CN116987262A - Nylon, anti-dripping flame-retardant material containing nylon and preparation method - Google Patents
Nylon, anti-dripping flame-retardant material containing nylon and preparation method Download PDFInfo
- Publication number
- CN116987262A CN116987262A CN202210444742.8A CN202210444742A CN116987262A CN 116987262 A CN116987262 A CN 116987262A CN 202210444742 A CN202210444742 A CN 202210444742A CN 116987262 A CN116987262 A CN 116987262A
- Authority
- CN
- China
- Prior art keywords
- nylon
- members
- monomer
- flame
- dripping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004677 Nylon Substances 0.000 title claims abstract description 132
- 229920001778 nylon Polymers 0.000 title claims abstract description 132
- 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 99
- 239000003063 flame retardant Substances 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title abstract description 33
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 21
- 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 abstract description 18
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims abstract description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 14
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 14
- 125000003944 tolyl group Chemical group 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims description 81
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 150000004985 diamines Chemical class 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 24
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- -1 decanediamine Chemical compound 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 3
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 claims description 3
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 3
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000011056 performance test Methods 0.000 description 24
- 239000002994 raw material Substances 0.000 description 23
- 239000004952 Polyamide Substances 0.000 description 14
- 229920002647 polyamide Polymers 0.000 description 14
- 238000007334 copolymerization reaction Methods 0.000 description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920002302 Nylon 6,6 Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- QEPVYYOIYSITJK-UHFFFAOYSA-N cyclohexyl-ethyl-dimethoxysilane Chemical compound CC[Si](OC)(OC)C1CCCCC1 QEPVYYOIYSITJK-UHFFFAOYSA-N 0.000 description 4
- ZVMRWPHIZSSUKP-UHFFFAOYSA-N dicyclohexyl(dimethoxy)silane Chemical compound C1CCCCC1[Si](OC)(OC)C1CCCCC1 ZVMRWPHIZSSUKP-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 3
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- VNKSKFJVASDGBE-UHFFFAOYSA-N 3-[(3-aminophenyl)-phenylphosphoryl]aniline Chemical compound NC1=CC=CC(P(=O)(C=2C=CC=CC=2)C=2C=C(N)C=CC=2)=C1 VNKSKFJVASDGBE-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Chemical class 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229960005137 succinic acid Drugs 0.000 description 2
- RTQKIKMYZZZGDE-UHFFFAOYSA-N (4-phenoxyphenyl)phosphane Chemical compound C1=CC(P)=CC=C1OC1=CC=CC=C1 RTQKIKMYZZZGDE-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- VWVRASTUFJRTHW-UHFFFAOYSA-N 2-[3-(azetidin-3-yloxy)-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound O=C(CN1C=C(C(OC2CNC2)=N1)C1=CN=C(NC2CC3=C(C2)C=CC=C3)N=C1)N1CCC2=C(C1)N=NN2 VWVRASTUFJRTHW-UHFFFAOYSA-N 0.000 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WWSJZGAPAVMETJ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethoxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OCC WWSJZGAPAVMETJ-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- FPIGBKDVHZUQJO-UHFFFAOYSA-N 2-hydroxyethyl(phenyl)phosphinic acid Chemical compound OCCP(O)(=O)C1=CC=CC=C1 FPIGBKDVHZUQJO-UHFFFAOYSA-N 0.000 description 1
- FYXPKOPFEGFWHG-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylphosphoryl]phenol Chemical compound C1=CC(O)=CC=C1P(=O)(C=1C=CC(O)=CC=1)C1=CC=CC=C1 FYXPKOPFEGFWHG-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 229920006152 PA1010 Polymers 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- BPYFPNZHLXDIGA-UHFFFAOYSA-N diphenylsilicon Chemical compound C=1C=CC=CC=1[Si]C1=CC=CC=C1 BPYFPNZHLXDIGA-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920006118 nylon 56 Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The invention relates to nylon, a molten drop resistant flame retardant material containing the nylon and a preparation method thereof, wherein the nylon comprises the following structure, m is an integer selected from 4-12, and n is an integer selected from 4-10; y and z are integers, y is more than or equal to 1, and z is more than or equal to 1; r is R 1 Is cyclopentyl, cyclohexyl, phenyl, tolyl, a saturated heterocyclic group of 5-6 members or a heteroaryl of 5-6 members; r is R 2 Is methyl, ethyl, cyclopentyl, cyclohexyl, phenyl, a saturated heterocyclic group of 5-6 members or a heteroaryl of 5-6 members. The nylon of the embodiment of the invention has good anti-dripping performance when being applied to flame retardant materials.
Description
Technical Field
The invention relates to nylon, in particular to nylon with good anti-dripping performance and a material thereof.
Background
Nylon is widely used in various fields due to its excellent properties, however, nylon itself does not have flame retardancy, so that fire may be caused or aggravated. Therefore, how to prepare nylon with good flame retardant properties by modification has been attracting attention of industry personnel. At present, although the copolymerization flame-retardant nylon is prepared, most copolymerization flame-retardant nylon has the problem of poor flame-retardant dripping and anti-dripping performance, and dripping has the ignition risk and can possibly cause scalding.
Some nylon anti-dripping processes or products disclosed in the prior art have poor anti-dripping effects or complex processes or influence the flame retardant property of nylon, and can not effectively solve the anti-dripping problem. For example, patent application CN112239601a produces anti-drip nylon materials by blending, which have the characteristics of surface migration and instability of the anti-drip agent. Patent application CN113336993A discloses that the nylon material is flame-retardant through a surface coating mode, the post-treatment process is complex, the flame-retardant treatment can only be carried out on a simple soaked structure, and the flame-retardant performance and the anti-dripping effect are poor after the treatment; in addition, the flame retardant effect of the coating is not achieved only on the surface, but also once the skin is peeled off or the material is damaged.
Disclosure of Invention
In view of the above analysis, an embodiment of the present invention is to provide a nylon, which is used to solve the problem of poor anti-dripping performance of the existing nylon.
In a first aspect, an embodiment of the present invention provides an anti-dripping nylon, comprising the following structure:
wherein m is an integer selected from 4 to 12, and n is an integer selected from 4 to 10; y and z are integers, y is more than or equal to 1, and z is more than or equal to 1; r is R 1 Is cyclopentyl, cyclohexyl, phenyl, tolyl, a saturated heterocyclic group of 5-6 members or a heteroaryl of 5-6 members; r is R 2 Is methyl, ethyl, cyclopentyl, cyclohexyl, phenyl, a saturated heterocyclic group of 5-6 members or a heteroaryl of 5-6 members.
In a second aspect, an embodiment of the present invention provides a nylon prepared by copolymerizing polymerized monomers including diamines, dicarboxylic acids, and silicone monomers, the silicone monomers including compounds of the formula:
wherein R is 1 Is cyclopentyl, cyclohexyl, phenyl, tolyl, a saturated heterocyclic group of 5-6 members or a heteroaryl of 5-6 members; r is R 2 Is methyl, ethyl, cyclopentyl, cyclohexyl, phenyl, a saturated heterocyclic group of 5 to 6 members or a heteroaryl group of 5 to 6 members; r is R 3 、R 4 Each independently selected from methyl, ethyl or hydrogen.
According to an embodiment of the invention, the silicone monomer is selected from one or more of the following compounds:
according to one embodiment of the invention, the sum m of the masses of the diamine and the dicarboxylic acid 1 Mass m with the organosilicon monomer 2 The ratio is m 1 :m 2 ＝100:(1～5)。
According to an embodiment of the present invention, the diamine comprises one or more of butanediamine, pentanediamine, hexanediamine, decanediamine, and dodecanediamine; the dicarboxylic acid comprises one or more of adipic acid, sebacic acid and dodecanedioic acid; and/or the number of the groups of groups,
the polymerized monomer also includes a phosphorus-containing monomer having flame retardant properties.
According to one embodiment of the present invention, the ratio of the sum of the masses of the diamine and the dicarboxylic acid to the mass of the phosphorus-containing monomer is 100 (4 to 10).
According to one embodiment of the invention, the intrinsic viscosity of the nylon is 1.8-3.2; the limiting oxygen index is 28 or more, and further 28 to 35.
In a third aspect, an embodiment of the present invention provides a method for preparing the above nylon, including mixing a polymerization monomer and a catalyst and then reacting to prepare the nylon;
wherein the polymerized monomers include diamines, dicarboxylic acids, and silicone monomers comprising compounds of the formula:
R 1 is cyclopentyl, cyclohexyl, phenyl, tolyl, a saturated heterocyclic group of 5-6 members or a heteroaryl of 5-6 members; r is R 2 Is methyl, ethyl, cyclopentyl, cyclohexyl, phenyl, a saturated heterocyclic group of 5 to 6 members or a heteroaryl group of 5 to 6 members; r is R 3 、R 4 Each independently selected from methyl, ethyl or hydrogen.
According to one embodiment of the invention, the method comprises reacting the diamine and the dicarboxylic acid to form a nylon salt, and then mixing the nylon salt with the organosilicon monomer and the catalyst; and/or the number of the groups of groups,
the reaction process of the reaction comprises the following steps: raising the temperature of the reaction system from room temperature to 220-250 ℃, starting pressure maintaining reaction for 1-4 hours after the system pressure reaches 1.5-2.5 MPa, then discharging the system to normal pressure, and reacting for 1-4 hours under normal pressure after the system temperature reaches 240-290 ℃.
In a fourth aspect, an embodiment of the present invention provides a melt-drip resistant flame retardant material comprising the nylon described above and an additive comprising a flame retardant.
Compared with the prior art, the invention has at least one of the following beneficial effects:
1. the nylon of the embodiment of the invention has good anti-dripping performance when being applied to flame retardant materials.
2. The anti-dripping flame retardant material provided by the embodiment of the invention has good flame retardance and anti-dripping property.
3. The preparation method of the nylon/anti-molten drop flame-retardant material provided by the embodiment of the invention has the advantages of simple process, shortened working procedures, reduced cost and suitability for large-scale production.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Detailed Description
The following detailed description of the preferred embodiments of the invention is provided to illustrate the principles of the invention and not to limit the scope of the invention.
An embodiment of the invention provides nylon, which comprises the following structure:
wherein m is an integer selected from 4 to 12, and n is an integer selected from 4 to 10; y and z are integers, and respectively represent the number of the repeating units, wherein y is more than or equal to 1, and z is more than or equal to 1; r is R 1 Is cyclopentyl, cyclohexyl, phenyl or tolyl (CH 3 -Ar-)，R 2 Is methyl, ethyl, cyclopentyl, cyclohexyl or phenyl. Wherein Ar-in the brackets mentioned above represents a phenyl group.
According to the nylon of the embodiment of the invention, the specific silicon-containing structure is bonded to the polymer chain, so that the problem of poor stability of the anti-dripping agent in the existing flame retardant material is solved, the anti-dripping performance of the material is greatly improved, and the nylon can show excellent anti-dripping performance only with a small amount of silicon structure; in addition, the preparation process of the nylon is simple, the working procedure is shortened, the cost is reduced, and the nylon is suitable for large-scale production.
In one embodiment, m may have a value of 5, 6, 10 or 12; the value of n may be 4, 8 or 10.
In one embodiment, R 1 Is phenyl or tolyl, further, tolyl can be p-tolyl; r is R 2 Is methyl or phenyl.
In one embodiment, the nylon has an intrinsic viscosity of 1.8 to 3.2, such as 2.0, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0; further, the ratio may be 2.2 to 2.8.
In one embodiment, the structure of formula I represents a partial segment of a polymer molecule, and does not represent the structure of the entire molecule.
The nylon of one embodiment of the present invention comprises polyamide molecules and modified polyamide molecules, wherein the polyamide molecules consist of a polyamide structure shown in the following; the modified polyamide molecule consists of a polyamide structure and a silicon-containing structure which are interpenetrated, for example, the modified polyamide molecule can comprise a structure shown in a formula I;
wherein x may be an integer of 2 or more.
The nylon of one embodiment of the present invention may be prepared by copolymerizing polymeric monomers including diamines, dicarboxylic acids and organosilicon monomers, the organosilicon monomers including compounds of the formula:
wherein R is 1 Is cyclopentyl, cyclohexyl, phenyl or tolyl, R 2 Methyl, ethyl, cyclopentyl, cyclohexyl, or phenyl; r is R 3 、R 4 Each independently selected from methyl, ethyl or hydrogen.
In one embodiment, the silicone monomer may be one or more of the following compounds:
in one embodiment, the presence of the silicone monomer during the copolymerization causes it to participate in the polymerization and intercalate into the polyamide chain, and the reaction that occurs can be represented by the formula:
the above reaction formula is merely an example, and the polymerization product is not limited, and if the content of the organosilicon monomer is large, two or more siloxane structures (-O-Si (R) in the above reaction formula are inserted into one polyamide molecular chain 1 R 2 ) -O-), forming modified polyamide molecules; if the content of the organosilicon monomer is small, a silica structure is inserted into one polyamide molecular chain, or a silica structure is inserted into only part of the polyamide molecular chain, namely, the formed nylon contains polyamide molecules and modified polyamide molecules.
In one embodiment, the sum of the masses of diamine and dicarboxylic acid m in the polymerized monomer 1 Mass m with organosilicon monomer 2 The ratio is m 1 :m 2 =100 (1-5), e.g. 100:2, 100:3, 100:4.
In one embodiment, the diamine is an aliphatic linear diamine of the formula NH 2 -(CH 2 ) m -NH 2 Wherein m represents the number of methylene groups, m may be an integer of 4 to 12, for example 5, 6,7, 8, 9,10 or 11; the dicarboxylic acid is aliphatic linear dicarboxylic acid, and its chemical formula can be HOOC- (CH) 2 ) n -COOH, wherein n represents the number of methylene groups, n may be an integer from 4 to 10, such as 5, 6,7, 8 or 9.
In one embodiment, the diamine may be one or more of butanediamine, pentanediamine, hexanediamine, decanediamine, and dodecanediamine, such as 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 10-decanediamine, 1, 12-dodecanediamine; the dicarboxylic acid may be one or more of adipic acid, sebacic acid, dodecanedioic acid.
In one embodiment, the polymerized monomer further comprises a phosphorus-containing monomer with flame retardant property, and the anti-dripping flame retardant nylon is prepared after copolymerization; the limiting oxygen index of the anti-dripping flame retardant nylon can be more than 28, and further 28-35, such as 29, 30, 31, 32, 33 and 34.
In one embodiment, the phosphorus-containing monomer may be, for example, DOPO-based reactive phosphorus flame retardant (9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), 2-hydroxyethyl phenyl phosphinic acid or bis (p-hydroxyphenyl) phenylphosphine oxide, 10- (2, 5-dicarboxyphenoxy) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPODP), 2- (dimethylphosphine) -4,6- (2 '-carboxyethylphosphine) -s-triazine (DPPAPO), 2-carboxyethylphosphine-phosphinic acid (CEPPA), [ (6-oxo-6H-dibenzo [ c, e ] [1,2] oxaphospha-6-yl) methyl ] butanedioic acid (DDP), 2-bis ((4-phenoxyphenylphosphine) -p-aminobenzoic acid) propane (OAP), 2- (dimethylphosphine) -4,6- (p-aminobenzoic acid) -s-Triazine (TPO), di-1-oxo-4, 6- (2' -carboxyethylphosphine) -s-triazine (DPPAPO), 2-oxo-6-hydroxy-2, 2-hydroxy-2- (2-hydroxy-3-hydroxy-7-methyl) butanedioic acid (DPP), 2-bis ((4-phenoxyphenylphosphine) or (BPP) 4- (2- (((carboxyethyl) (phenyl) phosphoryl) oxy) ethoxy) -4-oxohexanoic acid (cppeoa), bis (3-aminophenyl) phenylphosphine oxide (BAPPO).
In one embodiment, the ratio of the sum of the masses of diamine and dicarboxylic acid (or the mass of nylon salt) to the mass of phosphorus-containing monomer in the polymerized monomer may be 100 (4-10), such as 100:5, 100:6, 100:8.
In one embodiment, a catalyst may be added to the reaction system to accelerate the copolymerization of the polymerized monomers; further, the catalyst may be hypophosphite, the sum m of the mass of diamine and dicarboxylic acid in the polymerized monomer 1 The ratio to the mass of the catalyst may be 100 (0.05 to 0.2), for example 100:0.06, 100:0.08, 100:0.1, 100:0.12, 100:0.15, 100:0.18.
In one embodiment, an antioxidant may be added to the reaction system, and the antioxidant may be one or more of antioxidant 168, antioxidant 1098, antioxidant 1010, and antioxidant 626.
In one embodiment, the diamine and dicarboxylic acid may be reacted to form a nylon salt and then mixed with the silicone monomer for copolymerization. Further, the mass ratio of nylon salt to silicone monomer may be 100 (1-5), such as 100:2, 100:3, 100:4; the mass ratio of nylon salt to catalyst may be 100 (0.01-0.5), such as 100:0.02, 100:0.05, 100:0.06, 100:0.08, 100:0.1, 100:0.15, 100:0.2, 100:0.25, 100:0.3, 100:0.35, 100:0.4, 100:0.45.
In one embodiment, the nylon salt may be one or more of PA46 salt, PA56 salt, PA66 salt, PA610 salt, PA612 salt, PA1010, PA1212 salt.
In one embodiment, the preparation process of the nylon salt comprises: and adding a certain amount of water into diamine, heating for dissolution, adding dibasic acid, stirring uniformly, and reacting for half an hour to obtain nylon salt.
In one embodiment, diamine and dicarboxylic acid are reacted to form nylon salt and then mixed with organosilicon monomer for reaction; wherein the polymerization reaction system may comprise the following components: 100 parts by mass of nylon salt, 10-100 parts by mass of water, 4-10 parts by mass of flame retardant, 1-5 parts by mass of organosilicon monomer, 0.1-1 part by mass of catalyst and 0.1-1 part by mass of antioxidant.
In one embodiment, the phosphorus-containing monomer is first prepared into a flame retardant salt solution by diamine before copolymerization reaction, the molar ratio of the phosphorus-containing monomer to the diamine can be 1:1-1:1.2, and the salifying reaction temperature is 60-90 ℃, such as 65 ℃, 70 ℃, 75 ℃, 80 ℃ and 85 ℃; the reaction time may be 0.5 to 3 hours, for example 1 hour, 2 hours, 2.5 hours; the solids content of the solution may be 30 to 80%, for example 40%, 50%, 60%, 70%.
In one embodiment, the diamine that is salified with the phosphorus-containing monomer may be the diamine of the aforementioned polymeric monomer.
In one embodiment, the nylon preparation process comprises: mixing nylon salt, organosilicon monomer and fire retardant salt solution, and then mixing with a catalyst and placing into a reaction container; the air in the reaction vessel is replaced by nitrogen, the temperature in the vessel is raised to 220-250 ℃ from room temperature, the pressure maintaining reaction is started for 1-4 hours after the pressure in the vessel reaches 1.5-2.5 MPa, then the reaction vessel is uniformly discharged to normal pressure, the reaction vessel is reacted for 1-4 hours under normal pressure after the temperature in the reaction vessel reaches 240-290 ℃, the vacuum pumping is carried out for 30-60 minutes, and the discharge is carried out after the torque is judged not to rise or the corresponding viscosity is reached.
In one embodiment, in the nylon preparation process, the temperature in the container can be raised to 230 ℃, 235 ℃ or 240 ℃ after the air in the reaction container is replaced by nitrogen; after the pressure in the container reaches 1.8MPa, 2MPa or 2.2MPa, the pressure maintaining reaction is started, wherein the pressure maintaining reaction time can be 1.5 hours, 2 hours, 2.5 hours, 3 hours or 3.5 hours, then the pressure is uniformly discharged to normal pressure, and after the temperature in the reaction container reaches 250 ℃, 260 ℃ or 270 ℃, the normal pressure reaction is carried out for 2 hours, 2.5 hours, 3 hours or 3.5 hours.
An embodiment of the invention further provides a molten drop resistant flame retardant material comprising the nylon and the additive.
In one embodiment, the polymeric monomer of the nylon comprises a phosphorus-containing monomer with flame retardant properties, and the anti-dripping flame retardant material may not require additional flame retardant.
In one embodiment, the polymeric monomer of the nylon does not include a monomer having flame retardant properties, and the additive of the anti-drip flame retardant material includes a flame retardant, which may be an existing flame retardant used for blending addition.
In one embodiment, the anti-drip flame retardant material may have an intrinsic viscosity of 1.8 to 3.2, such as 2.0, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0; further, the ratio may be 2.2 to 2.8.
In one embodiment, the anti-drip flame retardant material has a limiting oxygen index of 28 or more, further 28 to 35, such as 29, 30, 31, 32, 33, 34.
The nylon/anti-dripping flame retardant material provided by the embodiment of the invention has good flame retardance and anti-dripping performance, and can maintain excellent mechanical properties.
The nylon/anti-molten drop flame retardant material of the embodiment of the invention does not need to compound flame retardant, has few types of added flame retardant and simple reaction process, and can finish the preparation of the nylon/anti-molten drop flame retardant material in a one-step kettle.
The anti-dripping nylon/anti-dripping flame-retardant nylon material provided by the embodiment of the invention has the advantages of simple preparation process, short time consumption of working procedures, cost reduction and suitability for large-scale production.
The preparation of the anti-dripping flame retardant nylon material according to an embodiment of the present invention is further described below with reference to specific examples. Wherein, intrinsic viscosity is measured by reference to standard GBT 12006.1-2009, limiting oxygen index is measured by reference to standard GB-2406-2009, flame retardant grade is measured by reference to standard GBT2408-2008, and tensile strength is measured by reference to standard GB/T1040-2006.
Example 1
Preparation of nylon salt
Adding water with a certain mass into a container filled with hexamethylenediamine, heating and dissolving, adding adipic acid, uniformly stirring the mixture, and reacting for half an hour to obtain the nylon 66 salt solution, wherein the mass ratio of the hexamethylenediamine to the adipic acid is 1:1.25-1.3.
Preparation of flame retardant salt solutions
A flame retardant salt solution was prepared by mixing 140g of CPDOA phosphorus-containing monomer flame retardant, 70g of hexamethylenediamine and 250g of water and then reacting at 60℃for 3 hours.
Preparation of nylon material
Taking the prepared nylon 66 salt solution (containing 2kg of nylon 66 salt), 100g of diphenyl silicon glycol, the prepared flame retardant salt solution, 2g of sodium hypophosphite and 20g of antioxidant 168, uniformly mixing and then placing into a reaction kettle; raising the temperature of the kettle from room temperature to 230 ℃, and maintaining the pressure for 2 hours after the pressure in the kettle reaches 2.2 MPa; and then uniformly discharging to normal pressure, reacting for 30 minutes at the normal pressure after the temperature of the kettle reaches 270 ℃, vacuumizing for 30 minutes, and discharging when the Torque (Torque) reaches 5.0 to obtain the anti-molten-drop flame-retardant nylon material.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 1-1
The same raw materials and steps as in example 1 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the mass of the organosilicon monomer diphenylsilanediol used was 20g.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Examples 1 to 2
The same raw materials and steps as in example 1 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the mass of the organosilicon monomer diphenylsilanediol used was 60g.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Examples 1 to 3
The same raw materials and steps as in example 1 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the mass of the organosilicon monomer diphenylsilanediol used was 200g.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 2
The same raw materials and steps as in example 1 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the organosilicon monomer used is p-toluenemethyldimethoxysilane.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 2-1
The same raw materials and steps as in example 2 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the mass of the organosilicon monomer p-toluenemethyldimethoxysilane used was 20g.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 3
The same raw materials and steps as in example 1 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the organosilicon monomer used is methyl phenyl dimethoxy silane.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 3-1
The same raw materials and steps as in example 3 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the mass of the organosilicon monomer methyl phenyl dimethoxy silane used was 20g.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 4
The same raw materials and steps as in example 1 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the organosilicon monomer used is diethoxymethylphenylsilane.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 4-1
The same raw materials and steps as in example 4 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the mass of the organosilicon monomer diethoxymethylphenylsilane used was 20g.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 5
The same raw materials and steps as in example 1 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the organosilicon monomer used is diphenyldimethoxysilane.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 5-1
The same raw materials and steps as in example 5 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the mass of the organosilicon monomer diphenyldimethoxysilane used was 20g.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 6
The same raw materials and steps as in example 1 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the organosilicon monomer used is methylcyclohexyldimethoxy silane.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 6-1
The same raw materials and steps as in example 6 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the mass of the organosilicon monomer methylcyclohexyldimethoxysilane used was 20g.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 7
The same raw materials and steps as in example 1 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the organosilicon monomer used is dicyclopentyl dimethoxy silane.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 7-1
The same raw materials and steps as in example 7 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the mass of the organosilicon monomer dicyclopentyl dimethoxy silane used was 20g.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 8
The same raw materials and steps as in example 1 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the organosilicon monomer used is cyclohexylethyldimethoxysilane.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 8-1
The same raw materials and steps as in example 8 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the mass of the organosilicon monomer cyclohexylethyldimethoxysilane used was 20g.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 9
The same raw materials and steps as in example 1 are adopted in the preparation of the anti-dripping flame-retardant nylon material, and the difference is that: the organosilicon monomer used is dicyclohexyl dimethoxy silane.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 9-1
The same raw materials and steps as in example 9 are adopted in the preparation of the anti-dripping flame retardant nylon material, and the difference is that: the mass of the organosilicon monomer dicyclohexyl dimethoxy silane used was 20g.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 10-1
The anti-dripping flame-retardant nylon material is prepared by adopting the same raw materials and steps as in the embodiment 1-1, and the difference is that: the nylon salt used was nylon 56.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Example 10-2
The anti-dripping flame-retardant nylon material is prepared by adopting the same raw materials and steps as in the embodiment 1-1, and the difference is that: the nylon salt used was nylon 610.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Comparative example 1
The same raw materials and steps as in example 1 are adopted to prepare the anti-dripping flame-retardant nylon material, and the difference is that: the organosilicon monomer is amino silicone oil, and the structural formula is as follows:
the prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
Comparative example 2
The same raw materials and steps as in example 1 are adopted to prepare the anti-dripping flame-retardant nylon material, and the difference is that: the organosilicon monomer used was 1, 3-bis (3-aminopropyl) -1, 3-tetramethyldisiloxane.
The prepared anti-dripping flame-retardant nylon material is subjected to relevant performance test, and specific results are shown in table 1.
TABLE 1
/>
Referring to the results in table 1, it can be seen that the nylon material prepared by adopting the specific type of organosilicon monomer in the embodiment of the invention has good flame retardance, excellent anti-dripping performance and better mechanical property. Although the organic silicon monomers are also polymerized in the comparative examples 1 and 2, the anti-dripping performance of the organic silicon monomers is poor, and dripping ignition still occurs; and the flame retardance and tensile strength of the nylon material are also worse than those of the example nylon material.
Further referring to the results of examples 1 to 1-3 and Table 1, it is understood that the nylon material of the examples of the present invention exhibits good anti-dripping performance at a mass ratio of nylon salt to silicone monomer of 100:1, i.e., good anti-dripping performance can be obtained by adding only a small amount of silicone monomer.
Comparing the characterization results of examples 1 to 9-1, it is seen that the nylon materials of examples 3, 3-1, 8-1, 9-1 have higher limiting oxygen index and tensile strength with the same amount of the silicone monomer, and thus the silicone monomer is preferably methylphenyl dimethoxy silane, cyclohexyl ethyl dimethoxy silane and dicyclohexyldimethoxy silane, and more preferably cyclohexyl ethyl dimethoxy silane and dicyclohexyldimethoxy silane.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (10)
1. A nylon comprising the structure:
wherein m is an integer selected from 4 to 12, and n is an integer selected from 4 to 10; y and z are integers, y is more than or equal to 1, and z is more than or equal to 1; r is R 1 Is cyclopentyl, cyclohexyl, phenyl, tolyl, a saturated heterocyclic group of 5-6 members or a heteroaryl of 5-6 members; r is R 2 Is methyl, ethyl, cyclopentyl, cyclohexyl, phenyl, a saturated heterocyclic group of 5-6 members or a heteroaryl of 5-6 members.
2. Nylon prepared by copolymerizing polymerized monomers comprising diamine, dicarboxylic acid and organosilicon monomers comprising compounds of the formula:
wherein R is 1 Is cyclopentyl, cyclohexyl, phenyl, tolyl, a saturated heterocyclic group of 5-6 members or a heteroaryl of 5-6 members; r is R 2 Is methyl, ethyl, cyclopentyl, cyclohexyl, phenyl, a saturated heterocyclic group of 5 to 6 members or a heteroaryl group of 5 to 6 members; r is R 3 、R 4 Each independently selected from methyl, ethyl or hydrogen.
3. The nylon of claim 2, wherein the silicone monomer is selected from one or more of the following compounds:
4. a nylon according to claim 2 or 3, wherein the sum of the masses of the diamine and the dicarboxylic acid, m 1 Mass m with the organosilicon monomer 2 The ratio is m 1 :m 2 ＝100:(1～5)。
5. The nylon of any of claims 2-4, wherein the diamine comprises one or more of butanediamine, pentanediamine, hexanediamine, decanediamine, and dodecanediamine; the dicarboxylic acid comprises one or more of adipic acid, sebacic acid and dodecanedioic acid; and/or the number of the groups of groups,
the polymerized monomer also includes a phosphorus-containing monomer having flame retardant properties.
6. The nylon according to claim 5, wherein the ratio of the sum of the masses of the diamine and the dicarboxylic acid to the mass of the phosphorus-containing monomer is 100 (4 to 10).
7. The nylon according to claim 2, having an intrinsic viscosity of 1.8 to 3.2; the limiting oxygen index is 28 or more, and further 28 to 35.
8. The method for producing nylon according to any one of claims 1 to 7, comprising mixing a polymerization monomer and a catalyst and then reacting to produce the nylon;
wherein the polymerized monomers include diamines, dicarboxylic acids, and silicone monomers comprising compounds of the formula:
R 1 is cyclopentyl, cyclohexyl, phenyl, tolyl, a saturated heterocyclic group of 5-6 members or a heteroaryl of 5-6 members; r is R 2 Is methyl, ethyl, cyclopentyl, cyclohexyl, phenyl, a saturated heterocyclic group of 5 to 6 members or a heteroaryl group of 5 to 6 members; r is R 3 、R 4 Each independently selected from methyl, ethyl or hydrogen.
9. The method of claim 8, comprising reacting the diamine and the dicarboxylic acid to form a nylon salt and then mixing with the silicone monomer and the catalyst; and/or the number of the groups of groups,
the reaction process of the reaction comprises the following steps: raising the temperature of the reaction system from room temperature to 220-250 ℃, starting pressure maintaining reaction for 1-4 hours after the system pressure reaches 1.5-2.5 MPa, then discharging the system to normal pressure, and reacting for 1-4 hours under normal pressure after the system temperature reaches 240-290 ℃.
10. A molten drop resistant flame retardant material comprising the nylon of any one of claims 1 to 7 and an additive comprising a flame retardant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210444742.8A CN116987262A (en) | 2022-04-26 | 2022-04-26 | Nylon, anti-dripping flame-retardant material containing nylon and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210444742.8A CN116987262A (en) | 2022-04-26 | 2022-04-26 | Nylon, anti-dripping flame-retardant material containing nylon and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116987262A true CN116987262A (en) | 2023-11-03 |
Family
ID=88523742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210444742.8A Pending CN116987262A (en) | 2022-04-26 | 2022-04-26 | Nylon, anti-dripping flame-retardant material containing nylon and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116987262A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1443114A (en) * | 1973-09-07 | 1976-07-21 | Ciba Geigy Ag | 1,2-oxaphospholanes |
| US4387176A (en) * | 1982-02-04 | 1983-06-07 | General Electric Company | Silicone flame retardants for plastics |
| CN104829831A (en) * | 2015-02-11 | 2015-08-12 | 杭州师范大学 | Halogen-free flame-retarding nylon-6 preparation method |
| CN107033345A (en) * | 2017-05-17 | 2017-08-11 | 东华大学 | A kind of resin of Environmentally-frieflame-retardant flame-retardant nylon 6 and preparation method thereof |
| CN107189061A (en) * | 2017-05-17 | 2017-09-22 | 东华大学 | A kind of Halogen melt-drip resistant inflaming retarding nylon 6 resin and preparation method thereof |
| CN109822999A (en) * | 2019-03-26 | 2019-05-31 | 桑顿新能源科技有限公司 | A kind of flame-retardant aluminum plastic film and preparation method thereof |
| CN110016139A (en) * | 2019-04-01 | 2019-07-16 | 东华大学 | A kind of Containing Schiff-bases hyperbranched polyorganosiloxane fire retardant and the preparation method and application thereof |
| CN112920410A (en) * | 2021-01-29 | 2021-06-08 | 浙江恒澜科技有限公司 | Phosphorus-silicon synergistic flame-retardant anti-dripping nylon 6 resin and preparation method thereof |
| CN113336993A (en) * | 2021-06-15 | 2021-09-03 | 北京理工大学 | Preparation method of anti-dripping nylon plate based on surface structured flame-retardant technology |
-
2022
- 2022-04-26 CN CN202210444742.8A patent/CN116987262A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1443114A (en) * | 1973-09-07 | 1976-07-21 | Ciba Geigy Ag | 1,2-oxaphospholanes |
| US4387176A (en) * | 1982-02-04 | 1983-06-07 | General Electric Company | Silicone flame retardants for plastics |
| CN104829831A (en) * | 2015-02-11 | 2015-08-12 | 杭州师范大学 | Halogen-free flame-retarding nylon-6 preparation method |
| CN107033345A (en) * | 2017-05-17 | 2017-08-11 | 东华大学 | A kind of resin of Environmentally-frieflame-retardant flame-retardant nylon 6 and preparation method thereof |
| CN107189061A (en) * | 2017-05-17 | 2017-09-22 | 东华大学 | A kind of Halogen melt-drip resistant inflaming retarding nylon 6 resin and preparation method thereof |
| CN109822999A (en) * | 2019-03-26 | 2019-05-31 | 桑顿新能源科技有限公司 | A kind of flame-retardant aluminum plastic film and preparation method thereof |
| CN110016139A (en) * | 2019-04-01 | 2019-07-16 | 东华大学 | A kind of Containing Schiff-bases hyperbranched polyorganosiloxane fire retardant and the preparation method and application thereof |
| CN112920410A (en) * | 2021-01-29 | 2021-06-08 | 浙江恒澜科技有限公司 | Phosphorus-silicon synergistic flame-retardant anti-dripping nylon 6 resin and preparation method thereof |
| CN113336993A (en) * | 2021-06-15 | 2021-09-03 | 北京理工大学 | Preparation method of anti-dripping nylon plate based on surface structured flame-retardant technology |
Non-Patent Citations (1)
| Title |
|---|
| 张军等: "聚合物燃烧与阻燃技术", 31 March 2005, 化学工业出版社, pages: 78 - 81 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103930488B (en) | Fire-resistant polyamide composite | |
| CN1266445A (en) | Polymer-bound non-halogen fire resistant compositions | |
| TW201120095A (en) | Polyamide and polyamide composition | |
| TWI631181B (en) | Polyamide composition, formed articles, peflection panel for led, and method for suppressing lowering of reflection rate caused by heat | |
| TW201510076A (en) | Flame retarded thermoplastic moulding composition | |
| EP3700976B1 (en) | Flame-retardant polymer; method for preparing it and thermoplastic polymer composition comprising it | |
| CN112812555A (en) | In-situ polymerization type N-P synergistic flame-retardant nylon and preparation method thereof | |
| JP2012107095A (en) | Method for producing polyurea | |
| CN113896886A (en) | Furan diacid based polyamide and preparation method thereof, and furan diacid based polyamide composition | |
| CN116987262A (en) | Nylon, anti-dripping flame-retardant material containing nylon and preparation method | |
| CN106488945A (en) | The polyamide of copolymerization, methods for making them and the mechanograph comprising which | |
| CN109734898B (en) | P-N-Si synergistic flame-retardant copolyamide 6 and preparation method thereof | |
| CN116987263A (en) | Nylon, anti-dripping flame-retardant material containing nylon and preparation method | |
| JP4096446B2 (en) | Transparent polyamide resin and method for producing the same | |
| JP2011063694A (en) | Method for controlling molecular weight of polyoxamide resin and polyoxamide resin | |
| JP2011236387A (en) | Process for producing polyoxamide resin by solid phase polymerization | |
| US5245005A (en) | Process for the production of linear amorphous polyamides with excess diamine | |
| US3553289A (en) | Polyoxamides from 3-aminomethyl-3,5,5-trimethyl cyclohexylamine | |
| JP5593978B2 (en) | Production method of polyoxamide resin | |
| KR20220092108A (en) | Process for Preparing a Polyamide by Copolymerization of Multiple Components, Polyamide Prepared Thereby, and Composition Comprising the Same | |
| WO2023201541A1 (en) | Hybridized dialkyl phosphinate salt, method for preparing same, and use thereof | |
| JP6485143B2 (en) | Production method of polyoxamide resin | |
| JP2016121217A (en) | Manufacturing method of polyoxamide resin | |
| WO2023120460A1 (en) | Polyamide composition | |
| US20230043028A1 (en) | Reactive phosporous contaning flame retardant and intrinsically flame retardant polymer obtainable by polycondensation with it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |