EP0000994B1 - Process of preparing plasticized compositions of pvc and butyl rubber - Google Patents
Process of preparing plasticized compositions of pvc and butyl rubber Download PDFInfo
- Publication number
- EP0000994B1 EP0000994B1 EP78300277A EP78300277A EP0000994B1 EP 0000994 B1 EP0000994 B1 EP 0000994B1 EP 78300277 A EP78300277 A EP 78300277A EP 78300277 A EP78300277 A EP 78300277A EP 0000994 B1 EP0000994 B1 EP 0000994B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- pvc
- butyl rubber
- graft copolymer
- ungrafted
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920005549 butyl rubber Polymers 0.000 title claims description 55
- 238000000034 method Methods 0.000 title claims description 16
- 239000000203 mixture Substances 0.000 title claims description 11
- 239000004800 polyvinyl chloride Substances 0.000 claims description 38
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 37
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 26
- 229920000578 graft copolymer Polymers 0.000 claims description 17
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkylaluminium compound Chemical class 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTOSJSSWYMWLIG-UHFFFAOYSA-J C(CCCCCCCCCCC)(=O)[O-].[Ba+2].[Cd+2].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-] Chemical compound C(CCCCCCCCCCC)(=O)[O-].[Ba+2].[Cd+2].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-] RTOSJSSWYMWLIG-UHFFFAOYSA-J 0.000 description 2
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000009975 flexible effect Effects 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
-
- 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
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
- C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Definitions
- the present invention relates to a novel process for the compatibilization of polyvinyl chloride (PVC) and butyl rubber (IIR) to prepare useful plasticized PVC compositions.
- PVC polyvinyl chloride
- IIR butyl rubber
- Butyl rubber, a random copolymer of isobutylene and a small percent isoprene can plasticize PVC, however, it has been difficult to add and maintain a relatively high content of butyl rubber in PVC either by blending or grafting.
- PVC and butyl rubber can be made compatible to some extent by the preparation of a graft product PVC-g-IIR. It is preferably known that polyvinyl chloride, in the presence of certain alkylaluminum compounds, will initiate polymerization of isobutylene (IB) to produce PVC-g-PIB copolymers.
- IB isobutylene
- One such cationic grafting process is disclosed in U.S. Pat. Nos. 3,904,708 and 3,933,942, wherein a halogenated polymer serves as a backbone for the graft of cationically polymerizable monomers such as isobutylene, styrene, isoprene, butadiene and the like.
- a process for preparing a plasticized composition of PVC and butyl rubber which comprises preparing the graft copolymer, PVC-g-IIR from a PVC backbone and a quantity of isobutylene and isoprene in the presence of a catalyst and a swelling agent and characterized by dissolving said graft copolymer, ungrafted butyl rubber and any ungrafted PVC in a solvent; and thereafter crosslinking said graft copolymer and ungrafted butyl rubber for a period of time of up to 60 hours to form a desired product having a butyl rubber content of from 5.0 to 95 per cent by weight.
- the PVC polymer may be suspended in a suitable solvent, a monomeric charge of isobutylene and isoprene is added, the mixture is cooled to approximately -40°C. and a catalytic amount of an alkylaluminum halide solution is added to initiate copolymerization of the isobutylene and isoprene from the PVC backbone.
- the polymerization reaction is terminated after a suitable time following which the graft copolymer and remaining ungrafted PVC and butyl rubber are dissolved in tetrahydrofuran (THF) and treated with S 2 cl 2 and allowed to cure for period of time of from 20 minutes to about 60 hours.
- THF tetrahydrofuran
- the cured product may be readily milled and molded by mixing it with a conventional processing aids and stabilizers. In this process substantially all of the butyl rubber formed is incorporated with the PVC being either grafted therefrom or crosslinked to the graft copolymer.
- the polymerization reaction conditions under which the graft copolymer, PVC-g-IIR may be prepared include polymerization times of from 5 minutes to 120 minutes with 20-90 minutes being preferred and a temperature of from -70°C to 0°C., with -55°C to -40°C. being preferred.
- the number-average molecular weight of the polymer may range from 5,000 to 200,000 with 30,000-130,000 g/mole being preferred.
- the graft butyl rubber branches may be any conventional unsaturated random copolymer of isobutylene and isoprene such as disclosed in U.S. Pat. Nos. 2,727,874 and 3,894,377, with number-average molecular weights of the graft, per branch, ranging from 15,000 to 1,000,000 g/mole.
- weight % it is believed that the amount of polymer backbone and the butyl rubber branches in the product may each range from 5 to 95 in any combination totalling 100.
- the preferred combination is from 25 to 65 percent by weight of butyl rubber in the total product.
- the percent by weight ratio of each to the other in the overall product is the percent by weight ratio of each to the other in the overall product. While in prior art techniques it has not been possible to incorporate unlimited amounts of butyl rubber by grafting, the process of the present invention permits essentially all of the butyl rubber formed to be incorporated with the PVC. Therefore, variations in the amount of butyl rubber, ranging from 5 wt.% to 95 wt.% are possible, and will vary the properties of the resultant graft product from hard plastic-like to soft elastomeric, respectively. Depending upon selected composition, the product may be used for flexible tubing, packaging films, pipes and protective coatings. However, raising the butyl rubber content to 54% provides very similar hardness of the PVC as when it has been plasticized with about 30% dioctyl phthalate.
- the catalyst system used in the present invention comprises a compound of the type AI(M) 2 R, where M is a branched or straight chain alkyl group having from 1 to 12 carbons and R is selected from M, hydrogen or halogen.
- M is a branched or straight chain alkyl group having from 1 to 12 carbons and R is selected from M, hydrogen or halogen.
- the compound i.e., alkylaluminum
- the catalyst works with the polymeric halide as a coinitiator system which will enable the cationic polymerization of the olefins to commence and proceed from the polymeric halide.
- Representative compounds which may be employed are listed in U.S. Pat. No. 3,694,377.
- a particularly useful compound is diethylaluminum chloride, Et 2 AICI.
- suitable solvents such as methylene chloride, ethylene, chloride, 1,2-dichlorobenzene or mixtures thereof may be employed as a swelling agent.
- a commercial PVC sample (FPC 9326 or FPC 9300, Firestone Plastic Co.) was utilized for grafting.
- Isobutylene Union Carbide Corporation
- Isoprene (Matheson, Coleman & Bell Co.)
- diethylaluminum chloride (Ethyl Corp.)
- methylene chloride (Matheson, Coleman Et Bell Co.) were each freshly distilled prior to use. All reactions and manipulations were conducted in a stainless steel safety enclosure under dry nitrogen atmosphere (moisture content less than 50 ppm). All parts are in terms of percent by weight unless otherwise specified.
- the disclosed invention carries out the objects of the invention set forth above.
- crosslinking the ungrafted butyl rubber branches to the graft copolymer prepared not only is a costly step of extraction eliminated but also, there is no waste of butyl rubber.
- much greater amounts of butyl rubber may be incorporated with the PVC than has been heretofore possible by grafting techniques alone.
- properties of the PVC and butyl rubber product can be varied by selection of the resultant molecular weight and percent composition of the product.
Description
- The present invention relates to a novel process for the compatibilization of polyvinyl chloride (PVC) and butyl rubber (IIR) to prepare useful plasticized PVC compositions. In order to impart useful, flexible properties to PVC it is necessary to incorporate a plasticizer. Butyl rubber, a random copolymer of isobutylene and a small percent isoprene can plasticize PVC, however, it has been difficult to add and maintain a relatively high content of butyl rubber in PVC either by blending or grafting.
- PVC and butyl rubber can be made compatible to some extent by the preparation of a graft product PVC-g-IIR. It is preferably known that polyvinyl chloride, in the presence of certain alkylaluminum compounds, will initiate polymerization of isobutylene (IB) to produce PVC-g-PIB copolymers. One such cationic grafting process is disclosed in U.S. Pat. Nos. 3,904,708 and 3,933,942, wherein a halogenated polymer serves as a backbone for the graft of cationically polymerizable monomers such as isobutylene, styrene, isoprene, butadiene and the like.
- Further work with cationic graft polymerization has been reported by J. P. Kennedy and D. L. Davidson, J. Polym. Sci. Chem. Ed. 13, 153 (1976), wherein isobutylene and isoprene were copolymerized in the presence of a PVC backbone and an alkylaluminum halide compound to form PVC-g-IIR copolymers. The product obtained was generally a mixture of PVC-g-IIR and ungrafted PVC and butyl rubber. The highest amount of butyl rubber in the graft product was reported as 39.1 % by weight. The grafting efficiency was 14.6%, indicating a large formation of ungrafted butyl rubber. After the copolymerization of the isobutylene and isoprene the reaction was terminated and the ungrafted butyl rubber was extracted. Tests were subsequently undertaken with solvent cast films of the graft copolymer uncured and cured with sulfur monochloride (S2CI2). The uncured product failed at 160 kg/cm2 while the cured product showed a reduction in stress properties, failing at about 130 kg/cm2.
- Thus, while the preparation of PVC-g-IIR has been described elsewhere, the product used as such has not been readily millable nor moldable, nor strong and homogeneous. In terms of processing, the extra step of extraction of ungrafted butyl rubber had been necessary and the ungrafted butyl rubber had merely become waste. Though the extracted product PVC-g-IIR possesses acceptable properties in films (solvent cast), it is still not readily millable or moldable under commonly utilized PVC processing conditions. Thus, the prior art has yielded a graft product which could not be utilized commercially except in a very limited sense, e.g., solvent cast films.
- It is therefore an object of the present invention to provide a novel process for the compatibilization of PVC and butyl rubber wherein butyl rubber branches are first grafted from a PVC backbone and then the graft copolymer and ungrafted butyl rubber are cured together.
- It is another object of the present invention to provide a novel process for the compatibilization of PVC and butyl rubber wherein a much higher amount of butyl rubber is incorporated with the PVC, as a plasticizer, than has heretofore been possible.
- It is yet another object of the present invention to provide a novel process for the compatibilization of PVC and butyl rubber wherein excess, ungrafted butyl rubber is not extracted from the total graft product thereby eliminating waste
- It is still another object of the present invention to provide a useful composition of PVC and butyl rubber which is strong, homogeneous, millable and moldable upon curing.
- These and other objects of the present invention shall become apparent from the specification and claims which follow.
- In accordance with the invention there is provided a process for preparing a plasticized composition of PVC and butyl rubber, which comprises preparing the graft copolymer, PVC-g-IIR from a PVC backbone and a quantity of isobutylene and isoprene in the presence of a catalyst and a swelling agent and characterized by dissolving said graft copolymer, ungrafted butyl rubber and any ungrafted PVC in a solvent; and thereafter crosslinking said graft copolymer and ungrafted butyl rubber for a period of time of up to 60 hours to form a desired product having a butyl rubber content of from 5.0 to 95 per cent by weight.
- The PVC polymer may be suspended in a suitable solvent, a monomeric charge of isobutylene and isoprene is added, the mixture is cooled to approximately -40°C. and a catalytic amount of an alkylaluminum halide solution is added to initiate copolymerization of the isobutylene and isoprene from the PVC backbone. The polymerization reaction is terminated after a suitable time following which the graft copolymer and remaining ungrafted PVC and butyl rubber are dissolved in tetrahydrofuran (THF) and treated with S2cl2 and allowed to cure for period of time of from 20 minutes to about 60 hours. The cured product may be readily milled and molded by mixing it with a conventional processing aids and stabilizers. In this process substantially all of the butyl rubber formed is incorporated with the PVC being either grafted therefrom or crosslinked to the graft copolymer.
- The polymerization reaction conditions under which the graft copolymer, PVC-g-IIR may be prepared include polymerization times of from 5 minutes to 120 minutes with 20-90 minutes being preferred and a temperature of from -70°C to 0°C., with -55°C to -40°C. being preferred.
- Selection of the polyvinyl chloride polymer is not necessarily critical. The number-average molecular weight of the polymer may range from 5,000 to 200,000 with 30,000-130,000 g/mole being preferred. Similarly, the graft butyl rubber branches may be any conventional unsaturated random copolymer of isobutylene and isoprene such as disclosed in U.S. Pat. Nos. 2,727,874 and 3,894,377, with number-average molecular weights of the graft, per branch, ranging from 15,000 to 1,000,000 g/mole. In terms of weight %, it is believed that the amount of polymer backbone and the butyl rubber branches in the product may each range from 5 to 95 in any combination totalling 100. For plasticized PVC, the preferred combination is from 25 to 65 percent by weight of butyl rubber in the total product.
- Perhaps somewhat more significant than selection of the components comprising the graft branches is the percent by weight ratio of each to the other in the overall product. While in prior art techniques it has not been possible to incorporate unlimited amounts of butyl rubber by grafting, the process of the present invention permits essentially all of the butyl rubber formed to be incorporated with the PVC. Therefore, variations in the amount of butyl rubber, ranging from 5 wt.% to 95 wt.% are possible, and will vary the properties of the resultant graft product from hard plastic-like to soft elastomeric, respectively. Depending upon selected composition, the product may be used for flexible tubing, packaging films, pipes and protective coatings. However, raising the butyl rubber content to 54% provides very similar hardness of the PVC as when it has been plasticized with about 30% dioctyl phthalate.
- The catalyst system used in the present invention comprises a compound of the type AI(M)2R, where M is a branched or straight chain alkyl group having from 1 to 12 carbons and R is selected from M, hydrogen or halogen. Although the compound, i.e., alkylaluminum, is referred to as the catalyst it is to be understood that the compound works with the polymeric halide as a coinitiator system which will enable the cationic polymerization of the olefins to commence and proceed from the polymeric halide. Representative compounds which may be employed are listed in U.S. Pat. No. 3,694,377. A particularly useful compound is diethylaluminum chloride, Et2AICI.
- In order to conduct the grafting efficiently, suitable solvents such as methylene chloride, ethylene, chloride, 1,2-dichlorobenzene or mixtures thereof may be employed as a swelling agent.
- In a typical laboratory synthesis of the graft copolymer, the procedures employed were as follows:
- A commercial PVC sample (FPC 9326 or FPC 9300, Firestone Plastic Co.) was utilized for grafting. Isobutylene (Union Carbide Corporation) was dried by passage over molecular sieves and barium oxide. Isoprene (Matheson, Coleman & Bell Co.), diethylaluminum chloride (Ethyl Corp.) and methylene chloride (Matheson, Coleman Et Bell Co.) were each freshly distilled prior to use. All reactions and manipulations were conducted in a stainless steel safety enclosure under dry nitrogen atmosphere (moisture content less than 50 ppm). All parts are in terms of percent by weight unless otherwise specified.
- 300 Mis. isobutylene and 40 mls. isoprene were charged to a suspension comprising 90.0 gms. of PVC in 100 mls. methylene chloride at -40°C., to which was added 20 mls. of diethylaluminum chloride solution (1.5 M in n-hexane) twice at intervals of 20 minutes with continuous stirring. The reaction was terminated with methanol after 60 minutes and the product which was subsequently precipitated in excess methanol and dried, weighed 110.2 gms indicating a content of 18.3% butyl rubber. The conversion, based upon the amount of isobutylene, was 8.5%. The product from this stage of the process should be understood to consist of the graft copolymer as well as any ungrafted butyl rubber and PVC.
- Six solutions were prepared for curing containing 5% wt./vol. of the product in THF. To this solution was added S2Cl2 to give a 1% vol./vol. solution of the latter in THF. The subsequent cross-linking reaction was allowed to proceed for various time periods ranging from about 20 minutes to 60 hours. The reaction was terminated with methanol and the product thereof was subsequently dried. Next, equal parts (1 part per 100 parts of the product) of calcium stearate, as a processing aid, and barium- cadmium laurate, as a stabilizer were added to the product. Although calcium stearate and barium- cadmium laurate were employed, it is to be understood that any conventional processing aid and stabilizer for PVC may be selected.
- While the uncured product could not be milled, was very sticky and became nonhomogeneous, as cure time increased, the product became less sticky and stronger. Compression molding of the cured product routinely carried out at 148-163°C. for 3-10 minutes was also quite feasible but not for the uncured product. Generally, an increase in the tensile strength of the product was observed to be directly related to an increase in the cure time as indicated in Table I for a graft product containing 18.3% butyl rubber. Although reduction in the cure time is possible without much sacrifice in tensile strength by employing peroxides with the S2C12, it has been found that the best results were obtained by allowing the product to cure slowly.
- In Table II, six graft products are presented wherein the weight percent of butyl rubber in the products ranges from 15-65%. Tensile strengths, ultimate elongation and hardness properties have been determined and are included. The curing was carried out as explained hereinabove, i.e., utilizing a 5% wtjvol. of the product in THF to which S2Cl2 is added to give a 1 % vol./vol. solution of the latter in THF.
- Thus, it can be seen that the disclosed invention carries out the objects of the invention set forth above. By crosslinking the ungrafted butyl rubber branches to the graft copolymer prepared not only is a costly step of extraction eliminated but also, there is no waste of butyl rubber. Furthermore, much greater amounts of butyl rubber may be incorporated with the PVC than has been heretofore possible by grafting techniques alone. As will be apparent to those skilled in the art, properties of the PVC and butyl rubber product can be varied by selection of the resultant molecular weight and percent composition of the product.
Claims (6)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US82575877A | 1977-08-18 | 1977-08-18 | |
US825758 | 1977-08-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000994A1 EP0000994A1 (en) | 1979-03-07 |
EP0000994B1 true EP0000994B1 (en) | 1981-10-21 |
Family
ID=25244859
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78300277A Expired EP0000994B1 (en) | 1977-08-18 | 1978-08-11 | Process of preparing plasticized compositions of pvc and butyl rubber |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0000994B1 (en) |
JP (1) | JPS5456649A (en) |
CA (1) | CA1114983A (en) |
DE (1) | DE2861196D1 (en) |
IT (1) | IT1098282B (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57179214A (en) * | 1981-04-28 | 1982-11-04 | Kanegafuchi Chem Ind Co Ltd | Modified polyvinyl chloride resin composition |
-
1978
- 1978-08-11 EP EP78300277A patent/EP0000994B1/en not_active Expired
- 1978-08-11 DE DE7878300277T patent/DE2861196D1/en not_active Expired
- 1978-08-17 IT IT26803/78A patent/IT1098282B/en active
- 1978-08-17 CA CA309,546A patent/CA1114983A/en not_active Expired
- 1978-08-18 JP JP10081078A patent/JPS5456649A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
IT1098282B (en) | 1985-09-07 |
JPS5456649A (en) | 1979-05-07 |
DE2861196D1 (en) | 1981-12-24 |
IT7826803A0 (en) | 1978-08-17 |
EP0000994A1 (en) | 1979-03-07 |
CA1114983A (en) | 1981-12-22 |
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