CN1262572C - 耐候嵌段共聚碳酸酯及含有它的共混物 - Google Patents
耐候嵌段共聚碳酸酯及含有它的共混物 Download PDFInfo
- Publication number
- CN1262572C CN1262572C CNB998152420A CN99815242A CN1262572C CN 1262572 C CN1262572 C CN 1262572C CN B998152420 A CNB998152420 A CN B998152420A CN 99815242 A CN99815242 A CN 99815242A CN 1262572 C CN1262572 C CN 1262572C
- Authority
- CN
- China
- Prior art keywords
- ester
- block
- block copolycarbonate
- blocks
- blend
- 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 - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 239000004417 polycarbonate Substances 0.000 claims abstract description 44
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 43
- -1 poly(alkylene carboxylates Chemical class 0.000 claims abstract description 41
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000728 polyester Polymers 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000000962 organic group Chemical group 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- XNXAGSAHKIBHBB-UHFFFAOYSA-N benzene-1,3-diol;terephthalic acid Chemical compound OC1=CC=CC(O)=C1.OC(=O)C1=CC=C(C(O)=O)C=C1 XNXAGSAHKIBHBB-UHFFFAOYSA-N 0.000 claims description 2
- 230000002051 biphasic effect Effects 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229930188104 Alkylresorcinol Natural products 0.000 claims 1
- 229940106691 bisphenol a Drugs 0.000 claims 1
- 125000005587 carbonate group Chemical group 0.000 claims 1
- 150000005677 organic carbonates Chemical class 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000704 physical effect Effects 0.000 abstract description 3
- 229920001230 polyarylate Polymers 0.000 abstract 1
- 229920001601 polyetherimide Polymers 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005494 tarnishing Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 206010023126 Jaundice Diseases 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 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
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- SRONXYPFSAKOGH-UHFFFAOYSA-N cyclopentadecane Chemical compound C1CCCCCCCCCCCCCC1 SRONXYPFSAKOGH-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/18—Block or graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08L69/005—Polyester-carbonates
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/126—Copolymers block
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
- F02B61/00—Adaptations of engines for driving vehicles or for driving propellers; Combinations of engines with gearing
- F02B61/04—Adaptations of engines for driving vehicles or for driving propellers; Combinations of engines with gearing for driving propellers
- F02B61/045—Adaptations of engines for driving vehicles or for driving propellers; Combinations of engines with gearing for driving propellers for outboard marine engines
Abstract
制备嵌段共聚碳酸酯的方法可以通过下述步骤进行：首先，使间苯二酚或者烷基或卤化间苯二酚和至少一种芳族二羧酸酰氯进行反应，优选所述酰氯为间苯二甲酰氯、对苯二甲酰氯或其混合物，来制备羟端基的聚酯中间体；然后，使该中间体与二羟基芳族化合物优选双酚A以及碳酰卤优选光气进行反应。所得产物具有优良物理性能，包括具有高度耐候性。它们可以与诸如聚碳酸酯和聚羧酸亚烷基二醇酯等其它聚合物共混，从而改善其耐候性。
Description
发明背景
本发明涉及物质的树脂组合物，更具体地说，涉及具有改善的耐候性的嵌段共聚碳酸酯。
聚碳酸酯和聚酯，特别是聚二羧酯亚烷基二醇酯，以及其共混物是一类广泛应用的聚合物，其部分原因在于它们具有优良的物理性能，包括具有高的冲击强度。但是，存在着长期色泽不稳定的问题。这会引起泛黄，有损于聚合物的透明性和吸引力。失去光泽也是一种不希望发生的长期现象。
聚碳酸酯和聚酯的泛黄主要由紫外辐射作用引起，这就是往往将这种泛黄称作“光致发黄”的原因。现已使用和提出抑制光致发黄的许多手段。这些手段之中，有许多都涉及在聚碳酸酯中混入紫外吸收化合物(UVA)。在大多数情况下，UVA是低分子量化合物，必须以较低用量来使用，一般说最高为1wt％，以避免聚合物物理性能降低，例如冲击强度和高温性能，后者反映为热畸变温度。
现已将其它聚合物与聚碳酸酯和/或聚酯进行共混，以便改善它们的耐紫外辐射降解性能和抗失去光泽性，下文往往将这些性能统称为“耐候性”。这类共混物的例子是聚碳酸酯和包含间/对苯二甲酸间苯二酚酯单元的共聚酯的耐天候共混物，任选与衍生自脂族或脂环族二羟基化合物或二羧酸的“软嵌段”酯单元相组合。然而，这些共混物是不相溶混的，所以其应用仅限于不要求透明性的情况下。另外，有价值的是制造种种耐天候的和改善耐候性的聚合物。
日本专利公开56/133,332叙述了一种“高交替取向”的共聚碳酸酯。它是由两步法制备的，第一步是制备聚合度为1～2的羟端基的聚酯低聚物，第二步是用碳酰卤如光气处理所述低聚物，制备聚酯和聚碳酸酯键基本交替的最终产物，即，碳酸酯嵌段的聚合度大约也为1～2。据说，这种共聚碳酸酯具有优良的耐热性、耐溶剂性和可模塑性。但未详细提供其耐候性情况。
发明概述
本发明以新发现的具有优良的耐候性的一类嵌段共聚碳酸酯为基础。所述共聚碳酸酯和其它聚合物的共混物，特别是聚碳酸酯和聚酯，具有抗失去光泽性和优良的物理性能。
因此，本发明的一方面是一类嵌段共聚碳酸酯，其包含与芳基化物嵌段交替的有机聚碳酸酯嵌段，所述芳基化物嵌段包含衍生自1，3-二羟基苯和至少一种芳族二羧酸的芳基化物结构单元，且聚合度至少为约4。
本发明的另一方面是，如上所述的嵌段共聚碳酸酯经Fries重排而获得的嵌段共聚物。
再一个方面是包含下述树脂共混物以及所述共混物的任何反应产物的组合物，所述共混物是如上所述嵌段共聚碳酸酯和至少一种选自聚碳酸酯、聚二羧酸亚烷基二醇酯和加聚物的其它聚合物的共混物。
还有一个方面是一种制备嵌段共聚碳酸酯的方法，包括：
(A)在碱性条件下使1，3-二羟基苯和至少一种芳族二羧酸酰氯进行反应，制备聚合度至少为4的羟端基的聚酯中间体，和
(B)使所述聚酯中间体和至少一种有机二羟基化合物和碳酰卤进行反应。
发明详述及优选实施方案
本发明的嵌段共聚碳酸酯包含交替的碳酸酯和芳基化物嵌段。它们包含含有通式为下述的部分的聚合物，
式中，R1是氢、卤素或C1-4烷基，每个R2独立地，为二价有机基团，m至少为约10，n至少为约4。芳基化物嵌段因此含1，3-二羟基苯部分，后者可以被卤素取代，通常被氯或溴取代，或者被甲基、乙基、丙基或丁基的C1-4烷基取代。所述烷基基团优选为伯或仲基团，更优选为甲基，其最经常的位置是在两个氧原子的邻位，但是也可以考虑位于其它位置。最优选的部分是间苯二酚部分，其中R1是氢。
所述1，3-二羟基苯部分键合到芳族二羧酸部分上，其可以是诸如间苯二甲酸酯或对苯二甲酸酯之类的单环部分，或者诸如萘二羧酸酯之类的多环部分。优选芳族二羧酸部分是间苯二甲酸酯和/或对苯二甲酸酯。可以存在所述部分的任何一种或者两者。对于大多数情况来说，两者均存在，间苯二甲酸酯和对苯二甲酸酯的摩尔比，范围为约0.25～4.0∶1，优选为约0.8～2.5∶1。
在碳酸酯嵌段中，每个R2独立地是有机基团。对于大多数情况来说，在聚合物中R2基团总数的至少约60％是芳族有机基团，其余的是脂族、脂环族或芳族自由基。适宜的R2基团包括间亚苯基、对亚苯基、亚4，4’-联苯基、亚4，4’-双(3，5-二甲基)联苯基、2，2-双(4-亚苯基)丙烷和相似的基团，后者例如相当于二羟基取代的芳烃者，正如在美国专利4,217,438中以名称或通式(一般的或具体的)所公开的，在此引入作为参考。
更优选，各个R2是芳族有机基团，还更优选通式为
(II)--A1--Y--A2--，的基团，式中A1和A2分别是单环二价芳基，Y是桥接基团，其中以一个或两个碳原子隔开A1和A2。通式II中的自由价键相对于Y而言通常在A1和A2的间位或对位。具有通式II的R2的化合物是双酚，为简便起见，在本文中往往使用术语“双酚”称呼二羟基取代的芳烃；然而，应当理解这种类型的非双酚化合物如果适当的话也可以使用。
在通式II中，A1和A2一般代表非取代的亚苯基或者其取代的衍生物，作为举例说明的取代基(一个或多个)是烷基、链烯基和卤素(特别是溴)。优选非取代的亚苯基。优选A1和A2两者是亚对苯基，虽然两者都可以是亚邻或亚间苯基，或者一者是亚邻或亚间苯基，而另一者是亚对苯基。
桥接基团Y是其中包含一个或两个原子隔开A1和A2者。优选实施方案是其中包含一个原子隔开A1和A2者。这种类型的说明的基团是-O-、-S-、-SO-、-SO2-、亚甲基、环己基-亚甲基、2-[2.2.1]-二环庚基亚甲基、亚乙基、亚异丙基、亚新戊基、亚环己基、亚环十五烷基、亚环十二烷基、亚金刚烷基以及具有以下通式的2，2，2′，2′-四氢-3，3，3′，3′-四甲基-1，1′螺二[1H-茚]6，6′-二醇；
芳基化物嵌段的聚合度(DP)，以n代表，至少为约4，优选至少为约5，还优选至少为约10，更优选至少为约20，最优选为约30～150。碳酸酯嵌段的DP，以m代表，一般至少约10，优选至少约20，最优选为约50～200。
嵌段分布应能够提供芳基化物嵌段与碳酸酯嵌段的重量比为任何所需重量比的共聚物。一般说，优选含有约10～90wt％芳基化物嵌段的共聚物。
在本发明的制备嵌段共聚碳酸酯方法的A步骤中，可以在碱性含水反应条件下使1，3-二羟基苯与至少一种芳族二羧酸酰氯相接触，前者可以是间苯二酚(优选)或者烷基或卤代间苯二酚，优选后者为间苯二甲酰氯、对苯二甲酰氯或它们的混合物。碱性条件一般通过加入碱金属氢氧化物来提供，通常采用氢氧化钠。通常还存在催化剂，大多数情况下用四烷基铵、四烷基鏻或卤化六烷基胍鎓；作为有机溶剂，一般采用水不溶混的溶剂，优选氯化脂肪族化合物如二氯甲烷。因此，一般情况下该反应在两相系统中进行，包括水相和水不溶混的有机溶剂相。
为了制造羟端基的聚酯中间体，优选间苯二酚与酰氯的摩尔比为1∶1以上，例如约1.01～1.90∶1。所存在碱与酰卤的摩尔比可以为约2～2.5∶1。催化剂的通常用量为约0.1～10mol％，以所混合的酰卤为基准计。反应温度常常为约25～50℃。
在聚酯中间体制备完成之后，在进行相分离之前，采用弱酸将两相体系的水相酸化有时是有利的。然后，使含有聚酯中间体的有机相经历形成嵌段共聚碳酸酯的反应-B步。然而，也可以考虑不经酸化或分离而进行B步，这样做常常能够无损于收率或纯度。
采用溶于有机液体的碱，完全在所述液体中制备聚酯中间体也属于本发明的范围。适于该应用的碱包括叔胺，如三乙胺。
在第二步中所使用的二羟基芳族化合物的通式通常为HO-R2-OH，其中R2如上文所限定。一般优选双酚A。优选碳酰卤为光气。该反应可以按本领域认可的界面法进行(即，也在两相体系中，包括水相和水不溶混的有机溶剂相)，使用适宜的界面聚合催化剂和碱性试剂，也优选氢氧化钠，并且任选使用支化剂如1，1，1-三(4-羟苯基)乙烷和/或链终止剂如苯酚或对枯基苯酚。为了抑制嵌段共聚物的混乱，对于光气化反应的起始阶段，保持pH为较低数值，一般为约5～9；而在所述反应的后期，则可以升高至约10～13。
在两个反应完成之后，可以采用惯用方法分离出嵌段共聚碳酸酯。所述方法可以包括，例如，反溶剂沉淀、干燥和挤压造粒。也可以考虑采用其它成酯方法进行第一步，例如，通过使用芳族二酯和1，3-二羟基苯在溶剂中或以熔体进行酯交换的方法。
本发明的嵌段共聚碳酸酯是具有优良物理性能的聚合物。其透光性与聚碳酸酯相似。因此，其是基本透明的，在要求改善耐候性时，可以作为制造透明片材的聚碳酸酯的代用品使用。
应当相信，本发明的嵌段共聚碳酸酯的耐候性和其它有益的性能，至少部分归因于发生了其中的芳基化物嵌段的热或光化学引导的Fries重排，从而生成了作为光稳定剂使用的二苯甲酮部分。例如，通式I部分能够重排生成下列通式部分，
式中，R1、R2、m和n如上文所限定。也可以考虑经合成和聚合引入通式III部分。
该嵌段共聚碳酸酯也可以用作其它聚合物的改善耐候性的添加剂，尤其是聚碳酸酯、聚酯和加聚物。本发明的共混组合物中的聚碳酸酯，在分子结构上大多相似于如上文所述的嵌段共聚碳酸酯的碳酸酯嵌段，一般优选双酚A均聚和共聚碳酸酯。聚酯常常为聚二羧酸亚烷基二醇酯，特别是聚芳烃二酸亚烷基二醇酯，优选聚对苯二甲酸乙二醇酯和聚对苯二甲酸1，4-丁二醇酯。加聚物包括均聚物和共聚物，特别是诸如苯乙烯等的链烯基芳族化合物与下述物质的共聚物，所述物质包括烯属不饱和腈如丙烯腈和甲基丙烯腈、二烯如丁二烯和异戊二烯、以及丙烯酸系单体如丙烯酸乙酯。这些包括ABS(丙烯腈-丁二烯-苯乙烯)和ASA(丙烯腈-苯乙烯-丙烯酸烷基酯)接技共聚物。
本发明的共混组合物可以通过诸如溶剂共混和经诸如挤出的熔体共混等惯用操作来制备。它们还可以含有本领域认可的添加剂，包括颜料、染料、冲击改善剂、稳定剂、助流剂和脱模剂。预计，共混组合物包括简单物理共混物及其任何反应产物，例如聚酯-聚碳酸酯酯交换产物。
在该共混物中嵌段共聚碳酸酯的比例主要由有效改善耐候性的芳基化物嵌段的最终比例来决定，一般比例为在共混物中提供约10～50wt％芳基化物嵌段。鉴于本发明的嵌段共聚碳酸酯和其中可以混入的聚碳酸酯和聚酯之间存在着某种程度的不溶混性，所述共混物常常是不透明的。然而，通过调节嵌段共聚碳酸酯中芳基化物嵌段的长度，可以制造透明的共混物。所述共混物的其它性能是优良的。
本发明的嵌段共聚碳酸酯及其共混物可以用于各种用途，特别是涉及户外应用和贮藏的、因此需要耐天候性的那些应用。所述用途包括汽车车体面板和装饰件，户外交通工具和设备如割草机、园艺用手扶拖拉机和户外工具，照明装置，以及电气和电讯系统外壳。
以如下实施例举例说明本发明。所有百分数和比例均以重量计，除非另有说明。分子量采用凝胶渗透色谱在氯仿中进行测定，以聚苯乙烯为标样，记作重均分子量(Mw)或数均分子量(Mn)。
实施例1～10
向若干装有机械搅拌器、氮气入口、回流冷凝器和两个均压加料漏斗的1升四颈烧瓶中，加入5mmol溴化四正丁基铵(TBAB)或氯化甲基三正丁基铵(MTBAC)、不同量的间苯二酚和150ml脱气二氯甲烷。然后用氮气吹扫烧瓶，在所述各加料漏斗中分别装入212mmol的15％氢氧化钠水溶液(保持在20℃下并用氮气吹扫)，以及溶解在100ml二氯甲烷中的间苯二甲酰氯和对苯二甲酰氯的各种脱气混合物。
将氢氧化钠溶液加入到氮气氛围下的烧瓶中，同时搅拌，随后间苯二酚溶解，形成半透明的两相混合物。然后加入间苯二甲酰氯/对苯二甲酰氯混合物，继续搅拌，随后放热导致弱回流。在35℃下继续搅拌1hr。然后用亚磷酸酸化所得混合物至pH为3，对两相进行分离，测定所得聚酯中间体的分子量。
将聚酯中间体溶液加入到光气化反应器中，所述反应器装有搅拌器、回流冷凝器、光气入口和控制pH值的氢氧化钠输入系统。加入不同比例双酚A、2mol％对枯基苯酚(以双酚A为基准计)，以及以每100mmol双酚A计，0.1ml三乙胺和0.5ml水。将120mmol光气，以每100mmol双酚A计，通入所得混合物中，历时22min；加入30％氢氧化钠水溶液控制pH值为8～9直至剩下最后5分钟，随后将pH升高至10.5～11。
所得混合物经稀盐酸酸化，分离出有机相，并用水洗涤。通过倾入甲醇中沉淀出所需的嵌段共聚碳酸酯，并在60℃下干燥过夜。
各个实施例的结果列于表1中。实施例6～9为反应规模较大者(每批2.2kg)。
表1
| 实施例 | 催化剂 | 间苯二甲酰氯/对苯二甲酰氯的摩尔比 | 聚酯中间体Mw | 聚酯中间体Mn | 间苯二酚，过量mol％ | 产物，聚酯嵌段％ | 产物Mw |
| 1 | TBAB | 50/50 | 19,200 | 9,500 | 5 | 35 | 73,000 |
| 2 | TBAB | 50/50 | 16,900 | 8,300 | 5 | 35 | 95,000 |
| 3 | MTBAC | 50/50 | 17,000 | 8,600 | 5 | 50 | 99,000 |
| 4 | TBAB | 50/50 | 12,500 | 6,200 | 10 | 50 | 75,200 |
| 5 | TBAB | 70/30 | 32,300 | 16,100 | 3 | 50 | 86,500 |
| 6 | MTBAC | 50/50 | 17,200 | 8,900 | 5 | 50 | 90,700 |
| 7 | MTBAC | 50/50 | 32,400 | 16,500 | 3 | 50 | 81,200 |
| 8 | MTBAC | 50/50 | 14,500 | 7,200 | 5 | 80 | 78,100 |
| 9 | MTBAC | 50/50 | 24,300 | 12,100 | 5 | 20 | 75,100 |
| 10 | MTBAC | 50/50 | 53,500 | 28,100 | 3 | 20 | 67,300 |
实施例11
将实施例6的产物样品(2g)和几种下文所述的其它材料溶解在二氯甲烷或氯仿(8ml)中，用刮板在玻璃板上涂布约250μm厚的薄膜。使溶剂蒸发，留下约40μm厚的薄膜，并用水使薄膜自玻璃板上浮起。采用Gardner XL-835雾度计测定所得薄膜的雾度值。
所得结果示于表II。评价了如下其它材料；市售双酚A聚碳酸酯(PC)，间苯二甲酸酯与对苯二甲酸酯基团之比为1∶1的、分子量约50,000的间苯二酚聚芳基化合物(RPA)，PC与实施例6的产物的共混物，以及两种PC-RPA共混物。
表11
| 薄膜材料 | 雾度％ |
| 实施例6 | 0.8 |
| PC | 0.8 |
| RPA | 0.8 |
| PC/实施例6，1.5∶1 | 12.7 |
| PC/RPA，4∶1 | 69.0 |
| PC/RPA，1∶1 | 38.5 |
这些结果说明，与不含碳酸酯嵌段的聚芳基化合物相比，实施例6的嵌段共聚碳酸酯与聚碳酸酯的共混物的相溶混性有所改善。
实施例12～16
向装有回流冷凝器、机械搅拌器和均压加料漏斗的1升三颈烧瓶中加入不同量间苯二酚和三乙胺以及100ml二氯甲烷。所述烧瓶用氮气保护，经4～8min滴加各10.151g(50mmol)的间苯二甲酰氯和对苯二甲酰氯在150ml二氯甲烷中的溶液，如此保持平稳回流。在回流温度下再搅拌该混合物30min，然后将其转移到分液漏斗中，用水洗涤一次，用稀盐酸洗涤二次，再用水洗涤一次。
将低聚物溶液移至与实施例1～10相似的光气化反应器中。在加入双酚A、三乙胺(以双酚A为基准计，为1mol％)、水和作为链终止剂的对枯基苯酚之后，如所述实施例叙述的那样，进行光气化反应。
所得结果和产物参数列于表III。所有共聚物均含有50％聚芳基化合物单元。
表III
| 实施例 | 间苯二酚g | 三乙胺ml | 双酚Ag | 用于光气化作用的CH2l2ml | 用于光气化作用的水ml | 聚酯中间体Mw | 聚酯中间体Mn | 产物Mw |
| 12 | 13.76 | 36 | 22 | 250 | 50 | 10,500 | 3,500 | 77,200 |
| 13 | 12.23 | 32 | 21.7 | 250 | 50 | 20,000 | 6,300 | 85,500 |
| 14 | 11.59 | 32 | 21.5 | 250 | 50 | 28,500 | 10,700 | 86,300 |
| 15 | 11.236 | 31 | 21.2 | 250 | 50 | 43,700 | 13,500 | 90,500 |
| 16 | 22.02 | 58 | 31 | 300 | 55 | 3,550 | 1,440 | 32,700 |
实施例17
将实施例12～16的各个嵌段共聚碳酸酯与市售双酚A聚碳酸酯进行溶液共混，采用实施例11的方法自这些溶液浇铸薄膜。进行雾度测定，所得结果示于表IV。
表IV
| 共聚物实施例 | 共聚物g | PC，g | 雾度％ |
| 12 | 0.4 | 1.6 | 4.32 |
| 12 | 0.8 | 1.2 | 5.54 |
| 12 | 1.0 | 1.0 | 22.6 |
| 12 | 1.5 | 0.5 | 14.6 |
| 12 | 2.0 | 0.0 | 0.33 |
| 13 | 2.0 | 0.0 | 0.27 |
| 14 | 2.0 | 0.0 | 0.29 |
| 15 | 2.0 | 0.0 | 0.22 |
| 16 | 0.4 | 1.6 | 0.58 |
| 16 | 0.8 | 1.2 | 1.09 |
| 16 | 1.0 | 1.0 | 1.27 |
| 16 | 1.5 | 0.5 | 2.75 |
| 16 | 2.0 | 0.0 | 0.39 |
显而易见，纯共聚物，以及采用实施例16的共聚碳酸酯的某些共混物均给出基本透明的无雾薄膜。
实施例18
通过干混、随后挤出制备PC与各种比例的RPA或实施例6的产物、以及与各种着色剂(二氧化钛为2％，碳黑为0.6％，黑色染料为0.47％)的共混物，将共混物注塑成试验样品。使所得样品经加速耐气候试验，所用仪器为Atlas Ci35a氙弧光天候老化仪，其装有硅硼酸盐内过滤器和外过滤器，辐照度为0.77w/m2(在340nm下)，所用操作周期为160min光照，5min黑暗，以及15min黑暗并喷水。在总计曝光量达935KJ/m2之后的光泽保留(60°角)比示于表V中。
表V
| 聚合物 | 着色剂 | 光泽保留性％ |
| PC | 二氧化钛 | 17 |
| PC/RPA 10％ | 二氧化钛 | 14 |
| PC/RPA 20％ | 二氧化钛 | 30 |
| PC/实施例610％ | 二氧化钛 | 36 |
| PC/实施例620％ | 二氧化钛 | 37 |
| PC | 碳黑 | 11 |
| PC/RPA 10％ | 碳黑 | 22 |
| PC/RPA 20％ | 碳黑 | 58 |
| PC/Ex.610％ | 碳黑 | 40 |
| PC/Ex.620％ | 碳黑 | 69 |
| PC | 黑色染料 | 70 |
| PC/RPA 10％ | 黑色染料 | 55 |
| PC/RPA 20％ | 黑色染料 | 77 |
| PC/实施例610％ | 黑色染料 | 70 |
| PC/实施例620％ | 黑色染料 | 87 |
所述结果说明，与简单的聚芳基化合物和纯聚碳酸酯相比，本发明嵌段共聚碳酸酯所提供的耐候性有改善。
实施例19
经干混、挤出制备PC、30％市售聚对苯二甲酸1，4-丁二醇酯(PBT)和0.47％实施例18的黑色染料的共混物，再经注塑制得试样，采用实施例18的设备对共混物试样单独地和与RPA和实施例6产物组合进行评价。对各个样品测定使光泽损失50％所需要的曝光量(在340nm下)单位为KJ/m2，所得结果示于表VI中。
表VI
| PC，％ | RPA，％ | 实施例6，％ | 曝光量kJ/m2 |
| 70 | - | - | 420 |
| 50 | 20 | - | 864 |
| 30 | - | 40 | 1,400 |
再次显而易见，本发明的嵌段共聚碳酸酯的存在显著改善了共混物的耐候性。
Claims (32)
1.一种嵌段共聚碳酸酯，其包含与芳基化物嵌段交替的有机碳酸酯嵌段，所述芳基化物嵌段包含衍生自1，3-二羟基苯和至少一种芳族二羧酸的芳基化物结构单元，且聚合度至少为4。
2.按照权利要求1的嵌段共聚碳酸酯，其中碳酸酯嵌段由双酚A碳酸酯单元组成。
3.按照权利要求1的嵌段共聚碳酸酯，其中碳酸酯嵌段的聚合度为至少10。
4.按照权利要求1的嵌段共聚碳酸酯，其中芳基化物嵌段是间苯二甲酸间苯二酚酯或对苯二甲酸间苯二酚酯嵌段，或者其混合物。
5.按照权利要求4的嵌段共聚碳酸酯，其中芳基化物嵌段衍生自间苯二甲酸和对苯二甲酸的混合物。
6.按照权利要求5的嵌段共聚碳酸酯，其中在芳基化物嵌段中的间苯二甲酸酯与对苯二甲酸酯的摩尔比为0.25～4.0∶1。
7.按照权利要求5的嵌段共聚碳酸酯，其中芳基化物嵌段的聚合度为至少10。
8.权利要求5的嵌段共聚碳酸酯，其包含10～90wt％芳基化物嵌段。
9.一种嵌段共聚碳酸酯，包含通式如下的部分：
式中R1是氢、卤素或C1-4烷基；各个R2独立地为二价有机基团；m为至少10，n为至少4。
10.按照权利要求9的嵌段共聚碳酸酯，其中，R1是氢，R2是亚对苯基亚异丙基，n为至少10，m为至少20，所述的共聚碳酸酯由摩尔比为0.8～2.5∶1的间苯二甲酸酯和对苯二甲酸酯嵌段组成。
11.按照权利要求1的嵌段共聚碳酸酯经Fries重排制得的嵌段共聚物。
12.按照权利要求11的嵌段共聚物，包含通式如下的部分：
式中R1是氢、卤素或C1-4烷基；各个R2独立地为二价有机基团；m为至少10，n为至少5。
13.按照权利要求12的嵌段共聚物，其中R1是氢，R2是亚对苯基亚异丙基，n为至少10，m为至少20，所述的共聚碳酸酯由摩尔比为0.8～2.5∶1的间苯二甲酸酯和对苯二甲酸酯嵌段组成。
14.一种组合物，包含按照权利要求1的嵌段共聚碳酸酯与至少一种其它聚合物的树脂共混物，所述其它聚合物选自聚碳酸酯、聚二羧酸亚烷基二醇酯和加聚物，以及包含其任何反应产物。
15.按照权利要求14的共混物，其中其它聚合物是聚碳酸酯。
16.按照权利要求15的共混物，其中其它聚合物是双酚A聚碳酸酯。
17.按照权利要求14的共混物，其中其它聚合物是聚二羧酸亚烷基二醇酯。
18.按照权利要求17的共混物，其中其它聚合物是聚对苯二甲酸1，4-丁二醇酯。
19.按照权利要求17的共混物，其中其它聚合物是聚对苯二甲酸乙二醇酯。
20.一种自权利要求14的组合物制造的制品。
21.按照权利要求20的制品，包括用于电气和电讯系统的外壳。
22.一种制备嵌段共聚碳酸酯的方法，包括：
(A)在碱性条件下使1，3-二羟基苯和至少一种芳族二羧酸酰氯进行反应，制备聚合度至少为4的羟端基的聚酯中间体，和
(B)使所述聚酯中间体和至少一种有机二羟基化合物和碳酰卤进行反应。
23.按照权利要求22的方法，其中在A步中间苯二酚或烷基间苯二酚与酰氯的摩尔比为1.01～1.90∶1。
24.按照权利要求22的方法，其中在A步中的1，3-二羟基苯是间苯二酚，二羧酸酰氯是间苯二甲酰氯、对苯二甲酰氯或其混合物。
25.按照权利要求22的方法，其中在B步中的有机二羟基化合物是双酚A，碳酰卤是光气。
26.按照权利要求22的方法，其中A步和B步均在两相系统中进行，包括水相和水不溶混的有机溶剂相。
27.按照权利要求22的方法，其中B步pH在所述起始阶段保持在5～9，在所述反应后期增加到10～13。
28.按照权利要求1的嵌段共聚碳酸酯，其中芳基化物嵌段的聚合度为至少10。
29.按照权利要求1的嵌段共聚碳酸酯，其中芳基化物嵌段的聚合度为至少20。
30.按照权利要求1的嵌段共聚碳酸酯，其中芳基化物嵌段的聚合度为30～150。
31.按照权利要求1的嵌段共聚碳酸酯，其中碳酸酯嵌段的聚合度为至少20。
32.按照权利要求1的嵌段共聚碳酸酯，其中碳酸酯嵌段的聚合度为50～200。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US18190298A | 1998-10-29 | 1998-10-29 | |
| US09/181,902 | 1998-10-29 | ||
| US09/181902 | 1998-10-29 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100778051A Division CN1865315B (zh) | 1998-10-29 | 1999-09-07 | 耐候嵌段共聚酯碳酸酯及含有它的共混物 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1332760A CN1332760A (zh) | 2002-01-23 |
| CN1262572C true CN1262572C (zh) | 2006-07-05 |
Family
ID=22666291
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998152420A Expired - Lifetime CN1262572C (zh) | 1998-10-29 | 1999-09-07 | 耐候嵌段共聚碳酸酯及含有它的共混物 |
| CN2006100778051A Expired - Lifetime CN1865315B (zh) | 1998-10-29 | 1999-09-07 | 耐候嵌段共聚酯碳酸酯及含有它的共混物 |
| CNB2006101421696A Expired - Lifetime CN100462388C (zh) | 1998-10-29 | 1999-10-19 | 耐候嵌段共聚酯碳酸酯、其制备方法和包含它们的共混物 |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100778051A Expired - Lifetime CN1865315B (zh) | 1998-10-29 | 1999-09-07 | 耐候嵌段共聚酯碳酸酯及含有它的共混物 |
| CNB2006101421696A Expired - Lifetime CN100462388C (zh) | 1998-10-29 | 1999-10-19 | 耐候嵌段共聚酯碳酸酯、其制备方法和包含它们的共混物 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US6559270B1 (zh) |
| EP (2) | EP1124878B1 (zh) |
| JP (2) | JP2002528614A (zh) |
| CN (3) | CN1262572C (zh) |
| AT (2) | ATE258199T1 (zh) |
| DE (2) | DE69914352T2 (zh) |
| ES (1) | ES2214046T3 (zh) |
| WO (1) | WO2000026274A1 (zh) |
Families Citing this family (114)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69914352T2 (de) * | 1998-10-29 | 2004-12-09 | General Electric Co. | Witterungsbeständige blockcopolyestercarbonate und diese enthaltende polymerlegierungen |
| US6306507B1 (en) | 1999-05-18 | 2001-10-23 | General Electric Company | Thermally stable polymers, method of preparation, and articles made therefrom |
| US7169859B2 (en) * | 1999-05-18 | 2007-01-30 | General Electric Company | Weatherable, thermostable polymers having improved flow composition |
| US7605221B2 (en) * | 1999-05-18 | 2009-10-20 | Sabic Innovative Plastics Ip B.V. | Weatherable, thermostable polymers having improved flow composition |
| US7790292B2 (en) * | 1999-05-18 | 2010-09-07 | Sabic Innovative Plastics Ip B.V. | Polysiloxane copolymers, thermoplastic composition, and articles formed therefrom |
| JP2002069281A (ja) * | 2000-09-01 | 2002-03-08 | Teijin Ltd | ポリカーボネート樹脂組成物 |
| US7200132B2 (en) | 2000-12-22 | 2007-04-03 | Terahop Networks, Inc. | Forming ad hoc RSI networks among transceivers sharing common designation |
| US6538065B1 (en) | 2001-07-26 | 2003-03-25 | General Electric Company | Method for preparing copolyestercarbonates and articles therefrom |
| US20030139529A1 (en) * | 2001-11-02 | 2003-07-24 | General Electric Company | Method of making block copolymers by solid state polymerization |
| US7799855B2 (en) * | 2001-11-12 | 2010-09-21 | Sabic Innovative Plastics Ip B.V. | Flame retardant thermoplastic polycarbonate compositions, use and method thereof |
| US8057903B2 (en) * | 2001-11-30 | 2011-11-15 | Sabic Innovative Plastics Ip B.V. | Multilayer articles comprising resorcinol arylate polyester and method for making thereof |
| US6486294B1 (en) | 2002-02-19 | 2002-11-26 | General Electric Company | Production of poly(carbonate-co-ester) copolymers |
| US6812320B2 (en) * | 2002-03-25 | 2004-11-02 | General Electric Company | Method for copolyestercarbonate synthesis |
| US7514147B2 (en) | 2003-01-14 | 2009-04-07 | Sabic Innovative Plastics Ip B.V. | Formable thermoplastic multi-layer laminate, a formed multi-layer laminate, an article, and a method of making an article |
| US7270882B2 (en) | 2003-02-21 | 2007-09-18 | General Electric Company | Weatherable multilayer articles and method for their preparation |
| WO2004085102A2 (en) * | 2003-02-21 | 2004-10-07 | General Electric Company | Weatherable multilayer articles and method for their preparation |
| US20060056031A1 (en) | 2004-09-10 | 2006-03-16 | Capaldo Kevin P | Brightness enhancement film, and methods of making and using the same |
| US6916528B2 (en) | 2003-05-30 | 2005-07-12 | General Electric Company | Methods for manufacturing silver multilayered films and the articles obtained therefrom |
| US7060217B2 (en) | 2003-06-12 | 2006-06-13 | General Electric Company | Composite articles comprising resorcinol arylate polyester and method for making thereof |
| US20050003208A1 (en) * | 2003-07-01 | 2005-01-06 | Graf John Frederick | Method of reducing the color contribution of a coated top layer in a multi-layer material |
| US7401843B2 (en) * | 2003-07-24 | 2008-07-22 | Tremco Incorporated | Recreational vehicle roofing coating |
| US20050049369A1 (en) * | 2003-08-12 | 2005-03-03 | General Electric Company | Method for preparing copolyestercarbonates |
| US20050048401A1 (en) * | 2003-08-29 | 2005-03-03 | Chisholm Bret Ja | Methods of photoaddressing a polymer composition and the articles derived therefrom |
| US7214432B2 (en) * | 2003-09-30 | 2007-05-08 | General Electric Company | Coating compositions, their preparation, and coated articles made therefrom |
| US7135538B2 (en) | 2003-11-12 | 2006-11-14 | General Electric Company | Transparent polycarbonate-polysiloxane copolymer blend, method for the preparation thereof, and article derived therefrom |
| US7078447B2 (en) * | 2003-11-21 | 2006-07-18 | General Electric Company | Ionizing radiation stable polyarylestercarbonate compositions |
| US7169615B2 (en) * | 2003-11-26 | 2007-01-30 | General Electric Company | Method of authenticating polymers, authenticatable polymers, methods of making authenticatable polymers and authenticatable articles, and articles made there from |
| US20050112768A1 (en) * | 2003-11-26 | 2005-05-26 | Thomas Evans | Method of authenticating tagged polymers |
| US7094364B2 (en) * | 2003-11-26 | 2006-08-22 | General Electric Company | Method of authenticating polymers, authenticatable polymers, methods of making authenticatable polymers and authenticatable articles, and articles made there from |
| US20090266991A1 (en) * | 2003-11-26 | 2009-10-29 | Sabic Innovative Plastics Ip B.V. | Method of authenticating tagged polymers |
| US20050110978A1 (en) * | 2003-11-26 | 2005-05-26 | Radislav Potyrailo | Method of authenticating articles, authenticatable polymers, and authenticatable articles |
| US20050144309A1 (en) * | 2003-12-16 | 2005-06-30 | Intel Corporation, A Delaware Corporation | Systems and methods for controlling congestion using a time-stamp |
| US7223804B2 (en) * | 2003-12-30 | 2007-05-29 | General Electric Company | Polycarbonate composition |
| US20050159543A1 (en) * | 2004-01-17 | 2005-07-21 | General Electric Company | Coating compositions, their preparation, and coated articles made therefrom |
| US20060093826A1 (en) * | 2004-01-17 | 2006-05-04 | General Electric Company | Compositions useful as coatings, their preparation, and articles made therefrom |
| US20050159542A1 (en) * | 2004-01-17 | 2005-07-21 | General Electric Company | Compositions useful as coatings, their preparation, and articles made therefrom |
| US7153576B2 (en) | 2004-01-20 | 2006-12-26 | General Electric Company | Weatherable multilayer article assemblies and method for their preparation |
| US7837911B2 (en) | 2004-01-26 | 2010-11-23 | Sabic Innovative Plastics Ip B.V. | Methods of forming a layered article |
| US20050228130A1 (en) * | 2004-04-12 | 2005-10-13 | General Electric Company | Thermoplastic composition providing a low gloss, textured surface, and method |
| US20050266232A1 (en) * | 2004-05-27 | 2005-12-01 | General Electric Company | Weatherable multilayer articles and process for making |
| US7109274B2 (en) * | 2004-06-28 | 2006-09-19 | General Electric Company | Polyarylate compositions |
| US7638091B2 (en) * | 2004-07-02 | 2009-12-29 | Sabic Innovative Plastics Ip B. V. | Methods of sterilizing polycarbonate articles and methods of manufacture |
| US20060004154A1 (en) * | 2004-07-02 | 2006-01-05 | Derudder James L | Thermoplastic polycarbonate compositions, method of manufacture, and method of use thereof |
| US7119140B2 (en) * | 2004-07-22 | 2006-10-10 | Ronald Basham | Transparent films, compositions, and method of manufacture thereof |
| US20060030647A1 (en) * | 2004-08-05 | 2006-02-09 | Thomas Ebeling | Flame retardant thermoplastic polycarbonate compositions, use, and method of manufacture thereof |
| JP4631349B2 (ja) * | 2004-08-10 | 2011-02-16 | 三菱化学株式会社 | 芳香族ポリエステルポリカーボネート樹脂及びその製造方法 |
| US7365125B2 (en) * | 2004-08-16 | 2008-04-29 | General Electric Company | Polycarbonate compositions, articles, and method of manufacture |
| US20060116487A1 (en) * | 2004-11-29 | 2006-06-01 | General Electric Company | Carboxy-terminated oligomeric polyester compositions and method for making |
| US20060142486A1 (en) * | 2004-12-23 | 2006-06-29 | Derudder James L | Thermoplastic polycarbonate compositions, articles made therefrom and method of manufacture |
| US7323535B2 (en) * | 2005-05-20 | 2008-01-29 | General Electric Company | Transparent compositions, methods for the preparation thereof, and articles derived therefrom |
| US7323536B2 (en) | 2005-05-20 | 2008-01-29 | General Electric Company | Transparent compositions, methods for the preparation thereof, and articles derived therefrom |
| US7273917B2 (en) * | 2005-05-20 | 2007-09-25 | General Electric Company | Transparent compositions, methods for the preparation thereof, and articles derived therefrom |
| US7326764B2 (en) | 2005-05-20 | 2008-02-05 | General Electric Company | Transparent compositions, methods for the preparation thereof, and articles derived therefrom |
| US20060287429A1 (en) * | 2005-06-17 | 2006-12-21 | Gaggar Satish K | Glass fiber thermoplastic composite |
| KR100645065B1 (ko) * | 2005-06-23 | 2006-11-10 | 삼성전자주식회사 | 핀 전계 효과 트랜지스터와 이를 구비하는 비휘발성 메모리장치 및 그 형성 방법 |
| US20070037960A1 (en) * | 2005-08-15 | 2007-02-15 | General Electric Company | Copolyester stilbene embossed film and methods of making the same |
| US20070060716A1 (en) * | 2005-09-13 | 2007-03-15 | Bala Ambravaneswaran | Fatigue resistant thermoplastic composition, method of making, and articles formed therefrom |
| US20070066737A1 (en) * | 2005-09-16 | 2007-03-22 | Gallucci Robert R | Flame retardant polymer blends |
| US7250612B2 (en) * | 2005-09-28 | 2007-07-31 | General Electric Company | Devices and methods capable of authenticating batteries |
| US7652107B2 (en) * | 2005-10-31 | 2010-01-26 | Sabic Innovative Plastics Ip B.V. | Flame resistant polymer blends |
| US20070129470A1 (en) | 2005-12-05 | 2007-06-07 | Kuvshinnikova Olga I | Weatherable resinous composition with low heat storage and method |
| US20070293626A1 (en) * | 2005-12-07 | 2007-12-20 | Shreyas Chakravarti | Polyamide blend compositions |
| US20070155913A1 (en) * | 2006-01-04 | 2007-07-05 | Shreyas Chakravarti | Thermoplastic composition, method of making, and articles formed therefrom |
| US7514523B2 (en) * | 2006-01-05 | 2009-04-07 | Sabic Innovative Plastics Ip B.V. | Polycarbonate compositions and articles formed therefrom, with matte surfaces and high light transmissions |
| US8263691B2 (en) * | 2006-02-21 | 2012-09-11 | Sabic Innovative Plastics Ip B.V. | Release agent for transparent polyimide blends |
| US7700696B2 (en) * | 2006-06-28 | 2010-04-20 | Sabic Innovative Plastics Ip B.V. | Polycarbonate composition having improved scratch resistance, and articles formed therefrom |
| US7709581B2 (en) * | 2006-09-29 | 2010-05-04 | Sabic Innovative Plastics Ip B.V. | Polycarbonate-polysiloxane copolymer compositions and articles formed therefrom |
| US7524919B2 (en) * | 2006-09-29 | 2009-04-28 | Sabic Innovative Plastics Ip B.V. | Polycarbonate-polysiloxane copolymers, method of making, and articles formed therefrom |
| US20080081895A1 (en) * | 2006-09-29 | 2008-04-03 | General Electric Company | Polycarbonate-polysiloxane copolymers, method of making, and articles formed therefrom |
| US20080091643A1 (en) * | 2006-10-17 | 2008-04-17 | Bellsouth Intellectual Property Corporation | Audio Tagging, Browsing and Searching Stored Content Files |
| US20080118729A1 (en) * | 2006-11-16 | 2008-05-22 | General Electric Company | Thermoplastic composition, method of making, and articles formed therefrom |
| US7686998B2 (en) * | 2006-11-22 | 2010-03-30 | Sabic Innovative Plastics Ip B.V. | Thermoplastic composition, method of manufacture thereof, and articles derived therefrom |
| US7686997B2 (en) * | 2006-11-22 | 2010-03-30 | Sabic Innovative Plastics Ip B.V. | Thermoplastic composition, method of manufacture thereof, and articles derived therefrom |
| US7691304B2 (en) * | 2006-11-22 | 2010-04-06 | Sabic Innovative Plastics Ip B.V. | Thermoplastic composition, method of manufacture thereof, and articles derived therefrom |
| US7687583B2 (en) * | 2007-04-30 | 2010-03-30 | Sabic Innovative Plastics Ip B.V. | Polyester polycarbonate compositions, methods of making, and articles formed therefrom |
| US7691950B2 (en) * | 2007-04-30 | 2010-04-06 | Sabic Innovative Plastics Ip B.V. | Polyester polycarbonate compositions, methods of making, and articles formed therefrom |
| US7829632B2 (en) * | 2007-04-30 | 2010-11-09 | Sabic Innovative Plastics Ip B.V. | Polyester polycarbonate compositions, methods of making, and articles formed therefrom |
| US20090043069A1 (en) * | 2007-08-06 | 2009-02-12 | General Electric Company | Activated esters for synthesis of sulfonated telechelic polycarbonates |
| WO2009043758A1 (de) | 2007-09-28 | 2009-04-09 | Basf Se | Verfahren zur herstellung flammgeschützter thermoplastischer formmassen |
| US8318851B2 (en) | 2007-10-16 | 2012-11-27 | Sabic Innovative Plastics Ip B.V. | Weatherable resinous compositions |
| US8481630B2 (en) | 2007-12-04 | 2013-07-09 | Styrolution GmbH | Process for the production of moldings with reduced formation of deposit |
| US20090186966A1 (en) * | 2008-01-22 | 2009-07-23 | Sabic Innovative Plastics Ip B.V. | Thermoplastic polyestercarbonate composition |
| JP5333720B2 (ja) * | 2008-06-09 | 2013-11-06 | 宇部興産株式会社 | オリゴアルキレンカーボネート化合物、及びポリアルキレンカーボネート化合物の製造方法 |
| US20100009207A1 (en) * | 2008-07-10 | 2010-01-14 | Sabic Innovative Plastics Ip B.V. | Formable thermoplastic multi-layer article, a formed multi-layer article, an article, and a method of making an article |
| US9260561B2 (en) * | 2008-11-21 | 2016-02-16 | Sabic Global Technologies B.V. | Polyestercarbonate copolymers with high scratch resistance |
| US20100168314A1 (en) * | 2008-12-29 | 2010-07-01 | Sabic Innovative Plastics Ip B.V. | Thermoplastic composition with improved low temperature ductility |
| WO2010078413A1 (en) | 2008-12-31 | 2010-07-08 | Apinee, Inc. | Preservation of wood, compositions and methods thereof |
| EP2216352A1 (de) | 2009-02-10 | 2010-08-11 | Bayer MaterialScience AG | 2K-Polyurethan-Lack für Trägerfolien |
| EP2216353A1 (de) | 2009-02-10 | 2010-08-11 | Bayer MaterialScience AG | Trägerfolie mit Polyurethan-Beschichtung |
| WO2011039301A1 (de) | 2009-10-01 | 2011-04-07 | Basf Se | Funktionalisierte expandierbare graphiteinlagerungsverbindungen |
| WO2011039292A1 (de) | 2009-10-01 | 2011-04-07 | Basf Se | Verfahren zur herstellung funktionalisierter expandierbarer graphiteinlagerungsverbindungen |
| US9034949B2 (en) | 2010-10-15 | 2015-05-19 | Styrolution Europe Gmbh | Method for producing flame-proofed thermoplastic molding compounds |
| US8350275B2 (en) * | 2011-04-01 | 2013-01-08 | Sabic Innovative Plastics Ip B.V. | Optoelectronic devices and coatings therefore |
| KR102015492B1 (ko) | 2011-05-12 | 2019-08-28 | 사빅 글로벌 테크놀러지스 비.브이. | 커패시터용 비정질 폴리카보네이트 필름, 이의 제조 방법, 및 이로부터 제조된 물품 |
| US9878464B1 (en) | 2011-06-30 | 2018-01-30 | Apinee, Inc. | Preservation of cellulosic materials, compositions and methods thereof |
| CN102898630B (zh) * | 2011-07-27 | 2015-09-09 | 上海杰事杰新材料(集团)股份有限公司 | 一种共聚芳酯及其制备方法 |
| US8557158B2 (en) | 2011-08-23 | 2013-10-15 | Sabic Innovative Plastics Ip B.V. | Molded article having enhanced aesthetic effect and method and system for making the molded article |
| KR101326916B1 (ko) | 2012-11-09 | 2013-11-11 | 아주대학교산학협력단 | 고분자량의 지방족 폴리카보네이트 공중합체 및 이의 제조 방법 |
| EP3039061B1 (en) | 2013-08-28 | 2018-07-25 | SABIC Global Technologies B.V. | Polycarbonate films for capacitors, methods of manufacture, and articles manufactured therefrom |
| US20150232661A1 (en) * | 2014-02-20 | 2015-08-20 | Sabic Innovative Plastics Ip B.V. | Thermoplastic composition and article |
| US20150232662A1 (en) | 2014-02-20 | 2015-08-20 | Sabic Innovative Plastics Ip B.V. | Thermoplastic composition and article |
| US20150240074A1 (en) * | 2014-02-27 | 2015-08-27 | Sabic Innovative Plastics Ip B.V. | Polyester-polycarbonate composition and article |
| WO2015200272A2 (en) | 2014-06-23 | 2015-12-30 | Sabic Global Technologies B.V. | Filler reinforced thermoplastic compositions with improved bonding strength |
| CN109071850B (zh) | 2016-05-12 | 2021-04-27 | 沙特基础工业全球技术有限公司 | 具有耐高温性能的电容器膜、其制造方法及其制品 |
| CN110214379A (zh) * | 2016-12-23 | 2019-09-06 | 沙特基础工业全球技术公司 | 导电性共聚酯碳酸酯基材料 |
| EP3634711B1 (en) | 2017-12-29 | 2020-09-16 | SABIC Global Technologies B.V. | Low dielectric constant (dk) and dissipation factor (df) material for nano-molding technology (nmt) |
| US20200407882A1 (en) | 2018-03-06 | 2020-12-31 | Basf Se | Filaments based on a core material comprising a fibrous filler |
| CN109776783B (zh) * | 2018-12-20 | 2021-03-26 | 聊城鲁西聚碳酸酯有限公司 | 一种耐候耐溶剂共聚聚碳酸酯制备方法 |
| EP3690978A1 (en) | 2019-02-01 | 2020-08-05 | SABIC Global Technologies B.V. | Injection moldable, flame retardant long glass fiber based materials for electric vehicle battery casing |
| CN111073229A (zh) * | 2019-12-27 | 2020-04-28 | 上海昶法新材料有限公司 | 一种含改性造纸废弃物的可生物降解母粒及其制备方法 |
| CN114634615B (zh) * | 2020-12-15 | 2023-10-20 | 万华化学集团股份有限公司 | 一种低介电常数、高耐候性、高抗冲击性的聚碳酸酯-聚酯共聚物 |
| EP4095199A1 (en) | 2021-05-28 | 2022-11-30 | SHPP Global Technologies B.V. | Articles and structures with colorable anti-static poly ether imide blends |
| EP4095197A1 (en) | 2021-05-28 | 2022-11-30 | SHPP Global Technologies B.V. | Articles and structures with colorable electro-static dissipative (esd) polycarbonate blends |
| EP4141073A1 (en) | 2021-08-31 | 2023-03-01 | SHPP Global Technologies B.V. | Filled conductive compositions with improved conductivity |
Family Cites Families (63)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE570531A (zh) | 1957-08-22 | |||
| US3030331A (en) | 1957-08-22 | 1962-04-17 | Gen Electric | Process for preparing copolyesters comprising reacting a carbonyl halide with a dicarboxylic acid and a dihydroxy compound in the presence of a tertiary amine |
| US3207814A (en) | 1961-01-03 | 1965-09-21 | Gen Electric | Carbonate-polyester copolymer resinous compositions |
| US3460961A (en) | 1965-04-21 | 1969-08-12 | Monsanto Co | Process of coating a substrate with a polymeric ultraviolet light barrier coating and the coated substrate |
| US3506470A (en) | 1965-07-08 | 1970-04-14 | Monsanto Co | Photoprints coated with polymeric ultraviolet light barrier coatings |
| US3492261A (en) | 1965-07-08 | 1970-01-27 | Monsanto Co | Solutions of polymeric ultraviolet light barrier coatings |
| US3444129A (en) | 1965-07-08 | 1969-05-13 | Monsanto Co | Polymeric ultraviolet barrier coatings |
| US3503779A (en) | 1965-07-08 | 1970-03-31 | Monsanto Co | Substrates coated with polymeric ultraviolet light barrier coatings |
| DE1927938A1 (de) | 1969-05-31 | 1970-12-03 | Dynamit Nobel Ag | Verfahren zur Herstellung von Polyarylestern |
| US3803085A (en) | 1972-12-29 | 1974-04-09 | Gen Electric | Method for making polyetherimides |
| JPS5541245B2 (zh) | 1973-05-31 | 1980-10-23 | ||
| US3905942A (en) | 1973-06-22 | 1975-09-16 | Gen Electric | Method for making polyetherimides and products produced thereby |
| US4156069A (en) | 1976-04-02 | 1979-05-22 | Allied Chemical Corporation | Bisphenol-A/terephthalate/carbonate melt processable copolymers |
| US4286083A (en) | 1976-12-29 | 1981-08-25 | General Electric Company | Method of preparing polyester carbonates |
| US4127560A (en) | 1977-08-08 | 1978-11-28 | Celanese Corporation | Melt polymerization process for preparing a melt processable resorcinol phthalate polyester utilizing a metal acetate catalyst |
| US4217438A (en) | 1978-12-15 | 1980-08-12 | General Electric Company | Polycarbonate transesterification process |
| US4194038A (en) | 1979-01-25 | 1980-03-18 | Allied Chemical Corporation | Poly(ester-carbonates) from dicarboxylic acid chlorides |
| JPS55131049A (en) | 1979-04-02 | 1980-10-11 | Sumitomo Chem Co Ltd | Novel thermoplastic resin composition |
| US4238597A (en) | 1979-04-26 | 1980-12-09 | General Electric Company | Process for producing copolyester-carbonates |
| US4238596A (en) | 1979-04-26 | 1980-12-09 | General Electric Company | Process for obtaining copolyester-carbonates |
| DE2940024A1 (de) | 1979-10-03 | 1981-04-16 | Bayer Ag, 5090 Leverkusen | Aromatische polyester, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von spritzgussartikeln, folien und ueberzuegen |
| US4281099A (en) | 1979-10-29 | 1981-07-28 | Union Carbide Corporation | Process for stabilizing polyarylates with an aromatic phenol |
| JPS56133332A (en) | 1980-03-22 | 1981-10-19 | Mitsubishi Gas Chem Co Inc | Preparation of aromatic polyester carbonate resin |
| US4454275A (en) | 1981-02-20 | 1984-06-12 | General Electric Company | Flame retardant copolyester-carbonate compositions |
| US4503121A (en) | 1981-12-29 | 1985-03-05 | Union Carbide Corporation | Laminate compositions with polyarylate and poly(aryl ether) |
| US4495325A (en) | 1983-02-25 | 1985-01-22 | E. I. Du Pont De Nemours And Company | Polymer-bound ultraviolet stabilizer coating compositions containing cross linkers |
| US4482694A (en) | 1983-04-25 | 1984-11-13 | Bayer Aktiengesellschaft | High molecular weight aromatic polyesters and processes for their production |
| US4487896A (en) | 1983-09-02 | 1984-12-11 | General Electric Company | Copolyester-carbonate compositions exhibiting improved processability |
| DE3346946A1 (de) | 1983-12-24 | 1985-07-04 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von farblosen aromatischen polyestern und polyestercarbonaten |
| US4506065A (en) | 1984-01-03 | 1985-03-19 | General Electric Company | Copolyestercarbonates |
| US4576842A (en) | 1984-03-19 | 1986-03-18 | Union Carbide Corporation | Cookware formed from a laminate |
| US5036150A (en) | 1984-03-20 | 1991-07-30 | Amoco Corporation | Polyarylates having improved hydrolytic stability |
| US4643937A (en) * | 1985-02-27 | 1987-02-17 | Union Carbide Corporation | Laminate formed from a polyarylate sheet and a polycarbonate and/or polyester sheet |
| DE3615764A1 (de) * | 1986-05-10 | 1987-11-12 | Bayer Ag | Folien aus polykondensaten |
| JPH01199841A (ja) | 1988-02-04 | 1989-08-11 | Teijin Ltd | 多層配向ボトル |
| JPH01201326A (ja) | 1988-02-04 | 1989-08-14 | Teijin Ltd | ポリエステル成形材料及び成形品 |
| US5030505A (en) | 1988-05-05 | 1991-07-09 | Amoco Corporation | Polyarylate-polyethylene composite laminated structures |
| US4931364A (en) | 1988-05-05 | 1990-06-05 | Amoco Corporation | Polyarylate-polyethylene composite laminated structures |
| DE3819943A1 (de) | 1988-06-11 | 1990-02-08 | Bayer Ag | Verfahren zur herstellung von aromatischen polycarbonaten, aromatischen polyestercarbonaten und aromatischen polyestern |
| JPH0236259A (ja) * | 1988-06-16 | 1990-02-06 | Mitsui Petrochem Ind Ltd | ポリエステル樹脂組成物 |
| US4992322A (en) | 1988-06-23 | 1991-02-12 | General Electric Company | Coextruded products with improved weatherability |
| JP2638981B2 (ja) | 1988-08-26 | 1997-08-06 | 東ソー株式会社 | 芳香族ポリエステル樹脂の製造方法 |
| JPH0333154A (ja) * | 1989-06-29 | 1991-02-13 | Mitsubishi Gas Chem Co Inc | 新規な樹脂組成物 |
| US5064704A (en) | 1989-09-29 | 1991-11-12 | E. I. Du Pont De Nemours And Company | Shaped structure of polyarylate copolymers having high tensile elongation at break |
| KR950013538B1 (ko) | 1989-12-22 | 1995-11-08 | 제네랄 일렉트릭 캄파니 | 코폴리에스테르카보네이트 수지 |
| DE4010029A1 (de) * | 1990-03-29 | 1991-10-02 | Bayer Ag | Polyester und polyestercarbonate auf basis von 3,8-dihydroxy-5a,10b-diphenylcumarano -2',3',2,3-cumaran |
| JPH0441524A (ja) * | 1990-06-07 | 1992-02-12 | Idemitsu Kosan Co Ltd | ポリエステルカーボネートとその製造法及びそれからなる光学材料 |
| DE4037402A1 (de) | 1990-08-01 | 1992-02-06 | Bayer Ag | Polyestercarbonate auf basis von 1,1-bis-(4-hydroxyphenyl)-alkylcycloalkanen und thermoplastische legierungen daraus |
| US5318850A (en) | 1991-11-27 | 1994-06-07 | General Electric Company | UV curable abrasion-resistant coatings with improved weatherability |
| US5552463A (en) | 1992-04-24 | 1996-09-03 | Alliedsignal Inc. | Semicrystalline blends of polyalkylene terephthalates and polyarylates |
| JP3176448B2 (ja) | 1992-10-12 | 2001-06-18 | 財団法人石油産業活性化センター | 芳香族ポリエステルの製法 |
| IT1264508B1 (it) * | 1993-05-24 | 1996-09-24 | Enichem Spa | Composizioni termoplastiche compatibili a base di poliesteri e policarbonati |
| WO1996010483A1 (fr) | 1994-09-30 | 1996-04-11 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Feuille en plastique optique stratifiee resistant a la chaleur et son procede de production |
| DE4444868A1 (de) | 1994-12-16 | 1996-06-20 | Bayer Ag | UV-geschützte, mehrschichtige Polycarbonatplatten |
| EP0736558A3 (en) * | 1995-04-08 | 1998-01-07 | General Electric Company | A polyester polycarbonate composition which is transparent and has outstanding thermal stability |
| US5714567A (en) | 1996-02-15 | 1998-02-03 | Council Of Scientific & Ind. Research | Process for the preparation of aromatic polyesters |
| US5777009A (en) * | 1996-10-25 | 1998-07-07 | General Electric Company | Flame retardant low Tg polyestercarbonate |
| JPH10231359A (ja) * | 1996-12-09 | 1998-09-02 | General Electric Co <Ge> | ヒドロキシフェニルインダノール類から誘導される光ディスクグレードのコポリエステルカーボネート |
| US5807965A (en) | 1997-12-23 | 1998-09-15 | General Electric Company | Interfacial copolyestercarbonate method using catalyst comprising hexaalkylguanidinium salt and tertiary amine |
| US5916997A (en) | 1998-02-25 | 1999-06-29 | General Electric Company | Weatherable copolymers |
| US6136441A (en) | 1998-03-24 | 2000-10-24 | General Electric Company | Multilayer plastic articles |
| US6143839A (en) | 1998-09-14 | 2000-11-07 | General Electric Company | Weatherable blends of polycarbonates with arylate polymers |
| DE69914352T2 (de) * | 1998-10-29 | 2004-12-09 | General Electric Co. | Witterungsbeständige blockcopolyestercarbonate und diese enthaltende polymerlegierungen |
-
1999
- 1999-09-07 DE DE69914352T patent/DE69914352T2/de not_active Expired - Lifetime
- 1999-09-07 EP EP99945533A patent/EP1124878B1/en not_active Expired - Lifetime
- 1999-09-07 ES ES99945533T patent/ES2214046T3/es not_active Expired - Lifetime
- 1999-09-07 CN CNB998152420A patent/CN1262572C/zh not_active Expired - Lifetime
- 1999-09-07 JP JP2000579657A patent/JP2002528614A/ja not_active Withdrawn
- 1999-09-07 AT AT99945533T patent/ATE258199T1/de not_active IP Right Cessation
- 1999-09-07 WO PCT/US1999/020413 patent/WO2000026274A1/en active IP Right Grant
- 1999-09-07 CN CN2006100778051A patent/CN1865315B/zh not_active Expired - Lifetime
- 1999-10-12 US US09/416,529 patent/US6559270B1/en not_active Expired - Lifetime
- 1999-10-19 EP EP05024810A patent/EP1624008B1/en not_active Expired - Lifetime
- 1999-10-19 JP JP2000579658A patent/JP4740457B2/ja not_active Expired - Lifetime
- 1999-10-19 CN CNB2006101421696A patent/CN100462388C/zh not_active Expired - Lifetime
- 1999-10-19 AT AT05024810T patent/ATE420912T1/de not_active IP Right Cessation
- 1999-10-19 DE DE69940328T patent/DE69940328D1/de not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP1124878B1 (en) | 2004-01-21 |
| CN1865315A (zh) | 2006-11-22 |
| EP1624008A1 (en) | 2006-02-08 |
| DE69914352T2 (de) | 2004-12-09 |
| EP1624008B1 (en) | 2009-01-14 |
| ES2214046T3 (es) | 2004-09-01 |
| EP1124878A1 (en) | 2001-08-22 |
| JP2004500442A (ja) | 2004-01-08 |
| DE69940328D1 (de) | 2009-03-05 |
| JP2002528614A (ja) | 2002-09-03 |
| ATE420912T1 (de) | 2009-01-15 |
| JP4740457B2 (ja) | 2011-08-03 |
| CN1332760A (zh) | 2002-01-23 |
| CN1865315B (zh) | 2012-11-28 |
| CN100462388C (zh) | 2009-02-18 |
| CN1948361A (zh) | 2007-04-18 |
| US6559270B1 (en) | 2003-05-06 |
| WO2000026274A1 (en) | 2000-05-11 |
| DE69914352D1 (de) | 2004-02-26 |
| ATE258199T1 (de) | 2004-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1262572C (zh) | 耐候嵌段共聚碳酸酯及含有它的共混物 | |
| CN1288187C (zh) | 耐候嵌段共聚酯碳酸酯、其制备方法和包含它们的共混物 | |
| US6043322A (en) | Clear polycarbonate and polyester blends | |
| US4994532A (en) | Polycarbonate-silicone block copolymer compositions | |
| US6011124A (en) | Blends of bisphenol a polycarbonate and polyesters | |
| JP4685406B2 (ja) | 改質耐候性ポリエステル成形用組成物 | |
| CN1745139A (zh) | 静电分散树脂组合物及其制造方法 | |
| CN1976995A (zh) | 聚芳基化物组合物 | |
| US5545692A (en) | Polyesters of dimer fatty acid and dimer fatty diol and their use for the production of polyester carbonates | |
| CN104039890A (zh) | 聚碳酸酯-聚酯组合物、制造方法及其制品 | |
| CA1225183A (en) | Composition | |
| US4614767A (en) | Moldable polyester-sulfone thermoplastic resin | |
| JPH0526826B2 (zh) | ||
| WO2008057306A2 (en) | Clear blends of bisphenol a polycarbonate and copolyesters | |
| JPH1072548A (ja) | 耐候性の改善された共押出ポリカーボネートシート | |
| EP0320655B1 (en) | Molding resins | |
| CN1137544A (zh) | 含有卤代芳族二醇和亚烷基二卤化物的缩合产物的乙烯基芳族树脂组合物 | |
| DE3926614A1 (de) | Thermoplastische legierungen mit polycarbonaten auf basis n-alkyl-substituierter cyclohexylidenbisphenole | |
| JP2003503568A (ja) | 光散乱性ブロックコポリカルボネート | |
| CN1382188A (zh) | 共混的聚碳酸酯组合物 | |
| JPH0195154A (ja) | ポリカーボネート樹脂組成物 | |
| JPH04248833A (ja) | ポリエステルカーボネート及び熱可塑性配合物 | |
| JP3065117B2 (ja) | ポリカーボネート樹脂組成物 | |
| US5196488A (en) | Blend of a polyester and a polycarbonate | |
| US5037889A (en) | Resin blends exhibiting improved impact properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| C10 | Entry into substantive examination | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SAUDI ARABIA BASE CREATION PLASTICS IP PRIVATE CO Free format text: FORMER OWNER: GENERAL ELECTRIC CO. Effective date: 20080822 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20080822 Address after: Holland city Aupu zoom Bergen Patentee after: Sabic Innovative Plastics IP Address before: American New York Patentee before: General Electric Company |
|
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: Holland city Aupu zoom Bergen Patentee after: Sabic Innovative Plastics IP Address before: Holland city Aupu zoom Bergen Patentee before: Sabic Innovative Plastics IP |
|
| CX01 | Expiry of patent term |
Granted publication date: 20060705 |
|
| CX01 | Expiry of patent term |