicyclic petroleum hydrocarbon resins and hydrogenated derivatives thereof.

Exemplary stabilizers or antioxidants include high molecular weight hindered phenols such as S-and P-containing phenols. Representative hindered phenols include 1,3,5-trimethyl, 2,4-tris (3,5-di-tertbutyl-4-hydroxy- benzyl) benzene; pentaerythrityl tetrakis-3-tris (3,5-di-tertbutyl-4-hydroxy- benzyl) propionate, and the like.

Plasticizing oils are preferably present in the adhesive composition to provide wetting action and/or viscosity control. Exemplary plasticizing oils include not only the usual plasticizing oils, but also olefin oligomers and low molecular weight polymers as well as vegetable and animal oils, and their derivatives.

Various petroleum-derived waxes may be used to impart fluidity in the molten condition to the adhesive and flexibility to the set adhesive.

Exemplary waxes include paraffin and microcrystalline waxes having a melting point within the range of about 55°C to 110°C, as well as synthetic waxes, such as low molecular weight polyethylene or Fischer-Tropsch waxes.

For example, a hot melt adhesive may be formed as follows : a) 15-40% by weight of a diblock/triblock composition; b) 40-70% of a compatible tackifying resin; c) 5 to 30% by weight of a plasticizing oil ; d) 0 to 5% by weight of a petroleum derived wax; and e) optionally, a small amount (0.1 to 2 weight percent) of a stabilizer.

The invention is further illustrated by the following examples, without intending to limit the scope of the invention.

EXAMPLES Examples 1-3: Diblock ?Triblock Composition from Styrene and Butadiene using HMI as Chain Transfer Agent A reactor fitted with a stirrer and heating/cooling jacket was charged with 10.0 kg hexane, 0.31 kg of a blend of 30.0% butadiene in hexane, 45.6 g butyl lithium catalyst (3% in hexane), and 2.0 g of a 15% solution (in hexane) of THF/oligomeric oxylanolpropane polar modifier (Firestone Polymers ; Akron, Ohio). The batch temperature was set at 77°C and heated for 30 minutes before the mixture was cooled to a temperature of 54°C. A second charge of 92. 5 g butyl lithium catalyst (3% in hexane) was added before 2.08 kg of a blend of 33.0% styrene in hexane was added as quickly as possible. The batch temperature was set to 54°C and the reaction allowed to proceed for another 30 minutes after reaching the peak. A sample of the mixture was taken into a clean, N2-purged bottle for analysis.

The reactor was then charged as quickly as possible with a further 3.76 kg of the blend of 33.0% butadiene in hexane. The batch temperature was set to 77°C and the reaction allowed to peak (77°C). The reaction was allowed to proceed for another 30 minutes after reaching the peak before 2.06 g HMI was added. This amount was sufficient to terminate about 33% of the polymer chains, leaving about 67% live polymer chains.

After another 5 minutes, a further 2.72 kg of a blend of 30.0% butadiene in hexane was added to the reactor. Thirty minutes after charging was complete, a further 1.36 kg of a blend of 33.0% styrene in hexane was added to the reactor. After another 30 minutes, cooling of the jacket was started.

The polymerization mixture was transferred to a holding tank to reduce the temperature quickly. Then, 1 g of a protic terminator, boric acid, and 31.8 g water was added to convert any remaining lithium in the interpol- ymers to LiOH. 25.4 g of an antioxidant, tris-nonyl phenyl phosphate, and 7.9 g lrganoxtm 1076 stabilizer (Ciba Geigy) were added to the polymeriza- tion mixture and agitated. The product was drum dried to remove solvent.

The method of Example 1 was repeated in Examples 2 and 3.

Example 4: DiblocSTriblock Formed by Partial Termination A reactor fitted with a stirrer and heating/cooling jacket was charged with 10.06 kg hexane, 0.27 kg of a blend of 33.0% butadiene in hexane, 45.4 g butyl lithium catalyst, and 2.0 g of a THF/oligomeric oxylanolpropane polar modifier. The batch temperature was set at 77°C and heated for 30 minutes before the mixture was cooled to a temperature of 32°C. A second charge of 92.1 g butyl lithium was added before 2.31 kg of a blend of 33.0% styrene in hexane was added as quickly as possible. The batch temperature was set to 54°C and the reaction allowed to proceed for another 30 minutes, after reaching the peak. A sample of the polymerization mixture was taken into a clean, Nz-purged bottle for analysis.

The reactor was then charged as quickly as possible with a further 5.85 kg of the blend of 33.0% butadiene in hexane. The batch temperature was set to 77°C and the reaction allowed to proceed for another 30 minutes after reaching the peak. Isopropanol, a protic terminator, was added to terminate about 50% of the catalyst, leaving about 50% live polymer chains.

After another 5 minutes, a further 1.13 kg of a blend of 33.0% styrene in hexane was added to the reactor.

After a further 30 minutes, cooling of the jacket was started. The polymerization mixture was transferred to a holding tank to reduce the temperature quickly. Additional isopropanol was added to convert any remaining lithium in the interpolymers to LiOH. 25.4 g of an antioxidant, tris- nonyl phenyl phosphate and 7.9 g of IrganoxTM 1076 stabilizer were added to the mixture and agitated.

The product was drum dried to remove solvent.

Example 5: Diblock/Triblock Composition (control-no functionality) The process of Example 4 was used to prepare a triblock composition although, in this case, no functional terminating agent was used.

Example 6: Diblock/Triblock Composition via Multiple Catalyst Charges The process of Example 4 was used to prepare a diblock/triblock composition although, in this case, the catalyst charge accompanying the first addition of styrene was adjusted to ensure that the styrene blocks were of equivalent molecular weight and the amount of the diblock in the interpolymer composition was about 50 weight percent.

Example 7: DibloclMTriblock Composition via Blending The process was similar to Example 4, except that a diblock of butadiene and styrene was separately prepared and charged to the reactor with the initial hexane, styrene, butyl lithium catalyst, and polar modifier.

The diblock was used in about 50% (by wt.) of the interpolymer composition.

The resulting interpolymer compositions prepared in Examples 1-7 and a sample of Stereon 840T" styrene-butadiene multiblock polymer with 43% styrene and an MFR of 12 (Firestone Polymers) were then subjected to a variety of analytical tests, as follows : Pressure Sensitive Adhesive (PSA) Tests For these tests the composition was dissolved in toluene and cast on to metalized polyester to produce a tape.

Viscosity, cP, after stripping the solvent from the adhesive, was measured at four different temperatures (149°, 163°, 177°, and 204°C) according to ASTM D2196.

Quick Stick, g/cm, was measured according to Pressure Sensitive Tape Council method PSTC-5.

Peel Adhesion, g/cm, was measured on three different substrates, stainless steel, polyethylene, and polypropylene, according to PSTC-1 (ASTM D3330).

SAFT, °C, was measured according to ASTM D4498.

Polyken Tack, g, was measured according to ASTM D2979.

Rolling Ball, cm, was measured according to PSTC-6 (ASTM D3121).

Gardner Color was measured according to ASTM D1544.

Coating Weight (measured in g/100 cm2) was measured by coating a sheet of metalized polyester (DuPont) of known weightlunit area with the composition, weighing a known area, and deducting the weight of polyester in the sample.

Hot Melt Adhesive Tests These tests were carried out on the composition in the form of a hot melt adhesive.

Adhesive Tensile, kg/cm2, was determined by pouring the composition into a mold and allowing it to cool. The specimen is removed from the mold and subjected to standard tensile tests at room temperature.

Viscosity, cP, was measured at four different temperatures (149°, 163°, 177° and 204°C) according to ASTM D 2196.

The results of these tests are provided in Table 2. Molecular weights for these compositions, and % styrene, % block styrene, % vinyl butadiene, and % melt indexes are recorded in Table 3. Melt index was determined according to ASTM D1238 (MFR 200/5. 0 (200°C, 5 kg)).

Table 2 Stereon 840 PSA RESULTS Viscosity (cP) @149°C 2538 2165 4050 3345 3475 4225 3588 2930 @163°C 1600 1315 2495 2100 2120 2675 2240 1825 @177°C 1065 878 1650 1385 1400 1745 1495 1208 @204°C 542 440 805 688 695 858 720 568 Quick Stick (g/cm) 382 858 894 771 820 666 914 689 Peel adhesion (9/CM) Stainless steel 1229 1165 1156 1247 1127 1377 1047 1262 Polyethylene 147 320 277 357 271 208 425 257 Polypropylene 997 1045 979 798 940 388 942 843 SAFT (°C) 58 48 62 54 56 114 60 57 Polyken Tack (g) >1000 >1000 >1000 >1000 966 >1000 >1000 >1000 Rolling ball (cm) >10 >10 >10 >10 >10 >10 >10 >10 Coating Weight 0.264 0.268 0.262 0.262 0. 272 0.294 0. 265 0. 290 HMA RESULTS Viscosity(cP) @149°C 2785 2065 2985 2720 3195 3688 3110 2790 @163°C 1720 1275 1880 1705 1975 2310 1915 1725 @177°C 1108 850 1268 1140 1290 1520 1260 1145 @204°C 552 425 638 570 638 745 640 565 Gardner Color 2 3 3 3 2 2 4 4 Adhesive Tensile 7.65 4.21 6.80 6.63 5.11 7.90 3.31 4.12 (kg/cm²) Table 3 1 2 3 4 5 6 7 Process employed CT¹ CT¹ CT¹ PT² n/a(control) MCC³ Blend Total MW Mon 42, 890 49,590 50,890 54,540 57,840 65,560 66,120 Mw 61,410 82, 570 71,280 72,710 78,360 75,680 74,450 Mw/Mn 1. 43 1.66 1.40 1.33 1.36 1.15 1.13 Block styrene MW Mn 13, 890 15,690 13,740 14,810 12,780 17,360 13,680 Mw 21,940 19,800 18,280 21,440 15,940 24,120 17,440 MI/Ml 1.58 1.26 1.33 1.45 1.25 1.39 1.28 Weight percentages Styrene 36.0 38. 0 36.4 35.7 36.7 34.9 38.3 Block styrene 36.8 39.4 38.5 42.5 37.3 36.8 26.8 Vinyl butadiene 11. 6 11. 1 9.9 11. 1 12.7 14. 2 22.4 Melt index (Cond. G) 38.5 4.0 13.1 11.6 5.9 6.2 8.0 1 Chain transfer 2 Partial termination 3 Multiple catalyst charge