CN100366668C - 阻燃聚碳酸酯组合物 - Google Patents
阻燃聚碳酸酯组合物 Download PDFInfo
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- CN100366668C CN100366668C CNB028277805A CN02827780A CN100366668C CN 100366668 C CN100366668 C CN 100366668C CN B028277805 A CNB028277805 A CN B028277805A CN 02827780 A CN02827780 A CN 02827780A CN 100366668 C CN100366668 C CN 100366668C
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- polycarbonate
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- 239000004417 polycarbonate Substances 0.000 title claims abstract description 80
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 75
- 239000000203 mixture Substances 0.000 title claims abstract description 70
- 239000003063 flame retardant Substances 0.000 title claims abstract description 48
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 22
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 39
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 23
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 23
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 13
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000004809 Teflon Substances 0.000 claims description 17
- 229920006362 Teflon® Polymers 0.000 claims description 17
- 239000003595 mist Substances 0.000 claims description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical group [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 claims description 6
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 1
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 11
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000006085 branching agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229960003742 phenol Drugs 0.000 description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 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 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000005027 hydroxyaryl group Chemical group 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- MXSFCLQVRKXOTH-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoropentanedioic acid;sodium Chemical compound [Na].[Na].OC(=O)C(F)(F)C(F)(F)C(F)(F)C(O)=O MXSFCLQVRKXOTH-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- HJSPWKGEPDZNLK-UHFFFAOYSA-N 4-benzylphenol Chemical compound C1=CC(O)=CC=C1CC1=CC=CC=C1 HJSPWKGEPDZNLK-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
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical class CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- XIEJBVCPGYVGDR-UHFFFAOYSA-N C(CCCCCC)C1C(CCCCC1)=C1CCCCCC1 Chemical compound C(CCCCCC)C1C(CCCCC1)=C1CCCCCC1 XIEJBVCPGYVGDR-UHFFFAOYSA-N 0.000 description 1
- MDNTXXADGNHVHA-UHFFFAOYSA-N CCCC.[Na] Chemical group CCCC.[Na] MDNTXXADGNHVHA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- PWSYABYHJUCCAT-UHFFFAOYSA-N ClC(=O)C1CC2C(C(=O)OC2=O)C=C1 Chemical compound ClC(=O)C1CC2C(C(=O)OC2=O)C=C1 PWSYABYHJUCCAT-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 1
- VKKWHZLEUPHDMO-UHFFFAOYSA-N [Na].FC1=C(C(=O)O)C=C(C=C1C(=O)O)S(=O)(=O)O Chemical compound [Na].FC1=C(C(=O)O)C=C(C=C1C(=O)O)S(=O)(=O)O VKKWHZLEUPHDMO-UHFFFAOYSA-N 0.000 description 1
- ZCZVZQYXVCHEKH-UHFFFAOYSA-N [O].OC(O)=O Chemical compound [O].OC(O)=O ZCZVZQYXVCHEKH-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- DCBMHXCACVDWJZ-UHFFFAOYSA-N adamantylidene Chemical group C1C(C2)CC3[C]C1CC2C3 DCBMHXCACVDWJZ-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- CJPIDIRJSIUWRJ-UHFFFAOYSA-N benzene-1,2,4-tricarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(C(Cl)=O)=C1 CJPIDIRJSIUWRJ-UHFFFAOYSA-N 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical class CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RPHYLOMQFAGWCD-UHFFFAOYSA-N ethane;phenol Chemical compound CC.OC1=CC=CC=C1 RPHYLOMQFAGWCD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 125000005067 haloformyl group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- SJDACOMXKWHBOW-UHFFFAOYSA-N oxyphenisatine Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2NC1=O SJDACOMXKWHBOW-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- AZLIIAMTCHKNJJ-UHFFFAOYSA-N potassium;trifluoromethanesulfonic acid Chemical compound [K].OS(=O)(=O)C(F)(F)F AZLIIAMTCHKNJJ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- 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
- C08K5/00—Use of organic ingredients
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- 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
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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Abstract
阻燃聚碳酸酯组合物，其包含支化聚碳酸酯树脂、聚四氟乙烯、无溴和氯的阻燃剂以及任选的硅氧烷。
Description
背景技术
本发明涉及聚碳酸酯组合物，更具体地涉及阻燃聚碳酸酯组合物。
基于其优异的电气特性、透明性、机械强度、尤其是冲击强度，聚碳酸酯树脂已被广泛应用于制造商业机器和无线电通讯装置(telecommunicationequipment)。商业机器和无线电通讯装置对于安全要求尤其是在阻燃方面比较严格。在薄壁制品，即壁厚小于2.5毫米(mm)的制品中，这种安全要求难以满足。为在薄壁制品中满足安全要求，以前的尝试包括使用非常低的熔体流动(高粘度)的聚碳酸酯，及使用具有高水平(high levels)聚四氟乙烯或高水平氯化或溴化阻燃剂的直链聚碳酸酯。然而这些方法也具有缺陷。不能通过注塑形成具有低熔体流动的聚碳酸酯。高水平的聚四氟乙烯导致高雾度和低透明度的半透明组合物，并且对于不使用氯化或溴化阻燃剂而满足安全要求日益变得更令人向往。
因此，很明显，在低雾度和高透明度的半透明聚碳酸酯组合物中满足安全要求的同时不使用氯化或溴化阻燃剂是非常具有挑战性的，尤其是在有助于注模和/或薄壁应用的组合物中。
发明概述
现有技术的上述和其它缺陷和不足已被阻燃的半透明聚碳酸酯组合物克服或减轻，该组合物包括支化聚碳酸酯、聚四氟乙烯树脂和不含氯和溴的阻燃剂；其中该聚碳酸酯组合物在大约3.2毫米厚下具有小于或等于约30％的雾度和大于或等于约70％的透光度(light transmission)，以及在小于或等于25毫米厚下根据UL94具有V1等级或更好。
另一方面，阻燃半透明聚碳酸酯组合物包括支化聚碳酸酯树脂；聚四氟乙烯树脂，其存在量为聚碳酸酯总重的约0.10重量％；无溴和氯的阻燃剂，其存在量为聚碳酸酯总重量的约0.01-0.15重量％，其中该聚碳酸酯组合物在小于或等于2.5毫米厚下根据UL 94具有V1等级或更好。
在另一个实施方式中，阻燃半透明聚碳酸酯组合物包括支化聚碳酸酯；聚四氟乙烯树脂；无溴和氯的阻燃剂；和硅氧烷，其中该聚碳酸酯组合物在小于或等于2.5毫米厚下根据UL 94具有V1等级或更好。
在另一个实施方式中，阻燃半透明聚碳酸酯组合物包括直链或支化的聚碳酸酯树脂、聚四氟乙烯、无溴和氯的阻燃剂、和环状硅氧烷。
根据下面的具体描述和从属权利要求，本领域技术人员将会理解上述和其它特征。
优选实施方式的详细描述
阻燃半透明聚碳酸酯组合物包括支化聚碳酸酯、聚四氟乙烯树脂、无溴和氯的阻燃剂、和任选的硅氧烷。半透明聚碳酸酯组合物具有良好的透明度和阻燃性能。透明度用雾度百分数和透光百分数描述。根据ASTM D1003确定本发明的雾度百分数和透光百分数。此处定义本发明的半透明组合物为在约为3.2毫米的厚度下具有小于或等于约30％，优选小于或等于约26％，最优选小于或等于约22％的雾度；和大于或等于约70％，优选大于或等于约73％、最优选大于或等于约75％的透光度。根据Underwriter Laboratoriesprotocol UL 94确定阻燃性。UL 94提供4种可能的等级：HB，V2，V1和V0。V0是最难达到的等级，要求具有5秒或更短的平均消焰时间而不滴流(dripping)的5棒自熄性(five bars self extinguish)。这里定义阻燃组合物为在厚度小于或等于约2.5毫米、优选小于或等于约2.3毫米、最优选小于或等于约2.0毫米下，具有V1等级或更好，优选V0等级。此处描述的半透明阻燃聚碳酸脂组合物不含有氯和溴，有助于注塑，能够在上述厚度达到V0等级。
聚碳酸脂是广为人知并且是可市购的。有用的聚碳酸脂包括具有式(I)结构单元的组分
其中R1基团总数的至少约60％为芳族有机基团，其余为脂肪族、脂环族或芳族基团。聚碳酸脂可通过二羟基化合物的界面反应制备。如在此使用的，术语“二羟基化合物”包括，例如具有如下通式(II)的双酚化合物：
HO-A1-Y1-A2-OH (II)
其中A1和A2各自为单环二价芳基；Y1为具有1或2个原子的将A1和A2分开的桥基。在列举的实施方式中，一个原子将A1和A2分开。此类非限定性实例为-O-、-S-、-S(O)-、-S(O)2-、-C(O)-、亚甲基、环己基-亚甲基、2-[2.2.1]双环亚庚基(bicycloheptylidene)，亚乙基、异亚丙基、新亚戊基、亚环己基、亚环十五烷基、亚环十二烷基、亚金刚烷基(adamantylidene)。桥基Y1可为烃基或饱和烃基如亚甲基、亚环己基、或异亚丙基。优选二羟基化合物具有通式(III)
其中Ra和Rb各自表示氢原子或一价烃基，它们可以相同或不同；p和q各自独立地为0-4的整数；Xa表示式(IV)所示基团
其中Rc和Rd各自独立地表示氢原子或一价直链或环状烃基；Re为二价烃基。
合用的优选二羟基化合物的其它实例性、非限制性的例子包括在美国专利US4217438中通过名称或结构式(通式或具体结构式)公开的二羟基取代的芳族化合物。可以由通式(III)所代表的该类双酚的非限制性具体实例包括：1，1-双(4-羟基苯基)甲烷、1，1-双(4-羟基苯基)乙烷、2，2-双(4-羟基苯基)丙烷(下文中称作“双酚A”或“BPA”)、2，2-双(4-羟基苯基)丁烷、2，2-双(4-羟基苯基)辛烷、1，1-双(4-羟基苯基)丙烷、1，1-双(4-羟基苯基)正丁烷、双(4-羟基苯基)苯甲烷、2，2-双(4-羟基甲基苯基)丙烷、1，1-双(4-羟基叔丁基苯基)丙烷；双(羟基芳基)烷烃例如1，1-双(4-羟基苯基)环戊烷；双(羟基芳基)环烷烃如1，1-双(4-羟基苯基)环己烷。
在对于应用优选碳酸酯共聚物而不是均聚物的情况下，还可以使用两种或多种不同二羟基酚，或使用二羟基酚与二醇或与羟基-或酸-封端的聚酯的共聚物，或与二元酸或羟基酸的共聚物。也可以使用多芳基化合物和聚酯-碳酸酯树脂或它们的共混物。
支化的聚碳酸酯可通过在聚合反应中加入支化剂来制备。支化剂是本领域所熟知的，可包括多官能团的有机化合物，其具有至少3个可为以下种类的官能团：羟基、羧基、羧酸酐、卤代甲酰基、及其混合物。具体的例子包括偏苯三酸、偏苯三酸酐、偏苯三酸三氯化物、三-对羟基苯乙烷(THPE)、2，6-双(2′-羟基-5′-甲基苄基)-4-甲基苯酚、靛红双酚、三-苯酚TC(1，3，5-三((对-羟基苯基)异丙基)苯)、三-苯酚PA(4(4(1，1-双(对-羟基苯基)乙基)、4-氯甲酰-邻苯二甲酸酐、1，3，5-苯三酸和二苯甲酮四羧酸。支化剂的加入水平为0.05-2.0％(重量)。支化剂及制造支化聚碳酸酯的步骤公开于美国专利US3635895和US4001184中。预期所有或绝大部分聚碳酸酯端基在阻燃聚碳酸酯组合物中有作用。
优选基于双酚A制备聚碳酸酯。优选聚碳酸酯的重均分子量约为5,000-100,000，更优选约为10,000-65,000，最优选约为15,000-40,000。
优选该组合物包括直链或支化的聚碳酸酯树脂。典型地，存在大于或等于约70％重量，优选大于或等于约75％重量，更优选大于或等于约80％重量的直链聚碳酸酯。直链聚碳酸酯的存在量典型地小于或等于约95％重量，优选小于或等于约90％重量，最优选小于或等于约85％重量。通常会有大于或等于约5％重量，优选大于或等于约10％重量，更优选大于或等于约15％的支化聚碳酸酯。支化聚碳酸酯的量可小于或等于约30％重量，优选小于或等于约25％重量，更优选小于或等于约20％重量。上述直链和支化聚碳酸酯的量基于聚碳酸脂的总重量。支化聚碳酸酯具有约0.05-0.8％，优选约0.1-0.6％，最优选约0.2-0.4％的支化。支化的百分比由每100重复单元分支的数量确定。组合物中最终的支化的量由支化和直链树脂的比率以及支化树脂中支化剂的水平确定。例如直链和支化树脂比为80∶20、支化树脂中支化0.3％的组合物将与直链和支化树脂比为90∶10、支化树脂中支化0.6％的组合物具有相同的支化度(degree of braching)。总之，直链和支化聚碳酸酯的组合具有约0.01-0.15的支化，优选约0.015-0.09％的支化，最优选约0.03-0.075％的支化。
聚四氟乙烯树脂是本领域熟知的。聚四氟乙烯树脂为典型地细碎的固体，当受到机械剪切时，具有形成超细原纤维(ultrafine fibrils)的能力。典型地作为水悬浮液，聚四氟乙烯是可被购买到的。为了易于分散，如欧洲专利申请EP899303中所教导的，优选将聚四氟乙烯树脂颗粒预分散于树脂母体如热塑树脂中(如苯乙烯-丙烯腈)中。包胶的聚四氟乙烯树脂颗粒的粒度典型地为约35-70微米，优选约40-65微米。基于聚碳酸脂总重，聚四氟乙烯树脂的用量典型地为小于或等于约0.1重量％，优选小于或等于约0.075重量％，最优选小于或等于约0.05重量％。聚氟烯烃的用量必须为在加热组合物时能优选防止其滴流的有效量，典型地大于或等于约0.025重量％。
有用的阻燃剂不含氯和溴。典型地，其包括以下化合物的碱和碱金属盐(作为阻燃剂，并且不会导致聚碳酸脂组合物的不透明性)：单体或者聚合的芳族磺酸、单体或者聚合的芳族砜磺酸、芳族酮的磺酸、杂环磺酸(heterocyclicsulfonic acid)、氟化甲磺酸、氟化非芳族羧酸、芳族硫化物的磺酸、单体或者聚合的芳族醚的磺酸、脂肪族和烯属的磺酸、未取代的或者氟化的氧碳酸(oxocarbon acid)、单体的或者聚合的芳族羧酸和酯的磺酸、氟化脂环族磺酸、单体的或者聚合的芳族酰胺磺酸；以及包括前述碱或者碱金属盐的至少一种的混合物。优选的盐包括碳原子数为约1-14的全氟烷烃磺酸钠和钾(全氟烷烃的磺酸盐)、萘-2，6-二磺酸二钠、4，4′-二氟联苯-3-磺酸钠、2，3，4，5，6-五氟-β苯乙基磺酸钠、4，4′-二氟二苯硫-3-磺酸钠、四氟二苯醚二磺酸二钠、4，4′-二氟二苯甲酮-3，3′-二磺酸二钠、2，5-二氟噻吩-3-磺酸钠、二苯砜-3-磺酸的钠盐、二苯砜-3-磺酸的钾盐、三甲基2，4，6-三氟-5-磺基间苯二甲酸钠、二氟苯基-2，4，5-三氟苯磺酸钾、2，4，5-三氟苯氨磺酰基(trifluorobenzenefonamide)-4′-磺酸的钙盐、六氟戊二酸二钠、三氟甲磺酸钾、全氟丁烷磺酸钾和包括至少一种前述盐的混合物。优选全氟丁烷磺酸钾。
当阻燃剂是全氟丁烷磺酸钠、全氟丁烷磺酸钾或者其混合物时，基于聚碳酸酯总重量，其有效量为小于或等于约0.15％重量，优选小于或等于约0.12％重量，最优选小于或等于约0.1％重量。并且基于聚碳酸酯的总重量，全氟丁烷磺酸钠或全氟丁烷磺酸钾的存在量为大于或等于约0.01％重量，优选大于或等于约0.03％重量，最优选大于或等于约0.05％重量。其它阻燃剂的量将随阻燃剂的性质(identity)而变化，并且本领域技术人员可以根据此处有关全氟丁烷磺酸盐的教导来确定。
有用的硅氧烷如但不局限于：特征在于下式的环状硅氧烷：
其中R在每种情况下独立地选自：具有1-约36个碳原子的烷基、具有1-约36个碳原子的烷氧基、具有约6-约14个碳原子的芳氧基、具有约7-约36个碳原子的芳基烷氧基、具有6-约14个碳原子的芳基、烷基取代的具有6-约14个碳原子的芳基(其中所述烷基取代基具有1-约30个碳原子)。优选R在每种情况下为苯基或苯氧基，更优选该硅氧烷选自八苯基环四硅氧烷、八苯氧基环四硅氧烷和烷氧基环硅氧烷。八苯基环四硅氧烷特别优选。
使用本领域的已知技术制备环状硅氧烷。如本领域已知的，例如它们可以通过水解卤化物母体，异构或者歧化直链聚合物来制备。
硅氧烷的有用量为小于或等于约0.25％重量，优选小于或等于约0.2％重量，更优选小于或等于约0.15％重量。典型地，硅氧烷的用量为大于或等于约0.01％重量，优选大于或等于约0.02％重量，更优选为大于或等于0.05％重量，各自基于聚碳酸酯的总用量。
阻燃聚碳酸酯组合物可包含惯用的添加剂，该添加剂为本领域已知用于包含在聚碳酸酯组合物中的。此添加剂包括但不局限于：稳定剂、脱模剂、光稳定剂、热稳定剂、颜料及染料。
可以通过任何已知用于混合热塑性塑料的混合手段，例如班伯里密炼机、维尔纳-普夫莱德雷尔混合机、挤出机或者轧制机，通过共混各成分来结合聚碳酸酯、聚四氟乙烯、阻燃剂和任选的硅氧烷。需要选择操作参数来维持组合物中各个成分的完整性，并且该参数可以很容易地由本领域普通技术人员确定。然后，该组合物可以使用本领域任何公知的方法来制成需要的制品，包括注塑。典型地，组合物的熔体体积速率(MVR)为约10-20cm3/10分，优选为约13-20cm3/10分，最优选为约15-20cm3/10分。令人惊奇的，这种半透明阻燃聚碳酸酯组合物在2.0毫米的厚度下根据UL94协议能够达到V0等级。
根据UL94，用于V0可燃性的标准可以简单的阐述如下。样品放置时其长轴与火焰成90°角，在移开点火的火焰以后，燃烧和/或闷烧(smoldering)的平均期间应该不超过5秒钟，并且垂直放置的样品不应该产生引燃脱脂棉的燃烧颗粒滴。
在此引入所有引用的专利作为参考。
本申请通过以下的非限制性实施例来进一步阐述。
实施例
下述的实施例使用了下表中的材料。分子量通过用聚碳酸酯树脂标准物，使用凝胶渗透色谱法来确定。
| 支化PC | 支化的聚碳酸酯树脂，包含0.3摩尔％的THPE，重均分子量为约38,000(摩尔％定义为与100摩尔双酚A共聚来制备支化聚碳酸酯的THPE的摩尔量) |
| 直链PC-1 | 直链双酚A聚碳酸酯，其重均分子量约22,000 |
| 直链PC-2 | 直链双酚A聚碳酸酯，其重均分子量约30,000 |
| PETS | 四硬脂酸季戊四醇酯，脱模剂 |
| KPFBS | 全氟丁烷磺酸钾 |
| TSAN | 包胶在苯乙烯丙烯腈中的聚四氟乙烯，含有50重量％的聚四氟乙烯 |
| 环状硅氧烷 | 八苯基环四硅氧烷 |
通过常规的挤出和模塑来制备以下给出的样品。所有的量都是基于聚碳酸酯总重量的重量份数。可燃性的结果通过“第一时间通过的可能性”或者p(FTP)来给出。通过UL94方法，灼烧了20个棒，并且使用消焰时间的平均值和标准偏差，以计算在5个棒的标准试验中，样品可以通过的可能性。通过第一时间90％的可能性(也就是说p(FTP)为0.9)被认为是可以接受的性能。明显低于0.9的值不能接受。p(FTP)仅计算在试验过程中没有因为滴流而失败的样品。那些被标记为“滴流”。获得阻燃性的结果用于厚度为2.3毫米和2.0毫米的棒。根据ASTM-D1238，使用300℃和1.2kg的条件测量熔体体积速率。雾度和透光度值根据ASTM D1003来测量。黄色指数根据ASTMD1925测量。
实施例1-6：
表1
| 1<sup>*</sup> | 2<sup>*</sup> | 3 | 4 | 5 | 6 | |
| 直链PC-1 | 70％ | 60％ | 82％ | 82％ | 82％ | 82％ |
| 支化PC | - | - | 18％ | 18％ | 18％ | 18％ |
| 直链PC-2 | 30％ | 40％ | - | - | - | - |
| PETS | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 |
| KPFBS | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
| TSAN | - | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| 环状硅氧烷 | 0.1 | 0.1 | - | 0.1 | 0.125 | 0.15 |
| MVR | 17.51 | 14.92 | 15.63 | 14.46 | 15.6 | 15.24 |
| p[FTP]@2.0毫米 | 滴流 | 0.4338 | 0.9985 | 0.9985 | 1 | 0.9999 |
| p[FTP]@2.3毫米 | 滴流 | 0.9152 | - | - | - | - |
| ％雾度 | 0.8 | 10.1 | 26.1 | 18.2 | 21.4 | 18.3 |
| ％透光度 | 90.7 | 77.3 | 74.2 | 78 | 76.4 | 77.7 |
| YI | 2.1 | 11.8 | 13.4 | 11.1 | 12.1 | 11.4 |
*对比实施例
实施例3-6和实施例2的比较说明在组合物中包含支化聚碳酸酯，导致在厚度为2.0毫米时达到了V0等级。实施例3和实施例4的比较说明添加环状硅氧烷降低了雾度和黄色指数，并且增加了透光度。
实施例7-12
表2
| 7 | 8 | 9 | 10 | 11 | 12 | |
| 直链PC-1 | 84 | 80 | 76 | 84 | 80 | 76 |
| 支化树脂 | 16 | 20 | 24 | 16 | 20 | 24 |
| PETS | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 |
| KPFBS | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
| 环状硅氧烷 | 0.1 | 0.1 | 0.1 | 0.125 | 0.125 | 0.125 |
| MVR，6分钟 | 17.61 | 15.43 | 13.32 | 16.66 | 15 | 13.5 |
| MVR，18分钟 | 17.62 | 15.15 | 13.42 | 16.88 | 14.86 | 13.65 |
| ％雾度 | 0.9 | 0.9 | 0.8 | 0.7 | 0.9 | 1.1 |
| ％透光度 | 89.9 | 90.2 | 90.4 | 90.6 | 90.4 | 90.5 |
| YI | 2 | 1.7 | 1.7 | 1.5 | 1.4 | 1.6 |
| p(FTP)2.3毫米 | 0.5179 | 滴流 | 0.4576 | 滴流 | 滴流 | 0.1648 |
实施例7-12是对比实施例，不合有聚四氟乙烯。
实施例7-12说明在2.3毫米时不满足V0性能。
实施例13-19：
表3
| 13<sup>*</sup> | 14 | 15<sup>*</sup> | 16<sup>*</sup> | 17 | 18<sup>*</sup> | 19<sup>*</sup> | |
| 直链PC-1 | 82 | 82 | 82 | 82 | 82 | 82 | 82 |
| 支化PC | 18 | 18 | 18 | 18 | 18 | 18 | 18 |
| PETS | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 |
| KPFBS | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
| TSAN | - | 0.1 | 0.2 | 0.3 | 0.1 | 0.2 | 0.3 |
| 环状硅氧烷 | - | - | - | - | 0.1 | 0.1 | 0.1 |
| MVR，6分钟 | 15.78 | 16.45 | 15.8 | 15.47 | 16.79 | 15.78 | 15.67 |
| MVR，18分钟 | 16.18 | 16.39 | 16.28 | 16.07 | 16.8 | 16.48 | 16.73 |
| ％透光度 | 90.3 | 75.1 | 66.2 | 61.3 | 76.4 | 65.1 | 60.7 |
| ％雾度 | 0.4 | 25.9 | 57.7 | 70.6 | 24.2 | 54.7 | 75.5 |
| p(FTP)2.3毫米 | 0.934 | 0.9999 | 1 | 1 | 1 | 1 | 1 |
| 平均消焰时间，秒 | 2.2 | 1.5 | 1.2 | 1.1 | 1.4 | 1.1 | 1 |
*对比实施例
通过比较对比实施例13、15、16、18、19和实施例14、17的结果，可以明显的看出聚四氟乙烯0.2或者更高的水平会导致具有高雾度百分比和低透光百分比的组合物。
实施例20-25：
表4
| 20<sup>*</sup> | 21<sup>*</sup> | 22 | 23 | 24 | 25 | |
| 直链PC-1 | 88％ | 70％ | 88％ | 88％ | 88％ | 88％ |
| 支化PC | 12％ | - | 12％ | 12％ | 12％ | 12％ |
| 直链PC-2 | - | 30％ | - | - | - | - |
| PETS | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 |
| KPFBS | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
| TSAN | - | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| 环状硅氧烷 | 0.1 | 0.1 | - | 0.1 | 0.125 | 0.15 |
| MVR | 19.12 | 17.52 | 17.72 | 17.94 | 18.43 | 18.56 |
| p[FTP]2.0毫米 | 滴流 | 滴流 | 0.9925 | 0.9969 | 0.8842 | 0.8165 |
| p[FTP]2.3毫米 | 0.2749 | 0.057 | - | - | - | 0.9996 |
| ％雾度 | 0.5 | 20.8 | 26.7 | 20 | 21.2 | 20.3 |
| ％透光度 | 90.6 | 76.1 | 74.2 | 77 | 76.7 | 77.3 |
| YI | 2 | 12.2 | 12.9 | 11.6 | 11.5 | 11.5 |
*对比实施例
实施例22和23说明在厚度为2.0毫米时，可通过包括直链或支化聚碳酸酯树脂、无溴和氯的阻燃剂、氟化聚烯烃和硅氧烷的组合物达到V0等级。
实施例26-31：
表5
| 26 | 27 | 28 | 29 | 30 | 31 | |
| 直链PC-1 | 80％ | 88％ | 95％ | 80％ | 88％ | 95％ |
| 支化PC | 20％ | 12％ | 5％ | 20％ | 12％ | 5％ |
| PETS | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 | 0.35 |
| TSAN | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| KPFBS | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 | 0.08 |
| 环状硅氧烷 | - | - | - | 0.1 | 0.1 | 0.1 |
| 熔体流动 | 15.29 | 19.73 | 24.83 | 15.39 | 18.12 | 24.05 |
| p[FTP]2.0毫米 | 0.9696 | 0.9518 | 0.992 | 0.9999 | 0.9804 | 0.5432 |
| p[FTP]2.3毫米 | 1 | 0.9707 | 0.9965 | 0.9972 | 0.9992 | 0.9933 |
| ％雾度 | 22.2 | 16.7 | 23.7 | 15.2 | 18 | 15.5 |
| ％透光度 | 76.8 | 79.3 | 76.8 | 80.5 | 79.2 | 79.7 |
| YI | 11.5 | 10.3 | 11 | 9.6 | 10 | 9.8 |
在实施例26-28中，在没有硅氧烷存在的条件下，改变直链和支化聚碳酸酯树脂的相对量，同时例如熔体体积速率和雾度百分比等性质也相应地变化。实施例29-31包含硅氧烷，并且和实施例26-28相似，改变直链和支化聚碳酸酯树脂的相对用量。在没有明显改变组合物其它特性的情况下，添加硅氧烷降低了雾度百分比。
通过前述的实施例可以看出，对于厚度为2.0毫米的聚碳酸酯组合物，在不损失如透明度等特性的条件下达到V0等级是可能的。这些组合物具有足以用于注塑的熔体体积速率。
虽然已经列举和解释了优选实施方式，但是在不违背本发明的精神和范围的前提下可进行各种变化和替换。由此，应该理解本发明所使用的说明方式是非限制性的。
Claims (21)
1.一种阻燃聚碳酸酯组合物，包括：
包含支化聚碳酸酯的聚碳酸酯树脂；
聚四氟乙烯树脂，其中所述聚四氟乙烯树脂的存在量基于所述聚碳酸酯的总重量为小于0.1重量％；
无溴和氯的阻燃剂；其中所述阻燃剂的存在量基于所述聚碳酸酯的总重量为0.01-0.15重量％；其中所述阻燃剂包括碳原子数为1-14的全氟烷烃磺酸钠或钾；
其中所述聚碳酸酯组合物在厚度为3.2毫米下，具有小于或等于30％的雾度和大于或等于70％的透光度，在厚度为小于或等于2.5毫米下根据UL94具有V1等级或更好。
2.权利要求1所述的组合物，其中所述聚碳酸酯树脂具有0.01-0.15％的支化。
3.权利要求1所述的组合物，其中所述聚四氟乙烯树脂的存在量基于所述聚碳酸酯的总重量为小于或等于0.075重量％。
4.权利要求3所述的组合物，其中所述聚四氟乙烯树脂的存在量基于所述聚碳酸酯的总重量为小于或等于0.05重量％。
5.权利要求1所述的组合物，其中所述聚四氟乙烯树脂为包胶的。
6.权利要求1所述的组合物，其中所述阻燃剂为全氟丁烷磺酸钾。
7.权利要求1所述的组合物，其中所述阻燃剂的存在量基于所述聚碳酸酯的总重量为0.03-0.12重量％。
8.权利要求7所述的组合物，其中所述阻燃剂的存在量基于所述聚碳酸酯的总重量为0.05-0.1重量％。
9.权利要求1所述的组合物，进一步包括硅氧烷。
10.权利要求9所述的组合物，其中所述硅氧烷为环状硅氧烷。
11.权利要求10所述的组合物，其中所述硅氧烷为下式的环状硅氧烷：
其中R各自独立地选自具有1-36个碳原子的烷基、具有1-36个碳原子的烷氧基、具有6-14个碳原子的芳氧基、具有7-36个碳原子的芳基烷氧基、具有6-14个碳原子的芳基、烷基取代的具有6-14个碳原子的芳基，其中所述烷基取代基具有1-30个碳原子。
12.权利要求11所述的组合物，其中所述硅氧烷选自八苯基环四硅氧烷、八苯氧基环四硅氧烷和烷氧基环硅氧烷。
13.权利要求12所述的组合物，其中所述硅氧烷为八苯基环四硅氧烷。
14.权利要求9所述的组合物，其中所述硅氧烷的存在量基于所述聚碳酸酯的总重量为0.01-0.25重量％。
15.权利要求14所述的组合物，其中所述硅氧烷的存在量基于所述聚碳酸酯的总重量为0.02-0.2重量％。
16.权利要求15所述的组合物，其中所述硅氧烷的存在量基于所述聚碳酸酯的总重量为0.05-0.15重量％。
17.权利要求1的阻燃聚碳酸酯组合物，还包括硅氧烷，其中所述硅氧烷的存在量基于所述聚碳酸酯的总重量小于或等于0.25重量％。
18.一种阻燃聚碳酸酯组合物，包括：
包含支化聚碳酸酯的聚碳酸酯树脂；
聚四氟乙烯树脂，其存在量基于所述聚碳酸酯树脂总重量为小于0.1重量％；
无溴和氯的阻燃剂，其存在量基于所述聚碳酸酯树脂总重量为0.01-0.15重量％；其中所述阻燃剂包括碳原子数为1-14的全氟烷烃磺酸钠或钾；
其中所述聚碳酸酯组合物在厚度小于或等于2.5毫米下，根据UL94具有V1等级或者更好。
19.权利要求18所述的组合物，进一步包括硅氧烷。
20.一种阻燃聚碳酸酯组合物，包括：
直链或支化的聚碳酸酯树脂；
聚四氟乙烯树脂，其存在量基于所述聚碳酸酯树脂总重量为小于0.1重量％；
无溴和氯的阻燃剂，其存在量基于所述聚碳酸酯树脂总重量为0.01-0.15重量％；其中所述阻燃剂包括碳原子数为1-14的全氟烷烃磺酸钠或钾；
环状硅氧烷，其中所述硅氧烷的存在量基于所述聚碳酸酯的总重量小于或等于0.25重量％。
21.一种阻燃聚碳酸酯组合物，包括：
包含支化聚碳酸酯树脂的聚碳酸酯树脂；
聚四氟乙烯树脂，其存在量基于所述聚碳酸酯树脂总重量为小于0.1重量％；
无溴和氯的阻燃剂，其存在量基于所述聚碳酸酯树脂总重量为0.01-0.15重量％；其中所述阻燃剂包括碳原子数为1-14的全氟烷烃磺酸钠或钾；
其中所述聚碳酸酯树脂具有0.01％到0.15％的支化，所述聚碳酸酯组合物在厚度为3.2毫米下具有小于或等于30％的雾度和大于或等于70％的透光度，在厚度为小于或等于2.5毫米时根据UL94具有V1等级或更好。
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| CN112063148A (zh) * | 2020-09-16 | 2020-12-11 | 横店集团得邦工程塑料有限公司 | 一种具有高阻燃性能的耐水解pc复合材料及其制备方法 |
| EP4092070A1 (de) | 2021-05-17 | 2022-11-23 | Covestro Deutschland AG | Reduzierung des gehalts spezieller salze von sulfonsäure-, sulfonamiden- oder sulfonimidderivaten im abwasser |
| EP4092075A1 (de) | 2021-05-17 | 2022-11-23 | Covestro Deutschland AG | Flammwidrige zusammensetzung umfassend 0,040 bis 0,095 gew.-% eines flammschutzmittels |
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- 2002-11-04 KR KR1020047008940A patent/KR100899506B1/ko active IP Right Grant
- 2002-11-04 JP JP2003551198A patent/JP2005511843A/ja active Pending
- 2002-11-04 CN CNB028277805A patent/CN100366668C/zh not_active Expired - Fee Related
- 2002-11-04 AU AU2002350134A patent/AU2002350134A1/en not_active Abandoned
- 2002-11-04 DE DE60223842T patent/DE60223842T2/de not_active Expired - Lifetime
- 2002-11-04 EP EP02786662A patent/EP1458799B1/en not_active Expired - Lifetime
- 2002-11-27 TW TW091134519A patent/TWI287558B/zh active
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Also Published As
| Publication number | Publication date |
|---|---|
| US6462111B1 (en) | 2002-10-08 |
| JP2005511843A (ja) | 2005-04-28 |
| EP1458799A1 (en) | 2004-09-22 |
| DE60223842T2 (de) | 2008-10-09 |
| CN1617905A (zh) | 2005-05-18 |
| WO2003050176A1 (en) | 2003-06-19 |
| AU2002350134A1 (en) | 2003-06-23 |
| TWI287558B (en) | 2007-10-01 |
| JP2010248527A (ja) | 2010-11-04 |
| KR100899506B1 (ko) | 2009-05-26 |
| TW200300782A (en) | 2003-06-16 |
| DE60223842D1 (de) | 2008-01-10 |
| JP5480041B2 (ja) | 2014-04-23 |
| EP1458799B1 (en) | 2007-11-28 |
| KR20040071714A (ko) | 2004-08-12 |
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