WO1997047672A1 - Copolymeres sequences et matieres thermoplastiques de moulage les contenant - Google Patents
Copolymeres sequences et matieres thermoplastiques de moulage les contenant Download PDFInfo
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- WO1997047672A1 WO1997047672A1 PCT/EP1997/002818 EP9702818W WO9747672A1 WO 1997047672 A1 WO1997047672 A1 WO 1997047672A1 EP 9702818 W EP9702818 W EP 9702818W WO 9747672 A1 WO9747672 A1 WO 9747672A1
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- Prior art keywords
- block
- monomers
- atoms
- alkyl radical
- block copolymers
- Prior art date
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 title description 6
- 229920001169 thermoplastic Polymers 0.000 title 1
- 239000004416 thermosoftening plastic Substances 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 239000007822 coupling agent Substances 0.000 claims abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 14
- 238000009757 thermoplastic moulding Methods 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims 1
- 229920002959 polymer blend Polymers 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 abstract description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 17
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 11
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 9
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 8
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 8
- 239000003999 initiator Substances 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000005456 glyceride group Chemical group 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000000944 linseed oil Substances 0.000 description 2
- 235000021388 linseed oil Nutrition 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000009419 refurbishment Methods 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- 101100172879 Caenorhabditis elegans sec-5 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N dimethyl-butadiene Natural products CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
Definitions
- Block copolymers and thermoplastic molding compositions containing them Block copolymers and thermoplastic molding compositions containing them
- the present invention relates to block copolymers with blocks A and B of the following general structure
- Ri H or alkyl radical with 1-22 C atoms
- R 2 H or alkyl radical with 1-22 C atoms
- n for an integer in the range from 1 to 5 and m for an integer in the range from 2 to 20
- the invention further relates to mixtures of the block copolymers according to the invention with copolymers of monomers of the formulas I and II and their use.
- Rubber-modified styrene polymers have been known for a long time and are produced industrially on a large scale. They have good toughness and flowability, but have the disadvantage that softening points above 98 ° C. are difficult to achieve. Therefore, attempts have already been made to lower the glass transition temperature by using ⁇ or nucleus-substituted compounds of the
- ⁇ -substituted polystyrenes such as e.g. Depolymerize poly- ⁇ -methylstyrene very easily and core-substituted polystyrenes cause only a slight increase in the softening point and are also very expensive.
- the object of the present invention was therefore to develop a product with increased softening point and low residual monomer content while maintaining the toughness and thermal resistance of impact polystyrene.
- block copolymers with blocks A and B of the general structures (AB) n , ABA, BAB, X [(AB) n ] m , X [(BA) n ] m , X (ABA) m and X (BAB ) m available, where A for a block based on dienes and B for a block of a copolymer of monomers of the general formula I and II, B for a block of polymers of the general formula II, X for the rest of a m-functional coupling tels, n is an integer in the range from 1 to 5 and m is an integer in the range from 2 to 20.
- dienes are suitable as diene components for block A, but those with conjugated double bonds such as butadiene, isoprene, dimethylbutadiene and phenylbutadiene are preferred.
- the molecular weights (weight average values M w ) of block A of the block copolymers according to the invention are generally in the range from 10,000 to 500,000, preferably from 50,000 to 350,000 and in particular from 70,000 to 250,000.
- the copolymer block B is built up from monomers of the formula I and II.
- the monomers of the general formula I are 1, 1-diphenylethylene and its derivatives which are optionally substituted on the aromatic rings by alkyl groups having up to 22 C atoms.
- Preferred alkyl groups as substituents are alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, i- and n-propyl and n-, i- or tert. Butyl, to name a few.
- the unsubstituted 1,1-diphenylethylene is particularly preferably used itself.
- the monomers of the general formula II are styrene and its derivatives substituted in the ⁇ -position or on the aromatic ring with alkyl groups having 1 to 4 carbon atoms.
- Preferred alkyl groups are those mentioned above for monomers of formal I as preferred; unsubstituted styrene itself is particularly preferred.
- the molar ratio of the units derived from monomers I to units derived from monomers II is generally in the range from 1: 1 to 1:25, preferably from 1: 1.05 to 1:15 and particularly preferably in the range of
- the copolymer block B is preferably constructed statistically from in each case one or more monomers of the structural formula I and in each case one or more monomers of the structural formula II.
- a copolymer of styrene and 1,1-diphenylethylene is particularly preferred.
- the statistical structure of the block B with that of the hard matrix is similar, particularly be preferred.
- the molecular weight M w of block B is generally 20,000 to 500,000, but preferably 50,000 to 300,000.
- the symbol "X" means the rest of an m-functional coupling means.
- the coupling center X is formed by the reaction of the living anionic chain ends with an at least bifunctional coupling agent. Examples of such compounds are found in U.S. Patents 3,985,830, 3,280,084, 3,637,554 and 4,091,053.
- the ratio of blocks A and B is generally in the range from 90:10 to 20:80.
- A: B ratios of 90:15 to 65:35 are preferred for producing the so-called cell structure of the disperse phase and from 60:40 to 45:55 for producing a capsule particle morphology.
- the relationships between the morphology of the block rubber and the morphology of the disperse phase in the impact-resistant polystyrene are described in detail (see, for example, A. Echte, Advances in Chem. Ser. 222 (1989, 15)).
- the block copolymers according to the invention can be prepared by customary methods of anionic chemistry, as described, for example, by M. Morton. (M. Morton> Anionic Polymerization: Pnnciples and Practice ⁇ Academic Press, New York 1983).
- Suitable coupling agents are found in US 3,985,830, 3,280,084, 3,637,554 and 4,091,053.
- Epoxidized glycerides such as epoxidized linseed oil or soybean oil may be mentioned here only by way of example; divinylbenzene is also suitable.
- the living anionic end is on the side of the B block, then it is preferably coupled with compounds which contain epoxy and / or ester groups; however, if the A block forms the active end, divinylbenzene is preferably used for the coupling.
- the block transitions can be both sharply separated and "smeared".
- a “smeared” transition means a chain piece of the molecule in which the monomers of block A are randomly distributed with the monomers of block B.
- the desired molecular weight of the blocks is set via the ratio of initiator to monomer.
- the diene blocks can be partially or completely hydrogenated. Methods for this are known and in the literature, e.g. EP 471 415, US 4,656,230 and US 4,629,767.
- thermoplastic molding compositions are made available which contain 1 to 99, preferably 3 to 70 and in particular 4 to 40% by weight of a block copolymer according to the invention and 1 to 99, preferably 30 to 97 and in particular 65 to Containing 96% by weight, based on the polymer content, of copolymers of the monomers of the formulas I and Ha (as described hereinabove), the polymerization of the latter component taking place in the presence of the block copolymers.
- the monomers of the formulas I and II reference is made to the description of block B of the block copolymers according to the invention in order to avoid repetitions.
- copolymers as component A are described in DE-A 44 20 917, to which reference is made here.
- the molar ratio of the units derived from monomers I to units derived from monomers II is generally in the range from 1: 1 to 1:25, preferably from 1: 1.05 to 1:15 and particularly preferably in the range of
- the block copolymers according to the invention are preferably dissolved in a monomer mixture of the structural formulas I and II and, if appropriate, an inert solvent, and this solution is preferably polymerized using organometallic initiators.
- inert solvent is understood to mean a solvent which does not react with the organometallic initiator.
- Suitable solvents are, for example, cyclohexane, methylcyclohexane, benzene, toluene, ethylbenzene or xylene.
- polar, aprotic solvents can be added. Diethyl ether, diisopropyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether or, in particular, tetrahydrofuran are suitable, for example.
- the polar cosolvent is added to the non-polar solvent in a small amount of approx.
- THF is particularly preferred in an amount of 0.1-0.3% by volume.
- the anionic polymerization is initiated using organometallic compounds.
- organometallic compounds Compounds of alkali metals, especially lithium, are preferred.
- initiators are methyl lithium, ethyl lithium, propyllithium, n-butyllithium, sec. Butyllithium and tert. Butyllithium.
- the organometallic compound is added as a solution in a chemically different (inert) hydrocarbon. The dosage depends on the desired molecular weight of the polymer, but is generally in the range from 0.002 to 5 mol%, if it is based on the monomers.
- the polymerization temperature can be between 0 ° and 130 ° C. Temperatures of 50 ° -90 ° C. are preferred. Generally, under isothermal conditions, i.e. polymerized while keeping the polymerization temperature constant.
- Block copolymers can be carried out continuously in one as well as in several process stages. To achieve better rubber utilization, ie to increase the soft phase portion, it is advisable to carry out the polymerization in at least two process stages, the monomer mixture being divided according to the conversion desired in the individual process stages and metered into each stage. A detailed description of a possible method of this type is described in DE 42 35 977. A further possibility of producing the desired impact-resistant products is first to produce the block rubber in a one-pot process and then to complete the polymerization with renewed initiation and further feeding in of the monomer mixture of the structural formulas I and II. The process is described in DE 42 35 978.
- the living chain ends are generally covered with a proton-active substance, e.g. Alcohols or acids such as carbonic acid or formic acid or deactivated with water.
- a proton-active substance e.g. Alcohols or acids such as carbonic acid or formic acid or deactivated with water.
- the solution can then be degassed by customary methods, if appropriate using stripping agents such as water or nitrogen, and - if desired - provided with auxiliary agents such as lubricants, antistatic agents, antioxidants, etc.
- the crosslinking of the rubber in the disperse particles has an influence on the mechanical properties of the polymer. It can be influenced either via the degassing temperature and / or by adding peroxides after the polymerization.
- reaction times are generally in the range from 0.1 to 24, preferably from 0.5 to 12 and in particular from 1 to 10 hours.
- component a) it is also possible to use block copolymers with blocks a x and a 2 of the general structures (a ⁇ -a2) n , al-a2- a l, a2- a l-a2,
- A represents a block of a copolymer of Mo ⁇ nomers of the general formulas I and II
- B for a block of polymers of the general formula II
- X for the remainder of an m-functional coupling agent
- n for an integer in the range from 1 to 5
- m for an integer in the range of 2 to 20 are available.
- the coupling agent X reacts with the living anionic chain ends, as a result of which the structures described above are formed.
- suitable coupling agents can be found in US Pat. Nos. 3,985,830, 3,280,084, 3,637,554 and 4,091,053.
- Epoxidized glycerides such as epoxidized linseed oil or soybean oil may be mentioned here only by way of example; divinylbenzene is also suitable.
- the living anionic end is on the side of the B block, then it is preferably coupled with compounds which contain epoxy and / or ester groups; forms but the A block is the active end, divinylbenzene is preferably used for coupling.
- the block transitions can be sharply separated or "smeared”.
- a “smeared” transition is understood as a chain piece of the molecule in which the monomers of block A are randomly distributed with the monomers of block B.
- the desired molecular weight of the blocks is set via the ratio of initiator to monomer.
- reaction times are generally in the range from 0.1 to 24, preferably from 0.5 to 12 and particularly preferably from 1 to 15-10 hours.
- the thermoplastic molding compositions according to the invention can contain 0 to 3000, preferably 0 to 2000 and particularly preferably 100 to 1000 ppm of monomers of the formula I. These are preferably monomers of the same formula as the monomers incorporated into component A) during the polymerization.
- thermoplastic molding compositions according to the invention can contain 0 to 500, preferably 0 to 200 and in particular 20 to 100 ppm of monomers of the formula II. These are preferably monomers of the same chemical formula as used in the production of component A) were used.
- components C) and D) relate to the weight of component A in the thermoplastic molding compositions.
- thermoplastic molding compositions according to the invention can be 0 to 90, preferably up to 60 and in particular up to
- Preferred polymers are styrene polymers such as impact-resistant or crystal-clear polystyrene or else polyphenylene ether polymers, optionally in a mixture with styrene polymers.
- thermoplastic molding compositions according to the invention can contain up to 50% by weight, based on the total weight of the thermoplastic molding composition, of further additives and processing aids as component F).
- additives are known to the person skilled in the art and are described in the literature, so that detailed information is unnecessary here. Examples include fibrous and particulate fillers, stabilizers against heat and UV light, mold release agents and lubricants. Pigmentation of the molding compositions according to the invention is of course also possible.
- Flame-proof products with a high softening point can be produced particularly advantageously with the molding compositions according to the invention.
- the molding compositions are treated with halogen or / and phosphorus or phosphorus-nitrogen-containing flame retardants by customary processes, e.g. by extrusion or calendering, be intimately mixed.
- Crude DPE (Aldrich or production by reacting phenylmagnesium bromide with acetophenone, acetylation with acetic anhydride and thermal elimination of acetic acid) is passed through a column with at least 50 theoretical plates (rotating belt column; for larger quantities, column with Sulzer packings) distilled to 99.8% purity.
- the mostly pale yellow distillate is filtered through a 20 cm Alox column (Woelm alumma for chromatography, anhydrous), titrated with 1.5 N sec-butyllithium until a strong red color and distilled in vacuo (1 mbar).
- the product thus obtained is completely colorless and can be used directly in the anionic polymerization.
- the cyclohexane (H) used as solvent was dried over anhydrous aluminum oxide and titrated with the adduct of sec-butyllithium and 1,1-diphenylethylene until it turned yellow.
- the butadiene (Bu) was derived from triisobutyl aluminum, the
- DPE 1, 1-D ⁇ phenylethylen
- s-BuLi sec-butyllithium
- S Styrene
- Bu stands for 1,3-butadiene, S for styrene and DPE for 1,1-diphenylethylene. Furthermore, the ratio information relates to the weight.
- Example 1a 2.52 kg of styrene, 1.68 kg of DPE and 7.8 kg of butadiene were polymerized analogously to Example 1a, starting with 150 ml of 1 m BuLi solution. Instead of isopropanol, 5.55 g of ethyl formate in 100 ml of cyclohexane were metered in over the course of 5 minutes and the procedure was then continued as in Example 1a.
- the individual reactors had a volume of 1 and 2 1 (boiler) and 4 1 each (tower reactors).
- the solution of the block copolymer from Example 1 in ethylbenzene was fed continuously to the first stirred kettle at a rate of 0.5 kg / h.
- a 1% n-butyllithium solution was also fed continuously to the reactor at a rate of 40 ml / h.
- the total feed of a mixture of styrene and diphenylethylene in a ratio of 2: 1 was 1.0 kg / h and was divided between the reactors in a ratio of 1: 2: 3: 3.
- the polymerization temperature in the individual reactors was 70 ° C. (Ri), 70 ° C. (R 2 ), 80 ° C. (Tx) and 90 ° C. (T 2 ).
- the conversion after the last tower reactor was 99.8%.
- the polymer stream flowing out of the last reactor was mixed with a 1.5-fold excess of water and CO 2 , based on the initiator.
- the polymer solution was then fed to a degassing device and degassed at 260 ° C. and 10 mbar.
- the block rubber produced according to Example 2 was, as in
- Example 3 described, processed to a molding composition according to the invention.
- the product was acidified with formic acid and stabilized with 1.35 g of Irganox 1076 and Irganox 3052 and 0.5% T ⁇ snonylphenyl phosphite.
- the cyclohexane (CH) was removed in vacuo overnight at 60 ° C.
- the white mass was subsequently dried at 180 ° C. for 2 hours and pressed into test specimens at 250 ° C.
- the electron micrograph showed capsule particles with an average particle diameter of 0.3 ⁇ m.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Inorganic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Priority Applications (1)
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EP97927084A EP0904308A1 (fr) | 1996-06-12 | 1997-05-30 | Copolymeres sequences et matieres thermoplastiques de moulage les contenant |
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DE1996123415 DE19623415A1 (de) | 1996-06-12 | 1996-06-12 | Blockcopolymerisate und diese enthaltende thermoplastische Formmassen |
DE19623415.8 | 1996-06-12 |
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WO1997047672A1 true WO1997047672A1 (fr) | 1997-12-18 |
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EP (1) | EP0904308A1 (fr) |
DE (1) | DE19623415A1 (fr) |
WO (1) | WO1997047672A1 (fr) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998045369A1 (fr) * | 1997-04-04 | 1998-10-15 | Basf Aktiengesellschaft | Matiere de moulage thermoplastique modifiee de maniere a resister aux chocs |
WO1999001487A1 (fr) * | 1997-06-30 | 1999-01-14 | Basf Aktiengesellschaft | Elastomeres thermoplastiques a base de 1,1-diphenylethylene |
WO2001079319A1 (fr) * | 2000-04-17 | 2001-10-25 | Kraton Polymers Research B.V. | Processus de couplage de copolymeres sequences styreniques |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102004011345B4 (de) * | 2004-03-05 | 2005-12-08 | Basf Ag | Verfahren zur Aufarbeitung von anionisch polymerisierten Styrolpolymeren |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0374961A2 (fr) * | 1988-12-23 | 1990-06-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Resine de polymère à fonction de mémoire de forme, composition de résine et produit moulé à fonction de mémoire |
WO1995034586A2 (fr) * | 1994-06-16 | 1995-12-21 | Basf Aktiengesellschaft | Matiere moulable thermoplastique |
-
1996
- 1996-06-12 DE DE1996123415 patent/DE19623415A1/de not_active Withdrawn
-
1997
- 1997-05-30 WO PCT/EP1997/002818 patent/WO1997047672A1/fr not_active Application Discontinuation
- 1997-05-30 EP EP97927084A patent/EP0904308A1/fr not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0374961A2 (fr) * | 1988-12-23 | 1990-06-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Resine de polymère à fonction de mémoire de forme, composition de résine et produit moulé à fonction de mémoire |
WO1995034586A2 (fr) * | 1994-06-16 | 1995-12-21 | Basf Aktiengesellschaft | Matiere moulable thermoplastique |
Non-Patent Citations (2)
Title |
---|
DATENBANK "CHEMICAL ABSTRACTS" (DATEN- ANBIETER: STN); Abs.115:161 018, Colombus,OH, USA; & JP 03 079 613 A (ASAHI CHEM.) 4.April 1991 * |
W. TREPKA: "Synthesis and properties of block polymers of 1,1 diphenylethylene/styrene and butadiene", JOURNAL OF POLYMER SCIENCE, PART B: POLYMER LETTERS, vol. 8, 1970, pages 499 - 503, XP002026769 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998045369A1 (fr) * | 1997-04-04 | 1998-10-15 | Basf Aktiengesellschaft | Matiere de moulage thermoplastique modifiee de maniere a resister aux chocs |
WO1999001487A1 (fr) * | 1997-06-30 | 1999-01-14 | Basf Aktiengesellschaft | Elastomeres thermoplastiques a base de 1,1-diphenylethylene |
WO2001079319A1 (fr) * | 2000-04-17 | 2001-10-25 | Kraton Polymers Research B.V. | Processus de couplage de copolymeres sequences styreniques |
Also Published As
Publication number | Publication date |
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DE19623415A1 (de) | 1997-12-18 |
EP0904308A1 (fr) | 1999-03-31 |
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