CN107189098B - Additive for polymer, preparation method and application thereof, and flame-retardant polymer molding composition composed of additive - Google Patents
Additive for polymer, preparation method and application thereof, and flame-retardant polymer molding composition composed of additive Download PDFInfo
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- CN107189098B CN107189098B CN201710358694.XA CN201710358694A CN107189098B CN 107189098 B CN107189098 B CN 107189098B CN 201710358694 A CN201710358694 A CN 201710358694A CN 107189098 B CN107189098 B CN 107189098B
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- Prior art keywords
- additive
- polymer
- sulfate
- mol
- sodium
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- 229920000642 polymer Polymers 0.000 title claims abstract description 140
- 239000000654 additive Substances 0.000 title claims abstract description 100
- 230000000996 additive effect Effects 0.000 title claims abstract description 92
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 239000003063 flame retardant Substances 0.000 title claims abstract description 33
- 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 abstract description 31
- 238000000465 moulding Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 23
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 47
- -1 ethylene, propylene, butylene Chemical group 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 150000002736 metal compounds Chemical class 0.000 claims description 17
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 17
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 14
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims description 10
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 10
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- VFNGKCDDZUSWLR-UHFFFAOYSA-N disulfuric acid Chemical compound OS(=O)(=O)OS(O)(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-N 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 229920001955 polyphenylene ether Polymers 0.000 claims description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 6
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 6
- 235000011151 potassium sulphates Nutrition 0.000 claims description 6
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 6
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 6
- 229960001763 zinc sulfate Drugs 0.000 claims description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 6
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- IOGRQIWFIRKXQV-UHFFFAOYSA-K aluminum dipropylphosphinate Chemical compound C(CC)P([O-])(=O)CCC.[Al+3].C(CC)P([O-])(=O)CCC.C(CC)P([O-])(=O)CCC IOGRQIWFIRKXQV-UHFFFAOYSA-K 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical group [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 claims description 2
- 239000012934 organic peroxide initiator Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 2
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 16
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000012545 processing Methods 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- 239000000047 product Substances 0.000 description 31
- 239000011259 mixed solution Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- KTLIMPGQZDZPSB-UHFFFAOYSA-M diethylphosphinate Chemical compound CCP([O-])(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-M 0.000 description 19
- LPFYDEANGXVAOA-UHFFFAOYSA-M sodium;diethylphosphinate Chemical compound [Na+].CCP([O-])(=O)CC LPFYDEANGXVAOA-UHFFFAOYSA-M 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 17
- 239000012065 filter cake Substances 0.000 description 14
- 239000003365 glass fiber Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 12
- 238000004679 31P NMR spectroscopy Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006386 neutralization reaction Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- AMVQGJHFDJVOOB-UHFFFAOYSA-H aluminium sulfate octadecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O AMVQGJHFDJVOOB-UHFFFAOYSA-H 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- TYFJTEPDESMEHE-UHFFFAOYSA-N 6,8-dihydroxy-3-[2-(4-methoxyphenyl)ethyl]-3,4-dihydroisochromen-1-one Chemical compound C1=CC(OC)=CC=C1CCC1OC(=O)C2=C(O)C=C(O)C=C2C1 TYFJTEPDESMEHE-UHFFFAOYSA-N 0.000 description 8
- SPWAXFLJYHRRJL-UHFFFAOYSA-N butyl(ethyl)phosphinic acid Chemical compound CCCCP(O)(=O)CC SPWAXFLJYHRRJL-UHFFFAOYSA-N 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000013329 compounding Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- GQZXNSPRSGFJLY-UHFFFAOYSA-N hydroxyphosphanone Chemical compound OP=O GQZXNSPRSGFJLY-UHFFFAOYSA-N 0.000 description 5
- 229940005631 hypophosphite ion Drugs 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 4
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- KSHDLNQYVGBYHZ-UHFFFAOYSA-N dibutylphosphinic acid Chemical compound CCCCP(O)(=O)CCCC KSHDLNQYVGBYHZ-UHFFFAOYSA-N 0.000 description 3
- NPEWVJINTXPNRF-UHFFFAOYSA-N dicyclohexylphosphinic acid Chemical compound C1CCCCC1P(=O)(O)C1CCCCC1 NPEWVJINTXPNRF-UHFFFAOYSA-N 0.000 description 3
- WMDPJKZHARKRQI-UHFFFAOYSA-N dipropylphosphinic acid Chemical compound CCCP(O)(=O)CCC WMDPJKZHARKRQI-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- HHYXZVYUIJDJAH-UHFFFAOYSA-L magnesium;diethylphosphinate Chemical compound [Mg+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC HHYXZVYUIJDJAH-UHFFFAOYSA-L 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- TXGSCOIHIBPDEJ-UHFFFAOYSA-M sodium dibutylphosphinate Chemical compound C(CCC)P([O-])(=O)CCCC.[Na+] TXGSCOIHIBPDEJ-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- SLKRGHBFYYVSLH-UHFFFAOYSA-K tris(dibutylphosphoryloxy)alumane Chemical compound [Al+3].CCCCP([O-])(=O)CCCC.CCCCP([O-])(=O)CCCC.CCCCP([O-])(=O)CCCC SLKRGHBFYYVSLH-UHFFFAOYSA-K 0.000 description 2
- SLEVEIJYRUXHGL-UHFFFAOYSA-K tris(dicyclohexylphosphoryloxy)alumane Chemical compound C1(CCCCC1)P([O-])(=O)C1CCCCC1.[Al+3].C1(CCCCC1)P([O-])(=O)C1CCCCC1.C1(CCCCC1)P([O-])(=O)C1CCCCC1 SLEVEIJYRUXHGL-UHFFFAOYSA-K 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- MTWVYGIIHVUGNL-UHFFFAOYSA-N CCCCP(O)=O Chemical compound CCCCP(O)=O MTWVYGIIHVUGNL-UHFFFAOYSA-N 0.000 description 1
- DGLXNOJGOHKWTN-UHFFFAOYSA-N CCCP(O)=O Chemical compound CCCP(O)=O DGLXNOJGOHKWTN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- ILYLJTAIQODOTI-UHFFFAOYSA-N cyclohexylphosphinic acid Chemical compound OP(=O)C1CCCCC1 ILYLJTAIQODOTI-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- NJCSSEVCDOCKRN-UHFFFAOYSA-M sodium dicyclohexylphosphinate Chemical compound C1(CCCCC1)P([O-])(=O)C1CCCCC1.[Na+] NJCSSEVCDOCKRN-UHFFFAOYSA-M 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The inventionAn additive for polymers is disclosed, comprising: a: a metal dialkylphosphinate having the structure shown in formula I:
i wherein R1，R2Identical or different, represented by H, C1-C6 alkyl or C6-C18 aryl; m is Mg, Ca, Al, Zn and Fe; m is 2-3; b: containing SO4 2‑Compound of (1), wherein SO4 2‑The weight content of the additive in the polymer is 210 ppm-500 ppm. Wherein the particle size of the additive for the polymer is 2-46 μm; the invention also discloses a preparation method and application of the additive for the polymer and a flame-retardant polymer molding composition composed of the additive. The SO-containing compound prepared by the invention4 2‑The dialkyl phosphinic acid metal salt is used as an additive for the polymer, the additive is applied to the polymer, the corrosion degree to metal parts of a processing device is greatly reduced in the processing process of the flame-retardant polymer, the additive is not easy to migrate and separate out from the polymer under the high-temperature and high-humidity conditions, and meanwhile, the influence of the additive on the mechanical property of the polymer is small; and the preparation process is simple, the production cost is low, and the large-scale production is facilitated.
Description
The present application is a divisional application entitled "an additive for polymers and a process for their preparation and use and flame-retardant polymer molding compositions composed thereof" filed as patent No. 2015107239319 filed as 2015-10-30.
Technical Field
The invention relates to an additive for a polymer, in particular to a polymer containing SO4 2-The additives for polymers, their preparation and use, and flame-retardant polymer molding compositions composed thereof.
Background
The dialkyl phosphinic acid and the metal dialkyl phosphinate are efficient halogen-free flame retardants, have the characteristics of high stacking density, small flame retardant consumption, good mechanical properties, good color and luster, low smoke density and high CTI (comparative tracking index) value, and are widely applied to thermoplastic and thermosetting plastics such as polyamide, polyester, unsaturated resin, epoxy resin, polyurethane and the like.
DE4430932 discloses a process for preparing dialkylphosphinic aluminum and calcium dialkylphosphinphosphates from dialkylphosphinic acids with aluminum hydroxide or calcium hydroxide and their use as flame retardants in polyester molding compositions.
DE19910232 and U.S. Pat. No. 6,921 disclose a process for the preparation of metal salts of disubstituted phosphinic acids. Patent US6359171B1 discloses a method for preparing aluminum dialkylphosphinate by first synthesizing monoalkylphosphinate from yellow phosphorus, then initiating ethylene with a radical, hydrolyzing to obtain dialkylphosphinate, and reacting the obtained dialkylphosphinate with aluminum salt to obtain the aluminum dialkylphosphinate flame retardant.
Chinese patents CN98811622.7, cn98811626.x, CN98811627.8, etc. disclose a method for preparing dialkyl phosphinic acid and its metal salt by using acetic acid or water as reaction medium, sodium hypophosphite monohydrate or 50% hypophosphorous acid as raw material, and initiating reaction between the raw material and alpha-olefin by azo initiator or peroxide initiator.
However, when the metal dialkylphosphinate prepared by the method is applied to a polymer, the metal dialkylphosphinate is easy to migrate and precipitate from the polymer when the flame-retardant polymer is used under high-temperature and high-humidity conditions, and the surface performance of a flame-retardant polymer product is influenced. Meanwhile, the polymer added with the dialkyl phosphinic acid metal salt seriously corrodes metal parts of a processing device in the processing process, and the performance of the polymer is greatly influenced.
In order to overcome the above-mentioned disadvantages of the metal dialkylphosphinate, it is necessary to develop an additive which is less likely to migrate and precipitate from the polymer when applied to the polymer, has little influence on the mechanical properties of the polymer, and has little corrosion on metal parts of processing equipment.
The invention unexpectedly discovers that when the dialkyl phosphinic acid metal salt additive contains SO with a content of a specific range4 2-Then, the obtained SO-containing4 2-The dialkyl phosphinic acid metal salt additive is not easy to migrate and separate out from the polymer, has small influence on the mechanical property of the polymer, and has small corrosion to metal parts of a processing device in the processing process of the polymer.
Technical content
The invention aims to provide an additive for a polymer, which is not easy to migrate and separate out from the polymer when applied to the polymer, has small influence on the mechanical property of the polymer and has small corrosion to metal parts of a processing device in the processing process of the polymer.
It is another object of the present invention to provide a method for preparing the above additive for polymers.
It is a further object of the present invention to provide the use of the above-mentioned additives for polymers.
It is a further object of the present invention to provide flame-retardant polymer molding compositions comprising the above-described additives for polymers.
The invention is realized by the following technical scheme:
an additive for a polymer comprising:
a: a metal dialkylphosphinate having the structure shown in formula I:
wherein R is1，R2Identical or different, is H, C1-C6 alkyl or C6-C18 aryl;
m is Mg, Ca, Al, Zn and Fe;
m is 2-3;
b: containing SO4 2-a compound of (a); wherein SO4 2-The weight content of the additive in the polymer is 210 ppm-500 ppm;
wherein the particle size of the additive for the polymer is 2-46 mu m.
Wherein the particle size and SO of the additive for polymer4 2-The weight content in the additive for the polymer satisfies the relationship shown in formula II or formula III:
when x is less than or equal to 32, y is less than or equal to-7.25 x +497 II;
when x is greater than 32, y is less than or equal to 16x-247 III;
wherein y represents SO4 2-The weight content in the additive for polymers, in ppm; x represents the particle size of the additive for the polymer in μm.
Wherein the particle size of the additive for the polymer and the SO in the additive4 2-The relationship of the weight content is as follows: the additive used for the polymer has small particle size and large specific surface area, and SO adsorbed by the additive used for the polymer in the preparation process of the additive used for the polymer4 2-High content, encapsulated SO4 2-The content is low; as the particle size of the additive for polymer is increased, the specific surface area is decreased, and SO adsorbed on the surface of the additive4 2-Reduced content of encapsulated SO4 2-The content is slightly increased; when the particle diameter of the additive for polymers is large to some extent, the additive for polymers is resistant to SO during the preparation process4 2-Increased wrapping degree and addition of SO4 2-The content increases.
Preferably, said R is1And R2Identical or different, is ethyl, propyl, butyl or cyclohexyl; and M is Mg, Al and Zn.
Preferably, the metal dialkylphosphinate is one or more of aluminum diethylphosphinate, aluminum dipropylphosphinate, aluminum dibutylphosphinate, aluminum dicyclohexylphosphinate, magnesium diethylphosphinate and zinc diethylphosphinate.
Preferably, the SO4 2-The weight content of the additive in the polymer is 260-425 ppm; preferably 310ppm to 380 ppm.
SO according to the invention4 2-By selecting the SO-containing compounds4 2-The reaction raw material of (1) is added with SO in the preparation process4 2-The compound (2) may contain SO in the metal dialkylphosphinate4 2-The compound of (1).
Wherein said SO is contained4 2-The compound (b) is one or a mixture of sulfuric acid, pyrosulfuric acid, oleum and sulfate.
Wherein the sulfate is one or a mixture of more of sulfate containing IA group elements, sulfate containing IIA group elements, sulfate containing IIIA group elements, sulfate containing IB group elements, sulfate containing IIB group elements or sulfate containing VIII group elements in the periodic table of elements.
Wherein the sulfate is one or a mixture of more of normal sulfate, acid sulfate, pyrosulfate and hydrated sulfate; preferably one or a mixture of more of potassium sulfate, sodium bisulfate, sodium sulfate decahydrate, magnesium sulfate, calcium sulfate, aluminum sulfate, zinc sulfate and ferric sulfate.
Wherein the water content of the additive for the polymer is 0.01wt% -10 wt%, and preferably 0.1wt% -1 wt%.
Wherein the additive for the polymer has a bulk density of 50g/L to 850g/L, preferably 200g/L to 650 g/L.
Wherein the solubility of the additive for polymers in water, organic solvents or mixtures of water and organic solvents is 0.005wt% to 9.99 wt%.
Wherein the polymer is one or more of polyester, polyamide, polyphenyl ether, epoxy resin, homopolymerized ABS, copolymerized ABS and polystyrene; preferably one or more of polyester, polyamide and polyphenyl ether.
The additive for the polymer can be prepared by one of the following three methods:
the method comprises the following steps:
a) adding hypophosphite/hypophosphorous acid and SO to the solvent4 2-With an olefin under the action of an initiator to obtain a compound containing SO4 2-The dialkylphosphinic salt/acid solution of (a);
b) will contain SO4 2-The dialkylphosphinic acid salt/acid solution is reacted with a metal compound to obtain a solution containing SO4 2-A metal dialkylphosphinate of (a);
wherein the hypophosphite is sodium hypophosphite or potassium hypophosphite;
the metal compound is a metal compound of Mg, Ca, Al, Zn and Fe; preferably a metal compound of Mg, Al, Zn;
said containing SO4 2-The compound (A) is one or more of sulfuric acid, fuming sulfuric acid and pyrosulfuric acid;
or the second method:
reacting the dialkylphosphinic salt solution with an aqueous solution of a metal compound containing the additive I to give the corresponding SO-containing solution4 2-A metal dialkylphosphinate of (a);
wherein the additive I is one or more of sulfuric acid, sodium sulfate, potassium sulfate, sodium bisulfate, sodium sulfate decahydrate, magnesium sulfate, calcium sulfate, aluminum sulfate, zinc sulfate and ferric sulfate;
the metal compound is a metal compound of Mg, Ca, Al, Zn and Fe; preferably a metal compound of Mg, Al, Zn;
the dialkyl phosphinate is sodium dialkyl phosphinate or potassium dialkyl phosphinate;
or the third method:
in the metal dialkylphosphinate productAdding additive II in the filtering process or washing process or drying process to obtain product containing SO4 2-A metal dialkylphosphinate of (a);
wherein the additive II is one or more of sulfuric acid, sodium sulfate, potassium sulfate, sodium bisulfate, sodium sulfate decahydrate, magnesium sulfate, calcium sulfate, aluminum sulfate, zinc sulfate and ferric sulfate;
wherein, the solvent in the first method is cyclohexane and/or cyclohexene; the initiator in the first method is an azo initiator, an organic peroxide initiator and an inorganic peroxide initiator; in the first method, the olefin is one or more of ethylene, propylene, butylene and cyclohexene.
The invention discloses the use of the additive for polymers as described above as a flame retardant.
The invention also discloses a flame-retardant polymer molding composition of the additive for the polymer, which comprises the following components in parts by weight: 5-25 parts of an additive for a polymer; 40 to 75 parts of a polymer or a mixture thereof; wherein the additives for the polymer comprise:
a: a metal dialkylphosphinate having the structure shown in formula I:
wherein R is1，R2Identical or different, is H, C1-C6 alkyl or C6-C18 aryl;
m is Mg, Ca, Al, Zn and Fe;
m is 2-3;
b: containing SO4 2-a compound of (a); wherein SO4 2-The weight content of the additive in the polymer is 210 ppm-500 ppm;
wherein the particle size of the additive for the polymer is 2-46 mu m.
Wherein the particle size and SO of the additive for polymer4 2-The weight content in the additive for polymer is satisfiedA relationship represented by formula II or formula III:
when x is less than or equal to 32, y is less than or equal to-7.25 x +497 II;
when x is greater than 32, y is less than or equal to 16x-247 III;
wherein y represents SO4 2-The weight content in the additive for polymers, in ppm; x represents the particle size of the additive for the polymer in μm.
Wherein, R is1And R2Identical or different, is ethyl, propyl, butyl or cyclohexyl; and M is Mg, Al and Zn.
Wherein the dialkyl phosphinate metal salt is one or more of aluminum diethyl phosphinate, aluminum dipropyl phosphinate, aluminum dibutyl phosphinate, aluminum dicyclohexyl phosphinate, magnesium diethyl phosphinate and zinc diethyl phosphinate.
Preferably, the SO4 2-The weight content of the additive in the polymer is 260-425 ppm; more preferably 310ppm to 380 ppm.
Wherein the polymer is one or more of polyester, polyamide, polyphenyl ether, epoxy resin, homopolymerized ABS, copolymerized ABS and polystyrene; preferably one or more of polyester, polyamide and polyphenyl ether.
The flame-retardant polymer molding composition of the additive for polymers of the present invention further comprises 0 to 30 parts by weight of a filler and 0 to 5 parts by weight of a processing aid.
Where the filler is a material commonly used to reinforce or fill polymers, mixtures of two or more inorganic fillers and/or reinforcing agents may also be used. The filler may include one or more of the following: glass fiber, glass flake, kaolin, clay, talc powder, wollastonite, calcium carbonate, silica, carbon fiber, potassium titanate, and the like.
Wherein the processing aid may be an additional component that does not interfere with the aforementioned desired properties but enhances other beneficial properties, such as antioxidants, lubricants, mold release agents, nucleating agents, colorants, light stabilizers.
Compared with the prior art, the invention has the following beneficial effects:
1) the SO-containing compound prepared by the invention4 2-The dialkyl phosphinic acid metal salt is used as an additive for the polymer, the additive is applied to the polymer, the corrosion degree of metal parts of a processing device is greatly reduced in the processing process of the flame-retardant polymer, and the influence on the mechanical property of the polymer is small.
2) The SO-containing compound prepared by the invention4 2-The dialkyl phosphinic acid metal salt is used as an additive for the polymer, the additive is applied to the polymer, the additive is not easy to migrate and separate out from the polymer under the high-temperature and high-humidity conditions, and the surface performance of the flame-retardant polymer is greatly optimized.
3) The additive for the polymer has the advantages of simple preparation process, low production cost and convenience for large-scale production.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
The raw materials used in the examples and comparative examples are now described below, but are not limited to these materials:
PBT: PBT 1100 + 211M (Taiwan Changchun group)
PA 66: PA66 EP-158 (Huafeng group)
PA 6: PA 6M 2000 (Guangdong Xinhui Mada Jinlun GmbH)
PPE: PPE 100Z (Japan Xuhua)
Glass fiber 1: ECS13-4.5-534 (huge stone group)
Glass fiber 2: ECS301-HP (Chongqing International composite Co., Ltd.);
antioxidant: 1010, (jinhaiyabao) antioxidant: 168 (Jinhai ya bao)
Lubricant: GLYCOLUBE-P (Nanjing friendly auxiliary chemical Co., Ltd.)
Releasing agent: silicone master batch (Dow Corning)
Nucleating agent: shalin (DUPONT)
Light stabilizer: 770 (Ciba Specialty Chemicals)
The particle size test method of the additive for polymers of the present invention is as follows:
the particle size distribution of the additive for polymer dispersed in the liquid phase was measured using a laser particle sizer. The specific operation is as follows: according to the particle size of the additive for the polymer, 0.05 g-1.0 g of sample is placed in a beaker, mixed solution of alcohol and water is added, stirred and dispersed, and poured into a laser particle size analyzer for about 1min, so that the particle size distribution of the additive for the polymer can be measured. The particle size of the additive for polymers of the present invention is evaluated by using D (50) measured by a laser particle sizer.
The additive bulk density test method for the polymer is determined according to GB 20316.2-determination of bulk density.
The method for testing the water content of the additive for the polymer refers to GBT 6284-2006-drying and reducing method which is a general method for testing the water content in chemical products.
The method for testing the solubility of the additives for polymers described in the present invention is the equilibrium method. The specific operation is as follows: adding an additive for a polymer into the solution at 25 ℃, stirring for a certain time at a constant temperature, and analyzing the composition of the upper layer solution after standing to be used as the solubility at the temperature; the solution is in water, an organic solvent or a mixture of water and an organic solvent.
SO in the additive for polymers according to the invention4 2-The weight content is measured by ion chromatography with reference to PREN 14582, determination of halogen content, and external standard method.
Notched impact strength: GB 1843-.
Evaluation of the invention the corrosion of the metal parts of the processing apparatus by the high-polymer molding compositions is determined by the degree of corrosion (. DELTA.D) of the screws. The Δ D was measured as follows:
the screw at the same position before and after production was measured every 100t of the flame-retardant polymer composition processed by the compounding assemblyDiameter of the rod (D)Front sideAnd DRear end) The difference Δ D = D in the screw diameter after 100t of flame-retardant polymer molding composition has been calculatedFront side-DRear endThe larger the Δ D value, the more severe the screw corrosion.
According to the invention, the corrosion degree delta D of the 30% glass fiber reinforced PBT high polymer molding composition to a screw of a compounding combination device is 0.25 mm-0.75 mm.
The degree of corrosion Delta D of the non-glass fiber reinforced PA66 high polymer molding composition to the screw of the compounding assembly is 0.05 mm-0.25 mm.
The degree of corrosion Delta D of the 30 percent glass fiber reinforced PA6/PPE alloy high polymer molding composition to the screw of the compounding and combining device is 0.40 mm-0.95 mm.
The 25 percent glass fiber reinforced PA6 high polymer molding composition has a screw corrosion degree Delta D of 0.40 mm-0.72 mm on a compounding combination device.
The method for evaluating the surface performance of the flame-retardant polymer is to measure the content of precipitates on the surface of a flame-retardant polymer workpiece in a high-temperature and high-humidity environment.
The specific test method comprises the following steps: and (3) injection molding a 2mm color plate, placing the color plate in a 95-percent constant temperature and humidity box for 24 hours at 95 ℃, placing the color plate in a standard laboratory with the ambient temperature of (23 +/-2) DEG C and the relative humidity of 45-55 percent, and measuring the change delta L of the L value before and after the color plate is treated by a color difference meter after adjusting for 48 hours. The larger Δ L, the more serious powder deposition.
The delta L value of the 30% glass fiber reinforced PBT high polymer molding composition is 0.01-0.40.
The delta L value of the non-glass fiber reinforced PA66 high polymer molding composition is 0.10-0.55.
The delta L value of the 30% glass fiber reinforced PA6/PPE alloy high polymer molding composition is 0.45-0.85.
The delta L value of the 25% glass fiber reinforced PA6 high polymer molding composition is 0.45-1.05.
Combustion performance: UL94 test for burning performance of plastics;
the UL94 flame rating was determined using test specimens having a thickness of 1.5mm for the test specimens from each mixture. The following are the UL94 specified combustion ratings:
v-0: after the sample strips leave the flame, the continuous burning time is not longer than 10s, the total continuous burning time of the 5 sample strips in 10 ignition times is not more than 50s, no molten drop drops, the flame does not spread to a clamp, and the afterglow burning time of the sample after the ignition is finished is not longer than 30 s.
V-1: after the sample leaves the flame, the sustained combustion time is not longer than 30s, the total of the sustained combustion time of the 5 samples in 10 ignition times does not exceed 250s, the afterglow combustion time of the sample after the ignition is finished is not longer than 60s, and other standards are like V-0.
V-2: after the sample strips leave the flame, molten drops appear in the continuous combustion process, and the molten drops can ignite the absorbent cotton indicator, and other standards are the same as V-1.
Non-classifiable (ncl): combustion grade V-2 is not satisfied.
Comparative example 1
2120.0g (20 mol) of sodium hypophosphite, 1320.0g (10 mol) of 50wt% hypophosphorous acid, 27.2g (0.3 mol% of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and 3000g of water are added into an autoclave, the autoclave is evacuated, replaced by nitrogen for 3 times, evacuated, ethylene is filled through a pressure reducer, the pressure is controlled to be 2.0MPa, the autoclave is heated to 87 ℃, the temperature is kept constant for 5 hours, the autoclave is heated to 95 ℃, 54.4g (0.6 mol% of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane is continuously supplemented in 5 hours, the temperature is raised to 100 ℃, the temperature is kept for 1 hour, and the mixture is cooled and emptied to obtain 8303.0g of a mixed solution of sodium diethylphosphinate and diethylphosphinate, which corresponds to an ethylene absorption capacity of 1779.9g (105.95% of theoretical capacity).
31P-NMR analysis:
mol content of diethylphosphinic acid: 96.7 percent
Ethyl butyl phosphinic acid mol content: 1.4 percent
The mol content of the ethylphosphinic acid: 0.9 percent
Other mol contents: 1.0 percent
830.3g of mixed solution of sodium diethylphosphinate and diethylphosphinate is taken, 1600g of water is added, 30% sodium hydroxide solution is used for neutralization to neutrality, the mixture is heated to 90 ℃, 78g (1 mol) of aluminum hydroxide is added, the mixture is kept at 90 ℃ for 5 hours, the mixture is filtered, and is washed for 3 times by 3000mL of water, the obtained filter cake is dried to constant weight at 130 ℃, and aluminum diethylphosphinate is obtained: 372.2g, yield: 95.4 percent.
Particle size D (50): 35 μm
SO4 2-The content is as follows: not detected or less than the detection limit of the method.
Comparative example 2
212.0g (2 mol) of sodium hypophosphite, 3696.0g (28 mol) of 50% hypophosphorous acid, 98g (0.5 mol) of 50% sulfuric acid solution, 27.2g (0.3 mol% of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and 3000g of water are added into an autoclave, the autoclave is evacuated, replaced by nitrogen for 3 times, evacuated, then filled with ethylene through a decompressor and controlled at a pressure of 2.0MPa, heated to 87 ℃ and kept at the constant temperature for 5h, heated to 95 ℃, and continuously supplemented with 54.4g (0.6 mol% of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane for 5h, heated to 100 ℃, kept at the temperature for 1h, cooled and emptied to obtain 8858.3g of a mixed solution of sodium diethylphosphinate and diethylphosphinate, which corresponds to 1770.7g of ethylene absorption (105.4% of the theoretical amount).
31P-NMR analysis:
mol content of diethylphosphinic acid: 95.9 percent
Ethyl butyl phosphinic acid mol content: 2.0 percent
The mol content of the ethylphosphinic acid: 1.1 percent
Other mol contents: 1.0 percent
885.8g of mixed solution of sodium diethylphosphinate and diethylphosphinate is taken, 1600g of water is added, 30% sodium hydroxide solution is used for neutralization to neutrality, the mixture is heated to 90 ℃, 78g (1 mol) of aluminum hydroxide is added, the mixture is kept at 90 ℃ for 5 hours, the mixture is filtered, and is washed for 3 times by 3000mL of water, the obtained filter cake is dried to constant weight at 130 ℃, and aluminum diethylphosphinate is obtained: 371.3g, yield: 95.2 percent.
Particle size D (50): 56 μm
SO4 2-The content is as follows: 681 ppm.
Example 1
212.0g (2 mol) of sodium hypophosphite, 3696.0g (28 mol) of 50% hypophosphorous acid, 19.6g (0.1 mol) of 50% sulfuric acid solution, 27.2g (0.3 mol% of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and 3000g of water are added into an autoclave, the autoclave is evacuated, replaced by nitrogen for 3 times, evacuated, filled with ethylene through a decompressor and controlled at a pressure of 2.0MPa, heated to 87 ℃ and kept at the constant temperature for 5 hours, heated to 95 ℃, and continuously supplemented with 54.4g (0.6 mol% of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane for 5 hours, heated to 100 ℃, kept at the temperature for 1 hour, cooled and emptied to obtain 8793.4g of a mixed solution of sodium diethylphosphinate and diethylphosphinate, which corresponds to 1784.2g of ethylene absorption (106.2% of the theoretical amount).
31P-NMR analysis:
mol content of diethylphosphinic acid: 96.0 percent
Ethyl butyl phosphinic acid mol content: 1.8 percent
The mol content of the ethylphosphinic acid: 1.2 percent of
Other mol contents: 1.0 percent
885.8g of mixed solution of sodium diethylphosphinate and diethylphosphinate is taken, 1600g of water is added, 30% sodium hydroxide solution is used for neutralization to neutrality, the mixture is heated to 90 ℃, 78g (1 mol) of aluminum hydroxide is added, the mixture is kept at 90 ℃ for 5 hours, the mixture is filtered, and is washed for 3 times by 3000mL of water, the obtained filter cake is dried to constant weight at 130 ℃, and aluminum diethylphosphinate is obtained: 372.5g, yield: 95.5 percent. Particle size D (50): 2 μm
SO4 2-The content is as follows: 500 ppm.
Example 2
212.0g (2 mol) of sodium hypophosphite, 3696.0g (28 mol) of 50% hypophosphorous acid, 59.3g (0.1 mol) of a 30% solution of pyrosulfuric acid, 27.2g (0.3 mol% of hypophosphite ion) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and 3000g of water were charged into an autoclave, evacuating, replacing 3 times with nitrogen, evacuating, filling ethylene through a pressure reducer, controlling the pressure to be 2.0MPa, heating to 87 ℃, keeping the temperature for 5 hours, heating to 95 ℃, continuously adding 54.4g (0.6% mol of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane in 5 hours, heating to 100 ℃, keeping the temperature for 1 hour, cooling and emptying to obtain 8843.1g of a mixed solution of sodium diethylphosphinate and diethylphosphinate, which is equivalent to 1794.2g (106.2% of theoretical amount) of ethylene absorption.
31P-NMR analysis:
mol content of diethylphosphinic acid: 96.3 percent
Ethyl butyl phosphinic acid mol content: 1.7 percent
The mol content of the ethylphosphinic acid: 1.1 percent
Other mol contents: 0.9 percent
884.3g of mixed solution of sodium diethylphosphinate and diethylphosphinate is taken, 1600g of water is added, 30% sodium hydroxide solution is used for neutralization to neutrality, the mixture is heated to 90 ℃, 78g (1 mol) of aluminum hydroxide is added, the mixture is kept at 90 ℃ for 5 hours, the mixture is filtered, and is washed for 3 times by 3000mL of water, the obtained filter cake is dried to constant weight at 130 ℃, and aluminum diethylphosphinate is obtained: 374.4g, yield: 96.0 percent. Particle size D (50): 30 μm
SO4 2-The content is as follows: 210 ppm.
Example 3
2120.0g (20 mol) of sodium hypophosphite, 1320.0g (10 mol) of 50wt% hypophosphorous acid, 27.2g (0.3 mol% of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and 3000g of water are added into an autoclave, the autoclave is evacuated, replaced by nitrogen for 3 times, evacuated, ethylene is filled through a pressure reducer, the pressure is controlled to be 2.0MPa, the autoclave is heated to 87 ℃, the temperature is kept constant for 5 hours, the autoclave is heated to 95 ℃, 54.4g (0.6 mol% of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane is continuously supplemented in 5 hours, the temperature is raised to 100 ℃, the temperature is kept for 1 hour, and the mixture is cooled and emptied to obtain 8303.0g of a mixed solution of sodium diethylphosphinate and diethylphosphinate, which corresponds to an ethylene absorption capacity of 1779.9g (105.95% of theoretical capacity).
31P-NMR analysis:
mol content of diethylphosphinic acid: 96.7 percent
Ethyl butyl phosphinic acid mol content: 1.4 percent
The mol content of the ethylphosphinic acid: 0.9 percent
Other mol contents: 1.0 percent
830.3g of mixed solution of sodium diethylphosphinate and diethylphosphinate is taken, 1600g of water is added, 30 percent sodium hydroxide solution is used for neutralization to neutrality, the mixture is heated to 90 ℃, an aluminum sulfate octadecahydrate solution prepared from 333g (0.5 mol) of aluminum sulfate octadecahydrate and 777g of water is added dropwise in 1.5h, the temperature is kept at 90 ℃ for 1h, the mixture is filtered, 3000mL of water is used for washing for 3 times, and the obtained filter cake is dried to constant weight at 130 ℃, so that the aluminum diethylphosphinate is obtained: 373.6g, yield: 95.8 percent. Particle size D (50): 32 μm
SO4 2-The content is as follows: 233 ppm.
Example 4
212.0g (2 mol) of sodium hypophosphite, 3696.0g (28 mol) of 50% hypophosphorous acid, 5.93g (0.01 mol) of a 30% solution of pyrosulfuric acid, 27.2g (0.3 mol% of hypophosphite ion) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and 3000g of water were charged into an autoclave, evacuating, replacing 3 times with nitrogen, evacuating, filling ethylene through a pressure reducer, controlling the pressure to be 2.0MPa, heating to 87 ℃, keeping the temperature for 5 hours, heating to 95 ℃, continuously adding 54.4g (0.6% mol of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane in 5 hours, heating to 100 ℃, keeping the temperature for 1 hour, cooling and emptying to obtain 8764.6g of a mixed solution of sodium diethylphosphinate and diethylphosphinate, which is equivalent to 1769.0g (105.3% of theoretical amount) of ethylene absorption.
31P-NMR analysis:
mol content of diethylphosphinic acid: 96.0 percent
Ethyl butyl phosphinic acid mol content: 1.6 percent
The mol content of the ethylphosphinic acid: 1.2 percent of
Other mol contents: 1.2 percent of
876.5g of mixed solution of sodium diethylphosphinate and diethylphosphinate is taken, 1600g of water is added, 30% sodium hydroxide solution is used for neutralization to neutrality, the mixture is heated to 90 ℃, an aluminum sulfate octadecahydrate solution prepared from 333g (0.5 mol) of aluminum sulfate octadecahydrate and 777g of water is added dropwise in 1.5h, the temperature is kept at 90 ℃ for 1h, the mixture is filtered, the mixture is washed for 3 times by 4500mL of water, and the obtained filter cake is dried to constant weight at 130 ℃, so that aluminum diethylphosphinate is obtained: 373.2g, yield: 95.7 percent. Particle size D (50): 36 μm
SO4 2-The content is as follows: 329 ppm.
Example 5
212.0g (2 mol) of sodium hypophosphite, 3696.0g (28 mol) of 50% hypophosphorous acid, 5.93g (0.01 mol) of a 30% solution of pyrosulfuric acid, 27.2g (0.3 mol% of hypophosphite ion) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and 3000g of water were charged into an autoclave, evacuating, replacing 3 times with nitrogen, evacuating, filling ethylene through a pressure reducer, controlling the pressure to be 2.0MPa, heating to 87 ℃, keeping the temperature for 5 hours, heating to 95 ℃, continuously adding 54.4g (0.6% mol of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane in 5 hours, heating to 100 ℃, keeping the temperature for 1 hour, cooling and emptying to obtain 8764.6g of a mixed solution of sodium diethylphosphinate and diethylphosphinate, which is equivalent to 1769.0g (105.3% of theoretical amount) of ethylene absorption.
31P-NMR analysis:
mol content of diethylphosphinic acid: 96.0 percent
Ethyl butyl phosphinic acid mol content: 1.6 percent
The mol content of the ethylphosphinic acid: 1.2 percent of
Other mol contents: 1.2 percent of
876.5g of mixed solution of sodium diethylphosphinate and diethylphosphinate is taken, 1600g of water is added, 30% sodium hydroxide solution is used for neutralization to neutrality, the mixture is heated to 90 ℃, magnesium sulfate heptahydrate solution prepared from 369.0g (1.5 mol) of magnesium sulfate heptahydrate and 861g of water is added dropwise in 1.5h, the temperature is kept at 90 ℃ for 1h, the mixture is filtered, 3000mL of water is used for washing for 3 times, and the obtained filter cake is dried to constant weight at 130 ℃, so that magnesium diethylphosphinate is obtained: 360.3g, yield: 90.3 percent. Particle size D (50): 39 μm
SO4 2-The content is as follows: 377 ppm.
Example 6
212.0g (2 mol) of sodium hypophosphite, 3696.0g (28 mol) of 50% hypophosphorous acid, 5.93g (0.01 mol) of a 30% solution of pyrosulfuric acid, 27.2g (0.3 mol% of hypophosphite ion) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and 3000g of water were charged into an autoclave, evacuating, replacing 3 times with nitrogen, evacuating, filling ethylene through a pressure reducer, controlling the pressure to be 2.0MPa, heating to 87 ℃, keeping the temperature for 5 hours, heating to 95 ℃, continuously adding 54.4g (0.6% mol of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane in 5 hours, heating to 100 ℃, keeping the temperature for 1 hour, cooling and emptying to obtain 8764.6g of a mixed solution of sodium diethylphosphinate and diethylphosphinate, which is equivalent to 1769.0g (105.3% of theoretical amount) of ethylene absorption.
31P-NMR analysis:
mol content of diethylphosphinic acid: 96.0 percent
Ethyl butyl phosphinic acid mol content: 1.6 percent
The mol content of the ethylphosphinic acid: 1.2 percent of
Other mol contents: 1.2 percent of
876.5g of mixed solution of sodium diethylphosphinate and diethylphosphinate is taken, 1600g of water is added, 30% sodium hydroxide solution is used for neutralization to neutrality, the mixture is heated to 90 ℃, a zinc sulfate heptahydrate solution prepared from 430.5g (1.5 mol) of zinc sulfate heptahydrate and 1004.5g of water is added dropwise in 1.5h, the temperature is kept at 90 ℃ for 1h, the mixture is filtered, 4000mL of water is used for washing for 3 times, and the obtained filter cake is dried to constant weight at 130 ℃, so that the zinc diethylphosphinate is obtained: 427.3g, yield: 92.2 percent. Particle size D (50): 38 μm
SO4 2-The content is as follows: 361 ppm.
Example 7
2120.0g (20 mol) of sodium hypophosphite, 1320.0g (10 mol) of 50% hypophosphorous acid, 27.2g (0.3% mol of hypophosphite ions) of 1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane and 3000g of water are added into an autoclave, the autoclave is evacuated, nitrogen is used for replacing 3 times, the evacuation is carried out, propylene is filled through a pressure reducer, the pressure is controlled to be 1.5MPa, the temperature is increased to 87 ℃, the temperature is kept constant for 6h, the temperature is heated to 95 ℃, 54.4g (0.6% mol of hypophosphite ions) of 1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane is continuously replenished in 5h, the temperature is increased to 100 ℃, the temperature is kept for 1h, the mixture is cooled and emptied to obtain 9146.4g of mixed solution of dipropyl sodium hypophosphite and dipropyl phosphinic acid, and the absorption amount of the propylene is equivalent to 2623.3 (103.10% of.
31P-NMR analysis:
dipropylphosphinic acid mol content: 95.0 percent
Mol content of propylphosphinic acid: 3.2 percent of
Other mol contents: 1.8 percent
914.6g of mixed solution of dipropyl sodium phosphinate and dipropyl phosphinic acid is taken, 1750g of water is added, 30 percent sodium hydroxide solution is used for neutralization to neutrality, the mixture is heated to 90 ℃, octadeca-hydrated aluminum sulfate solution prepared by 3.22g (0.01 mol) of sodium sulfate decahydrate, 333.0g (0.5 mol) of octadeca-hydrated aluminum sulfate and 777g of water is added dropwise in 1.5h, the temperature is kept at 90 ℃ for 1h, the mixture is filtered, 3000mL of water is used for washing for 3 times, and the obtained filter cake is dried to constant weight at 130 ℃, so that dipropyl aluminum phosphinate is obtained: 443.7g, yield: 93.6 percent.
Particle size D (50): 31 μm
SO4 2-The content is as follows: 272 ppm.
Example 8
2120.0g (20 mol) of sodium hypophosphite, 1320.0g (10 mol) of 50% phosphinic acid, 27.2g (0.3 mol% of hypophosphite ion) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and 3000g of water are added into an autoclave, evacuated, replaced by nitrogen for 3 times, evacuated, then filled with butene through a pressure reducer and the pressure is controlled to be 1.0MPa,
heating to 87 ℃, keeping the temperature for 5h, heating to 95 ℃, continuously adding 54.4g (0.6% mol of hypophosphite ions) of 1, 1-di-tert-butyl peroxy-3, 3, 5-trimethylcyclohexane in 5h, heating to 100 ℃, keeping the temperature for 1h, cooling and emptying to obtain 8298.1g of mixed solution of sodium dibutylphosphinate and dibutylphosphinic acid, wherein the mixed solution is equivalent to 1775.0g of butene absorption (105.65% of theoretical amount).
31P-NMR analysis:
dibutyl phosphinic acid mol content: 95.4 percent
Butyl phosphinic acid mol content: 2.9 percent of
Other mol contents: 1.7 percent
829.8g of mixed solution of sodium dibutylphosphinate and dibutylphosphinic acid is taken, 1600g of water is added, 30 percent sodium hydroxide solution is used for neutralization to neutrality, the mixture is heated to 90 ℃, an aluminum sulfate octadecahydrate solution prepared by 9.8g (0.05 mol) of 50 percent sulfuric acid solution, 333.0g (0.5 mol) of aluminum sulfate octadecahydrate and 777g of water is added dropwise in 1.5h, the temperature is kept at 90 ℃ for 1h, the mixture is filtered, 3000mL of water is used for washing for 3 times, and the obtained filter cake is dried to constant weight at 130 ℃, so that the aluminum dibutylphosphinate is obtained: 518.4g, yield: 92.9 percent.
Particle size D (50): 16 μm
SO4 2-The content is as follows: 381 ppm.
Example 9
2120.0g (20 mol) of sodium hypophosphite, 1320.0g (10 mol) of 50% hypophosphorous acid, 5412g (66 mol) of cyclohexene, 27.2g (0.3% mol of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane and 3000g of water are added into an autoclave, evacuated, replaced by nitrogen for 3 times, evacuated, heated to 87 ℃, kept at the constant temperature for 5 hours, heated to 95 ℃, continuously supplemented with 54.4g (0.6% mol of hypophosphite ions) of 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane for 5 hours, heated to 100 ℃, insulated for 1 hour, cooled and exhausted to obtain 11933.6g of a mixed solution of dicyclohexyl sodium hypophosphite and dicyclohexyl phosphinic acid.
31P-NMR analysis:
dicyclohexylphosphinic acid mol content: 93.8 percent
Cyclohexyl phosphinic acid mol content: 3.4 percent
Other mol contents: 2.8 percent of
1193.4g of mixed solution of sodium dicyclohexylphosphinate and dicyclohexylphosphinic acid is taken, 1600g of water is added, 30% sodium hydroxide solution is used for neutralization to neutrality, the solution is heated to 90 ℃, an aluminum sulfate octadecahydrate solution prepared from 13.6g (0.1 mol) of calcium sulfate, 333.0g (0.5 mol) of aluminum sulfate octadecahydrate and 777g of water is added dropwise in 1.5h, the solution is kept warm for 1h at 90 ℃, the solution is filtered, and is washed for 3 times by 2000mL of water, the obtained filter cake is dried to constant weight at 130 ℃, and the aluminum dicyclohexylphosphinate is obtained: 554.1g, yield: 77.6 percent.
Particle size D (50): 8 μm
SO4 2-The content is as follows: 439 ppm.
Example 10
Preparing a mixed solution of sodium diethylphosphinate and diethylphosphinate as in comparative example 1, adding 830.3g of water, neutralizing with 30% sodium hydroxide solution to neutrality, heating to 90 ℃, dropwise adding an aluminum sulfate octadecahydrate solution prepared from 333.0g (0.5 mol) of aluminum sulfate octadecahydrate and 1332g of water within 1.5h, keeping the temperature at 90 ℃ for 1h, filtering, washing with 3000mL of water for 3 times, spraying 10.4g of an aqueous sodium sulfate decahydrate solution with the mass fraction of 0.01% into the filter cake, and drying at 130 ℃ to constant weight to obtain aluminum diethylphosphinate: 373.1 g. The yield was 95.2%. Particle size D (50): 25 μm
SO4 2-The content is as follows: 315 ppm.
Example 11
Preparing a mixed solution of sodium diethylphosphinate and diethylphosphinate as in comparative example 1, adding 830.3g of water, neutralizing with 30% sodium hydroxide solution to be neutral, heating to 90 ℃, dropwise adding a zinc sulfate heptahydrate solution prepared from 430.5g (1.5 mol) of zinc sulfate heptahydrate and 1004.5g of water within 1.5h, keeping the temperature at 90 ℃ for 1h, adding 142g (0.05 mol) of sodium sulfate aqueous solution with the mass fraction of 5%, filtering, washing with 3000mL of water for 3 times, and drying the obtained filter cake at 130 ℃ to constant weight to obtain the zinc diethylphosphinate: 427.3 g. The yield was 92.8%.
Particle size D (50): 15 μm
SO4 2-The content is as follows: 388ppm of phenol.
Example 12
Preparing a mixed solution of sodium diethylphosphinate and diethylphosphinate as in comparative example 1, adding 830.3g of water, neutralizing with 30% sodium hydroxide solution to be neutral, heating to 90 ℃, dropwise adding magnesium sulfate heptahydrate solution prepared from 369.0g (1.5 mol) of magnesium sulfate heptahydrate and 861g of water within 1.5h, keeping the temperature at 90 ℃ for 1h, filtering, washing with 1000mL of sulfuric acid solution with the mass fraction of 1% for 1 time, washing with 2000mL of water for 2 times, and drying the obtained filter cake to constant weight at 130 ℃ to obtain magnesium diethylphosphinate: 361.9 g. The yield was 90.7%.
Particle size D (50): 13 μm
SO4 2-The content is as follows: 402 ppm.
Examples 13 to 35: preparation of flame-retardant Polymer Molding compositions
Weighing the polymer, the additive for the polymer and the processing aid according to the weight percentage in the table 1, uniformly mixing in a high-speed stirring mixer, and then feeding into a double-screw extruder; adding glass fiber through a side feeding system of a double-screw extruder, performing melt extrusion through the double-screw extruder, cooling in a water bath, and granulating to obtain the flame-retardant polymer molding composition; and the UL-94 flame retardant rating, corrosion degree delta D, color difference delta L and notch impact strength are measured, and specific test data are listed in a table.
TABLE 1 concrete compounding ratio (wt%) of each composition in examples 13 to 24 and test results thereof
| SO4 2-Content (wt.) ppm | Examples 13 | Examples 14 | Examples 15 | Examples 16 | Examples 17 | Examples 18 | Examples 19 | Examples 20 | Examples 21 | Examples 22 | Examples 23 | Examples 24 | |
| PBT | 65 | 45 | 45 | 45 | 45 | 45 | |||||||
| PA66 | 70 | 70 | 70 | 70 | 70 | 95 | |||||||
| Glass fiber 1 | 30 | 30 | 30 | 30 | 30 | 30 | |||||||
| Processing aid | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | 5 | |
| Comparative example 1 product | Not detected out | 20 | 25 | ||||||||||
| Comparative example2 products of | 681 | 20 | |||||||||||
| Example 1 product | 500 | 20 | |||||||||||
| Example 2 product | 210 | 25 | |||||||||||
| Example 3 product | 233 | ||||||||||||
| Example 4 product | 329 | 20 | |||||||||||
| Example 5 product | 377 | 25 | |||||||||||
| Example 6 product | 361 | 25 | |||||||||||
| Example 7 product | 272 | 20 | |||||||||||
| Example 8 product | 381 | 25 | |||||||||||
| Example 9 product | 439 | ||||||||||||
| Example 10 product | 315 | ||||||||||||
| Example 11 product | 388 | ||||||||||||
| Example 12 product | 402 | ||||||||||||
| Flame retardant Properties (1.5 mm) | ncl | V-1 | V-1 | V-1 | V-1 | V-1 | V-0 | V-1 | V-1 | V-1 | V-0 | ncl | |
| Degree of Corrosion Δ D (mm) | 0.28 | 1.59 | 0.95 | 0.67 | 0.41 | 0.33 | 0.62 | 0.15 | 0.12 | 0.08 | 0.23 | 0.06 | |
| ΔL | 0.05 | 0.87 | 0.61 | 0.38 | 0.25 | 0.14 | 0.88 | 0.38 | 0.23 | 0.20 | 0.52 | 0.12 | |
| Notched impact strength (KJ- m2) | 9.2 | 7.4 | 8.7 | 8.7 | 8.8 | 8.9 | 7.0 | 7.8 | 8.0 | 8.2 | 7.4 | 8.5 |
TABLE 1 shows the concrete proportions (wt%) of the components in examples 25 to 35 and the test results thereof
| SO4 2-Content (wt.) ppm | Examples 25 | Examples 26 | Examples 27 | Examples 28 | Examples 29 | Examples 30 | Examples 31 | Examples 32 | Examples 33 | Examples 34 | Examples 35 | |
| PA6 | 72 | 54 | 54 | 54 | 54 | 54 | 18 | 18 | 18 | 18 | 18 | |
| PPE | 32 | 32 | 32 | 32 | 32 | |||||||
| Glass fiber 2 | 25 | 25 | 25 | 25 | 25 | 25 | 30 | 30 | 30 | 30 | 30 | |
| Processing aid | 3 | 3 | 3 | 3 | 3 | 3 | 4 | 4 | 4 | 4 | 4 | |
| Comparative example 1 product | Not detected out | 16 | ||||||||||
| Comparative example 2 product | 681 | 18 | 16 | |||||||||
| Example 1 product | 500 | |||||||||||
| Example 2 product | 210 | |||||||||||
| Example 3 product | 233 | |||||||||||
| Example 4 product | 329 | 18 | ||||||||||
| Example 5 product | 377 | |||||||||||
| Example 6 product | 361 | |||||||||||
| Example 7 product | 272 | 18 | ||||||||||
| Example 8 product | 381 | 18 | ||||||||||
| Example 9 product | 439 | 18 | ||||||||||
| Example 10 product | 315 | 16 | ||||||||||
| Example 11 product | 388 | 16 | ||||||||||
| Example 12 product | 402 | 16 | ||||||||||
| Flame retardant Properties (1.5 mm) | ncl | V-0 | V-0 | V-1 | V-1 | V-2 | V-0 | V-0 | V-0 | V-1 | V-1 | |
| Degree of Corrosion Δ D (mm) | 0.42 | 1.01 | 0.41 | 0.45 | 0.48 | 0.55 | 1.77 | 1.36 | 0.45 | 0.63 | 0.67 | |
| ΔL | 0.46 | 1.77 | 0.51 | 0.72 | 0.78 | 0.96 | 1.64 | 1.49 | 0.51 | 0.66 | 0.68 | |
| Notched impact strength (KJ- m2) | 8.5 | 7.7 | 8.1 | 8.0 | 8.0 | 7.9 | 7.5 | 7.7 | 8.0 | 7.9 | 7.7 |
As can be seen from Table 1 above, the SO-containing compounds prepared according to the present invention4 2-And metal dialkylphosphinate salts as polymerization catalystsAdditive of (a) which is applied to a polymer, in contrast to a SO not according to the invention4 2-The additive for the polymer within the content range greatly reduces the corrosion degree to metal parts of a processing device in the processing process of the flame-retardant polymer, and meanwhile, the flame-retardant polymer has excellent surface performance under the conditions of high temperature and high humidity, is not easy to migrate and separate out from the polymer and has small influence on the mechanical property of the polymer.
Claims (10)
1. An additive for a polymer comprising:
a: a metal dialkylphosphinate having the structure shown in formula I:
wherein R is1，R2Identical or different, is H, C1-C6 alkyl or C6-C18 aryl;
m is Mg, Ca, Al, Zn and Fe;
m is 2-3;
b: containing SO4 2-a compound of (a);
wherein the particle size of the additive for the polymer is 2-46 mu m; particle size and SO of the additive for polymer4 2-The weight content in the additive for the polymer satisfies the relationship shown in formula II or formula III:
when x is less than or equal to 32, y is less than or equal to-7.25 x +497 II;
when x is greater than 32, y is less than or equal to 16x-247 III;
wherein y represents SO4 2-The weight content in the additive for polymers, in ppm; x represents the particle size of the additive for the polymer in μm;
the R is1And R2Identical or different, is ethyl, propyl, butyl or cyclohexyl; m is Mg, Al and Zn;
the dialkyl phosphinate metal salt is one or more of aluminum diethyl phosphinate, aluminum dipropyl phosphinate, aluminum dibutyl phosphinate, aluminum dicyclohexyl phosphinate, magnesium diethyl phosphinate and zinc diethyl phosphinate;
the SO4 2-The weight content of the additive in the polymer is 310 ppm-380 ppm;
said containing SO4 2The compound is one or more selected from sodium sulfate, potassium sulfate, sodium bisulfate, sodium sulfate decahydrate, magnesium sulfate, calcium sulfate, aluminum sulfate, zinc sulfate and ferric sulfate;
the water content of the additive for the polymer is 0.1-1 wt%;
the additive for the polymer has a bulk density of 200-650 g/L;
the solubility of the additive for the polymer in water, an organic solvent or a mixture of water and an organic solvent is 0.005-9.99 wt%;
the polymer is selected from one or more of polyester, polyamide and polyphenyl ether.
2. A method of preparing an additive for a polymer according to claim 1, wherein one of the following methods is used:
the method comprises the following steps:
a) adding hypophosphite/hypophosphorous acid and SO to the solvent4 2-With an olefin under the action of an initiator to obtain a compound containing SO4 2-The dialkylphosphinic salt/acid solution of (a);
b) will contain SO4 2-The dialkylphosphinic acid salt/acid solution is reacted with a metal compound to obtain a solution containing SO4 2-A metal dialkylphosphinate of (a);
wherein the hypophosphite is sodium hypophosphite or potassium hypophosphite;
the metal compound is a metal compound of Mg, Ca, Al, Zn and Fe;
said containing SO4 2-The compound (A) is one or more of sulfuric acid, fuming sulfuric acid and pyrosulfuric acid;
or the second method:
reacting the dialkylphosphinic salt solution with an aqueous solution of a metal compound containing the additive I to give the corresponding SO-containing solution4 2-A metal dialkylphosphinate of (a);
wherein the additive I is one or more of sulfuric acid, sodium sulfate, potassium sulfate, sodium bisulfate, sodium sulfate decahydrate, magnesium sulfate, calcium sulfate, aluminum sulfate, zinc sulfate and ferric sulfate;
the metal compound is Mg, Ca, Al, Zn and Fe
The dialkyl phosphinate is sodium dialkyl phosphinate or potassium dialkyl phosphinate;
or the third method:
adding an additive II into the dialkyl phosphinic acid metal salt product in the filtering process or the washing process or the drying process to obtain the product containing SO4 2-A metal dialkylphosphinate of (a);
the additive II is one or more of sulfuric acid, sodium sulfate, potassium sulfate, sodium bisulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, zinc sulfate and ferric sulfate.
3. The method of claim 2, wherein the metal compound is a metal compound of Mg, Al or Zn.
4. The method of claim 2, wherein the metal compound is a metal compound of Mg, Al or Zn.
5. The method of claim 3, wherein the sodium sulfate is sodium sulfate decahydrate.
6. The method for preparing an additive for polymers according to claim 2, wherein the solvent in the first method is cyclohexane and/or cyclohexene; the initiator in the first method is an azo initiator, an organic peroxide initiator and an inorganic peroxide initiator; in the first method, the olefin is one or more of ethylene, propylene, butylene and cyclohexene.
7. Use of the additive for polymers according to claim 1 as flame retardant.
8. A flame-retardant polymer molding composition comprising the additive for polymers of claim 1, comprising the following components in parts by weight: 5-25 parts of an additive for a polymer; 40 to 75 parts of a polymer or a mixture thereof; wherein the additives for the polymer comprise:
a: a metal dialkylphosphinate having the structure shown in formula I:
wherein R is1，R2Identical or different, is H, C1-C6 alkyl or C6-C18 aryl;
m is Mg, Ca, Al, Zn and Fe;
m is 2-3;
b: containing SO4 2-a compound of (a); wherein SO4 2-The weight content of the additive in the polymer is 310 ppm-380 ppm;
wherein the particle size of the additive for the polymer is 2-46 mu m.
9. Flame retardant polymer molding composition according to claim 8, wherein the polymer is one or several of polyesters, polyamides, polyphenylene ethers.
10. The flame retardant polymer molding composition of claim 8 further comprising 0 to 30 parts by weight of a filler and 0 to 5 parts by weight of a processing aid.
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| KR101863421B1 (en) * | 2015-12-30 | 2018-05-31 | 한화토탈 주식회사 | Halogen-free Flame retarding Polypropylene Resin Composition |
| CN107353436B (en) * | 2017-05-23 | 2019-07-12 | 广州铂钡信息科技有限公司 | A kind of additive and preparation method thereof for polymer |
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| CN118420663A (en) * | 2019-04-15 | 2024-08-02 | 黎杰 | Metal polydialkylphosphinate double salts and uses thereof |
| JP2023177156A (en) * | 2022-06-01 | 2023-12-13 | 日華化学株式会社 | Flame-retardant composition, and flame-retardant synthetic leather using the same |
| CN116925132B (en) * | 2023-07-03 | 2024-06-14 | 太仓维龙化工有限公司 | Preparation method of fine-particle-size dialkyl phosphinate |
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| CA2867720A1 (en) * | 2012-03-20 | 2013-09-26 | Rhodia Operations | Flame retardant polymer compositions |
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| CN1660858A (en) * | 2003-12-19 | 2005-08-31 | 科莱恩有限公司 | Process for preparation of dialkylphosphinic salts |
| CN103102367A (en) * | 2013-02-27 | 2013-05-15 | 广州金凯新材料有限公司 | Preparation method and application of dialkyl phosphinate with high density and large diameter |
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| CN107189098A (en) | 2017-09-22 |
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