CN111748203B - Caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and preparation method thereof - Google Patents
Caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and preparation method thereof Download PDFInfo
- Publication number
- CN111748203B CN111748203B CN202010630429.4A CN202010630429A CN111748203B CN 111748203 B CN111748203 B CN 111748203B CN 202010630429 A CN202010630429 A CN 202010630429A CN 111748203 B CN111748203 B CN 111748203B
- Authority
- CN
- China
- Prior art keywords
- caprolactam
- boehmite
- temperature nylon
- nylon material
- situ modified
- 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.)
- Active
Links
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims description 65
- 239000000463 material Substances 0.000 title claims description 64
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical class O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 title claims description 52
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 48
- 239000003063 flame retardant Substances 0.000 title claims description 48
- 239000004677 Nylon Substances 0.000 title claims description 44
- 229920001778 nylon Polymers 0.000 title claims description 44
- 230000002195 synergetic effect Effects 0.000 title claims description 24
- 238000011065 in-situ storage Methods 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title claims description 22
- 229910001593 boehmite Inorganic materials 0.000 claims description 29
- 239000003365 glass fiber Substances 0.000 claims description 14
- 239000012783 reinforcing fiber Substances 0.000 claims description 12
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 10
- XFDQYYUJIBWHQS-UHFFFAOYSA-N 3,10-dioxabicyclo[10.2.2]hexadeca-1(14),12,15-triene-2,11-dione Chemical compound O=C1OCCCCCCOC(=O)C2=CC=C1C=C2 XFDQYYUJIBWHQS-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 6
- 229910006636 γ-AlOOH Inorganic materials 0.000 claims description 6
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 claims description 4
- 229920002748 Basalt fiber Polymers 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 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 claims description 3
- 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 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 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 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 claims description 3
- 229920006117 poly(hexamethylene terephthalamide)-co- polycaprolactam Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000004033 plastic Substances 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DGZQEAKNZXNTNL-UHFFFAOYSA-N 1-bromo-4-butan-2-ylbenzene Chemical class CCC(C)C1=CC=C(Br)C=C1 DGZQEAKNZXNTNL-UHFFFAOYSA-N 0.000 description 1
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000011990 functional testing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009347 mechanical transmission Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K3/2279—Oxides; Hydroxides of metals of antimony
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and a preparation method thereof. The composition is prepared from the following components in parts by mass: 32.4-60.3 parts of high-temperature nylon, 10-50 parts of reinforcing fibers, 12-20 parts of brominated flame retardant, 3-6 parts of boehmite, 1-3 parts of caprolactam, 0.5-1 part of antioxidant and 0.2-0.6 part of lubricant. The prepared caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material has high strength (tensile strength, bending strength, impact strength and dielectric strength) and good flame-retardant effect, and reaches the V-0 level. The heat distortion temperature is higher relative to the tracking index. Meanwhile, the product particles have compact appearance, do not foam and have light yellow or yellow color. Meeting the market demand.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and a preparation method thereof.
Background
The semi-aromatic nylon has the characteristics of high mechanical strength, high temperature resistance, chemical resistance, good thermal stability, excellent electrical performance and the like, and is widely applied to the field of electronics and electricity. Due to the requirements of miniaturization and high performance of electronic, electrical and information related equipment, various electrical elements are smaller and smaller, and more rigorous requirements are provided for the electrical, flame retardant and insulating properties of plastic elements. At present, the most economical and convenient method is to add an additive with a flame-retardant function into a plastic matrix to enable the material to meet the requirement of difficult combustion, and the flame-retardant additive is divided into a halogen-containing halogen flame retardant and a halogen-free flame retardant containing flame-retardant elements such as phosphorus, nitrogen, sulfur, silicon and the like. The halogen flame retardant is commonly used for brominated flame retardants such as brominated polystyrene, brominated triazine and the like, the melting point of the halogen flame retardants is matched with that of a plastic substrate, the halogen flame retardants are co-melted with a plastic melt during processing, the material popularity is good, the mechanical property is not influenced, the main mechanism is gas-phase flame retardance, the bond of C-Br can be decomposed to produce HBr gas to block oxygen and capture free radicals, but the HBr has low density and can not completely block oxygen, and the combustion surface of the plastic substrate can not form a compact blocking layer, so the single use efficiency is low, and the halogen flame retardants need to be matched with metal oxides for use. The industrial use of the material is generally metal oxides such as antimony trioxide and zinc borate, the addition of the antimony trioxide can reduce the electric breakdown strength and the relative tracking index of the material, the material is easy to corrode a mold and is easy to discolor at high temperature, the zinc borate generally contains crystal water, the water loss temperature is about 300 ℃, the water loss temperature is lower than that of the high-temperature nylon processing, the material is easy to foam, and the anhydrous zinc borate is easy to absorb water and is not beneficial to storage; the halogen-free flame retardant has a high melting point which is generally far greater than that of the plastic matrix, exists in the form of solid small particles, and has poor compatibility with the plastic matrix. The flame retardant is required to be added in a large amount to meet the flame retardant requirement, so that the physical properties of the material are deteriorated, the material is easy to separate out, and the material is not resistant to boiling and is not suitable for being applied to plastic shells and transmission parts with mechanical strength requirements and in severe working environments; when boehmite is used as a synergistic flame retardant, the boehmite surface has a large amount of hydroxyl groups, the surface polarity is large, the compatibility with a plastic matrix is poor, and the boehmite powder is easily dispersed unevenly, so that the flame retardant effect and the impact strength of the material are reduced.
Disclosure of Invention
The invention aims to provideThe caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material has good flame-retardant effect, high strength and high relative tracking index. The impact strength of the material added with caprolactam is from 10kj/m2Increased to 12kj/m2The flame retardant grade is improved from the original V-1 to V-0, and the bonding strength of the interface of the two can be improved and the dispersion of boehmite can be promoted by adding caprolactam for compatibilization.
In order to achieve the purpose, the invention provides a caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material which is characterized by being prepared from the following components in parts by mass:
further, the high-temperature nylon is one or more than one of copolymer of poly (hexamethylene terephthalate) and m-hexamethylene diamine, namely PA6T/6I, copolymer of poly (hexamethylene terephthalate) and caprolactam, namely PA6T/6, copolymer of poly (hexamethylene terephthalate) and hexamethylene diamine adipate, namely PA 6T/66; preferably, the high-temperature nylon has a nylon concentration of 0.05g/ml, a m-toluene solvent and an intrinsic viscosity of 0.6-1.0 at 25 ℃.
Further, the reinforcing fiber is at least one of glass fiber, carbon fiber, boron fiber and basalt fiber; preferably, the reinforcing fiber is glass fiber with the chopped length of 3-5mm and the diameter of 7-11 mu M.
Further, the brominated flame retardant is brominated polystyrene, the bromine content of which is 68.5 percent, and the molecular weight of which is 67000-15000.
Further, the boehmite is gamma-AlOOH white powder; preferably, the whiteness is more than 95%, and the particle size D50 is 0.8-8 μm of gamma-AlOOH white powder.
Further, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 9228 and antioxidant 168.
Further, the lubricant is one or two of modified high molecular weight silicone lubricant E525 and ethylene acrylic acid copolymer AC 540A.
Further, the preparation method comprises the following steps of,
preparing a premix: weighing high-temperature nylon, a brominated flame retardant, boehmite, an antioxidant and a lubricant according to a proportioning table, and uniformly mixing in a low-speed mixer to obtain a premix;
extruding: adding the premix into a double-screw extruder, adding the reinforcing fiber from a side feed according to the mass ratio, wherein the extrusion temperature is 280-320 ℃, and the rotating speed is 350-500 r/min; preferably, the twin-screw extruder has a major axis of 36 to 44 and a medium-strength screw is used.
The reinforcing fiber is added from the side feed, so that the glass fiber is prevented from being too short, and the flame retardant property is prevented from being influenced. Because the single glass fiber is very fragile, strong shearing force can be formed between the screw rods and the cylinder of the plastic particles which are not melted, the glass fiber is broken, and the length of the fiber needs to be larger than the critical length required by the material to have the reinforcing effect.
The proportion of caprolactam used as a compatilizer is increased along with the increase of the boehmite content, the content of the flame retardant and the content of the reinforcing fiber are matched with each other, so that the material can reach UL-94V-0 grade, and the content of the glass fiber is changed along with the difference of end application of the material.
According to the invention, caprolactam in-situ modified boehmite is used, and caprolactam is utilized to open rings at high temperature to react with hydroxyl on the surface of boehmite and amino and carboxyl at the end of high-temperature nylon, so that the reaction compatibilization effect is achieved. The boehmite prepared by the hydrothermal method is in a fiber shape or a strip shape, has a certain reinforcing effect, has the Mohs hardness of 3.5 which is far lower than the hardness of the glass fiber, is not easy to break the glass fiber in the processing process, and can improve or maintain the mechanical property of the material; the aspect of synergistic flame retardance: compared with zinc borate (dehydration at 300 ℃), boehmite has the decomposition temperature of more than 400 ℃, has the characteristic of difficult dehydration at the processing temperature of high-temperature nylon of about 300 ℃, can improve the condition that zinc borate is added when high electrical performance is required, and anhydrous zinc borate has high cost and is difficult to store; the hydrous zinc borate is easy to lose water at the processing temperature, so that the material is foamed and the processing is poor. On the other hand, compared with antimony trioxide, boehmite has the advantages that the electrical performance of the material is not easily reduced, and the defect that the antimony trioxide is easily reduced into an antimony simple substance at high temperature to blacken the material can be avoided.
The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material prepared in the embodiment has high strength (tensile strength, bending strength, impact strength and dielectric strength) and good flame-retardant effect, and all the flame-retardant effects reach V-0 level. The heat distortion temperature is higher relative to the tracking index. Meanwhile, the product particles have compact appearance, do not foam and have light yellow or yellow color. The requirements of electronic and electric products, such as automobile electronics, personal consumer terminals and the like in the field sensitive to the weight of the product are met.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material is characterized by being prepared from the following components in parts by mass:
further, the high-temperature nylon is one or more than one of copolymer of poly (hexamethylene terephthalate) and m-hexamethylene diamine, namely PA6T/6I, copolymer of poly (hexamethylene terephthalate) and caprolactam, namely PA6T/6, copolymer of poly (hexamethylene terephthalate) and hexamethylene diamine adipate, namely PA 6T/66; preferably, the high-temperature nylon has a nylon concentration of 0.05g/ml, a m-toluene solvent and an intrinsic viscosity of 0.6-1.0 at 25 ℃.
Further, the reinforcing fiber is at least one of glass fiber, carbon fiber, boron fiber and basalt fiber; preferably, the reinforcing fiber is glass fiber with the chopped length of 3-5mm and the diameter of 7-11 mu M.
Further, the brominated flame retardant is brominated polystyrene, the bromine content of which is 68.5 percent, and the molecular weight of which is 67000-15000.
Further, the boehmite is gamma-AlOOH white powder; preferably, the whiteness is more than 95%, and the particle size D50 is 0.8-8 μm of gamma-AlOOH white powder.
Further, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 9228 and antioxidant 168.
Further, the lubricant is one or two of modified high molecular weight silicone lubricant E525 and ethylene acrylic acid copolymer AC 540A.
Further, the preparation method comprises the following steps of,
preparing a premix: weighing high-temperature nylon, a brominated flame retardant, boehmite, an antioxidant and a lubricant according to a proportioning table, and uniformly mixing in a low-speed mixer to obtain a premix;
extruding: adding the premix into a double-screw extruder, adding the reinforcing fiber from a side feed according to the mass ratio, wherein the extrusion temperature is 280-320 ℃, and the rotating speed is 350-500 r/min; preferably, the twin-screw extruder has a major axis of 36 to 44 and a medium-strength screw is used.
Example 1: preparation of caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Example 2: preparation of caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Example 3: preparation of caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Comparative example 1: preparation of nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Comparative example 2: preparation of nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Comparative example 3: preparation of nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Comparative example 4: preparation of nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
Comparative example 5: preparation of nylon material
Materials: see table 1.
The preparation method comprises the following steps:
and (3) performance testing: see table 2.
TABLE 1 tables for the amounts of the examples and comparative examples in the data sheet (parts by weight)
Note: PA6T/66 terephthalic acid: adipic acid: the molar ratio of the hexamethylene diamine is 1:1: 2.
TABLE 2 table of functional test results of examples and comparative examples
When the boehmite loses water at 400 ℃, a large amount of heat can be absorbed, the sheet structure of the boehmite forms a labyrinth effect, combustible substances can be prevented from migrating to the combustion surface, a fuel channel is cut off, and therefore a compact alumina layer is formed through dehydration at high temperature. Reduce smoke while isolating oxygen, and part of aluminum can react with HBr to produce AlBr3The boehmite prepared by the hydrothermal method is in a fiber shape or a strip shape and has a certain reinforcing effect, the Mohs hardness is 3.5 and is far lower than the hardness of the glass fiber, the glass fiber is not easy to break in the processing process, and the mechanical property of the material can be improved or maintained. Compared with the comparative example 1, the flame retardant property of the material is improved from V-2 to V-0 by adding the boehmite in the example 2, which shows that the boehmite has a synergistic flame retardant effect and a certain strength enhancing effect. The decomposition temperature of boehmite is more than 400 ℃, the boehmite has the characteristic of being difficult to dehydrate at the processing temperature of about 300 ℃ of high-temperature nylon, and compared with the comparative example 2, the appearance of the particles added with boehmite is dense, and the foaming phenomenon cannot occur; the metal oxides such as antimony trioxide can be catalyzed and promoted to form carbon, so that the dielectric strength of the material is reduced, and compared with the comparative example 3, by adding the antimony trioxide in the example 2, the boehmite can maintain the dielectric strength and the relative tracking index of the material and can not cause blackening of the material due to discoloration; the melting point of the halogen-free flame retardant is far higher than the processing temperature of the material, the halogen-free flame retardant is distributed in a plastic matrix in the form of filler in the processing process, and the addition is large, so that the physical properties of the material are easily deteriorated, and the embodiment 2 and the comparative example 4 show that compared with the halogen-free flame retardant material, the material compounded by adding the brominated flame retardant and the boehmite has more mechanical strength and can be used for a shell and a mechanical transmission part with mechanical strength requirements; the compatibility of boehmite and matrix resin is low in interfacial bonding strength when compatibilized without addition of caprolactam, and the boehmite and the matrix resin are easily debonded under the action of external force to form pores, which causes stress concentration and deteriorates the mechanical strength and impact strength of the material, which can be obtained by comparing example 2 with comparative example 5, wherein impact strength of the material added with caprolactam is lower than that of the material added with caprolactamIntensity from 10kj/m2Increased to 12kj/m2The flame retardant grade is improved from the original V-1 to V-0, and the bonding strength of the interface of the two can be improved and the dispersion of boehmite can be promoted by adding caprolactam for compatibilization.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (11)
1. The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material is characterized by being prepared from the following components in parts by mass:
32.4-60.3 parts of high-temperature nylon;
10-50 parts of reinforcing fiber;
12-20 parts of a brominated flame retardant;
3-6 parts of boehmite prepared by a hydrothermal method;
1-3 parts of caprolactam;
0.5-1 part of antioxidant;
0.2-0.6 part of lubricant;
the preparation method comprises the following steps of,
preparing a premix: weighing high-temperature nylon, a brominated flame retardant, boehmite, an antioxidant and a lubricant according to a proportioning table, and uniformly mixing in a low-speed mixer to obtain a premix;
extruding: adding the premix into a double-screw extruder, adding the reinforcing fiber from a side feed according to the mass ratio, wherein the extrusion temperature is 280-320 ℃, and the rotating speed is 350-500 r/min.
2. The caprolactam in-situ modified boehmite synergistic flame retardant reinforced high temperature nylon material as claimed in claim 1, wherein the high temperature nylon is one or more of poly (hexamethylene terephthalate) and m-hexamethylene diamine terephthalate copolymer (PA 6T/6I), poly (hexamethylene terephthalate) and caprolactam copolymer (PA 6T/6), poly (hexamethylene terephthalate) and hexamethylene diamine adipate copolymer (PA 6T/66).
3. The caprolactam in-situ modified boehmite synergistic flame retardant reinforced high temperature nylon material as claimed in claim 1, wherein the high temperature nylon is high temperature nylon with nylon concentration of 0.05g/ml, m-toluene solvent, and intrinsic viscosity of 0.6-1.0 at 25 ℃.
4. The caprolactam in-situ modified boehmite synergistic flame retardant reinforced high temperature nylon material as claimed in claim 1, wherein the reinforcing fiber is at least one of glass fiber, carbon fiber, boron fiber and basalt fiber.
5. The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material as claimed in claim 1, wherein the reinforcing fiber is glass fiber with chopped length of 3-5mm and diameter of 7-11 μm.
6. The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material as set forth in claim 1, wherein the brominated flame retardant is brominated polystyrene, the bromine content of which is 68.5%, and the molecular weight of which is 67000-15000.
7. The caprolactam in-situ modified boehmite synergistic flame retardant reinforced high temperature nylon material as claimed in claim 1, wherein the boehmite is gamma-AlOOH white powder.
8. The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material as claimed in claim 1, wherein the boehmite is gamma-AlOOH white powder with whiteness of >95% and particle size D50 of 0.8-8 μm.
9. The caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material as claimed in claim 1, wherein the antioxidant is one or a mixture of more than one of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 9228 and antioxidant 168.
10. The caprolactam in-situ modified boehmite synergistic flame retardant reinforced high temperature nylon material as claimed in claim 1, wherein the lubricant is one or two of modified high molecular weight silicone lubricant E525, ethylene acrylic acid copolymer AC 540A.
11. The caprolactam in-situ modified boehmite synergistic flame retardant reinforced high temperature nylon material as claimed in claim 1, wherein the long diameter of the twin-screw extruder is 36-44, and a medium strength screw is adopted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010630429.4A CN111748203B (en) | 2020-07-03 | 2020-07-03 | Caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010630429.4A CN111748203B (en) | 2020-07-03 | 2020-07-03 | Caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111748203A CN111748203A (en) | 2020-10-09 |
| CN111748203B true CN111748203B (en) | 2021-11-19 |
Family
ID=72678833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010630429.4A Active CN111748203B (en) | 2020-07-03 | 2020-07-03 | Caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111748203B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116315437A (en) * | 2021-12-21 | 2023-06-23 | 北京宇程科技有限公司 | A modified composite diaphragm and its preparation method |
| CN114672160B (en) * | 2022-03-17 | 2023-11-21 | 金发科技股份有限公司 | Red phosphorus flame-retardant polyamide composition with high tracking resistance, and preparation method and application thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010018684A1 (en) * | 2010-04-29 | 2011-11-03 | Clariant International Ltd. | Process for the preparation of mixtures of alkylphosphonous salts and dialkylphosphinic acid salts |
| DE102011120200A1 (en) * | 2011-12-05 | 2013-06-06 | Clariant International Ltd. | Flame retardant mixtures containing flame retardants and aluminum phosphites, process for their preparation and their use |
| CN105504799B (en) * | 2016-01-20 | 2017-12-29 | 惠州市华聚塑化科技有限公司 | Nylon composite materials |
| CN106543709A (en) * | 2016-11-25 | 2017-03-29 | 西华大学 | A kind of antibacterial fire-retardant nylon composite and preparation method thereof |
| CN108250741A (en) * | 2016-12-29 | 2018-07-06 | 上海杰事杰新材料(集团)股份有限公司 | A kind of corrosion-resistant and high-temperature resistant fire-retardant nylon composite material and preparation method thereof |
| CN108559076A (en) * | 2018-04-08 | 2018-09-21 | 金发科技股份有限公司 | A kind of Semi-aromatic polyamide resin and preparation method thereof and the polyamide moulding composition being made from it |
| CN109320775A (en) * | 2018-09-20 | 2019-02-12 | 安徽江淮汽车集团股份有限公司 | A kind of preparation method of the fire-retardant compounded mix of low VOC |
-
2020
- 2020-07-03 CN CN202010630429.4A patent/CN111748203B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111748203A (en) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1997698B (en) | Polyester compositions flame-retarded with halogen-free additives | |
| CN101573411B (en) | Flame retardant thermoplastic polyester resin composition | |
| CN112592566B (en) | Low-smoke-density halogen-containing flame-retardant reinforced PBT/PET compound and preparation method and application thereof | |
| CN111748203B (en) | Caprolactam in-situ modified boehmite synergistic flame-retardant reinforced high-temperature nylon material and preparation method thereof | |
| CN106009585A (en) | Halogen-free flame retardation polycarbonate material and preparation method thereof | |
| CN111748179A (en) | Low-smoke-density high-performance halogen-containing flame-retardant reinforced PBT (polybutylene terephthalate) compound and preparation method thereof | |
| CN103013081B (en) | High temperature resistant scratch resistant halogen-free flame retardant polycarbonate film | |
| CN114213829A (en) | Flame-retardant light-blocking high-reflectivity PC material and preparation method thereof | |
| CN110483941B (en) | Low-smoke environment-friendly 5 VA-grade flame-retardant ABS material and preparation method thereof | |
| CN114015164A (en) | Flame-retardant polypropylene material and preparation method thereof | |
| JPH11349809A (en) | Flame-retarded polyamide resin composition | |
| CN113956588A (en) | Anti-aging flame-retardant PVC material, preparation method and application thereof in wires or cables | |
| CN112480675A (en) | Cooling liquid resistant PPS composite material and preparation method and application thereof | |
| CN110591267B (en) | Low-smoke environment-friendly 5 VA-grade flame-retardant ASA material with excellent weather resistance and preparation method thereof | |
| CN115353744B (en) | Halogen-free low-smoke flame-retardant polyolefin insulating material for nuclear-grade cable | |
| CN113683878B (en) | Spiral substituted polyolefin and preparation method thereof, and polycarbonate composition and preparation method thereof | |
| EP0889094B1 (en) | Flame-retardant resin composition | |
| JP3404154B2 (en) | Flame retardant polyester resin composition | |
| TW552291B (en) | Fire-retardant resin compositions | |
| CN116178939A (en) | Halogen-free flame-retardant high GWIT high-heat-conductivity polyamide 6 material and preparation method thereof | |
| CN114395249A (en) | High-oxygen-index polyamide composition and preparation method and application thereof | |
| CN113402828A (en) | High-flame-retardant class-A low-smoke low-halogen PVC (polyvinyl chloride) sheath material for rail transit and preparation method thereof | |
| CN112778710A (en) | high-PTI (polybutylene terephthalate) and high-toughness PBT (polybutylene terephthalate) composition as well as preparation method and application thereof | |
| JP3270144B2 (en) | Phenolic resin molding material | |
| CN115260639B (en) | A kind of high flame-retardant insulating material for electric cable and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |