CN105751644A - Polyamide five-layer coextruded composite film with boron-silicon synergistic flame retardant effect and method for preparing same - Google Patents
Polyamide five-layer coextruded composite film with boron-silicon synergistic flame retardant effect and method for preparing same Download PDFInfo
- Publication number
- CN105751644A CN105751644A CN201610145549.9A CN201610145549A CN105751644A CN 105751644 A CN105751644 A CN 105751644A CN 201610145549 A CN201610145549 A CN 201610145549A CN 105751644 A CN105751644 A CN 105751644A
- Authority
- CN
- China
- Prior art keywords
- layer
- polyamide
- flame retardant
- borosilicate
- epoxy
- 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.)
- Granted
Links
- 239000004952 Polyamide Substances 0.000 title claims abstract description 126
- 229920002647 polyamide Polymers 0.000 title claims abstract description 126
- 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 103
- 239000003063 flame retardant Substances 0.000 title claims abstract description 103
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 230000000694 effects Effects 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 12
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 title abstract 5
- 230000002195 synergetic effect Effects 0.000 title abstract 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 36
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 34
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052796 boron Inorganic materials 0.000 claims abstract description 28
- 229920001558 organosilicon polymer Polymers 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims description 48
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 37
- -1 alkoxy silane Chemical compound 0.000 claims description 33
- 229920001296 polysiloxane Polymers 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 26
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 20
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 239000000376 reactant Substances 0.000 claims description 16
- 229910000077 silane Inorganic materials 0.000 claims description 16
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 claims description 14
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- MLSKXPOBNQFGHW-UHFFFAOYSA-N methoxy(dioxido)borane Chemical compound COB([O-])[O-] MLSKXPOBNQFGHW-UHFFFAOYSA-N 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 10
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 238000013517 stratification Methods 0.000 claims description 10
- SCWWDULYYDFWQV-UHFFFAOYSA-N (2-hydroxyphenoxy)boronic acid Chemical compound OB(O)OC1=CC=CC=C1O SCWWDULYYDFWQV-UHFFFAOYSA-N 0.000 claims description 9
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 9
- CVLQFCFFFPADRZ-UHFFFAOYSA-N NCCC[Si](OCC)(OCC)OCC.C(C)O[SiH](OCC)OCC Chemical compound NCCC[Si](OCC)(OCC)OCC.C(C)O[SiH](OCC)OCC CVLQFCFFFPADRZ-UHFFFAOYSA-N 0.000 claims description 8
- NIBADJGLXVMKLY-UHFFFAOYSA-N NC[Si]1(O[SiH2]O[SiH2]O[SiH2]O1)C1=CC=CC=C1 Chemical compound NC[Si]1(O[SiH2]O[SiH2]O[SiH2]O1)C1=CC=CC=C1 NIBADJGLXVMKLY-UHFFFAOYSA-N 0.000 claims description 8
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 8
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims description 8
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 8
- ZYGAMJLTPLERBC-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid propan-2-ol Chemical compound B(O)(O)OC(C)(C)C(C)(C)O.C(C)(C)O ZYGAMJLTPLERBC-UHFFFAOYSA-N 0.000 claims description 7
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims description 7
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 7
- 229920000571 Nylon 11 Polymers 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229920002292 Nylon 6 Polymers 0.000 claims description 5
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical group CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 5
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- 229920006375 polyphtalamide Polymers 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 claims description 3
- ZZPNDIHOQDQVNU-UHFFFAOYSA-N 2-hydroxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC1(C)OB(O)OC1(C)C ZZPNDIHOQDQVNU-UHFFFAOYSA-N 0.000 claims description 3
- 229920000299 Nylon 12 Polymers 0.000 claims description 3
- RBIILJCATVGHHI-UHFFFAOYSA-N [diethoxy(phenyl)silyl]methanamine Chemical compound NC[Si](OCC)(OCC)C1=CC=CC=C1 RBIILJCATVGHHI-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- MIYIEQPMRUWKCQ-UHFFFAOYSA-N 3-triethoxysilylpropan-1-amine trimethoxysilane Chemical compound CO[SiH](OC)OC.CCO[Si](CCCN)(OCC)OCC MIYIEQPMRUWKCQ-UHFFFAOYSA-N 0.000 claims description 2
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 claims description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000004954 Polyphthalamide Substances 0.000 claims description 2
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 claims description 2
- 229920006020 amorphous polyamide Polymers 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000012212 insulator Substances 0.000 abstract description 3
- 238000009413 insulation Methods 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 2
- 125000003277 amino group Chemical group 0.000 abstract 2
- 239000011347 resin Substances 0.000 abstract 2
- 229920005989 resin Polymers 0.000 abstract 2
- 229910052710 silicon Inorganic materials 0.000 abstract 2
- 239000010703 silicon Substances 0.000 abstract 2
- 230000035939 shock Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 119
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000006837 decompression Effects 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 238000003475 lamination Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003656 Daiamid® Polymers 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000206 moulding compound Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- TZPUFQUQYUYVQC-UHFFFAOYSA-N phenylsilylmethanamine Chemical compound NC[SiH2]C1=CC=CC=C1 TZPUFQUQYUYVQC-UHFFFAOYSA-N 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/05—5 or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
Abstract
The invention discloses a polyamide five-layer coextruded composite film with boron-silicon synergistic flame retardant effect and a method for preparing the same, comprising the specific steps: preparing silicon resin comprising amino groups and boron, synthesizing epoxy-terminated organosilicon polymer, reacting the silicon resin comprising amino groups and boron and the epoxy-terminated organosilicon polymer with polyamide in a molten state to obtain polyamide with boron-silicon synergistic flame retardant effect, and adding the polyamide with boron-silicon synergistic flame retardant effect, nanoparticles and an antioxidant into an extruder for co-extruding so as to obtain a boron-silicon synergistic flame retardant polyamide five-layer coextruded composite film with good properties.In the above-mentioned manner, the composite film of the invention has excellent flame retardancy, has advantages of both polyamide and organosilicon materials, has the advantages such as excellent insulation, system voltage resistance, high dimensional stability, thermal stability, good chemical properties, wear resistance, self-lubricating performance, low hygroscopicity, thermal shock resistance and extreme climate resistance, and is useful in the solar backboard film field, insulator field and other fields.
Description
Technical field
Polyamide five-layer co-squeezing composite membrane that the present invention relates to a kind of borosilicate cooperative flame retardant and preparation method thereof.
Background technology
Polyamide has good caking property, excellent machinery, wear-resisting, self-lubricating property and good thermostability, simultaneously also with the EVA(ethylene-vinyl acetate copolymer as encapsulating material) glued membrane and have good caking property as the silica gel being filled with a sealing, it is expected to become important solar energy back veneer material, obtains the concern of researcher in recent years.International monopoly WO2008/138021A2 discloses and utilizes polytype polyamide to replace polyester as the material in photovoltaic module backboard.Chinese patent CN102324440A is prepared for the solar cell backboard of a kind of single layer structure with polyamide for main body；Chinese patent CN10931018A then discloses the photovoltaic module monochrome printing film that a kind of moulding compound based on polyamide manufactures.In order to reduce daiamid composition water suction and promote the dimensional stability of goods, Chinese invention patent application 201080047306.2 report adopts phenolic compound for preparing the polyamide of borosilicate cooperative flame retardant.
It addition, coextrusion technology is to be extruded by multiple polymers composite with two or more screw extruders simultaneously, and in a head, it is shaped to the one-step shaping processing method of multi-layer plate-type or laminated structure.This method avoid cost height in traditional method, also need the shortcomings such as complicated lamination or coating process, can conveniently be shaped to the thin layer or superthin layer with property, production cost is low, technique is simple, energy consumption is low, and production efficiency is high, goods kind is many, is particularly suitable for producing laminated film goods.Chinese invention patent application 201210582704.5 discloses a kind of polyamide solar energy backboard, includes endosexine, sandwich layer and extexine three layers from inside to outside.Endosexine and extexine are by polyamide, filler and additive are made, sandwich layer is the Amilan polyamide resin composition composition of borosilicate cooperative flame retardant, and final products have excellent caking property, while splitting power, also there is performance ageing-resistant, especially wet and heat ageing resistant, also there is low saturated water absorption, the electrical insulation capability of low moisture-vapor transmission and excellence, and preparation technology simultaneously easy, cost is low, is suitable for industrialized production.
Therefore, the Chinese invention patent (application number CN201510008519.9) of our company's application adopts epoxy-capped organosilicon polymer to join melt blending and five-layer co-squeezing in extruder go out with amide, nanoparticle and antioxidant, obtain polyamide five-layer co-squeezing composite membrane, overcome disadvantages mentioned above.
But, the polyamide coextrusion-lamination film flame retardant effect that above-mentioned preparation method obtains is not good, when a fire, it is easy to deflagrate also causes that other property catches fire, and even jeopardizes human life's safety.For this reason, it may be necessary to develop Flameproof polyamide coextrusion-lamination film.The material adding Halogen combustion adjuvant can produce smog when burning, harmful, causes so many people in fire to suffocate and die, and precision equipment is paralysed.Traditional method by adding the inorganic combustion inhibitor such as aluminium hydroxide and magnesium hydroxide, although the fire resistance that polymer is good can be given, but owing to the compatibility between inorganic matter and organic polymer is poor, often reduce mechanical property and the processing characteristics of material.Silicon-series five-retardant is except can giving base material fire resistance (such as low burning rate, low heat release, anti-drippage), other performance (such as processing characteristics, mechanical performance, heat resistance etc.) of base material can also be improved, ecological friendly, thus people can be met to the increasingly stricter requirement of polyamide coextrusion-lamination film.Chinese invention patent (application number 201410189021.2) discloses a kind of method that reactive extrursion prepares Polyimidesiloxane/carbon fibre composite, specifically after Homogeneous phase mixing Amino End Group methyl phenyl siloxane performed polymer, aromatic dianhydride, aromatic diamine and chain-transferring agent, open extruder, by measurement charging device, the mixture after Homogeneous phase mixing is added extruder by main spout, carbon fiber is added by the side spout in extruder stage casing, simultaneously complete in an extruder Polyimidesiloxane polyreaction and with the compound of carbon fiber.But, carbon fiber and polymer base material poor compatibility in this method, viscosity is high, it is easy to produces to be separated, is not easy to co-extrusion for coextrusion-lamination film；Amino End Group methyl phenyl siloxane performed polymer large usage quantity in composite polymer matrix, and prepare the raw material aminomethyl phenyl ring body of Amino End Group methyl phenyl siloxane performed polymer or aminomethyl phenyl silane is more expensive, so that product cost is very high.
Summary of the invention
The technical problem that present invention mainly solves polyamide five-layer co-squeezing composite membrane being to provide a kind of borosilicate cooperative flame retardant and preparation method thereof, the polyamide five-layer co-squeezing composite membrane obtained has excellent fire resistance.
For solving above-mentioned technical problem, the technical scheme that the present invention adopts is: provide the polyamide five-layer co-squeezing composite membrane of a kind of borosilicate cooperative flame retardant, including ground floor, the second layer, third layer, the 4th layer and layer 5, described ground floor, the described second layer, described third layer, described 4th layer, described layer 5 is successively adjacent from top to bottom, described ground floor is identical with the material of described layer 5, and the described second layer is identical with the material of described 4th layer.
In a preferred embodiment of the present invention, described ground floor and described layer 5 are weathering layer, and described weathering layer is to add nanometer materials ageing-resistant, uvioresistant, raising mechanical performance in the polyamide of borosilicate cooperative flame retardant to reach weather-proof requirement and formed；The described second layer and described 4th layer are barrier layer, and described barrier layer is to add the nano level gas-barrier material that blocks water in the polyamide of borosilicate cooperative flame retardant, form, by molecule interlocking, effect that closed-loop structure reaches to intercept and are formed；Described third layer is the polyamide PA substrate layer of borosilicate cooperative flame retardant.
In a preferred embodiment of the present invention, the thickness of described ground floor and described layer 5 is 0.01～0.12mm, the thickness of the described second layer and described 4th layer is 0.01～0.12mm, the thickness of described third layer is 0.06～0.30mm, and the thickness of the polyamide five-layer co-squeezing composite membrane of described borosilicate cooperative flame retardant is 0.10～0.78mm.
In a preferred embodiment of the present invention, the preparation method of the polyamide five-layer co-squeezing composite membrane of described borosilicate cooperative flame retardant includes step and is: (1) adopts borate, carries out cohydrolysis condensation with the alkoxy silane of amino, two functional alkoxysilanes and trifunctional alkoxy silane, the preparation silicones containing amino and boron；(2) with cyclosiloxane be monomer, Tetramethylammonium hydroxide alkali glue obtain epoxy-capped organosilicon polymer for catalyst and epoxy-capped dose of ring-opening polymerisation；(3) the described silicones containing amino and boron, described epoxy-capped organosilicon polymer and polyamide are obtained by reacting in the molten state the polyamide of borosilicate cooperative flame retardant；(4) polyamide of described borosilicate cooperative flame retardant, nanoparticle and antioxidant are joined coextrusion in extruder, obtain the polyamide five-layer co-squeezing composite membrane of borosilicate cooperative flame retardant.
nullIn a preferred embodiment of the present invention，In step (1), the concrete preparation method of silicones containing amino and boron is: by the alkoxy silane with amino、Borate、Two functional alkoxysilanes and trifunctional alkoxy silane carry out being mixed to get reactant，Reactant is added drop-wise in the mixture of solvent and water，Under agitation，After 20～80 DEG C of cohydrolysis 0.5～24h，Through stratification，After oil phase is removed solvent and low molecule when 30～80 DEG C/20mmHg，Obtain the silicones containing amino and boron，The consumption of wherein said borate is 0.5～10wt% of described reactant，0.5～the 15wt% that consumption is described reactant of the described alkoxy silane with amino，10～the 65wt% that consumption is described reactant of described two functional alkoxysilanes，0～the 10wt% that consumption is described reactant of described trifunctional alkoxy silane，The quality of described solvent is 0.3～4 times of described reactant quality，Described water is 0.8～3 times of described reactant molal quantity.
In a preferred embodiment of the present invention, two functional alkoxysilanes described in step (1) are the mixture of one or more in dimethyldimethoxysil,ne, dimethyldiethoxysilane, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane；Described trifunctional alkoxy silane is a kind of and several mixture in MTMS, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane；Borate described in step (1) is the mixture of one or more in methyl borate., triethyl borate, triisopropanolamine ring borate, duplex catechol borate, isopropanol pinacol borate, connection boric acid pinacol ester, duplex (2-methyl-2,4-PD) borate, duplex (D-diethyl tartrate .) borate；Preferably, described borate is the mixture of one or more in methyl borate., triethyl borate, triisopropanolamine ring borate, duplex catechol borate；The described alkoxy silane with amino is the mixture of one or more in γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, aminopropyltriethoxysilane trimethoxy silane, aminopropyltriethoxysilane triethoxysilane.
In a preferred embodiment of the present invention, cyclosiloxane described in step (2) is the mixture of one or more in octamethylcy-clotetrasiloxane, aminomethyl phenyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane；Described epoxy-capped dose is 1,3-bis-(3-shrink propyl group)-1,1,3,3-four disiloxane；Described epoxy-capped organosilicon polymer is the mixture of one or more in epoxy-capped dimethyl polysiloxane, epoxy-capped methyl phenyl silicone, epoxy-capped dimethyl diphenyl polysiloxanes, epoxy-capped dimethyl-methylphenyl polysiloxanes；Polymerization temperature prepared by epoxy-capped organosilicon polymer described in step (2) is 80～100 DEG C, and polymerization time is 1～24h, is polymerized complete, polymerization reaction system is heated to 135～145 DEG C of decomposition catalyst 1～4h, namely obtains epoxy-capped organosilicon polymer；The viscosity of described epoxy-capped organosilicon polymer is 5～30000mpa s；Preferably, the viscosity of described epoxy-capped organosilicon polymer is 10～5000mpa s；Most preferably, the viscosity of described epoxy-capped organosilicon polymer is 10～1000mpa s.
In a preferred embodiment of the present invention, polyamide described in step (3) is polycaprolactam PA6, polyhexamethylene adipamide PA66, nylon 9 PA9, polycaprinlactam PA10, nylon 11 PA11, nylon 12 PA12, polynonamethylene adipamide PA69, polyhexamethylene sebacamide PA610, poly-12 acyl hexamethylene diamine PA612, amorphous polyamides PA6-3-T, gathers one or more in () phthalic acid hexamethylene diamine PA61, polyphthalamide PPA；The described consumption containing amino and the silicones of boron is 0.5 ~ 15wt% of polyamide；5 ~ the 15wt% that consumption is polyamide of described epoxy-capped organosilicon polymer.
In a preferred embodiment of the present invention, nanoparticle described in step (4) is the mixture of one or more in nano titanium oxide, nano-calcium carbonate, nano zine oxide, nano zircite, nano silicon；The particle diameter of described nanoparticle is 0.5～500nm；Preferably, the particle diameter of described nanoparticle is 2～200nm；Most preferably, the particle diameter of described nanoparticle is 10～80nm；Described nanoparticle consumption is 1～80wt% of the polyamide of described borosilicate cooperative flame retardant；Preferably, described nanoparticle consumption is 5～60wt% of the polyamide of described borosilicate cooperative flame retardant；Described antioxidant is Hinered phenols antioxidant N, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine or sub-antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester；Described antioxidant consumption is 0.01～5wt% of the polyamide of described borosilicate cooperative flame retardant；Preferably, described antioxidant consumption is 0.05～2wt% of the polyamide of described borosilicate cooperative flame retardant.
In a preferred embodiment of the present invention, extruder warm area totally 9 warm areas in extruder coextrusion process described in step (4), temperature range is 80 DEG C～180 DEG C, and mould is divided into 6 warm areas, and temperature range is 180～280 DEG C.
The invention has the beneficial effects as follows: polyamide five-layer co-squeezing composite membrane of the borosilicate cooperative flame retardant of the present invention and preparation method thereof, composite membrane has excellent flame retardant effect, flame retardant effect is up to UL-94V-0 rank, oxygen index (OI) is 25～33, and the advantage having polyamide and organosilicon material concurrently, there is the advantages such as superior insulation, resistance to system voltage, high-dimensional stability, heat stability, good mechanical performance, wear-resisting, self-lubricating property, hygroscopicity are little, cold-hot impact, resistance to extreme climate, can be used for the fields such as solar energy backboard membrane, insulator.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme in the embodiment of the present invention, below the accompanying drawing used required during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawing according to these accompanying drawings, wherein:
Fig. 1 is the structural representation of polyamide five-layer co-squeezing composite membrane one preferred embodiment of the borosilicate cooperative flame retardant of the present invention.
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, all other embodiments that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention.
Embodiment one:
Refer to Fig. 1, the polyamide five-layer co-squeezing composite membrane of a kind of borosilicate cooperative flame retardant is provided, including ground floor, the second layer, third layer, the 4th layer and layer 5, i.e. A layer shown in Fig. 1, B layer and C layer, it is followed successively by A layer, B layer, C layer, B layer and A layer as shown in Figure 1 from the top down.Five layers, all with the polyamide of borosilicate cooperative flame retardant for base material, meet the key propertys such as excellent anti-flammability, high-insulativity, resistance to system voltage, high-dimensional stability, heat stability.Wherein A layer is high durable layer, is add nanometer materials ageing-resistant, uvioresistant, raising mechanical performance in the polyamide of borosilicate cooperative flame retardant to reach the requirement of high durable；B layer is high-obstruction, is add the nano level gas-barrier material that blocks water in the polyamide of borosilicate cooperative flame retardant, by controlling of production process, forms closed-loop structure by molecule interlocking, reaches the effect of high-barrier；C layer is the polyamide PA substrate layer of borosilicate cooperative flame retardant.
Described A layer thickness is 0.01～0.12mm, and described B layer thickness is 0.01～0.12mm, and described C layer thickness is 0.06～0.30mm, and the thickness of the polyamide five-layer co-squeezing composite membrane of described borosilicate cooperative flame retardant is 0.10～0.78mm.
The preparation method that the polyamide five-layer co-squeezing composite membrane of a kind of borosilicate cooperative flame retardant is provided, including step be:
(1) in the clean there-necked flask of 3L, 500g toluene and 500g deionized water are added, under agitation start to drip by the mixture of 272g γ-aminopropyltrimethoxysilane, 480g dimethyldiethoxysilane, 408g MTMS and 50g methyl borate. in 30 DEG C, after dripping off in 0.5 ~ 1h, it is warmed up to 80 DEG C of backflow 4h, stratification, by oil phase under 50 DEG C/20mmHg after removed under reduced pressure solvent and low molecule, it is thus achieved that 465g is containing the silicones of amino and boron.
(2) there-necked flask of, nitrogen protection clean to 1L adds octamethylcy-clotetrasiloxane 400g, epoxy-capped dose of 18.64g and Tetramethylammonium hydroxide alkali glue 8g; 4h it is polymerized at 100 DEG C; decomposition catalyst 1h at 140 DEG C; then after low molecule is deviate from decompression, it is thus achieved that the epoxy-capped dimethyl polysiloxane of viscosity 350mpa s.
(3) then take the gained silicones 60g containing amino and boron, epoxy-capped dimethyl polysiloxane 40g, and and polyamide 6 (PA6) 360g, be heated to 160 DEG C, Depressor response 4h, it is thus achieved that the polyamide 460g of borosilicate cooperative flame retardant.
(4) by nano titanium oxide 160g that the polyamide 200g of gained borosilicate cooperative flame retardant, particle diameter are 100nm and antioxidant N, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine 1g adds First extruder；The polyamide 100g of gained borosilicate cooperative flame retardant and antioxidant N, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine 0.5g adds second extruder；The polyamide 100g of gained borosilicate cooperative flame retardant adds the 3rd extruder.These 9 temperature of three extruders are the warm area of 160 DEG C, are quickly expressed into the warm area of 6 temperature respectively 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C and 230 DEG C, and bubble 30min, then extrusion molding are deviate from decompression, it is thus achieved that five-layer co-squeezing polyamide composite film.Wherein A layer 0.08MM, B layer 0.10MM, C layer 0.20MM, finished product five-layer co-squeezing polyamide composite film thickness 0.56MM.This composite membrane flame retardant effect is up to UL-94V-0 level, and oxygen index (OI) is 33.
Embodiment two:
The preparation method that the polyamide five-layer co-squeezing composite membrane of a kind of borosilicate cooperative flame retardant is provided, identical with embodiment one on the polyamide five-layer co-squeezing structure of composite membrane obtained, including step be:
(1) in the clean there-necked flask of 3L, 1000g toluene and 500g deionized water are added, under agitation start to drip by the mixture of 136g gamma-aminopropyl-triethoxy-silane, 360g dimethyldiethoxysilane, 210g aminomethyl phenyl diethoxy silane, 534g MTES and 30g methyl borate. and 60g triethyl borate in 30 DEG C, after dripping off in 0.5 ~ 1h, it is warmed up to 40 DEG C of reaction 24h, stratification, by oil phase under 60 DEG C/20mmHg after removed under reduced pressure solvent and low molecule, it is thus achieved that 545g is containing the silicones of amino and boron.
(2) there-necked flask of, nitrogen protection clean to 1L adds octamethylcy-clotetrasiloxane 200g, aminomethyl phenyl cyclotetrasiloxane 200g, epoxy-capped dose of 18.64g and Tetramethylammonium hydroxide alkali glue 8g; 4h it is polymerized at 100 DEG C; decomposition catalyst 1h at 140 DEG C; then after low molecule is deviate from decompression, it is thus achieved that the epoxy-capped methyl phenyl silicone of viscosity 590mpa s.
(3) then take the gained silicones 40g containing amino and boron, epoxy-capped methyl phenyl silicone 40g and polyamide 66 (PA66) 360g, be heated to 160 DEG C, Depressor response 4h, it is thus achieved that the polyamide 440g of borosilicate cooperative flame retardant.
(4) nano zine oxide 20g and antioxidant Asia antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 1g that the polyamide 200g of gained borosilicate cooperative flame retardant, particle diameter are 2nm are added First extruder；The polyamide 100g of gained borosilicate cooperative flame retardant and antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 0.5g adds second extruder；The polyamide 100g of gained borosilicate cooperative flame retardant adds the 3rd extruder.These 9 temperature of three extruders are the warm area of 160 DEG C, quickly it is expressed into the warm area of 6 temperature respectively 190 DEG C, 210 DEG C, 230 DEG C, 240 DEG C, 250 DEG C and 260 DEG C, bubble 30min is deviate from decompression, then extrusion molding, obtain five-layer co-squeezing polyamide composite film, wherein A layer 0.12MM, B layer 0.01MM, C layer 0.30MM, finished product thickness 0.56MM.This composite membrane flame retardant effect is up to UL-94V-0 level, and oxygen index (OI) is 30.
Embodiment three:
The preparation method that the polyamide five-layer co-squeezing composite membrane of a kind of borosilicate cooperative flame retardant is provided, identical with embodiment one on the polyamide five-layer co-squeezing structure of composite membrane obtained, including step be:
(1) in the clean there-necked flask of 3L, 800g toluene and 500g deionized water are added, under agitation start dropping by 136g γ-aminopropyltrimethoxysilane in 30 DEG C, 135g aminopropyltriethoxysilane triethoxysilane, 240g dimethyldiethoxysilane, 244g dimethoxydiphenylsilane, 204g MTMS, 198g phenyltrimethoxysila,e, the mixture of 20g triisopropanolamine ring borate and 40g methyl borate., after dripping off in 0.5 ~ 1h, it is warmed up to 65 DEG C of reaction 8h, stratification, by oil phase under 60 DEG C/20mmHg after removed under reduced pressure solvent and low molecule, obtain the 639g silicones containing amino and boron.
(2) there-necked flask of, nitrogen protection clean to 1L adds octamethylcy-clotetrasiloxane 200g, octaphenylcyclotetrasiloxane 200g, epoxy-capped dose of 18.64g, Tetramethylammonium hydroxide alkali glue 8g; 4h it is polymerized at 100 DEG C; decomposition catalyst 1h at 140 DEG C; then after low molecule is deviate from decompression, it is thus achieved that the epoxy-capped dimethyl diphenyl polysiloxanes of viscosity 780mpa s.
(3) gained silicones 25g containing amino and boron, epoxy-capped dimethyl diphenyl polysiloxanes 40g and and polyamide 9(PA9 are then taken) 360g, it is heated to 160 DEG C, Depressor response 4h, it is thus achieved that the polyamide 425g of borosilicate cooperative flame retardant.
(4) the nano zine oxide 40g and antioxidant Asia antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 0.25g of the polyamide 200g of gained borosilicate cooperative flame retardant, particle diameter to be the nano zine oxide 20g of 500nm, particle diameter be 40nm are added First extruder；The polyamide 100g of gained borosilicate cooperative flame retardant and antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 0.125g adds second extruder；The polyamide 100g of gained borosilicate cooperative flame retardant adds the 3rd extruder.These 9 temperature of three extruders are the warm area of 160 DEG C, quickly it is expressed into the warm area of 6 temperature respectively 180 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C and 240 DEG C, bubble 30min is deviate from decompression, then extrusion molding, obtain five-layer co-squeezing polyamide composite film, wherein A layer 0.04MM, B layer 0.12MM, C layer 0.18MM, finished product thickness 0.52MM.This composite membrane flame retardant effect is up to UL-94V-0 level, and oxygen index (OI) is 30.
Embodiment four:
The preparation method that the polyamide five-layer co-squeezing composite membrane of a kind of borosilicate cooperative flame retardant is provided, identical with embodiment one on the polyamide five-layer co-squeezing structure of composite membrane obtained, including step be:
(1) in the clean there-necked flask of 3L, 1800g toluene and 500g deionized water are added, under agitation start dropping by 68g γ-aminopropyltrimethoxysilane in 30 DEG C, 67.5g aminopropyltriethoxysilane triethoxysilane, 120g dimethyldiethoxysilane, 122g diphenyl diethoxy silane, 102g MTES, 99g phenyl triethoxysilane, 10g duplex catechol borate, 5g isopropanol pinacol borate, 15g joins the mixture of boric acid pinacol ester and 5g methyl borate., after dripping off in 0.5 ~ 1h, it is warmed up to 65 DEG C of reaction 4h, stratification, by oil phase under 60 DEG C/20mmHg after removed under reduced pressure solvent and low molecule, obtain the 393g silicones containing amino and boron.
(2) there-necked flask of, nitrogen protection clean to 1L adds octamethylcy-clotetrasiloxane 150g and aminomethyl phenyl cyclotetrasiloxane 150g; epoxy-capped dose of 55.92g; Tetramethylammonium hydroxide alkali glue 6g; 4h it is polymerized at 100 DEG C; decomposition catalyst 1h at 140 DEG C; then after low molecule is deviate from decompression, it is thus achieved that the epoxy-capped methyl phenyl silicone of viscosity 35mpa s.
(3) gained silicones 40g containing amino and boron, epoxy-capped methyl phenyl silicone 40g, polyamide 11(PA11 are then taken) 360g, it is heated to 160 DEG C, Depressor response 4h, it is thus achieved that the polyamide 440g of borosilicate cooperative flame retardant.
(4) the nano zircite 20g and antioxidant Asia antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 10g of the polyamide 200g of gained borosilicate cooperative flame retardant, particle diameter to be the nano zine oxide 20g of 100nm, particle diameter be 40nm are added First extruder；The polyamide 100g of gained borosilicate cooperative flame retardant and antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 5g adds second extruder；The polyamide 100g of gained borosilicate cooperative flame retardant adds the 3rd extruder.These 9 temperature of three extruders are the warm area of 160 DEG C, quickly it is expressed into the warm area of 6 temperature respectively 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 260 DEG C and 280 DEG C, bubble 30min is deviate from decompression, then extrusion molding, obtain five-layer co-squeezing polyamide composite film, wherein A layer 0.10MM, B layer 0.06MM, C layer 0.30MM, finished product thickness 0.62MM.This composite membrane flame retardant effect is up to UL-94V-0 level, and oxygen index (OI) is 31.5.
Embodiment five:
The preparation method that the polyamide five-layer co-squeezing composite membrane of a kind of borosilicate cooperative flame retardant is provided, identical with embodiment one on the polyamide five-layer co-squeezing structure of composite membrane obtained, including step be:
(1) in the clean there-necked flask of 3L, 1800g toluene and 500g deionized water are added, under agitation start dropping by 68g γ-aminopropyltrimethoxysilane in 30 DEG C, 67.5g aminopropyltriethoxysilane triethoxysilane, 120g dimethyldiethoxysilane, 122g diphenyl diethoxy silane, 102g MTES, 99g phenyl triethoxysilane, 10g duplex catechol borate, 5g isopropanol pinacol borate, the mixture of 15g duplex (D-diethyl tartrate .) borate and 5g methyl borate., after dripping off in 0.5 ~ 1h, it is warmed up to 65 DEG C of reaction 4h, stratification, by oil phase under 60 DEG C/20mmHg after removed under reduced pressure solvent and low molecule, obtain the 393g silicones containing amino and boron.
(2) there-necked flask of, nitrogen protection clean to 1L adds octamethylcy-clotetrasiloxane 100g and aminomethyl phenyl cyclotetrasiloxane 100g; epoxy-capped dose of 55.92g; Tetramethylammonium hydroxide alkali glue 6g; 4h it is polymerized at 100 DEG C; decomposition catalyst 1h at 140 DEG C; then after low molecule is deviate from decompression, it is thus achieved that the epoxy-capped methyl phenyl silicone of viscosity 12mpa s.
(3) gained silicones 5g containing amino and boron, epoxy-capped methyl phenyl silicone 40g, polyamide 12(PA12 are then taken) 360g, it is heated to 160 DEG C, Depressor response 4h, it is thus achieved that the polyamide 405g of borosilicate cooperative flame retardant.
(4) by nano titanium oxide 80g and the N of the polyamide 200g of gained borosilicate cooperative flame retardant, particle diameter to be the nano silicon 20g of 0.5nm, particle diameter be 80nm; N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine 0.05g adds First extruder；The polyamide 100g of gained borosilicate cooperative flame retardant and antioxidant N, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine 0.025g adds second extruder；The polyamide 100g of gained borosilicate cooperative flame retardant adds the 3rd extruder.These 9 temperature of three extruders are the warm area of 160 DEG C, quickly it is expressed into the warm area of 6 temperature respectively 180 DEG C, 190 DEG C, 220 DEG C, 240 DEG C, 260 DEG C and 280 DEG C, bubble 30min is deviate from decompression, then extrusion molding, obtain five-layer co-squeezing polyamide composite film, wherein A layer 0.12MM, B layer 0.12MM, C layer 0.20MM, finished product thickness 0.68MM.This composite membrane flame retardant effect is up to UL-94V-0 level, and oxygen index (OI) is 27.
Embodiment six:
The preparation method that the polyamide five-layer co-squeezing composite membrane of a kind of borosilicate cooperative flame retardant is provided, identical with embodiment one on the polyamide five-layer co-squeezing structure of composite membrane obtained, including step be:
(1) in the clean there-necked flask of 3L, 1800g toluene and 500g deionized water are added, under agitation start dropping by 68g γ-aminopropyltrimethoxysilane in 30 DEG C, 67.5g aminopropyltriethoxysilane triethoxysilane, 120g dimethyldiethoxysilane, 122g diphenyl diethoxy silane, 102g MTES, 99g phenyl triethoxysilane, 10g duplex catechol borate, 5g isopropanol pinacol borate, the mixture of 15g duplex (D-diethyl tartrate .) borate and 5g methyl borate., after dripping off in 0.5 ~ 1h, it is warmed up to 65 DEG C of reaction 4h, stratification, by oil phase under 60 DEG C/20mmHg after removed under reduced pressure solvent and low molecule, obtain the 393g silicones containing amino and boron.
(2) there-necked flask of, nitrogen protection clean to 1L adds octamethylcy-clotetrasiloxane 200g and aminomethyl phenyl cyclotetrasiloxane 200g; epoxy-capped dose of 1.864g; Tetramethylammonium hydroxide alkali glue 8g; 4h it is polymerized at 100 DEG C; decomposition catalyst 1h at 140 DEG C; then after low molecule is deviate from decompression, it is thus achieved that the epoxy-capped methyl phenyl silicone of viscosity 5000mpa s.
(3) take the gained silicones 20g containing amino and boron, epoxy-capped methyl phenyl silicone 40g, polyamide 66 (PA66) 360g, be heated to 160 DEG C, Depressor response 4h, it is thus achieved that the polyamide 420g of borosilicate cooperative flame retardant.
(4) the nano silicon 100g and antioxidant Asia antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 1g of the polyamide 200g of gained borosilicate cooperative flame retardant, particle diameter to be the nano silicon 20g of 0.5nm, particle diameter be 100nm are added First extruder；The polyamide 100g of gained borosilicate cooperative flame retardant and antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 0.5g adds second extruder；The polyamide 100g of gained borosilicate cooperative flame retardant adds the 3rd extruder.These 9 temperature of three extruders are the warm area of 160 DEG C, quickly it is expressed into the warm area of 6 temperature respectively 180 DEG C, 200 DEG C, 210 DEG C, 230 DEG C, 240 DEG C and 260 DEG C, bubble 30min is deviate from decompression, then extrusion molding, obtain five-layer co-squeezing polyamide composite film, wherein A layer 0.08MM, B layer 0.08MM, C layer 0.40MM, finished product thickness 0.72MM.This composite membrane flame retardant effect is up to UL-94V-0 level, and oxygen index (OI) is 29.5.
Embodiment seven:
The preparation method that the polyamide five-layer co-squeezing composite membrane of a kind of borosilicate cooperative flame retardant is provided, identical with embodiment one on the polyamide five-layer co-squeezing structure of composite membrane obtained, including step be:
(1) in the clean there-necked flask of 3L, 1800g toluene and 500g deionized water are added, under agitation start dropping by 68g γ-aminopropyltrimethoxysilane in 30 DEG C, 67.5g aminopropyltriethoxysilane triethoxysilane, 120g dimethyldiethoxysilane, 122g diphenyl diethoxy silane, 102g MTES, 99g phenyl triethoxysilane, 10g duplex catechol borate, 5g isopropanol pinacol borate, the mixture of 15g duplex (D-diethyl tartrate .) borate and 5g methyl borate., after dripping off in 0.5 ~ 1h, it is warmed up to 65 DEG C of reaction 4h, stratification, by oil phase under 60 DEG C/20mmHg after removed under reduced pressure solvent and low molecule, obtain the 393g silicones containing amino and boron.
(2) there-necked flask of, nitrogen protection clean to 1L adds octamethylcy-clotetrasiloxane 200g and aminomethyl phenyl cyclotetrasiloxane 200g; epoxy-capped dose of 0.932g; Tetramethylammonium hydroxide alkali glue 8g; 4h it is polymerized at 100 DEG C; decomposition catalyst 1h at 140 DEG C; then after low molecule is deviate from decompression, it is thus achieved that the epoxy-capped methyl phenyl silicone of viscosity 28000mpa s.
(3) then take the gained silicones 2g containing amino and boron, epoxy-capped methyl phenyl silicone 40g, polyamide 66 (PA66) 360g, be heated to 160 DEG C, Depressor response 4h, it is thus achieved that the polyamide 400g of borosilicate cooperative flame retardant.
(4) the nano-calcium carbonate 100g and antioxidant Asia antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 1g of the polyamide 200g of gained borosilicate cooperative flame retardant, particle diameter to be the nano silicon 20g of 40nm, particle diameter be 100nm are added First extruder；The polyamide 100g of gained borosilicate cooperative flame retardant and antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 0.5g adds second extruder；The polyamide 100g of gained borosilicate cooperative flame retardant adds the 3rd extruder.These 9 temperature of three extruders are the warm area of 160 DEG C, quickly it is expressed into the warm area of 6 temperature respectively 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C and 230 DEG C, bubble 30min is deviate from decompression, then extrusion molding, obtain five-layer co-squeezing polyamide composite film, wherein A layer 0.06MM, B layer 0.06MM, C layer 0.20MM, finished product thickness 0.44MM.This composite membrane flame retardant effect is up to UL-94V-0 level, and oxygen index (OI) is 27.8.
Embodiment eight:
The preparation method that the polyamide five-layer co-squeezing composite membrane of a kind of borosilicate cooperative flame retardant is provided, identical with embodiment one on the polyamide five-layer co-squeezing structure of composite membrane obtained, including step be:
(1) in the clean there-necked flask of 3L, 1800g toluene and 500g deionized water are added, under agitation start dropping by 68g γ-aminopropyltrimethoxysilane in 30 DEG C, 67.5g aminopropyltriethoxysilane triethoxysilane, 120g dimethyldiethoxysilane, 122g diphenyl diethoxy silane, 102g MTES, 99g phenyl triethoxysilane, 10g duplex catechol borate, 5g isopropanol pinacol borate, the mixture of 15g duplex (D-diethyl tartrate .) borate and 5g methyl borate., after dripping off in 0.5 ~ 1h, it is warmed up to 65 DEG C of reaction 4h, stratification, by oil phase under 60 DEG C/20mmHg after removed under reduced pressure solvent and low molecule, obtain the 393g silicones containing amino and boron.
(2) there-necked flask of, nitrogen protection clean to 1L adds octamethylcy-clotetrasiloxane 200g and aminomethyl phenyl cyclotetrasiloxane 200g; epoxy-capped dose of 0.932g; Tetramethylammonium hydroxide alkali glue 8g; 4h it is polymerized at 100 DEG C; decomposition catalyst 1h at 140 DEG C; then after low molecule is deviate from decompression, it is thus achieved that the epoxy-capped methyl phenyl silicone of viscosity 28000mpa s.
(3) then take the gained silicones 0.2g containing amino and boron, epoxy-capped methyl phenyl silicone 40g, polyamide 66 (PA66) 360g, be heated to 160 DEG C, Depressor response 4h, it is thus achieved that the polyamide 400g of borosilicate cooperative flame retardant.
(4) the nano-calcium carbonate 100g and antioxidant Asia antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 1g of the polyamide 200g of gained borosilicate cooperative flame retardant, particle diameter to be the nano silicon 20g of 40nm, particle diameter be 100nm are added First extruder；The polyamide 100g of gained borosilicate cooperative flame retardant and antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester 0.5g adds second extruder；The polyamide 100g of gained borosilicate cooperative flame retardant adds the 3rd extruder.These 9 temperature of three extruders are the warm area of 160 DEG C, quickly it is expressed into the warm area of 6 temperature respectively 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C and 230 DEG C, bubble 30min is deviate from decompression, then extrusion molding, obtain five-layer co-squeezing polyamide composite film, wherein A layer 0.06MM, B layer 0.06MM, C layer 0.20MM, finished product thickness 0.44MM.This composite membrane flame retardant effect is up to UL-94V-0 level, and oxygen index (OI) is 25.0.
The present invention carries out copolyreaction by epoxy-capped organosilicon polymer and polyamide, develop the polyamide of a kind of new borosilicate cooperative flame retardant, and it is mixed with antioxidant, antiager and Nano filling etc., five-layer co-squeezing is adopted to go out technology, be prepared for that mechanical mechanics property is excellent, pliability good, water absorption is low, cold-hot impacts and the Polyurethane five-layer co-squeezing composite membrane of borosilicate cooperative flame retardant of resistance to extreme climate, ultraviolet light resistant etc., can be used for the fields such as solar energy backboard membrane, insulator.
Solar energy backboard prepared by the Polyurethane five-layer co-squeezing composite membrane of the borosilicate cooperative flame retardant of gained of the present invention is adopted to have excellent caking property, while splitting power, ageing-resistant and resistance to extreme climate, there is low saturated water absorption simultaneously, the electrical insulating property of low-temperature impact resistance, low water vapour permeability and excellence, can be used for manufacturing solar module.The method of the invention can be effectively improved the flame retardant effect of five-layer co-squeezing film, can improve again the mechanical mechanics property of compound five-layer co-squeezing film.
Due to borosilicate cooperative flame retardant, this five-layer co-squeezing film flame retardant effect is up to UL-94V-0 level, oxygen index (OI) is 25～33, very difficult to burn, even if burning at relatively high temperatures, no matter it is seldom produce smog when flaming combustion or flameless combustion, more will not produce the etchant gases such as hydrogen halides, thus without jeopardizing the life of people or machinery equipment being constituted corrosivity infringement.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every equivalent structure utilizing description of the present invention to make or equivalence flow process conversion; or directly or indirectly it is used in other relevant technical field, all in like manner include in the scope of patent protection of the present invention.
Claims (10)
1. the polyamide five-layer co-squeezing composite membrane of a borosilicate cooperative flame retardant, it is characterized in that, including ground floor, the second layer, third layer, the 4th layer and layer 5, described ground floor, the described second layer, described third layer, described 4th layer, described layer 5 is successively adjacent from top to bottom, described ground floor is identical with the material of described layer 5, and the described second layer is identical with the material of described 4th layer.
2. the polyamide five-layer co-squeezing composite membrane of borosilicate cooperative flame retardant according to claim 1, it is characterized in that, described ground floor and described layer 5 are weathering layer, and described weathering layer is to add nanometer materials ageing-resistant, uvioresistant, raising mechanical performance in the polyamide of borosilicate cooperative flame retardant to reach weather-proof requirement and formed；The described second layer and described 4th layer are barrier layer, and described barrier layer is to add the nano level gas-barrier material that blocks water in the polyamide of borosilicate cooperative flame retardant, form, by molecule interlocking, effect that closed-loop structure reaches to intercept and are formed；Described third layer is the polyamide PA substrate layer of borosilicate cooperative flame retardant.
3. the polyamide five-layer co-squeezing composite membrane of borosilicate cooperative flame retardant according to claim 1, it is characterized in that, the thickness of described ground floor and described layer 5 is 0.01～0.12mm, the thickness of the described second layer and described 4th layer is 0.01～0.12mm, the thickness of described third layer is 0.06～0.30mm, and the thickness of the polyamide five-layer co-squeezing composite membrane of described borosilicate cooperative flame retardant is 0.10～0.78mm.
4. the preparation method of the polyamide five-layer co-squeezing composite membrane of borosilicate cooperative flame retardant according to claim 1, it is characterized in that, including step it is: (1) adopts borate, carries out cohydrolysis condensation with the alkoxy silane of amino, two functional alkoxysilanes and trifunctional alkoxy silane, the preparation silicones containing amino and boron；(2) with cyclosiloxane be monomer, Tetramethylammonium hydroxide alkali glue obtain epoxy-capped organosilicon polymer for catalyst and epoxy-capped dose of ring-opening polymerisation；(3) the described silicones containing amino and boron, described epoxy-capped organosilicon polymer and polyamide are obtained by reacting in the molten state the polyamide of borosilicate cooperative flame retardant；(4) polyamide of described borosilicate cooperative flame retardant, nanoparticle and antioxidant are joined coextrusion in extruder, obtain the polyamide five-layer co-squeezing composite membrane of borosilicate cooperative flame retardant.
null5. preparation method according to claim 4，It is characterized in that，In step (1), the concrete preparation method of silicones containing amino and boron is: by the alkoxy silane with amino、Borate、Two functional alkoxysilanes and trifunctional alkoxy silane carry out being mixed to get reactant，Reactant is added drop-wise in the mixture of solvent and water，Under agitation，After 20～80 DEG C of cohydrolysis 0.5～24h，Through stratification，After oil phase is removed solvent and low molecule when 30～80 DEG C/20mmHg，Obtain the silicones containing amino and boron，The consumption of wherein said borate is 0.5～10wt% of described reactant，0.5～the 15wt% that consumption is described reactant of the described alkoxy silane with amino，10～the 65wt% that consumption is described reactant of described two functional alkoxysilanes，0～the 10wt% that consumption is described reactant of described trifunctional alkoxy silane，The quality of described solvent is 0.3～4 times of described reactant quality，Described water is 0.8～3 times of described reactant molal quantity.
6. the preparation method according to claim 4 or 5, it is characterized in that, two functional alkoxysilanes described in step (1) are the mixture of one or more in dimethyldimethoxysil,ne, dimethyldiethoxysilane, aminomethyl phenyl dimethoxysilane, aminomethyl phenyl diethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane；Described trifunctional alkoxy silane is a kind of and several mixture in MTMS, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane；Borate described in step (1) is the mixture of one or more in methyl borate., triethyl borate, triisopropanolamine ring borate, duplex catechol borate, isopropanol pinacol borate, connection boric acid pinacol ester, duplex (2-methyl-2,4-PD) borate, duplex (D-diethyl tartrate .) borate；Preferably, described borate is the mixture of one or more in methyl borate., triethyl borate, triisopropanolamine ring borate, duplex catechol borate；The described alkoxy silane with amino is the mixture of one or more in γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy-silane, aminopropyltriethoxysilane trimethoxy silane, aminopropyltriethoxysilane triethoxysilane.
7. preparation method according to claim 4, it is characterised in that cyclosiloxane described in step (2) is the mixture of one or more in octamethylcy-clotetrasiloxane, aminomethyl phenyl cyclotetrasiloxane, octaphenylcyclotetrasiloxane；Described epoxy-capped dose is 1,3-bis-(3-shrink propyl group)-1,1,3,3-four disiloxane；Described epoxy-capped organosilicon polymer is the mixture of one or more in epoxy-capped dimethyl polysiloxane, epoxy-capped methyl phenyl silicone, epoxy-capped dimethyl diphenyl polysiloxanes, epoxy-capped dimethyl-methylphenyl polysiloxanes；Polymerization temperature prepared by epoxy-capped organosilicon polymer described in step (2) is 80～100 DEG C, and polymerization time is 1～24h, is polymerized complete, polymerization reaction system is heated to 135～145 DEG C of decomposition catalyst 1～4h, namely obtains epoxy-capped organosilicon polymer；The viscosity of described epoxy-capped organosilicon polymer is 5～30000mpa s；Preferably, the viscosity of described epoxy-capped organosilicon polymer is 10～5000mpa s；Most preferably, the viscosity of described epoxy-capped organosilicon polymer is 10～1000mpa s.
8. preparation method according to claim 4, it is characterized in that, polyamide described in step (3) is polycaprolactam PA6, polyhexamethylene adipamide PA66, nylon 9 PA9, polycaprinlactam PA10, nylon 11 PA11, nylon 12 PA12, polynonamethylene adipamide PA69, polyhexamethylene sebacamide PA610, poly-12 acyl hexamethylene diamine PA612, amorphous polyamides PA6-3-T, gathers one or more in () phthalic acid hexamethylene diamine PA61, polyphthalamide PPA；The described consumption containing amino and the silicones of boron is 0.5 ~ 15wt% of polyamide；5 ~ the 15wt% that consumption is polyamide of described epoxy-capped organosilicon polymer.
9. preparation method according to claim 4, it is characterised in that nanoparticle described in step (4) is the mixture of one or more in nano titanium oxide, nano-calcium carbonate, nano zine oxide, nano zircite, nano silicon；The particle diameter of described nanoparticle is 0.5～500nm；Preferably, the particle diameter of described nanoparticle is 2～200nm；Most preferably, the particle diameter of described nanoparticle is 10～80nm；Described nanoparticle consumption is 1～80wt% of the polyamide of described borosilicate cooperative flame retardant；Preferably, described nanoparticle consumption is 5～60wt% of the polyamide of described borosilicate cooperative flame retardant；Described antioxidant is Hinered phenols antioxidant N, N '-bis--(3-(3,5-di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine or sub-antioxidant three [2.4-di-tert-butyl-phenyl] phosphite ester；Described antioxidant consumption is 0.01～5wt% of the polyamide of described borosilicate cooperative flame retardant；Preferably, described antioxidant consumption is 0.05～2wt% of the polyamide of described borosilicate cooperative flame retardant.
10. preparation method according to claim 4, it is characterised in that extruder warm area totally 9 warm areas in extruder coextrusion process described in step (4), temperature range is 80 DEG C～180 DEG C, and mould is divided into 6 warm areas, and temperature range is 180～280 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610145549.9A CN105751644B (en) | 2016-03-15 | 2016-03-15 | A kind of polyamide five-layer co-squeezing composite membrane of borosilicate cooperative flame retardant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610145549.9A CN105751644B (en) | 2016-03-15 | 2016-03-15 | A kind of polyamide five-layer co-squeezing composite membrane of borosilicate cooperative flame retardant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105751644A true CN105751644A (en) | 2016-07-13 |
| CN105751644B CN105751644B (en) | 2017-10-31 |
Family
ID=56333146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610145549.9A Active CN105751644B (en) | 2016-03-15 | 2016-03-15 | A kind of polyamide five-layer co-squeezing composite membrane of borosilicate cooperative flame retardant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105751644B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107083063A (en) * | 2016-10-20 | 2017-08-22 | 深圳市新纶科技股份有限公司 | A kind of transparent flame-retardant organic silicon gel combination and preparation method thereof |
| CN110204732A (en) * | 2019-06-25 | 2019-09-06 | 荆州市江汉精细化工有限公司 | A kind of preparation method of boracic silane coupling agent copolymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070244231A1 (en) * | 2004-11-22 | 2007-10-18 | Borade Pravin K | Flame retardant poly(arylene ether)/polyamide compositions, methods, and articles |
| CN102604377A (en) * | 2012-02-17 | 2012-07-25 | 金发科技股份有限公司 | Polyamide composition with flame retardance and thermoplasticity |
| CN103057223A (en) * | 2012-12-28 | 2013-04-24 | 苏州度辰新材料有限公司 | Polyamide backplane for solar energy assembly |
| CN104527180A (en) * | 2015-01-08 | 2015-04-22 | 苏州鼎九新材料科技有限公司 | Polyamide five-layer co-extrusion composite film and preparation method thereof |
-
2016
- 2016-03-15 CN CN201610145549.9A patent/CN105751644B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070244231A1 (en) * | 2004-11-22 | 2007-10-18 | Borade Pravin K | Flame retardant poly(arylene ether)/polyamide compositions, methods, and articles |
| CN102604377A (en) * | 2012-02-17 | 2012-07-25 | 金发科技股份有限公司 | Polyamide composition with flame retardance and thermoplasticity |
| CN103057223A (en) * | 2012-12-28 | 2013-04-24 | 苏州度辰新材料有限公司 | Polyamide backplane for solar energy assembly |
| CN104527180A (en) * | 2015-01-08 | 2015-04-22 | 苏州鼎九新材料科技有限公司 | Polyamide five-layer co-extrusion composite film and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107083063A (en) * | 2016-10-20 | 2017-08-22 | 深圳市新纶科技股份有限公司 | A kind of transparent flame-retardant organic silicon gel combination and preparation method thereof |
| CN107083063B (en) * | 2016-10-20 | 2020-04-21 | 深圳市新纶科技股份有限公司 | Transparent flame-retardant organic silicon gel composition and preparation method thereof |
| CN110204732A (en) * | 2019-06-25 | 2019-09-06 | 荆州市江汉精细化工有限公司 | A kind of preparation method of boracic silane coupling agent copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105751644B (en) | 2017-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102163683B (en) | Optical semiconductor device | |
| CN102804367A (en) | Use of ionomeric silicone thermoplastic elastomers in electronic devices | |
| CN104788968B (en) | Organosilicon heat conductive isolation sheet and preparation method thereof | |
| CN103848990B (en) | High index of refraction Vinylphenyl silicon resin is used in a kind of LED encapsulation | |
| CN102181055B (en) | Preparation method of reactive MQ silicon resin | |
| CN104788969B (en) | Organosilicon heat conductive insulating composition and heat-conducting insulation material | |
| TW200726791A (en) | Method of producing high molecular weight organopolysiloxane, composition comprising the high molecular weight organopolysiloxane, and optical semiconductor device sealed with cured product thereof | |
| CN103489988A (en) | Encapsulating sheet, light emitting diode device, and producing method thereof | |
| CN104845049B (en) | Preparation method of phosphorus-containing flame-retardant organic-inorganic hybrid silsesquioxane/epoxy resin hybrid material | |
| CN103178195A (en) | Producing method of light emitting diode device | |
| CN101516970A (en) | Silicone resin composition and method for forming trench isolation | |
| CN105751644A (en) | Polyamide five-layer coextruded composite film with boron-silicon synergistic flame retardant effect and method for preparing same | |
| CN104497575A (en) | High-thermal-conductivity organosilicone mud and preparation method thereof | |
| TWI644981B (en) | Curable resin composition and cured product thereof, and semiconductor device using the same | |
| CN104527180B (en) | A kind of polyamide five-layer co-squeezing composite membrane and preparation method thereof | |
| CN105542476A (en) | Heat-conducting silicone rubber with high electric dielectric strength and preparation method of heat-conducting silicone rubber | |
| TW201420692A (en) | Paint, preparing method thereof, and film formed from the paint | |
| CN109134864B (en) | Trapezoidal polysilsesquioxane derivative and preparation method thereof | |
| CN101302343A (en) | Flame-retardant organosilicon powder encapsulating material for electronic component | |
| CN100492713C (en) | Organic electroluminescent device and method of manufacturing the same | |
| EP3714506A1 (en) | Device for cooling and/or heating a battery of an electric or hybrid motor vehicle | |
| KR20140103818A (en) | Polysiloxane composition and light emitting diode device including the same | |
| Wang et al. | Adjustable boron nitride segregated framework in epoxy resin for high performance thermal management and flame retardant applications | |
| CN103937445B (en) | Preparation method of transparent organic silica gel with high refractive index for high brightness and large power COB-LED encapsulation | |
| CN106751346A (en) | The synthetic method of fluorochemical monomer modified organosilicon encapsulating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240206 Address after: No. 1198, North District, Nige Industrial Park, Yong'an City, Sanming City, Fujian Province, 366000 Patentee after: Fujian Dingjiu Tiancheng Technology Co.,Ltd. Country or region after: China Address before: No. 22 Dongbang Road, Chengxiang Town, Taicang City, Suzhou City, Jiangsu Province, 215000 Patentee before: SUZHOU TOP GIANT NEW MATERIAL TECHNOLOGY Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |