CA2247670A1 - Block copolymers interpolymerized with in situ polystyrene and process for preparation thereof - Google Patents
Block copolymers interpolymerized with in situ polystyrene and process for preparation thereof Download PDFInfo
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- CA2247670A1 CA2247670A1 CA002247670A CA2247670A CA2247670A1 CA 2247670 A1 CA2247670 A1 CA 2247670A1 CA 002247670 A CA002247670 A CA 002247670A CA 2247670 A CA2247670 A CA 2247670A CA 2247670 A1 CA2247670 A1 CA 2247670A1
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- Prior art keywords
- block
- polymer
- aromatic hydrocarbon
- vinyl aromatic
- interpolymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
Abstract
A process for interpolymerizing a vinyl aromatic hydrocarbon polymer and a block polymer is disclosed. The process includes the following steps:
a) forming a block polymer precursor of at least one polymeric block containing conjugated diene monomer contributed units in the presence of an anionic initiator and in an inert diluent, the block polymer precursor having living ends;
(b) thereafter adding to the block polymer precursor a charge of a vinyl aromatic hydrocarbon monomer and an additional charge of an anionic initiator to simultaneously form (1) a block polymer having a terminal block formed from the charge of vinyl aromatic hydrocarbon monomer attached to the block polymer precursor and (2) a poly(vinyl aromatic hydrocarbon) polymer interpolymerized with the block polymer.
The practice of this process produces a vinyl aromatic hydrocarbon block terminated block polymer, such as SBS, interpolymerized with a polymer formed from vinyl aromatic hydrocarbon monomer, such as polystyrene. The resultant interpolymer has a high Gardner Impact strength and good processibility.
a) forming a block polymer precursor of at least one polymeric block containing conjugated diene monomer contributed units in the presence of an anionic initiator and in an inert diluent, the block polymer precursor having living ends;
(b) thereafter adding to the block polymer precursor a charge of a vinyl aromatic hydrocarbon monomer and an additional charge of an anionic initiator to simultaneously form (1) a block polymer having a terminal block formed from the charge of vinyl aromatic hydrocarbon monomer attached to the block polymer precursor and (2) a poly(vinyl aromatic hydrocarbon) polymer interpolymerized with the block polymer.
The practice of this process produces a vinyl aromatic hydrocarbon block terminated block polymer, such as SBS, interpolymerized with a polymer formed from vinyl aromatic hydrocarbon monomer, such as polystyrene. The resultant interpolymer has a high Gardner Impact strength and good processibility.
Description
' CA 02247670 1998-09-17 RELATED APPLICATION DATA
2 This application is a Collli,luation-in-part of Application Serial Number 08/334,989, filed 3 November 7, 1994.
This invention relates generally to processes for incorporating poly~lylene in block 6 copolymers and to the compositions produced thereby. More specifically, the invention relates 7 to a process for producing a vinyl aromatic hydrocarbon block termin~ted block polymer, such as 8 SBS, interpolymerized with a polymer formed from vinyl aromatic hydrocarbon monomer 9 contributed units, such as polystyrene; and a product having a substantially improved Gardner 1 0 impact strength, produced by such a process.
1 2 The prior art has long strived to improve the physical plopel Lies of styrenic polymers. For 1 3 instance, United States Patent 4,267,283 to Whitehead teaches a two-component graft copolymer 14 composition having improved toughness. The first graft polymer component is disclosed as 1 5 consisting essentially of: from about 8.0 to about l 6.0 parts by weight of a mixture of an AB A block 1 6 copolymer and an A'B'A' tapered block copolymer in a weight ratio of the A B A copolymer to the 17 A'B'A' copolymer of between about 25 :75 and about 75 :25. Each A segment is an essentially pure 1 8 polymer block of styrene having a number average molecular weight of between about l 4,000 and 1 9 about l 8,000. Each B segment is an essentially pure polymer block of butadiene having a number average molecular weight of between about 60,000 and about 80,000; the B block having a glass 21 transition tel~lpel~Lllre of about -105~C.+/-5~C. The weight ratio oftotal A to B being between about 22 l: l .8 and about l :2.7. Each A' segment represents essentially polymerized styrene. The balance of ' CA 02247670 1998-09-17 the A' segment is polymerized butadiene. The B' segment represe~ ess~nti~lly polymerized 2 butadiene. The balance of the B' segm~nt is polymerized styrene. The weight ratio of total A' to B' 3 being from about 1 :2.6 to about 1 :3.6, the number average molecular weight of said A'B'A' block 4 copolymers being between about 400,000 and about 660,000. The B' block has a glass transition temperature of about -90~C.+/-5~C. The second graft component consists essçnti~lly of from about 6 92.0 to about 84.0 parts by weight of monomeric styrene polymerized in the presence of the ABA
7 and A'B'A' copolymers.
8 Similarly, United States Patent No. 3,954,696 to Roest, teaches a process for the ple~a.~lion 9 of block copolymers of the general formula A--B--C. This process includes the steps of 1 0 polymerizing at least one monomer to form a living polymer block A; adding a further monomer and 11 continuing polymerization to form polymer block B bound to polymer block A, and continllin~;
12 polymerization while adding at least one monomer to form termin~l polymer block C, so as to 1 3 produce an A--B--C block copolymer. Each of the polymer blocks A and C consist of either a 14 non-elastomer homopolymer or copolymer having a glass transition temperature over 25~C. and a 1 5 number average molecular weight between 200 and 100,000. The polymer block B consists of a 16 conjugated diene, derived from preferably 1,3-butadiene or isoprene, having a glass transition 1 7 temperature below -10~C. and a number average molecular weight between 25,000 and 1,000,000.
1 8 The cont~min~nt~ contained in the monomers forming blocks A and C are theleanel deactivated.
19 As his improvement over the prior art, Roest includes Cont~min~nts in the conjugated diene monomer forming polymer block B, that have not been deactivated and that are capable of killing 21 1-50% ofthe living polymer block A upon introduction of conjugated diene monomer to the reaction 22 mass. Each of the polymer blocks A and C are disclosed as consisting of a non-elastomeric polymer ' CA 02247670 1998-09-17 block having a glass transition point over 50~C and a number average molecular weight between 500 2 and 50,000. The polymer block B is disclosed as con~icting of an el~tom~nc polymer block having 3 a glass transition point below -25~C and a number average molecular weight between S0,000 and 4 S00,000. At least one of polymer blocks A and C is derived from a monovinylaromatic hydrocarbon.
United States Patent No. 3,265,765 to Holden et al, discloses an unvulcanized el~ctom~ric 6 block copolymer having the general configuration A-B-A. Holden discloses that block A is an 7 independently selected non-elastomeric monovinyl aromatic hydrocarbon polymer block having an 8 average molecular weight of 2,000 - lO0,000 and a glass transition temperature above about 25~C.
9 The total block A content being l O- 50% by weight of the copolymer. Block B is an elastomeric conjugated diene polymer block having an average molecular weight between about 25,000 and 11 l ,000,000 and a glass transition temperature below about l O~C. The copolymer is prepared with a 1 2 lithium-based catalyst and has a tensile strength at 23~C, in excess of about 1400 pounds per square 1 3 inch.
14 In yet another similar United State Patent No. 3,231,635 to Holden et al, an unvulc~ni7çd 1 5 elastomeric block copolymer having the general configuration A - B - A is disclosed. Block A is an 1 6 independently selected non-elastomeric monovinyl aromatic hydrocarbon polymer block having an 1 7 average molecular weight of 2,000 - l O0,000 and a glass transition temperature above about 25~C.
1 8 The total block A content being l O - 50% by weight of the copolymer. Block B is an elastomeric 19 conjugated diene polymer block having an average molecular weight between about 25,000 and l ,000,000 and a glass transition temperature below about l O~ C. The copolymer is prepared with 21 a lithium-based catalyst and has a tensile strength at 23~C, in excess of about 1400 pounds per square 22 inch.
' CA 02247670 1998-09-17 United States Patent No. 3,239,478 to Harlan, teaches an adhesive composition that 2 comprises components. The first component of the composition comprises 100 parts by weight of 3 a block copolymer having the general configuration A - B - A. Each A block is an independently 4 selected polymer block of a vinyl arene. The average molecular weight of each A block is between about S,000 and about 125,000. The B block is a polymer block of a conjugated diene. The average 6 molecular weight of the B block is between about 15,000 and about 250,000. The total of the A
7 blocks is less than about 800io by weight of the copolymer. The second component of the 8 composition comprises about 25 - 300 parts by weight of a tackifying resin. Finally, the third 9 component of the composition comprises 5 - 200 parts by weight of an extender oil. The oil is substantially compatible with homopolymers of the conjugated diene.
11 Finally, United States Patent No. 3,149,182 to Porter teaches a process for preparing an 12 elastomeric three component block copolymer. The copolymer comprises the first step of:
13 contacting a monomer of the group con~i~ting of diolefins cont~ining from 4 to 10 carbon atoms, 14 mono alkenyl-substituted aromatic hydrocarbons and mono-alkenyl-s~lbstit lte-l pryidine compounds with a hydrocarbon lithium compound in an inert atmosphere and under substantially anhydrous 16 conditions until the unpolymerized monomer in the reaction mixture is consumed. Next, without 17 further treating the reaction, adding a monomer of the above group which is similar to that used in 18 the initial reaction. Thereafter, continuing the polymerization under the above conditions until the 19 dissimilar monomer has been polymerized. Next, without further tre~tmt nt of the reaction mixture, adding a third monomer which is different from the aforementioned ~lic~imil~r monomer and selected 21 from the above group of monomers. Finally, the polymerization is continued under the ' CA 02247670 1998-09-17 aforedescribed conditions until the third monomer has been completely consumed. At least one of 2 the foregoing monomers is a diolefin.
3 Despite the foregoing prior art, there nonetheless exists a long felt need for a process for 4 predicably producing styreffic polymers exhibiting high Gardner impact strengths in excess of at least 60 ft lb/in, as well as such other polymers and articles produce thelefro~6 Sul~lisi-lgly, the instant inventors have discovered that by merely manipulating the weight 7 proportions of the respective polymers of the interpolymer mix, dramatic increases in the Gardner 8 Impact Strength of the product may be achieved.
9 Polystyrene is a well-known thermoplastic material finding a wide variety of uses. It is often added to polymers including block copolymers to increase the mold flow characteristic of 11 the polymer, thus preventing the polymer from sticking to the injection molder cavity.
12 Heretofore, polystyrene has been blended with block copolymers to increase the processability of 13 the block copolymer. United States Patent No. 4,308,358 to Miller, discloses a process for 14 making high impact polystyrene comprising mixing, at an elevated temperature, an AB block copolymer and a styrene polymer. This blending process creates disadvantageous properties in 16 the blend, namely the impact strength of the block copolymer is severely reduced upon the 17 addition of as low as l .5 % by weight of crystal polystyrene to the block copolymer. While not 18 wishing to be bound by any particular theory, Applicants believe that the lower impact strength 19 resulting from the blending of polystyrene and block copolymer is due to the different molecular weights and physical properties of the components thereby causing phase separation to occur in 21 the resulting product. The poor interphase adhesion characteristic of highly incompatible blends ' CA 02247670 1998-09-17 usually results in very poor m-och~ni-~l pro~ellies, e.g., tensile strength, elongation and impact 2 strength.
3 It is ther~fole an object of the present invention to provide a process for producing an 4 interpolymer of poly~lylelle and a block copolymer exhibiting good ~.oçh~nic~l plo~lLies. It is a further object of this invention to provide polystyrene and block copolymer products exhibiting 6 high impact strength.
7 SUMMARY OF T~ INVENTION
8 In contrast to the foregoing prior art, the instant invention provides a process for 9 interpolymerizing a blend of a vinyl aromatic hydrocarbon polymer and copolymer product is disclosed. The process includes the following steps:
11 a) forming in a suitable diluent a block polymer pl~-,ulsor having a living end and 12 having at least one polymeric block cont~ining conjugated diene monomer contributed units in the 13 presence of an anionic initiator;
14 (b) thereafter adding to the block polymer precursor a charge of vinyl aromatic hydrocarbon monomer and an additional amount of anionic initiator to simultaneously form (1) 16 a block polymer having a terminal block, formed from the vinyl aromatic hydlocall.on monomer, 17 attached to the block polymer precursor and (2) poly(vinyl aromatic hydrocarbon) 18 interpolymerized with the block polymer of (l).
19 The practice of this process produces a vinyl aromatic hydrocarbon block tennin~t~l block polymer, such as SBS, interpolymerized with a polymer formed from vinyl aromatic hydrocarbon 21 monomer contributed units, such as polystyrene.
' CA 02247670 1998-09-17 S~l~lisingly, the instant inventors have discovered that by merely manipulating the weight 2 proportions of the respective block polymer and polyvinyl aromatic hydrocarbon polymer of the 3 interpolymer mix, dramatic increases of in excess of about 60 ft lb/in to at least about 200 ft lb/in 4 of the Gardner Impact Strength of the final product may be achieved.
' CA 02247670 1998-09-17 BRIEF DESCRIPTION OF THE FIGURES
2 Figure l illustrates the relationship belweell the Gardner Impact Strength (measured in ft-3 lb/inch) of interpolymers cont~ining polystyrene and a block polymer as prepared in Example 1 4 and the percent by weight of in situ polystyrene formed from the total styrene monomer charge used to plepale the terminal poly~lylelle block and in situ polystyrene during formation of the 6 interpolymer. The interpolymers le~l~sellLed in this figure were produced using the in situ process 7 of the present invention.
8 Figure 2 illustrates the r~l~tio~chir belween the Gardner Impact Strength (measured in ft-9 lb/inch) of a block polymer/poly~lyl~,ne blend and the amount by weight of crystal polystyrene added to the polymer as shown in Comparative Example A.
11 Figure 3 illustrates the relationship between the Gardner Impact Strength (measured in ft-12 lb/inch) of a block polymer/poly~lylelle blend and the amount by weight of crystal polystyrene 13 added to the polymer as shown in Comparative Example B.
The process of the present invention prepares an interpolymer of (l) a block polymer 16 having a precursor polymer block ~tt~rh~d to a terminal block of a poly(vinyl aromatic 17 hydrocarbon) and (2) a poly(vinyl aromatic hydrocarbon). The precursor polymer block of the 18 block polymer preferably contains diene monomer contributed block units, and optionally contains 19 vinyl aromatic monomer (VAM) contributed units including random blocks of butadiene and styrene (B/S).
21 The block polymers to be interpolymerized in accordance with the present invention 22 preferably contain conjugated diene monomers and vinyl substituted aromatic hydrocarbons ' CA 02247670 1998-09-17 contributed units. Polymerizable 1,3-diene monomers that can be employed in the production of 2 the copolymers of the present invention are one or more 1,3-conjugated dienes cont~ining from 3 four to twelve, inclusive, carbon atoms per molecule. Exemplary monomers include 1,3-4 bl~t~lien~-; isoprene; 2,3-dimethyl-1,3-but~ n~; 1,3-pent~ie~ (piperylene); 2-methyl-3-ethyl-1,3-butadiene; 3-methyl-1,3-pent~tlie~e; 1,3-h~Y~ie~; 2-methyl-1,3-hexadiene; 3-butyl-1,3-6 octadiene; and the like. Among the dialkyl-1,3-b~lt~ n~-s~ it is preferred that the alkyl groups 7 contain from one to three carbon atoms. The plerel.ed 1,3-diene monomer for use in the process 8 of the present invention is 1,3-b~lt~(lie~e.
9 Exemplary vinyl substituted aromatic hydrocarbon monomers, commonly referred to as vinyl aromatic hydrocarbon monomers or VAM, for use in either the preparation the block 11 polymer precursor and/or the terminal block and the poly(vinyl aromatic hydrocarbon), include:
12 styrene, alpha-methylstyrene; l-vinylnaphthalene; 2-vinyl-naphthalene; 1-alpha-13 methylvillylndphthalene; 2-alphalll~ yl-vinylnaphthalene; and mixtures of these as well as alkyl, 14 cycloaLkyl, aryl, alkaryl and aralkyl derivatives thereof in which the total number of carbon atoms in the combined hydrocarbon is generally not greater than 12. Examples of these latter compounds 16 include: 4-methylstyrene; vinyl toluene; 3,5-diethylstyrene; 2-ethyl4-benzylstyrene; 4-17 phenylstyrene; 4-para-tolylstyrene; and 4,5-dimethyl-1-vinylnaphthalene. Occasionally, di- and 18 tri- vinyl aromatic hydrocarbons are used in small amounts in addition with mono-vinyl aromatlc 19 hydrocarbons. The preferred vinyl aromatic hydrocarbon is styrene.
The total amount of vinyl aromatic hydrocarbon monomer in the final monomer charge 21 used to prepare both the terminal vinyl aromatic block and the interpolymerized poly(vinyl 22 aromatic hydrocarbon) is an amount of from 6.3 to 70.2% by weight, preferably from 28.3 to ' CA 02247670 1998-09-17 61.7% by weight, more preferably from 50.6 to 57.6% by weight, based on the total weight of 2 the block polymer. The weight percent of interpolymerized vinyl aromatic hydlocalbon polymer 3 of the total amount of both of the terminal poly(vinyl aromatic hydrocarbon) block and vinyl 4 aromatic hydrocarbon polymer is in the range of from S to 35 % by weight, preferably from 9 to 26% by weight, more preferably from 10 to 20% by weight. These weight pe~lllages reflect the 6 percentage of monomer, such as styrene, of the final monomer charge that is polymerized due to 7 the additional charge of anionic initiator to the reaction zone. The final monomer charge is used 8 to prepare both the terminal block added onto the block polymer precursor and the 9 interpolymerized poly(vinyl aromatic monomer).
The block polymers produced according to the instant invention must terminate in a vinyl 11 aromatic hydrocarbon block. The res-lltin~ structure of the block polymers may be linear, 12 br~nrhPd, tapered, or star as long as the structure has a live end. Exemplary block precursors 13 include block polymers cont~ining at least one polymeric block, a diblock polymer, triblock 14 polymers and tetrablock polymers, random copolymer blocks, graft-copolymers blocks, block-copolymers of a conjugated diolefin and a vinyl aromatic hydrocarbon, and mixtures thereof.
16 Typical examples of the various structures of the block polymer precursors useful in the present 17 invention are as follows:
(B-S)n- linear, 2 S-(B-S)n- linear, 3 B-(S-B)- linear, - 4 B/S-B-S- linear, [B(S)-B-B(S)-B-B(S)-B-B]n- branched, 6 B-, S-B-, S-(B-S)n-B-, (B-S)n-B-, (B/S) n~B~~ B-(B/S )n~~ S-(B/S) n~~ and (B/S) n~; wherein S is a 7 polymer block primarily cont~ining vinyl aromatic hydrocarbon monomer contributed units, B is 8 a polymer block primarily cont~ining conjugated diene monomer contributed units, and n is an 9 integer of one or more. The rubbery diene portion of the polymer may contain some copolymer 10 vinyl aromatic hydrocarbon in order to adjust the glass transition temperature (Tg) or the solubility 11 parameter. The block polymers produced in accordance with the present invention are represented 12 by any of the above-di~cussed block polymer precursor structures additionally cont~ining a 13 terminal block formed from vinyl aromatic hydrocarbon contributed units.
14 The process according to the present invention is performed in the following manner.
15 First, any desirable block polymer precursor is prepared in a reactor or reaction zone by 16 polymerizing suitable monomers, particularly diene monomers and/or vinyl aromatic monomers, 17 to form one or more blocks in a suitable diluent in the presence of an anionic initiator. The 18 res~lting block polymer precursor is "living", because a catalytically active anion is present at the 19 terminal end of the block polymer precursor. The anion is capable of initi~ting polymerization 20 of further monomers in the reaction zone.
21 After formation of the block polymer precursor, charges of additional anionic initiator and 22 vinyl aromatic hydrocarbon monomer are simlllt~n~ously or sequentially added to the reaction zone cont~ining the "living" block polymer precursor. A portion of the vinyl aromatic 2 hydrocarbon monomer charge att~-h~s to the "living" block polymer precursor. The additional 3 charge of anionic initiator initi~tes polymerization of an equimolar amount the additionally 4 charged vinyl aromatic hydrocarbon monomer thereby creating "living" vinyl arolllaLic 5 hydrocarbon polymers. Thus, the additional anionic initiator is added to create competition for 6 the additional charge of vinyl aromatic hydrocarbon monomer res-llting in the sim~ neous 7 production of (l) a terrnin~l block of vinyl aromatic hydrocarbon monomer contributed units 8 attaching to the "living" block polymer precursor and (2) poly(vinyl aromatic hydrocarbon) 9 having a living end. The resulting interpolymer is an interpolyll~.i~ed blend of a block polymer 10 and a poly(vinyl aromatic hydrocarbon) having living ends.
1 2 The prior art has long strived to improve the physical plopel Lies of styrenic polymers. For 1 3 instance, United States Patent 4,267,283 to Whitehead teaches a two-component graft copolymer 14 composition having improved toughness. The first graft polymer component is disclosed as 1 5 consisting essentially of: from about 8.0 to about l 6.0 parts by weight of a mixture of an AB A block 1 6 copolymer and an A'B'A' tapered block copolymer in a weight ratio of the A B A copolymer to the 17 A'B'A' copolymer of between about 25 :75 and about 75 :25. Each A segment is an essentially pure 1 8 polymer block of styrene having a number average molecular weight of between about l 4,000 and 1 9 about l 8,000. Each B segment is an essentially pure polymer block of butadiene having a number average molecular weight of between about 60,000 and about 80,000; the B block having a glass 21 transition tel~lpel~Lllre of about -105~C.+/-5~C. The weight ratio oftotal A to B being between about 22 l: l .8 and about l :2.7. Each A' segment represents essentially polymerized styrene. The balance of ' CA 02247670 1998-09-17 the A' segment is polymerized butadiene. The B' segment represe~ ess~nti~lly polymerized 2 butadiene. The balance of the B' segm~nt is polymerized styrene. The weight ratio of total A' to B' 3 being from about 1 :2.6 to about 1 :3.6, the number average molecular weight of said A'B'A' block 4 copolymers being between about 400,000 and about 660,000. The B' block has a glass transition temperature of about -90~C.+/-5~C. The second graft component consists essçnti~lly of from about 6 92.0 to about 84.0 parts by weight of monomeric styrene polymerized in the presence of the ABA
7 and A'B'A' copolymers.
8 Similarly, United States Patent No. 3,954,696 to Roest, teaches a process for the ple~a.~lion 9 of block copolymers of the general formula A--B--C. This process includes the steps of 1 0 polymerizing at least one monomer to form a living polymer block A; adding a further monomer and 11 continuing polymerization to form polymer block B bound to polymer block A, and continllin~;
12 polymerization while adding at least one monomer to form termin~l polymer block C, so as to 1 3 produce an A--B--C block copolymer. Each of the polymer blocks A and C consist of either a 14 non-elastomer homopolymer or copolymer having a glass transition temperature over 25~C. and a 1 5 number average molecular weight between 200 and 100,000. The polymer block B consists of a 16 conjugated diene, derived from preferably 1,3-butadiene or isoprene, having a glass transition 1 7 temperature below -10~C. and a number average molecular weight between 25,000 and 1,000,000.
1 8 The cont~min~nt~ contained in the monomers forming blocks A and C are theleanel deactivated.
19 As his improvement over the prior art, Roest includes Cont~min~nts in the conjugated diene monomer forming polymer block B, that have not been deactivated and that are capable of killing 21 1-50% ofthe living polymer block A upon introduction of conjugated diene monomer to the reaction 22 mass. Each of the polymer blocks A and C are disclosed as consisting of a non-elastomeric polymer ' CA 02247670 1998-09-17 block having a glass transition point over 50~C and a number average molecular weight between 500 2 and 50,000. The polymer block B is disclosed as con~icting of an el~tom~nc polymer block having 3 a glass transition point below -25~C and a number average molecular weight between S0,000 and 4 S00,000. At least one of polymer blocks A and C is derived from a monovinylaromatic hydrocarbon.
United States Patent No. 3,265,765 to Holden et al, discloses an unvulcanized el~ctom~ric 6 block copolymer having the general configuration A-B-A. Holden discloses that block A is an 7 independently selected non-elastomeric monovinyl aromatic hydrocarbon polymer block having an 8 average molecular weight of 2,000 - lO0,000 and a glass transition temperature above about 25~C.
9 The total block A content being l O- 50% by weight of the copolymer. Block B is an elastomeric conjugated diene polymer block having an average molecular weight between about 25,000 and 11 l ,000,000 and a glass transition temperature below about l O~C. The copolymer is prepared with a 1 2 lithium-based catalyst and has a tensile strength at 23~C, in excess of about 1400 pounds per square 1 3 inch.
14 In yet another similar United State Patent No. 3,231,635 to Holden et al, an unvulc~ni7çd 1 5 elastomeric block copolymer having the general configuration A - B - A is disclosed. Block A is an 1 6 independently selected non-elastomeric monovinyl aromatic hydrocarbon polymer block having an 1 7 average molecular weight of 2,000 - l O0,000 and a glass transition temperature above about 25~C.
1 8 The total block A content being l O - 50% by weight of the copolymer. Block B is an elastomeric 19 conjugated diene polymer block having an average molecular weight between about 25,000 and l ,000,000 and a glass transition temperature below about l O~ C. The copolymer is prepared with 21 a lithium-based catalyst and has a tensile strength at 23~C, in excess of about 1400 pounds per square 22 inch.
' CA 02247670 1998-09-17 United States Patent No. 3,239,478 to Harlan, teaches an adhesive composition that 2 comprises components. The first component of the composition comprises 100 parts by weight of 3 a block copolymer having the general configuration A - B - A. Each A block is an independently 4 selected polymer block of a vinyl arene. The average molecular weight of each A block is between about S,000 and about 125,000. The B block is a polymer block of a conjugated diene. The average 6 molecular weight of the B block is between about 15,000 and about 250,000. The total of the A
7 blocks is less than about 800io by weight of the copolymer. The second component of the 8 composition comprises about 25 - 300 parts by weight of a tackifying resin. Finally, the third 9 component of the composition comprises 5 - 200 parts by weight of an extender oil. The oil is substantially compatible with homopolymers of the conjugated diene.
11 Finally, United States Patent No. 3,149,182 to Porter teaches a process for preparing an 12 elastomeric three component block copolymer. The copolymer comprises the first step of:
13 contacting a monomer of the group con~i~ting of diolefins cont~ining from 4 to 10 carbon atoms, 14 mono alkenyl-substituted aromatic hydrocarbons and mono-alkenyl-s~lbstit lte-l pryidine compounds with a hydrocarbon lithium compound in an inert atmosphere and under substantially anhydrous 16 conditions until the unpolymerized monomer in the reaction mixture is consumed. Next, without 17 further treating the reaction, adding a monomer of the above group which is similar to that used in 18 the initial reaction. Thereafter, continuing the polymerization under the above conditions until the 19 dissimilar monomer has been polymerized. Next, without further tre~tmt nt of the reaction mixture, adding a third monomer which is different from the aforementioned ~lic~imil~r monomer and selected 21 from the above group of monomers. Finally, the polymerization is continued under the ' CA 02247670 1998-09-17 aforedescribed conditions until the third monomer has been completely consumed. At least one of 2 the foregoing monomers is a diolefin.
3 Despite the foregoing prior art, there nonetheless exists a long felt need for a process for 4 predicably producing styreffic polymers exhibiting high Gardner impact strengths in excess of at least 60 ft lb/in, as well as such other polymers and articles produce thelefro~6 Sul~lisi-lgly, the instant inventors have discovered that by merely manipulating the weight 7 proportions of the respective polymers of the interpolymer mix, dramatic increases in the Gardner 8 Impact Strength of the product may be achieved.
9 Polystyrene is a well-known thermoplastic material finding a wide variety of uses. It is often added to polymers including block copolymers to increase the mold flow characteristic of 11 the polymer, thus preventing the polymer from sticking to the injection molder cavity.
12 Heretofore, polystyrene has been blended with block copolymers to increase the processability of 13 the block copolymer. United States Patent No. 4,308,358 to Miller, discloses a process for 14 making high impact polystyrene comprising mixing, at an elevated temperature, an AB block copolymer and a styrene polymer. This blending process creates disadvantageous properties in 16 the blend, namely the impact strength of the block copolymer is severely reduced upon the 17 addition of as low as l .5 % by weight of crystal polystyrene to the block copolymer. While not 18 wishing to be bound by any particular theory, Applicants believe that the lower impact strength 19 resulting from the blending of polystyrene and block copolymer is due to the different molecular weights and physical properties of the components thereby causing phase separation to occur in 21 the resulting product. The poor interphase adhesion characteristic of highly incompatible blends ' CA 02247670 1998-09-17 usually results in very poor m-och~ni-~l pro~ellies, e.g., tensile strength, elongation and impact 2 strength.
3 It is ther~fole an object of the present invention to provide a process for producing an 4 interpolymer of poly~lylelle and a block copolymer exhibiting good ~.oçh~nic~l plo~lLies. It is a further object of this invention to provide polystyrene and block copolymer products exhibiting 6 high impact strength.
7 SUMMARY OF T~ INVENTION
8 In contrast to the foregoing prior art, the instant invention provides a process for 9 interpolymerizing a blend of a vinyl aromatic hydrocarbon polymer and copolymer product is disclosed. The process includes the following steps:
11 a) forming in a suitable diluent a block polymer pl~-,ulsor having a living end and 12 having at least one polymeric block cont~ining conjugated diene monomer contributed units in the 13 presence of an anionic initiator;
14 (b) thereafter adding to the block polymer precursor a charge of vinyl aromatic hydrocarbon monomer and an additional amount of anionic initiator to simultaneously form (1) 16 a block polymer having a terminal block, formed from the vinyl aromatic hydlocall.on monomer, 17 attached to the block polymer precursor and (2) poly(vinyl aromatic hydrocarbon) 18 interpolymerized with the block polymer of (l).
19 The practice of this process produces a vinyl aromatic hydrocarbon block tennin~t~l block polymer, such as SBS, interpolymerized with a polymer formed from vinyl aromatic hydrocarbon 21 monomer contributed units, such as polystyrene.
' CA 02247670 1998-09-17 S~l~lisingly, the instant inventors have discovered that by merely manipulating the weight 2 proportions of the respective block polymer and polyvinyl aromatic hydrocarbon polymer of the 3 interpolymer mix, dramatic increases of in excess of about 60 ft lb/in to at least about 200 ft lb/in 4 of the Gardner Impact Strength of the final product may be achieved.
' CA 02247670 1998-09-17 BRIEF DESCRIPTION OF THE FIGURES
2 Figure l illustrates the relationship belweell the Gardner Impact Strength (measured in ft-3 lb/inch) of interpolymers cont~ining polystyrene and a block polymer as prepared in Example 1 4 and the percent by weight of in situ polystyrene formed from the total styrene monomer charge used to plepale the terminal poly~lylelle block and in situ polystyrene during formation of the 6 interpolymer. The interpolymers le~l~sellLed in this figure were produced using the in situ process 7 of the present invention.
8 Figure 2 illustrates the r~l~tio~chir belween the Gardner Impact Strength (measured in ft-9 lb/inch) of a block polymer/poly~lyl~,ne blend and the amount by weight of crystal polystyrene added to the polymer as shown in Comparative Example A.
11 Figure 3 illustrates the relationship between the Gardner Impact Strength (measured in ft-12 lb/inch) of a block polymer/poly~lylelle blend and the amount by weight of crystal polystyrene 13 added to the polymer as shown in Comparative Example B.
The process of the present invention prepares an interpolymer of (l) a block polymer 16 having a precursor polymer block ~tt~rh~d to a terminal block of a poly(vinyl aromatic 17 hydrocarbon) and (2) a poly(vinyl aromatic hydrocarbon). The precursor polymer block of the 18 block polymer preferably contains diene monomer contributed block units, and optionally contains 19 vinyl aromatic monomer (VAM) contributed units including random blocks of butadiene and styrene (B/S).
21 The block polymers to be interpolymerized in accordance with the present invention 22 preferably contain conjugated diene monomers and vinyl substituted aromatic hydrocarbons ' CA 02247670 1998-09-17 contributed units. Polymerizable 1,3-diene monomers that can be employed in the production of 2 the copolymers of the present invention are one or more 1,3-conjugated dienes cont~ining from 3 four to twelve, inclusive, carbon atoms per molecule. Exemplary monomers include 1,3-4 bl~t~lien~-; isoprene; 2,3-dimethyl-1,3-but~ n~; 1,3-pent~ie~ (piperylene); 2-methyl-3-ethyl-1,3-butadiene; 3-methyl-1,3-pent~tlie~e; 1,3-h~Y~ie~; 2-methyl-1,3-hexadiene; 3-butyl-1,3-6 octadiene; and the like. Among the dialkyl-1,3-b~lt~ n~-s~ it is preferred that the alkyl groups 7 contain from one to three carbon atoms. The plerel.ed 1,3-diene monomer for use in the process 8 of the present invention is 1,3-b~lt~(lie~e.
9 Exemplary vinyl substituted aromatic hydrocarbon monomers, commonly referred to as vinyl aromatic hydrocarbon monomers or VAM, for use in either the preparation the block 11 polymer precursor and/or the terminal block and the poly(vinyl aromatic hydrocarbon), include:
12 styrene, alpha-methylstyrene; l-vinylnaphthalene; 2-vinyl-naphthalene; 1-alpha-13 methylvillylndphthalene; 2-alphalll~ yl-vinylnaphthalene; and mixtures of these as well as alkyl, 14 cycloaLkyl, aryl, alkaryl and aralkyl derivatives thereof in which the total number of carbon atoms in the combined hydrocarbon is generally not greater than 12. Examples of these latter compounds 16 include: 4-methylstyrene; vinyl toluene; 3,5-diethylstyrene; 2-ethyl4-benzylstyrene; 4-17 phenylstyrene; 4-para-tolylstyrene; and 4,5-dimethyl-1-vinylnaphthalene. Occasionally, di- and 18 tri- vinyl aromatic hydrocarbons are used in small amounts in addition with mono-vinyl aromatlc 19 hydrocarbons. The preferred vinyl aromatic hydrocarbon is styrene.
The total amount of vinyl aromatic hydrocarbon monomer in the final monomer charge 21 used to prepare both the terminal vinyl aromatic block and the interpolymerized poly(vinyl 22 aromatic hydrocarbon) is an amount of from 6.3 to 70.2% by weight, preferably from 28.3 to ' CA 02247670 1998-09-17 61.7% by weight, more preferably from 50.6 to 57.6% by weight, based on the total weight of 2 the block polymer. The weight percent of interpolymerized vinyl aromatic hydlocalbon polymer 3 of the total amount of both of the terminal poly(vinyl aromatic hydrocarbon) block and vinyl 4 aromatic hydrocarbon polymer is in the range of from S to 35 % by weight, preferably from 9 to 26% by weight, more preferably from 10 to 20% by weight. These weight pe~lllages reflect the 6 percentage of monomer, such as styrene, of the final monomer charge that is polymerized due to 7 the additional charge of anionic initiator to the reaction zone. The final monomer charge is used 8 to prepare both the terminal block added onto the block polymer precursor and the 9 interpolymerized poly(vinyl aromatic monomer).
The block polymers produced according to the instant invention must terminate in a vinyl 11 aromatic hydrocarbon block. The res-lltin~ structure of the block polymers may be linear, 12 br~nrhPd, tapered, or star as long as the structure has a live end. Exemplary block precursors 13 include block polymers cont~ining at least one polymeric block, a diblock polymer, triblock 14 polymers and tetrablock polymers, random copolymer blocks, graft-copolymers blocks, block-copolymers of a conjugated diolefin and a vinyl aromatic hydrocarbon, and mixtures thereof.
16 Typical examples of the various structures of the block polymer precursors useful in the present 17 invention are as follows:
(B-S)n- linear, 2 S-(B-S)n- linear, 3 B-(S-B)- linear, - 4 B/S-B-S- linear, [B(S)-B-B(S)-B-B(S)-B-B]n- branched, 6 B-, S-B-, S-(B-S)n-B-, (B-S)n-B-, (B/S) n~B~~ B-(B/S )n~~ S-(B/S) n~~ and (B/S) n~; wherein S is a 7 polymer block primarily cont~ining vinyl aromatic hydrocarbon monomer contributed units, B is 8 a polymer block primarily cont~ining conjugated diene monomer contributed units, and n is an 9 integer of one or more. The rubbery diene portion of the polymer may contain some copolymer 10 vinyl aromatic hydrocarbon in order to adjust the glass transition temperature (Tg) or the solubility 11 parameter. The block polymers produced in accordance with the present invention are represented 12 by any of the above-di~cussed block polymer precursor structures additionally cont~ining a 13 terminal block formed from vinyl aromatic hydrocarbon contributed units.
14 The process according to the present invention is performed in the following manner.
15 First, any desirable block polymer precursor is prepared in a reactor or reaction zone by 16 polymerizing suitable monomers, particularly diene monomers and/or vinyl aromatic monomers, 17 to form one or more blocks in a suitable diluent in the presence of an anionic initiator. The 18 res~lting block polymer precursor is "living", because a catalytically active anion is present at the 19 terminal end of the block polymer precursor. The anion is capable of initi~ting polymerization 20 of further monomers in the reaction zone.
21 After formation of the block polymer precursor, charges of additional anionic initiator and 22 vinyl aromatic hydrocarbon monomer are simlllt~n~ously or sequentially added to the reaction zone cont~ining the "living" block polymer precursor. A portion of the vinyl aromatic 2 hydrocarbon monomer charge att~-h~s to the "living" block polymer precursor. The additional 3 charge of anionic initiator initi~tes polymerization of an equimolar amount the additionally 4 charged vinyl aromatic hydrocarbon monomer thereby creating "living" vinyl arolllaLic 5 hydrocarbon polymers. Thus, the additional anionic initiator is added to create competition for 6 the additional charge of vinyl aromatic hydrocarbon monomer res-llting in the sim~ neous 7 production of (l) a terrnin~l block of vinyl aromatic hydrocarbon monomer contributed units 8 attaching to the "living" block polymer precursor and (2) poly(vinyl aromatic hydrocarbon) 9 having a living end. The resulting interpolymer is an interpolyll~.i~ed blend of a block polymer 10 and a poly(vinyl aromatic hydrocarbon) having living ends.
11 The reaction mixture is then treated to inactivate the living ends and recover the 12 interpolymer product. While it is to be understood that any suitable treating method can be 13 employed, one method for accomplishing the desired treatment coll~,ises adding a catalyst-14 inactivating material. Exemplary catalyst-inactivating materials include water, alcohol, an organic 15 acid, an inorganic acid, or the like. It is generally preferred to add only an amount of the catalyst-16 inactivating material sufficient to deactivate the catalyst without causing ~lecipilation of the 17 dissolved polymer. It has also been found to be advantageous to add an antioxidant to the polymer 18 solution prior to isolation of the polymer. After the addition of the catalyst-inactivating material 19 and the antioxidant, the polymer present in the solution can then be precipitated by the addition 20 of an excess of the catalyst-inactivating material or isolated by fl~hing the solvent. Deactivation 21 of the catalyst and precipitation of the polymer can be accomplished in a single step. The 22 precipitated polymer can then be recovered by filtration, ~ec~nt~tion, or the like. In order to ' CA 02247670 1998-09-17 purify the polymer, the separated polymer can be redissolved in a solvent, such as those suitable 2 for the polymerization, and again precipitated by the addition of an alcohol. Thereafter, the 3 polymer is again recovered by a suitable separation means, as in-lirated hereinbefore, and dried.
4 The solvent and alcohol can be separated, for example, by fractional d~stillation, and recycled.
5 The antioxidant can be added to the reaction mixture prior to precipitation of the polymer, to the 6 solution of redissolved polymer, or to the solvent in which the polymer is to be subsequently 7 redissolved. Polymerization can be carried out at any convenient ten~elature employed in the 8 polymerization arts. Exemplary temperatures lie in the range of from less than about 0~ to 200~C, 9 or more, preferably polymerization temperatures range from about 40~ to 100~C, for each step.
10 The pressures employed can be convenient, and preferably are ples~ules sufficient to m~int~in 11 monomers and diluents substantially in the liquid phase. The polymerization times can vary 12 widely as may be convenient, and will, of course, be affected by polymerization telll~eialul~s 13 chosen. The times should be chosen, for each step, such that substantially complete 14 polymerization is obtained.
15Any anionic initiator that is known in the art as useful in the copolymerization of diene 16 monomers with vinyl aromatic hydrocarbons can be employed in the process of the instant 17 invention. Exemplary organo-lithium catalysts include lithium compounds having the formula 18R(Li),~, wherein R represents a hydrocarbyl radical of 1 to 20, preferably 2 to 8, carbon atoms per 19 R group and x is an integer from 1 to 4. Typical R groups include aliphatic radicals and 20 cycloaliphatic radicals, such as alkyl, cycloalkyl, cycloalkylalkyl, alkylcycloalkyl, aryl and 21 alkylaryl radicals. Specific examples of R groups for substitution in the above formulas include 22 primary, secondary and tertiary groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, n-decyl, cyclopentyl-methyl, cyclohexyl-ethyl, 2 cyclopentyl-ethyl, methylcyclopentylethyl, cyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, 3 methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, isopropylcyclohexyl, and the like.
4 Specific example of other suitable lithium catalysts include: p-tolyllithinm, 4-phenylbutyl-lithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyl-lithium, lithium dialkyl amines, lithium 6 dialkyl phosphines, lithium alkyl aryl phosphine, lithium diaryl phosphines and the like.
7 The preferred catalyst for use in the present invention is n-butyllithium and sec-8 butyllithium 9 In accordance with the process of the present invention, two separate charges of anionic initiator must be made into the reaction zone. The first charge of anionic initiator is used to 11 initiate polymerization of the monomer charges used to prepare the block polymer precursor of 12 the present invention. The second charge of anionic initiator is added to the reaction zone 13 cont~ining the formed block polymer precursor in solution prior to or siml-lt~nPously with the final 14 charge of vinyl aromatic monomer used to simlllt~n~ously prepare the terminal block onto the block polymer precursor and the interpolymerized poly(vinyl aromatic hydrocarbon). The 16 amounts of anionic initiator employed in both: (1) the plep~alion of the block polymer precursor 17 and (2) the preparation of the terminal block and interpolymerized poly(vinyl aromatic 18 hydrocarbon) can vary over a broad range. In general, the first charge or amount of iniliator used 19 to initiate polymerization of the block polymer precursor will be in the range of from 0. l to 5 milliequivalents of initiator per 100 parts by weight of total amount of monomer charged into the 21 reaction zone and will preferably be in the range of from 0.4 to 2 milliequivalents of initiator per 22 100 parts by weight of total monomer charged. Likewise, the amount of additional anionic ' CA 02247670 1998-09-17 initiator used to initiate polymerization of a portion of the final vinyl aromatic hydrocarbon 2 monomer charge will be in the range of from 0.01 to 30 milliequivalents of il~iliator per 100 parts 3 by weight of the monomers charged and will preferably be in the range of from 0.05 to 7.6 4 milliequivalents of initiator per 100 parts by weight of the monomer charged into the reaction zone. Variance of the amount of the second charge of the anionic initiator is used to control the 6 amount of poly(vinyl aromatic hydfocarbon) interpolymerized with the block polymer.
7 A 1,2-microstructure controlling agent or randomizing modifier can be used during 8 formation of the polymer blocks to control the 1,2-microstructure in the diene contributed units 9 and to randomize the amount of vinyl aromatic monomers, such as styrene, incorporated with the diene monomer, such as bllt~ n~, in the rubbery phase. Suitable modifiers include, but are not 11 limited to, tetramethylçn~ min~ (TMEDA), oligomeric oxolanyl propanes (OOPS), 2,2-bis-(4-12 methyl dioxane) (BMD), tetrahydrofuran (THF), bistetrahydrofuryl plopalle and the like. One or 13 more randomizing, modifiers can be used. The amount of the modifier to the weight of the 14 monomers in the reactor can vary from a minim~lm as low as 0 to a maximum as great as 400 millimoles, preferably 0.01 to 300.0 millimoles, of modifier per hundred grams of monomer 16 currently charged into the reactor. As the modifier charge increases, the percentage of 1,2-17 microstructure increases in the diene monomer contributed units. A polar organic compound such 18 as ether, polyether, tertiary amine, polyamine, thioether and hexamethylphosphortriamide may be 19 used to control the vinyl linkage content in the conjugated diene component. The vinyl linkage content can be controlled by the amount added of the polar organic compound, and by the 21 polymerization temperature.
' CA 02247670 1998-09-17 Modifiers such as te~ lyl THP can be used to increase initiation of the first polystyrene 2 block without err~c~ g microstructure of the rubber block if low levels are used.
3 The process of this invention is preferably carried out in the presence of a hydrocarbon 4 diluent. ~liph~tic, aromatic l~)/dlocall~ons, paraffins, and cycloparaffins may be employed. The plefelled hydrocarbons are those cont~ining from 3 to 12, inclusive, carbon atoms, particularly 6 n-hexane. Examples of dilllent~ include propane, isobutene, n-pentane, isooctane, n-do~ec~ne, 7 cyclopen~le, cyclohexane, methylcycloh~x~n~, bel~lle, toluene, xylene, and the like. Mixtures 8 of two or more of these hydrocarbons may also be used.
9 The polymerization process may be con~llcted under batch or semi-batch conditions.
The polymers of this invention may be compounded further with other polymers, oils, 11 fillers, reinforcements, antioxidants, stabilizers, fire retardants, tackifiers, vulc~ni7~tion 12 accelerators, vulc~ni7ing agents, processing aids, antiblocking agents and other rubber plastic 13 compounding ingredients without departing from the scope of this invention. These colnpoullding 14 ingredients are incorporated in suitable amounts depending upon the colltelll~lated use of the 1 5 product.
16 A reinforcement may be defined as the material that is added to a resinous matrix to 17 improve the strength of the polymer. Most of these lcil~Ol~ lg materials are inorganic or organic 18 products of high molecular weight. Various examples include glass fibers, asbestos, boron fibers, 19 carbon and graphite fibers, whiskers, quart7 and silica fibers, ceramic fibers, metal fibers, natural organic fibers, and synthetic organic fibers.
21 The interpolymers of the instant invention can be used as is or can be incorporated into 22 injection molding resins or in any other compositions typically cont~ining high impact polymers.
Particularly, the interpolymers of the present invention have improved processability over prior 2 art blends of polystyrene and block polymers. The interpolymers produced according to the 3 process of the present invention possess a Gardner Impact Strength of at least 60 ft-lb/inch, 4 preferably at least lO0 ft-lb/inch, more preferably at least lS0 ft-lb/inch, and most preferably at least 200 ft-lb/inch.
6 The following examples are ~lese,,led for purposes of illustration only and are not to be 7 construed in a limiting sense. All pel~;entages are by weight unless otherwise specified.
2 An interpolymer was produced according to the present invention. The structural 3 characteristics of the triblock polymer produced by anionic polylllel~tion are displayed in Table 4 1. The first block of this triblock polymer was prepared by charging a stirred reactor with (1) 18.2 lbs. of a 33% by weight charge of styrene in hexane, (2) 10.9 lbs. of hexane, (3) 0.69 kg of 6 a 3 % solution of n-butyllithillm in hexane together with 1.634 grams of modifier, 10.0 kg of a 7 15% solution of a styrene/b lt~ diblock dispersant. This ll~i~ was heated at 120~F for 30 8 mimltes and then cooled to 110~F to produce a first block as displayed in Table 1. A charge of 9 40.0 lbs. of a 33% by weight solution of 1,3-b~-t~lien~ in hexane was added to the reactor as the 1 0 temperature of the reactor was raised to 170~F and heated until 30 mimltes after peak te"l~,el~ture.
11 The composition of the second block is disclosed in Table 1. The reactor was then additionally 12 charged with 0.07 kg of a 3% solution of n-butyllithillm in hexane followed by a charge of 134.8 1 3 lbs. of a 33 % solution of styrene in hexane. The contenl~ of the reactor was heated to 170~F for 14 thirty miml~es after reaching the peak te"lpe,~ture. The reaction was termin~ted by adding 272.4 grams of a 3% aqueous solution of boric acid, and a 5.55 lbs of a hexane solution cont~ining 16 antioxidant was added. The molecular weight of the third block of the triblock polymer as 1 7 displayed in Table 1 was 56,470. The molecular weight of the polystyrene produced in situ was 18 also 56,470.
2 An interpolymer was produced according to the procedure of Example 1. The first block 3 of this triblock polymer was prepared by charging a reactor with (1) 25.8 lbs. of a 33% by weight 4 charge of styrene in hexane, (2) 33.6 Ibs. of hexane, (3) 0.81 kg of a 3% solution of n-butyllithi~lm in hexane together with 10 grams of modifier, 14.1 kg of a styrene/butadiene diblock 6 dispersant. This mixture was heated at 120~F for 30 minl-tes and then cooled to 100~F to produce 7 a first block as displayed in Table 1. Separate charges of 56.7 lbs. of a 33 % by weight solutions 8 of 1~3-bllt~lien~ in hexane and styrene in hexane were added to the reactor as the temperature of 9 the reactor was raised to 170~F and heated until 30 minutes after peak temperature. The reactor 1 0 was then additionally charged with 0.16 kg of a 3 % solution of n-butyllithium in hexane (20 % of 1 1 the initial catalyst charge) followed by a charge of 142.2 lbs. of a 33% solution of styrene in 1 2 hexane. The contents of the reactor was heated to 170~F for thirty min~-tes after reaching the peak 1 3 temperature. The reaction was termin~t~d by adding 11.57 grams of boric acid and 374 grams of 14 water, followed by the addition of a 6.80 lbs. of a hexane solution cont~ining antioxidant. As can 1 5 be easily recognized from the results displayed in Fig. 1, all interpolymers produced according 1 6 to the process of the present invention possess measured Gardner Impact Strengths exceeding 200 1 7 ft-lb/inch. The amount of crystal polystyrene incorporated in the interpolymer varied in amount 18 ranging from 9.0% to 26.0%, by weight of the final styrene monomer charge. The amount of m 1 9 situ polystyrene present in the interpolymer did not adversely affect the Gardner Impact Strength (measured in ft-lb/inch) of the interpolymer, nor did the interpolymer stick in the injection molder 21 cavity.
2Physical Characteristics of the Triblock Polymer 3Produced According to the Instant Invention 4 Example First Block Second Block Third Block No. Total MWTotal MWl % MW % MW % % STY
6 1 8,420 10018,530 0 56,470 100 83,42077.8 7 2 10,160 10044,690 50 46,720 100 101,57078.0 8 lMolecular Weight 9 2Percent Styrene p~ in-ler Butadiene 11 A triblock polymer was prepared by anionic polymerization techniques having the 1 2 structural characteristics displayed in Table 2. The triblock polymer exhibited a Gardner Impact 13 of about 175 ft-lb/inch, but the polymer adhered to the injection molder cavity. Crystal 14 polystyrene was physically blended with the triblock polymer in amounts ranging from 1.5% to 15 7.0% by weight in order to improve the mold flow characteristics of the block polymer. The 16 Gardner Impact Strength of the block polymer after the addition by blending of the crystal 1 7 polystyrene was measured. The Gardner Impact Strength of the blend of triblock polymer of 1 8 Table 2 and the crystalline polystyrene versus the percent by weight of crystalline polystyrene 1 9 added to the triblock polymer is depicted in Figure 2 in units of ft-lb/inch. The Gardner Impact Strength of the polymer blend was less than 25 ft-lb/inch upon the addition by blending of 1.5%
2 by weight or more of the crystal polystyrene.
4Physical Characteristics of Block Polymer 5Utilized in Comparative Example A
6 First BlockSecond Block Third Block TotalTotal % % % MW %
7 MWl sTy2 MW STY MW STY STY
8 8,980 99 37,330 47.6 42,670 100 88,98077.9 9 1Molecular Weight 2Percent Styrene Remainder Butadiene 12 A triblock polymer was prepared by anionic polymerization techniques having the 13 structural characteristics displayed in Table 3. The block polymer exhibited a Gardner Impact of 14 about 200 ft-lb/inch, but the polymer adhered to the injection molder cavity. Crystal polystyrene 15 was physically blended with the block polymer in amounts ranging from 1.5% to 7.0 % by weight 16 in order to improve the mold flow characteristics of the triblock polymer. The Gardner Impact 17 Strength of the triblock polymer decreased dramatically upon the addition by blending of 1.5%
18 by weight or more of crystal polystyrene. The Gardner Impact Strengths of the polymer blends of Coll~alali~/e Example B were about 20 ft-lb/inch and are displayed in Figure 3 as measured in 2 ft-lb/inch. The addition of polystyrene to the triblock polymer resulted in a loss of appro~ ately 3 90% of the Gardner Impact Strength of the original triblock polymer.
.
4 T~BLE 3 5Physical Characteristics of Block Polymer 6Utilized in Comparative Example B
7 First BlockSecond BlockThird Block Total Total % % % MW %
8 MWl sTy2 MW STY MW STY STY
9 8,620 99 37,540 50 39,250 100 85,41077.9 'Molecular Weight 11 2Percent Styrene P~m~intler Butadiene
4 The solvent and alcohol can be separated, for example, by fractional d~stillation, and recycled.
5 The antioxidant can be added to the reaction mixture prior to precipitation of the polymer, to the 6 solution of redissolved polymer, or to the solvent in which the polymer is to be subsequently 7 redissolved. Polymerization can be carried out at any convenient ten~elature employed in the 8 polymerization arts. Exemplary temperatures lie in the range of from less than about 0~ to 200~C, 9 or more, preferably polymerization temperatures range from about 40~ to 100~C, for each step.
10 The pressures employed can be convenient, and preferably are ples~ules sufficient to m~int~in 11 monomers and diluents substantially in the liquid phase. The polymerization times can vary 12 widely as may be convenient, and will, of course, be affected by polymerization telll~eialul~s 13 chosen. The times should be chosen, for each step, such that substantially complete 14 polymerization is obtained.
15Any anionic initiator that is known in the art as useful in the copolymerization of diene 16 monomers with vinyl aromatic hydrocarbons can be employed in the process of the instant 17 invention. Exemplary organo-lithium catalysts include lithium compounds having the formula 18R(Li),~, wherein R represents a hydrocarbyl radical of 1 to 20, preferably 2 to 8, carbon atoms per 19 R group and x is an integer from 1 to 4. Typical R groups include aliphatic radicals and 20 cycloaliphatic radicals, such as alkyl, cycloalkyl, cycloalkylalkyl, alkylcycloalkyl, aryl and 21 alkylaryl radicals. Specific examples of R groups for substitution in the above formulas include 22 primary, secondary and tertiary groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl, n-octyl, n-decyl, cyclopentyl-methyl, cyclohexyl-ethyl, 2 cyclopentyl-ethyl, methylcyclopentylethyl, cyclopentyl, dimethylcyclopentyl, ethylcyclopentyl, 3 methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, isopropylcyclohexyl, and the like.
4 Specific example of other suitable lithium catalysts include: p-tolyllithinm, 4-phenylbutyl-lithium, 4-butylcyclohexyllithium, 4-cyclohexylbutyl-lithium, lithium dialkyl amines, lithium 6 dialkyl phosphines, lithium alkyl aryl phosphine, lithium diaryl phosphines and the like.
7 The preferred catalyst for use in the present invention is n-butyllithium and sec-8 butyllithium 9 In accordance with the process of the present invention, two separate charges of anionic initiator must be made into the reaction zone. The first charge of anionic initiator is used to 11 initiate polymerization of the monomer charges used to prepare the block polymer precursor of 12 the present invention. The second charge of anionic initiator is added to the reaction zone 13 cont~ining the formed block polymer precursor in solution prior to or siml-lt~nPously with the final 14 charge of vinyl aromatic monomer used to simlllt~n~ously prepare the terminal block onto the block polymer precursor and the interpolymerized poly(vinyl aromatic hydrocarbon). The 16 amounts of anionic initiator employed in both: (1) the plep~alion of the block polymer precursor 17 and (2) the preparation of the terminal block and interpolymerized poly(vinyl aromatic 18 hydrocarbon) can vary over a broad range. In general, the first charge or amount of iniliator used 19 to initiate polymerization of the block polymer precursor will be in the range of from 0. l to 5 milliequivalents of initiator per 100 parts by weight of total amount of monomer charged into the 21 reaction zone and will preferably be in the range of from 0.4 to 2 milliequivalents of initiator per 22 100 parts by weight of total monomer charged. Likewise, the amount of additional anionic ' CA 02247670 1998-09-17 initiator used to initiate polymerization of a portion of the final vinyl aromatic hydrocarbon 2 monomer charge will be in the range of from 0.01 to 30 milliequivalents of il~iliator per 100 parts 3 by weight of the monomers charged and will preferably be in the range of from 0.05 to 7.6 4 milliequivalents of initiator per 100 parts by weight of the monomer charged into the reaction zone. Variance of the amount of the second charge of the anionic initiator is used to control the 6 amount of poly(vinyl aromatic hydfocarbon) interpolymerized with the block polymer.
7 A 1,2-microstructure controlling agent or randomizing modifier can be used during 8 formation of the polymer blocks to control the 1,2-microstructure in the diene contributed units 9 and to randomize the amount of vinyl aromatic monomers, such as styrene, incorporated with the diene monomer, such as bllt~ n~, in the rubbery phase. Suitable modifiers include, but are not 11 limited to, tetramethylçn~ min~ (TMEDA), oligomeric oxolanyl propanes (OOPS), 2,2-bis-(4-12 methyl dioxane) (BMD), tetrahydrofuran (THF), bistetrahydrofuryl plopalle and the like. One or 13 more randomizing, modifiers can be used. The amount of the modifier to the weight of the 14 monomers in the reactor can vary from a minim~lm as low as 0 to a maximum as great as 400 millimoles, preferably 0.01 to 300.0 millimoles, of modifier per hundred grams of monomer 16 currently charged into the reactor. As the modifier charge increases, the percentage of 1,2-17 microstructure increases in the diene monomer contributed units. A polar organic compound such 18 as ether, polyether, tertiary amine, polyamine, thioether and hexamethylphosphortriamide may be 19 used to control the vinyl linkage content in the conjugated diene component. The vinyl linkage content can be controlled by the amount added of the polar organic compound, and by the 21 polymerization temperature.
' CA 02247670 1998-09-17 Modifiers such as te~ lyl THP can be used to increase initiation of the first polystyrene 2 block without err~c~ g microstructure of the rubber block if low levels are used.
3 The process of this invention is preferably carried out in the presence of a hydrocarbon 4 diluent. ~liph~tic, aromatic l~)/dlocall~ons, paraffins, and cycloparaffins may be employed. The plefelled hydrocarbons are those cont~ining from 3 to 12, inclusive, carbon atoms, particularly 6 n-hexane. Examples of dilllent~ include propane, isobutene, n-pentane, isooctane, n-do~ec~ne, 7 cyclopen~le, cyclohexane, methylcycloh~x~n~, bel~lle, toluene, xylene, and the like. Mixtures 8 of two or more of these hydrocarbons may also be used.
9 The polymerization process may be con~llcted under batch or semi-batch conditions.
The polymers of this invention may be compounded further with other polymers, oils, 11 fillers, reinforcements, antioxidants, stabilizers, fire retardants, tackifiers, vulc~ni7~tion 12 accelerators, vulc~ni7ing agents, processing aids, antiblocking agents and other rubber plastic 13 compounding ingredients without departing from the scope of this invention. These colnpoullding 14 ingredients are incorporated in suitable amounts depending upon the colltelll~lated use of the 1 5 product.
16 A reinforcement may be defined as the material that is added to a resinous matrix to 17 improve the strength of the polymer. Most of these lcil~Ol~ lg materials are inorganic or organic 18 products of high molecular weight. Various examples include glass fibers, asbestos, boron fibers, 19 carbon and graphite fibers, whiskers, quart7 and silica fibers, ceramic fibers, metal fibers, natural organic fibers, and synthetic organic fibers.
21 The interpolymers of the instant invention can be used as is or can be incorporated into 22 injection molding resins or in any other compositions typically cont~ining high impact polymers.
Particularly, the interpolymers of the present invention have improved processability over prior 2 art blends of polystyrene and block polymers. The interpolymers produced according to the 3 process of the present invention possess a Gardner Impact Strength of at least 60 ft-lb/inch, 4 preferably at least lO0 ft-lb/inch, more preferably at least lS0 ft-lb/inch, and most preferably at least 200 ft-lb/inch.
6 The following examples are ~lese,,led for purposes of illustration only and are not to be 7 construed in a limiting sense. All pel~;entages are by weight unless otherwise specified.
2 An interpolymer was produced according to the present invention. The structural 3 characteristics of the triblock polymer produced by anionic polylllel~tion are displayed in Table 4 1. The first block of this triblock polymer was prepared by charging a stirred reactor with (1) 18.2 lbs. of a 33% by weight charge of styrene in hexane, (2) 10.9 lbs. of hexane, (3) 0.69 kg of 6 a 3 % solution of n-butyllithillm in hexane together with 1.634 grams of modifier, 10.0 kg of a 7 15% solution of a styrene/b lt~ diblock dispersant. This ll~i~ was heated at 120~F for 30 8 mimltes and then cooled to 110~F to produce a first block as displayed in Table 1. A charge of 9 40.0 lbs. of a 33% by weight solution of 1,3-b~-t~lien~ in hexane was added to the reactor as the 1 0 temperature of the reactor was raised to 170~F and heated until 30 mimltes after peak te"l~,el~ture.
11 The composition of the second block is disclosed in Table 1. The reactor was then additionally 12 charged with 0.07 kg of a 3% solution of n-butyllithillm in hexane followed by a charge of 134.8 1 3 lbs. of a 33 % solution of styrene in hexane. The contenl~ of the reactor was heated to 170~F for 14 thirty miml~es after reaching the peak te"lpe,~ture. The reaction was termin~ted by adding 272.4 grams of a 3% aqueous solution of boric acid, and a 5.55 lbs of a hexane solution cont~ining 16 antioxidant was added. The molecular weight of the third block of the triblock polymer as 1 7 displayed in Table 1 was 56,470. The molecular weight of the polystyrene produced in situ was 18 also 56,470.
2 An interpolymer was produced according to the procedure of Example 1. The first block 3 of this triblock polymer was prepared by charging a reactor with (1) 25.8 lbs. of a 33% by weight 4 charge of styrene in hexane, (2) 33.6 Ibs. of hexane, (3) 0.81 kg of a 3% solution of n-butyllithi~lm in hexane together with 10 grams of modifier, 14.1 kg of a styrene/butadiene diblock 6 dispersant. This mixture was heated at 120~F for 30 minl-tes and then cooled to 100~F to produce 7 a first block as displayed in Table 1. Separate charges of 56.7 lbs. of a 33 % by weight solutions 8 of 1~3-bllt~lien~ in hexane and styrene in hexane were added to the reactor as the temperature of 9 the reactor was raised to 170~F and heated until 30 minutes after peak temperature. The reactor 1 0 was then additionally charged with 0.16 kg of a 3 % solution of n-butyllithium in hexane (20 % of 1 1 the initial catalyst charge) followed by a charge of 142.2 lbs. of a 33% solution of styrene in 1 2 hexane. The contents of the reactor was heated to 170~F for thirty min~-tes after reaching the peak 1 3 temperature. The reaction was termin~t~d by adding 11.57 grams of boric acid and 374 grams of 14 water, followed by the addition of a 6.80 lbs. of a hexane solution cont~ining antioxidant. As can 1 5 be easily recognized from the results displayed in Fig. 1, all interpolymers produced according 1 6 to the process of the present invention possess measured Gardner Impact Strengths exceeding 200 1 7 ft-lb/inch. The amount of crystal polystyrene incorporated in the interpolymer varied in amount 18 ranging from 9.0% to 26.0%, by weight of the final styrene monomer charge. The amount of m 1 9 situ polystyrene present in the interpolymer did not adversely affect the Gardner Impact Strength (measured in ft-lb/inch) of the interpolymer, nor did the interpolymer stick in the injection molder 21 cavity.
2Physical Characteristics of the Triblock Polymer 3Produced According to the Instant Invention 4 Example First Block Second Block Third Block No. Total MWTotal MWl % MW % MW % % STY
6 1 8,420 10018,530 0 56,470 100 83,42077.8 7 2 10,160 10044,690 50 46,720 100 101,57078.0 8 lMolecular Weight 9 2Percent Styrene p~ in-ler Butadiene 11 A triblock polymer was prepared by anionic polymerization techniques having the 1 2 structural characteristics displayed in Table 2. The triblock polymer exhibited a Gardner Impact 13 of about 175 ft-lb/inch, but the polymer adhered to the injection molder cavity. Crystal 14 polystyrene was physically blended with the triblock polymer in amounts ranging from 1.5% to 15 7.0% by weight in order to improve the mold flow characteristics of the block polymer. The 16 Gardner Impact Strength of the block polymer after the addition by blending of the crystal 1 7 polystyrene was measured. The Gardner Impact Strength of the blend of triblock polymer of 1 8 Table 2 and the crystalline polystyrene versus the percent by weight of crystalline polystyrene 1 9 added to the triblock polymer is depicted in Figure 2 in units of ft-lb/inch. The Gardner Impact Strength of the polymer blend was less than 25 ft-lb/inch upon the addition by blending of 1.5%
2 by weight or more of the crystal polystyrene.
4Physical Characteristics of Block Polymer 5Utilized in Comparative Example A
6 First BlockSecond Block Third Block TotalTotal % % % MW %
7 MWl sTy2 MW STY MW STY STY
8 8,980 99 37,330 47.6 42,670 100 88,98077.9 9 1Molecular Weight 2Percent Styrene Remainder Butadiene 12 A triblock polymer was prepared by anionic polymerization techniques having the 13 structural characteristics displayed in Table 3. The block polymer exhibited a Gardner Impact of 14 about 200 ft-lb/inch, but the polymer adhered to the injection molder cavity. Crystal polystyrene 15 was physically blended with the block polymer in amounts ranging from 1.5% to 7.0 % by weight 16 in order to improve the mold flow characteristics of the triblock polymer. The Gardner Impact 17 Strength of the triblock polymer decreased dramatically upon the addition by blending of 1.5%
18 by weight or more of crystal polystyrene. The Gardner Impact Strengths of the polymer blends of Coll~alali~/e Example B were about 20 ft-lb/inch and are displayed in Figure 3 as measured in 2 ft-lb/inch. The addition of polystyrene to the triblock polymer resulted in a loss of appro~ ately 3 90% of the Gardner Impact Strength of the original triblock polymer.
.
4 T~BLE 3 5Physical Characteristics of Block Polymer 6Utilized in Comparative Example B
7 First BlockSecond BlockThird Block Total Total % % % MW %
8 MWl sTy2 MW STY MW STY STY
9 8,620 99 37,540 50 39,250 100 85,41077.9 'Molecular Weight 11 2Percent Styrene P~m~intler Butadiene
Claims (21)
1 . A process for producing an interpolymer comprising:
(a) forming a polyvinyl aromatic hydrocarbon first polymer block in a hydrocarbon diluent in the presence of a block dispersant;
(b) forming a block polymer precursor by polymerizing onto the first polymer block formed in step (a) a second block comprising at least one polymeric block containing conjugated diene monomer contributed units in the presence of an anionic initiator and a hydrocarbon diluent in a reaction zone, wherein said block polymer precursor has a living end;
(c) forming an interpolymer having a Gardner impact strength of at least 60 ft-lb/inch comprising: (1) a block polymer comprising a poly(vinyl aromatic hydrocarbon) terminal block attached to the living end of said block polymer precursor, and (2) a poly(vinyl aromatic hydrocarbon), by adding an additional amount of anionic initiator to the reaction zone prior to the addition of a vinyl aromatic hydrocarbon monomer in an amount ranging from about 6.3 to 70.2 %
by weight of the total weight of the subsequently formed block polymer; and wherein the weight percent of interpolymerized vinyl aromatic hydrocarbon polymer is in the range of from 5 to 35 %
by weight of the total amount of both of the terminal poly(vinyl aromatic hydrocarbon) block and the interpolymerized vinyl aromatic hydrocarbon polymer;
(d) inactivating the catalyst and recovering the interpolymer.
(a) forming a polyvinyl aromatic hydrocarbon first polymer block in a hydrocarbon diluent in the presence of a block dispersant;
(b) forming a block polymer precursor by polymerizing onto the first polymer block formed in step (a) a second block comprising at least one polymeric block containing conjugated diene monomer contributed units in the presence of an anionic initiator and a hydrocarbon diluent in a reaction zone, wherein said block polymer precursor has a living end;
(c) forming an interpolymer having a Gardner impact strength of at least 60 ft-lb/inch comprising: (1) a block polymer comprising a poly(vinyl aromatic hydrocarbon) terminal block attached to the living end of said block polymer precursor, and (2) a poly(vinyl aromatic hydrocarbon), by adding an additional amount of anionic initiator to the reaction zone prior to the addition of a vinyl aromatic hydrocarbon monomer in an amount ranging from about 6.3 to 70.2 %
by weight of the total weight of the subsequently formed block polymer; and wherein the weight percent of interpolymerized vinyl aromatic hydrocarbon polymer is in the range of from 5 to 35 %
by weight of the total amount of both of the terminal poly(vinyl aromatic hydrocarbon) block and the interpolymerized vinyl aromatic hydrocarbon polymer;
(d) inactivating the catalyst and recovering the interpolymer.
2. The process of claim I wherein said block polymer precursor comprises a repeating structure selected from the group consisting of:
(B-S)n- linear, S-(B-S)- linear, B-(S-B)n- linear, B/S-B-S- linear, [B(S)-B-B(S)-B-B(S)-B-B]n- branched, B-, S-B-, S-(B-S) n-B-, (B-S) n-B-, (B/S)n-B-, B-(B/S)n-, S-(B/S)n-, (B/S)n - and combinations thereof; wherein S is a polymer block primarily containing vinyl aromatic hydrocarbon monomer contributed units, B is a polymer block primarily containing conjugated diene monomer contributed units, and n is an integer of one or more.
(B-S)n- linear, S-(B-S)- linear, B-(S-B)n- linear, B/S-B-S- linear, [B(S)-B-B(S)-B-B(S)-B-B]n- branched, B-, S-B-, S-(B-S) n-B-, (B-S) n-B-, (B/S)n-B-, B-(B/S)n-, S-(B/S)n-, (B/S)n - and combinations thereof; wherein S is a polymer block primarily containing vinyl aromatic hydrocarbon monomer contributed units, B is a polymer block primarily containing conjugated diene monomer contributed units, and n is an integer of one or more.
3. The product according to claim 1 wherein said vinyl aromatic hydrocarbon monomer is styrene.
4. The process according to claim 1 wherein said conjugated diene monomer is 1,3-butadiene.
5. The process according to claim 1 wherein said anionic initiator is an organo-lithium compound.
6. The process according to claim 1 wherein said anionic initiator is n-butyllithium or sec-butyllithium.
7. The process according to claim 1 wherein said block polymer precursor comprises a block polymer selected from the group consisting of a polymer block, a block copolymer, a random copolymer block, a graft-copolymer block, a triblock polymer, and a tetrablock polymer.
8. The process according to claim 1 wherein the amount of anionic initiator added in step (a) is from 0.1 to 5 % milliequivalents of initiator per 100 parts by weight of the monomers.
9. The process according to claim 1 wherein the amount of anionic initiator added in step (b) is from 0.01 to 30% milliequivalents of initiator per 100 parts by weight of the monomers.
10. The process according to claim 1 wherein the amount of vinyl aromatic hydrocarbon monomer added in step (b) is from 6.3 to 70.2% based on the total weight of the block polymer precursor.
11. An interpolymer comprising:
(a) a block polymer comprising at least two block segments wherein one of said block segments is a terminal block comprising vinyl aromatic hydrocarbon monomer contributed units; and (b) a vinyl aromatic hydrocarbon polymer formed from vinyl aromatic hydrocarbon monomer contributed units;
wherein said vinyl aromatic hydrocarbon polymer is simultaneously produced during the formation of said block polymer; and, wherein said interpolymer has a Gardner impact strength of at least 60 ft-lb/inch.
(a) a block polymer comprising at least two block segments wherein one of said block segments is a terminal block comprising vinyl aromatic hydrocarbon monomer contributed units; and (b) a vinyl aromatic hydrocarbon polymer formed from vinyl aromatic hydrocarbon monomer contributed units;
wherein said vinyl aromatic hydrocarbon polymer is simultaneously produced during the formation of said block polymer; and, wherein said interpolymer has a Gardner impact strength of at least 60 ft-lb/inch.
12. The interpolymer according to claim 11 wherein said vinyl aromatic hydrocarbon monomer contributed units are styrene.
13. The interpolymer according to claim 11 wherein said block polymer is a styrene-butadiene-styrene block polymer.
14. The interpolymer according to claim 11 wherein said block polymer comprises a polystyrene block terminated block polymer.
15. The interpolymer according to claim 11 wherein the vinyl aromatic hydrocarbon polymer comprises between about 5 to 35 percent by weight of the total combined weight of the terminal block and the vinyl aromatic hydrocarbon polymer.
16. The interpolymer according to claim 11 wherein the vinyl aromatic hydrocarbon polymer comprises between about 9 to 26 percent by weight of the total combined weight of the terminal block and the vinyl aromatic hydrocarbon polymer.
17. The interpolymer according to claim 11 wherein the vinyl aromatic hydrocarbon polymer comprises between about 10 to 20 percent by weight of the total combined weight of the terminal block and the vinyl aromatic hydrocarbon polymer.
18. An interpolymer comprising:
(a) a block polymer comprising at least two block segments wherein one of said block segments is a terminal block comprising vinyl aromatic hydrocarbon monomer contributed units; and (b) a vinyl aromatic hydrocarbon polymer formed from vinyl aromatic hydrocarbon monomer contributed units;
wherein said interpolymer has a Gardner Impact strength of at least 60 ft-lb/inch.
(a) a block polymer comprising at least two block segments wherein one of said block segments is a terminal block comprising vinyl aromatic hydrocarbon monomer contributed units; and (b) a vinyl aromatic hydrocarbon polymer formed from vinyl aromatic hydrocarbon monomer contributed units;
wherein said interpolymer has a Gardner Impact strength of at least 60 ft-lb/inch.
19. The interpolymer according to claim 18 wherein said interpolymer has a Gardner Impact strength of at least 100 ft-lb/inch.
20. The interpolymer according to claim 18 wherein said interpolymer has a Gardner Impact strength of at least 150 ft-lb/inch.
21. The interpolymer according to claim 18 wherein said interpolymer has a Gardner Impact strength of at least 200 ft-lb/inch.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/935,773 | 1997-09-23 | ||
| US08/935,773 US6162874A (en) | 1994-11-07 | 1997-09-23 | Block copolymers interpolymerized with in situ polystyrene and process for preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2247670A1 true CA2247670A1 (en) | 1999-03-23 |
Family
ID=25467643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002247670A Abandoned CA2247670A1 (en) | 1997-09-23 | 1998-09-17 | Block copolymers interpolymerized with in situ polystyrene and process for preparation thereof |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US6162874A (en) |
| EP (1) | EP0903359A1 (en) |
| JP (1) | JPH11171948A (en) |
| CA (1) | CA2247670A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6362282B1 (en) * | 2000-09-29 | 2002-03-26 | Firestone Polymers, Llc | Polymers with high vinyl end segments |
| US6417270B1 (en) * | 2001-01-09 | 2002-07-09 | Firestone Polymers, Llc | Means of producing high diblock content thermoplastic elastomers with functional termination |
| US6359075B1 (en) * | 2001-01-09 | 2002-03-19 | Bridgestone/Firestone, Inc. | Means of producing high diblock content thermoplastic elastomers via chain transfer |
| US20040142910A1 (en) * | 2002-10-21 | 2004-07-22 | Aegis Biosciences Llc | Sulfonated styrene copolymers for medical uses |
| US20050070663A1 (en) * | 2003-09-29 | 2005-03-31 | Fina Technology, Inc. | Impact modified polystyrene and process for preparing same |
| US9732178B1 (en) | 2008-07-24 | 2017-08-15 | Bridgestone Corporation | Block copolymers including high vinyl segments |
| CN105801784B (en) * | 2016-03-03 | 2018-07-17 | 中国石油化工股份有限公司 | A kind of linear functional SBS and technique prepared by difunctional coupling agent |
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| US3149182A (en) * | 1957-10-28 | 1964-09-15 | Shell Oil Co | Process for preparing block copolymers utilizing organolithium catalysts |
| US3030346A (en) * | 1960-03-18 | 1962-04-17 | Phillips Petroleum Co | Production of block copolymers |
| NL136313C (en) * | 1962-01-29 | |||
| US3239478A (en) | 1963-06-26 | 1966-03-08 | Shell Oil Co | Block copolymer adhesive compositions and articles prepared therefrom |
| US3231635A (en) | 1963-10-07 | 1966-01-25 | Shell Oil Co | Process for the preparation of block copolymers |
| US3728300A (en) * | 1967-08-26 | 1973-04-17 | Asahi Chemical Ind | Process for producing polymer blends |
| US3560593A (en) * | 1968-01-02 | 1971-02-02 | Phillips Petroleum Co | Production of block copolymers |
| US3954696A (en) * | 1969-12-19 | 1976-05-04 | Stamicarbon, B.V. | Process of preparing A-B-C elastomeric block copolymers |
| US3700748A (en) * | 1970-05-22 | 1972-10-24 | Shell Oil Co | Selectively hydrogenated block copolymers |
| US3823203A (en) * | 1971-03-29 | 1974-07-09 | Shell Oil Co | Vulcanizable selectively hydogenated block copolymer compositions |
| US3792005A (en) * | 1972-02-07 | 1974-02-12 | Shell Oil Co | Low molecular weight block copolymers and coating compositions thereof |
| US3819764A (en) * | 1972-05-30 | 1974-06-25 | Firestone Tire & Rubber Co | Process for the grafting of styrene onto polymeric butadiene or isoprene prereacted with an alkyl lithium or sodium and a sec-alkyl chloride |
| US3806557A (en) * | 1972-05-30 | 1974-04-23 | Firestone Tire & Rubber Co | Process for grafting polystyrene branches onto polymeric butadiene or isoprene in the presence of an alkyl lithium or sodium and a sec.-alkyl chloride |
| US3896068A (en) * | 1974-04-15 | 1975-07-22 | Phillips Petroleum Co | Printable anti-blocking resinous block copolymer |
| US4208356A (en) * | 1974-09-17 | 1980-06-17 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing mixture of block copolymers |
| DE2550226C2 (en) * | 1975-11-08 | 1984-12-13 | Basf Ag, 6700 Ludwigshafen | Branched block copolymers and process for their preparation |
| US4153647A (en) * | 1977-06-15 | 1979-05-08 | Glukhovskoi Vladimir S | Process for producing-impact polystyrene |
| US4163764A (en) * | 1977-06-23 | 1979-08-07 | Phillips Petroleum Company | Coupled block copolymers with improved tack for adhesives |
| DE2920641A1 (en) | 1978-06-07 | 1979-12-20 | Fiber Industries Inc | METHOD FOR REDUCING THE CARBOXYL END GROUP CONCENTRATION OF POLYESTER FIBERS |
| US4248983A (en) * | 1979-02-05 | 1981-02-03 | Arco Polymers, Inc. | Clear impact resistant thermoplastic star-block copolymers |
| US4248981A (en) * | 1979-04-30 | 1981-02-03 | Arco Polymers, Inc. | Clear impact resistant thermoplastic star-block copolymers |
| US4248982A (en) * | 1979-04-30 | 1981-02-03 | Arco Polymers, Inc. | Clear impact resistant thermoplastic star-block copolymers |
| US4248984A (en) * | 1979-05-11 | 1981-02-03 | Arco Polymers, Inc. | Clear impact resistant thermoplastic star-block copolymers |
| US4239859A (en) * | 1979-08-29 | 1980-12-16 | Shell Oil Company | High impact polystyrene blend compositions |
| DE2940861A1 (en) * | 1979-10-09 | 1981-04-23 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING MIXTURES OF LINEAR THREE-BLOCK COPOLYMERS AND MOLDED PARTS THEREOF |
| US4309515A (en) * | 1980-08-05 | 1982-01-05 | Shell Oil Company | Translucent impact polymers |
| JPS5952885B2 (en) * | 1980-11-12 | 1984-12-21 | 旭化成株式会社 | Novel manufacturing method for block copolymer resin |
| JPS60181112A (en) * | 1984-02-28 | 1985-09-14 | Sumitomo Chem Co Ltd | Production of polystyrene |
| US4584346A (en) * | 1984-02-29 | 1986-04-22 | Phillips Petroleum Company | Craze-resistant transparent resinous polymodal block copolymers |
| CA2028410C (en) * | 1990-01-02 | 1996-09-17 | William J. Trepka | Tapered block styrene/butadiene copolymers |
| US5227419A (en) * | 1990-12-20 | 1993-07-13 | Phillips Petroleum Company | Tapered block styrene/butadiene copolymers |
| US5272207A (en) * | 1992-01-31 | 1993-12-21 | Bridgestone Corporation | Process for continuously producing cyclicly tapered SBR-type copolymers |
| DE69530652T2 (en) * | 1994-11-07 | 2004-03-11 | Firestone Polymers, LLC, Akron | Block copolymers interpolymerized with "in-situ" polystyrene |
| AU4162796A (en) * | 1994-11-30 | 1996-06-19 | Chevron Chemical Company | Styrenic polymer resins achieving improved gloss and impact resistance |
| DE4445141A1 (en) * | 1994-12-17 | 1996-06-20 | Basf Ag | Process for the production of impact modified polystyrene molding compounds |
-
1997
- 1997-09-23 US US08/935,773 patent/US6162874A/en not_active Expired - Lifetime
-
1998
- 1998-09-09 EP EP98117207A patent/EP0903359A1/en not_active Withdrawn
- 1998-09-17 CA CA002247670A patent/CA2247670A1/en not_active Abandoned
- 1998-09-18 JP JP10282100A patent/JPH11171948A/en active Pending
-
2000
- 2000-09-29 US US09/676,239 patent/US6362283B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US6362283B1 (en) | 2002-03-26 |
| JPH11171948A (en) | 1999-06-29 |
| US6162874A (en) | 2000-12-19 |
| EP0903359A1 (en) | 1999-03-24 |
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