CN114621586A - Flame-retardant bio-based polyamide material and preparation method thereof - Google Patents
Flame-retardant bio-based polyamide material and preparation method thereof Download PDFInfo
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- CN114621586A CN114621586A CN202111030414.5A CN202111030414A CN114621586A CN 114621586 A CN114621586 A CN 114621586A CN 202111030414 A CN202111030414 A CN 202111030414A CN 114621586 A CN114621586 A CN 114621586A
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- Prior art keywords
- bio
- based polyamide
- flame retardant
- hypophosphite
- acid
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- 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 82
- 229920006021 bio-based polyamide Polymers 0.000 title claims abstract description 82
- 239000003063 flame retardant Substances 0.000 title claims abstract description 82
- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 34
- 239000000945 filler Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 28
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 27
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 27
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 25
- -1 dimethyl hypophosphite Chemical compound 0.000 claims description 24
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical group [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 18
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 17
- 235000013539 calcium stearate Nutrition 0.000 claims description 17
- 239000008116 calcium stearate Substances 0.000 claims description 17
- 239000000314 lubricant Substances 0.000 claims description 15
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052621 halloysite Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002071 nanotube Substances 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- 229920001971 elastomer Polymers 0.000 claims description 12
- 239000000806 elastomer Substances 0.000 claims description 12
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 claims description 2
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 2
- XPNLOZNCOBKRNJ-UHFFFAOYSA-N ethyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C=C.COC(=O)C(C)=C XPNLOZNCOBKRNJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-M octacosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O UTOPWMOLSKOLTQ-UHFFFAOYSA-M 0.000 claims description 2
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 2
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- XKCQASMZNPBLKI-UHFFFAOYSA-N phosphorosooxymethane Chemical class COP=O XKCQASMZNPBLKI-UHFFFAOYSA-N 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 238000005728 strengthening Methods 0.000 abstract description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 14
- 230000000379 polymerizing effect Effects 0.000 description 12
- 239000004952 Polyamide Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 7
- 238000010170 biological method Methods 0.000 description 7
- 229920002647 polyamide Polymers 0.000 description 7
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 6
- 239000004472 Lysine Substances 0.000 description 6
- 108010048581 Lysine decarboxylase Proteins 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- KTLIMPGQZDZPSB-UHFFFAOYSA-M diethylphosphinate Chemical compound CCP([O-])(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-M 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000004962 Polyamide-imide Substances 0.000 description 3
- 229920002312 polyamide-imide Polymers 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical class CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention relates to C08L, in particular to a flame-retardant bio-based polyamide material and a preparation method thereof. The flame-retardant bio-based polyamide material comprises the following raw materials in parts by weight: 60-80 parts of bio-based polyamide, 10-20 parts of flame retardant, 1-20 parts of filler, 2-8 parts of compatibilizer and 1-10 parts of auxiliary agent. By utilizing the bio-based polyamide, the composite flame retardant and the auxiliary agent, the flame retardant material with good compatibility and high mechanical strength is realized, the synergistic flame retardant effect of the flame retardant, the matrix and the auxiliary agent is realized through interaction, and the bio-based polyamide material can realize toughening, strengthening and super toughening at normal and low temperature; the flame-retardant bio-based polyamide material provided by the invention has high flame-retardant performance and also has good toughness and mechanical strength.
Description
Technical Field
The invention relates to C08L, in particular to a flame-retardant bio-based polyamide material and a preparation method thereof.
Background
Polyamide, which is a thermoplastic resin, is widely used in the fields of textiles, engineering, and electronic devices because of its excellent abrasion resistance and heat resistance. In order to respond to the development of the new environment protection situation, the preparation of polyamide by a biological method is receiving more and more attention, can replace petroleum-based like products, and has the advantages of low carbon and environmental protection.
CN102732033B discloses a flame-retardant heat-conducting insulating polyamide imide composition for an LED light source, wherein the polyamide imide used in the invention is soluble bio-based long-carbon-chain semi-alicyclic polyamide imide, is a renewable green biomaterial, and has excellent heat conductivity, flame retardance and insulating property; CN109181297A discloses a high-fluidity bio-based polyamide 56 resin composition, which adopts renewable biomass as a raw material, is green and environment-friendly, and improves the fluidity and crystallization performance of the material while ensuring good wear resistance.
The biomass in the bio-based polyamide is mainly from grease and polysaccharide, and the bio-based polyamide shows excellent moisture absorption and wear resistance, but the self flame retardance of the bio-based polyamide does not meet the flame retardance requirement in the fields of automobiles, chemical engineering and electronics.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a flame retardant bio-based polyamide material, which is prepared from the following raw materials in parts by weight: 60-80 parts of bio-based polyamide, 10-20 parts of flame retardant, 1-20 parts of filler, 2-8 parts of compatibilizer and 1-10 parts of auxiliary agent.
Bio-based polyamides
The bio-based polyamide is formed by polymerizing pentanediamine and dibasic acid.
The pentanediamine is prepared from bio-based raw materials by a biological method; the dibasic acid is at least one of oxalic acid, terephthalic acid, isophthalic acid, dodecanoic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, undecanedioic acid, octadecanedioic acid and maleic acid.
The bio-based pentanediamine is obtained by removing carboxyl groups at two ends of lysine or lysine salt under the action of lysine decarboxylase.
The dibasic acid is oxalic acid and terephthalic acid; the weight ratio of the oxalic acid to the terephthalic acid is 1: (1-1.2).
The weight ratio of the bio-based pentanediamine to the dibasic acid is 1: 1.
the bio-based polyamide is prepared by polymerizing bio-based pentamethylene diamine and dibasic acid in a one-step high-pressure kettle.
The applicant finds that the matrix material adopted by the invention is bio-based polyamide, has biodegradability, can effectively reduce consumption of petrochemical resources and pollution to the environment compared with the traditional polyamide raw material, and has excellent wear resistance and moisture absorption performance.
Flame retardant
The flame retardant is hypophosphite or melamine cyanurate.
The hypophosphite is at least one of dimethyl hypophosphite, ethyl methyl hypophosphite, diethyl hypophosphite, methyl n-propyl hypophosphite, methane di (methyl hypophosphite) salt, benzene-1, 4- (dimethyl hypophosphite) salt, methyl phenyl hypophosphite and diphenyl hypophosphite.
The hypophosphite salt is diethyl hypophosphite; the diethylphosphinate was OP1230, available from rayne, switzerland.
The applicant unexpectedly finds that when diethyl hypophosphite is added as a flame retardant, strong flame retardant effect can be achieved by dispersing and reinforcing in the bio-based polyamide material, but the diethyl hypophosphite can simultaneously obstruct the movement of the molecular chain of the bio-based polyamide, so that the toughness of the whole material is poor, in addition, due to the addition of the diethyl hypophosphite, an acidic environment can be generated, the bio-based polyamide material can generate a self-decomposition effect under the acidic environment, so that the stability of the bio-based polyamide material can be influenced, and a component with a flame retardant function and capable of improving the toughness needs to be added to enhance the use effect.
The flame retardant also includes melamine cyanurate.
The melamine cyanurate is purchased from Guanao biotechnology limited company in Hubei, and has the product number of GA 564165-9.
The weight ratio of the hypophosphite to the melamine cyanurate is 1: (0.4-0.6).
The melamine cyanurate has enough hardness and strength, and the melamine cyanurate and the hypophosphite have the effect of synergistically improving the flame retardant property and the mechanical property, and can be combined with other fillers to improve the overall stability of the bio-based polyamide material; the melamine cyanurate has good corrosion resistance, can coexist with hypophosphite for a long time in an acidic environment, improves the stability through the action with the hypophosphite, and promotes the improvement of the flame retardant property.
Filler
The filler is at least one of kaolin, diatomite, glass fiber, halloysite nanotubes, fumed silica, calcium carbonate, nano alumina and titanium dioxide.
The filler is halloysite nanotubes.
The halloysite nanotubes were purchased from Longchuan Material works, Lingshui county, under a goods number of 1026.
The halloysite nanotube is interacted with melamine cyanurate through hydrogen bonds, a filler network is constructed in a polymer through a self-assembly behavior, and meanwhile, a barrier is formed on a volatile product by a hollow tubular structure of the halloysite nanotube, so that the thermal stability of the polymer is improved; the introduction of the halloysite nanotube can reduce the load of melamine cyanurate, so that the flame retardant effect and the mechanical property are not influenced, and the halloysite nanotube and the melamine cyanurate are synergistic in flame retardant.
Compatibilizer
The compatibilizer is at least one of maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted polyethylene, maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted ethylene propylene diene monomer, maleic anhydride grafted ethylene-vinyl acetate, maleic anhydride grafted ethylene-butadiene-styrene copolymer, methyl methacrylate-ethyl acrylate and methyl methacrylate-butadiene-styrene terpolymer.
The compatibilizer is maleic anhydride grafted polyolefin elastomer (POE-g-GMA) which is purchased from DuPont China group Co., Ltd.
The applicant finds that the maleic anhydride grafted polyolefin elastomer is particularly suitable for improving the compatibility of a bio-based polyamide material, and has obvious effects on improving the impact toughness and the elongation of the polymer; the maleic anhydride grafted polyolefin elastomer is prepared by taking polyolefin as a matrix, grafting a high-reactivity maleic anhydride monomer, and orderly embedding a spatial structure of the maleic anhydride grafted polyolefin elastomer and a reticular structure formed by halloysite nanotubes in a polymer to form a three-dimensional ordered spatial structure, so that the toughening, the reinforcement and the super toughening of the bio-based polyamide material at normal and low temperatures are realized while the high mechanical property is realized.
Auxiliary agent
The auxiliary agent is a silane coupling agent and a lubricating agent.
The lubricant is at least one of N, N' -ethylene bis stearamide, oxidized polyethylene wax, polyethylene-vinyl acetate wax, pentaerythritol stearate, montanate, oleamide, erucamide, calcium stearate, sodium stearate, barium stearate and calcium stearate.
The lubricant is calcium stearate which is purchased from Shanghai sparkling chemical auxiliary agent company Limited.
The silane coupling agent is a silane coupling agent KH-570 which is purchased from Anhui silicon treasure.
The weight ratio of the silane coupling agent KH-570 to the calcium stearate is 1: (0.5 to 1).
The silane coupling agent KH-570 has good compatibility with the bio-based polyamide, the binding force of the filler and the polyamide matrix is better improved, and the flow property of the melt can be effectively improved; the grafting modification effect of the silane coupling agent KH-560 realizes the grafting of hydroxyl on the surface of calcium stearate and the base material of the bio-based polyamide resin, endows the polyamide material with excellent corrosion resistance, and can effectively weaken the acidic corrosion effect brought by hypophosphite in the flame retardant.
The second aspect of the invention provides a preparation method of the flame-retardant bio-based polyamide material, which comprises the following steps: (1) mixing the bio-based polyamide and the compatibilizer in a high-speed mixer at the rotating speed of 400-500r/min for 4-6min to obtain a mixed material A; mixing the flame retardant, the filler and the auxiliary agent in a high-speed mixer at the rotating speed of 400-500r/min for 4-6min to obtain a mixed material B; (2) adding the mixed materials A and B into a screw extruder, wherein the temperature of the screw extruder is as follows from a main feeding section to a die head: 150-170 ℃, 200-220 ℃, 220-240 ℃, 240-260 ℃, 250-270 ℃ and 260-280 ℃, and the double-screw rotating speed is 100-300rpm, and the extrusion is carried out.
Compared with the prior art, the invention has the following beneficial effects:
(1) by utilizing the bio-based polyamide, a certain flame retardant effect is achieved on the main material, and the flame retardant and the auxiliary agent are compounded, so that the flame retardant material with good compatibility and high mechanical strength is realized;
(2) the synergistic flame-retardant effect of the flame retardant, the matrix and the auxiliary agent is realized through the interaction of the flame retardant and the bio-based polyamide matrix;
(3) the compatibilizer has good compatibility with the bio-based polyamide, improves the mechanical property and realizes toughening, strengthening and super toughening of the bio-based polyamide material at normal and low temperature;
(4) the auxiliary agent better improves the binding force between the filler and the polyamide matrix and endows the polyamide material with excellent corrosion resistance;
(5) the invention adopts the bio-based polyamide, the hypophosphite and the halogen-free flame retardant, has no pollution, low carbon and environmental protection, and the flame retardance meets the flame retardance requirement in the fields of automobiles, chemical engineering and electronics.
Detailed Description
Examples
Example 1
The embodiment provides a flame-retardant bio-based polyamide material, which is prepared from the following raw materials in parts by weight: 60 parts of bio-based polyamide, 10 parts of flame retardant, 5 parts of filler, 4 parts of compatibilizer and 2 parts of auxiliary agent.
The bio-based polyamide is formed by polymerizing pentanediamine and dibasic acid.
The pentanediamine is prepared from bio-based raw materials through a biological method.
The bio-based pentanediamine is obtained by removing carboxyl groups at two ends of lysine or lysine salt under the action of lysine decarboxylase.
The dibasic acid is oxalic acid and terephthalic acid; the weight ratio of the oxalic acid to the terephthalic acid is 1: 1.
the weight ratio of the bio-based pentanediamine to the dibasic acid is 1: 1.
the bio-based polyamide is prepared by polymerizing bio-based pentamethylene diamine and dibasic acid in a one-step high-pressure kettle.
The flame retardant is hypophosphite or melamine cyanurate.
The hypophosphite salt is diethyl hypophosphite; the diethylphosphinate was OP1230, available from rayne, switzerland.
The flame retardant also includes melamine cyanurate.
The melamine cyanurate is purchased from Guanao Biotech Co., Ltd, Hubei, under the trade name GA 564165-9.
The weight ratio of the hypophosphite to the melamine cyanurate is 1: 0.4.
the filler is halloysite nanotubes, purchased from Longchuan materials works in Ling shou county, with a commodity number of 1026.
The solubilizer is maleic anhydride grafted polyolefin elastomer (POE-g-GMA) which is purchased from DuPont China group Co.
The auxiliary agent is a silane coupling agent and a lubricating agent.
The lubricant is calcium stearate which is purchased from Shanghai sparkling chemical auxiliary agent company Limited.
The silane coupling agent is a silane coupling agent KH-570 which is purchased from Silibao Anhui.
The weight ratio of the silane coupling agent KH-570 to the calcium stearate is 1: 0.5.
the second aspect of the invention provides a preparation method of the flame-retardant bio-based polyamide material, which comprises the following steps: (1) mixing the bio-based polyamide and the compatibilizer in a high-speed mixer at the rotating speed of 400r/min for 4min to obtain a mixed material A; mixing the flame retardant, the filler and the auxiliary agent in a high-speed mixer at the rotating speed of 400r/min for 4min to obtain a mixed material B; (2) adding the mixed materials A and B into a screw extruder, wherein the temperature of the screw extruder is as follows from a main feeding section to a die head: extruding at 150 deg.C, 200 deg.C, 220 deg.C, 240 deg.C, 250 deg.C, 255 deg.C and 260 deg.C, and rotating speed of twin screw at 100 rpm.
Example 2
The embodiment provides a flame-retardant bio-based polyamide material, which is prepared from the following raw materials in parts by weight: 70 parts of bio-based polyamide, 15 parts of flame retardant, 10 parts of filler, 6 parts of compatibilizer and 5 parts of auxiliary agent.
The bio-based polyamide is formed by polymerizing pentanediamine and dibasic acid.
The pentanediamine is prepared from bio-based raw materials through a biological method.
The bio-based pentanediamine is obtained by removing carboxyl groups at two ends of lysine or lysine salt under the action of lysine decarboxylase.
The dibasic acid is oxalic acid and terephthalic acid; the weight ratio of the oxalic acid to the terephthalic acid is 1: 1.1.
the weight ratio of the bio-based pentanediamine to the dibasic acid is 1: 1.
the bio-based polyamide is prepared by polymerizing bio-based pentamethylene diamine and dibasic acid in a one-step high-pressure kettle.
The flame retardant is hypophosphite or melamine cyanurate.
The hypophosphite salt is diethyl hypophosphite; the diethylphosphinate salt was OP1230, available from rayne, switzerland.
The flame retardant also includes melamine cyanurate.
The melamine cyanurate is purchased from Guanao biotechnology limited company in Hubei, and has the product number of GA 564165-9.
The weight ratio of the hypophosphite to the melamine cyanurate is 1: 0.5.
the filler is halloysite nanotubes purchased from Longchuan Material works, Lingshu county, under a goods number of 1026.
The solubilizer is maleic anhydride grafted polyolefin elastomer (POE-g-GMA) which is purchased from DuPont China group Co.
The auxiliary agent is a silane coupling agent and a lubricating agent.
The lubricant is calcium stearate which is purchased from Shanghai sparkling chemical auxiliary agent company Limited.
The silane coupling agent is a silane coupling agent KH-570 which is purchased from Anhui silicon treasure.
The weight ratio of the silane coupling agent KH-570 to the calcium stearate is 1: 0.8.
the second aspect of the invention provides a preparation method of the flame-retardant bio-based polyamide material, which comprises the following steps: (1) mixing the bio-based polyamide and the compatibilizer in a high-speed mixer at the rotating speed of 450r/min for 5min to obtain a mixed material A; mixing the flame retardant, the filler and the auxiliary agent in a high-speed mixer at the rotating speed of 450r/min for 5min to obtain a mixed material B; (2) adding the mixed materials A and B into a screw extruder, wherein the temperature of the screw extruder is as follows from a main feeding section to a die head: extruding at 160 deg.C, 210 deg.C, 230 deg.C, 250 deg.C, 260 deg.C, 265 deg.C and 270 deg.C, and with a twin-screw rotation speed of 200 rpm.
Example 3
The embodiment provides a flame-retardant bio-based polyamide material, which is prepared from the following raw materials in parts by weight: 80 parts of bio-based polyamide, 20 parts of flame retardant, 15 parts of filler, 8 parts of compatibilizer and 8 parts of auxiliary agent.
The bio-based polyamide is formed by polymerizing pentanediamine and dibasic acid.
The pentanediamine is prepared from bio-based raw materials through a biological method.
The bio-based pentanediamine is obtained by removing carboxyl groups at two ends of lysine or lysine salt under the action of lysine decarboxylase.
The dibasic acid is oxalic acid and terephthalic acid; the weight ratio of the oxalic acid to the terephthalic acid is 1: 1.2.
the weight ratio of the bio-based pentanediamine to the dibasic acid is 1: 1.
the bio-based polyamide is prepared by polymerizing bio-based pentamethylene diamine and dibasic acid in a one-step high-pressure kettle.
The flame retardant is hypophosphite or melamine cyanurate.
The hypophosphite salt is diethyl hypophosphite salt; the diethylphosphinate was OP1230, available from rayne, switzerland.
The flame retardant also includes melamine cyanurate.
The melamine cyanurate is purchased from Guanao Biotech Co., Ltd, Hubei, under the trade name GA 564165-9.
The weight ratio of the hypophosphite to the melamine cyanurate is 1: 0.6.
the filler is halloysite nanotubes purchased from Longchuan Material works, Lingshu county, under a goods number of 1026.
The solubilizer is maleic anhydride grafted polyolefin elastomer (POE-g-GMA) which is purchased from DuPont China group Co., Ltd.
The auxiliary agent is a silane coupling agent and a lubricating agent.
The lubricant is calcium stearate which is purchased from Shanghai sparkling chemical auxiliary agent company Limited.
The silane coupling agent is a silane coupling agent KH-570 which is purchased from Anhui silicon treasure.
The weight ratio of the silane coupling agent KH-570 to the calcium stearate is 1: 1.
the second aspect of the invention provides a preparation method of the flame-retardant bio-based polyamide material, which comprises the following steps: (1) mixing the bio-based polyamide and the compatibilizer in a high-speed mixer at the rotating speed of 500r/min for 6min to obtain a mixed material A; mixing the flame retardant, the filler and the auxiliary agent in a high-speed mixer at the rotating speed of 500r/min for 6min to obtain a mixed material B; (2) adding the mixed materials A and B into a screw extruder, wherein the temperature of the screw extruder is as follows from a main feeding section to a die head: extruding at 170 deg.C, 220 deg.C, 240 deg.C, 260 deg.C, 270 deg.C and 280 deg.C, and rotating speed of twin screw at 300 rpm.
Comparative example 1
The embodiment provides a flame-retardant bio-based polyamide material, which is prepared from the following raw materials in parts by weight: 70 parts of bio-based polyamide, 15 parts of flame retardant, 10 parts of filler, 6 parts of compatibilizer and 5 parts of auxiliary agent.
The bio-based polyamide is formed by polymerizing pentanediamine and dibasic acid.
The pentanediamine is prepared from bio-based raw materials through a biological method.
The bio-based pentanediamine is obtained by removing carboxyl groups at two ends of lysine or lysine salt under the action of lysine decarboxylase.
The dibasic acid is oxalic acid and terephthalic acid; the weight ratio of the oxalic acid to the terephthalic acid is 1: 1.1.
the weight ratio of the bio-based pentanediamine to the dibasic acid is 1: 1.
the bio-based polyamide is prepared by polymerizing bio-based pentamethylene diamine and dibasic acid in a one-step high-pressure kettle.
The flame retardant is hypophosphite.
The hypophosphite salt is diethyl hypophosphite; the diethylphosphinate was OP1230, available from rayne, switzerland.
The filler is halloysite nanotubes purchased from Longchuan Material works, Lingshu county, under a goods number of 1026.
The solubilizer is maleic anhydride grafted polyolefin elastomer (POE-g-GMA) which is purchased from DuPont China group Co.
The auxiliary agent is a silane coupling agent and a lubricating agent.
The lubricant is calcium stearate and is purchased from Shanghai sparkling chemical auxiliary agent company Limited.
The silane coupling agent is a silane coupling agent KH-570 which is purchased from Anhui silicon treasure.
The weight ratio of the silane coupling agent KH-570 to the calcium stearate is 1: 0.8.
the second aspect of the invention provides a preparation method of the flame-retardant bio-based polyamide material, which comprises the following steps: (1) mixing the bio-based polyamide and the compatibilizer in a high-speed mixer at the rotating speed of 450r/min for 5min to obtain a mixed material A; mixing the flame retardant, the filler and the auxiliary agent in a high-speed mixer at the rotating speed of 450r/min for 5min to obtain a mixed material B; (2) adding the mixed materials A and B into a screw extruder, wherein the temperature of the screw extruder is as follows from a main feeding section to a die head: extruding at 160 deg.C, 210 deg.C, 230 deg.C, 250 deg.C, 260 deg.C, 265 deg.C and 270 deg.C, and with a twin-screw rotation speed of 200 rpm.
Comparative example 2
The embodiment provides a flame-retardant bio-based polyamide material, which is prepared from the following raw materials in parts by weight: 70 parts of bio-based polyamide, 15 parts of flame retardant, 10 parts of filler and 5 parts of auxiliary agent.
The bio-based polyamide is formed by polymerizing pentamethylene diamine and dibasic acid.
The pentanediamine is prepared from bio-based raw materials through a biological method.
The bio-based pentanediamine is obtained by removing carboxyl groups at two ends of lysine or lysine salt under the action of lysine decarboxylase.
The dibasic acid is oxalic acid and terephthalic acid; the weight ratio of the oxalic acid to the terephthalic acid is 1: 1.1.
the weight ratio of the bio-based pentanediamine to the dibasic acid is 1: 1.
the bio-based polyamide is prepared by polymerizing bio-based pentamethylene diamine and dibasic acid in a one-step high-pressure kettle.
The flame retardant is hypophosphite or melamine cyanurate.
The hypophosphite salt is diethyl hypophosphite; the diethylphosphinate was OP1230, available from rayne, switzerland.
The flame retardant also includes melamine cyanurate.
The melamine cyanurate is purchased from Guanao Biotech Co., Ltd, Hubei, under the trade name GA 564165-9.
The weight ratio of the hypophosphite to the melamine cyanurate is 1: 0.5.
the filler is halloysite nanotubes purchased from Longchuan Material works, Lingshu county, under a goods number of 1026.
The auxiliary agent is a silane coupling agent and a lubricating agent.
The lubricant is calcium stearate which is purchased from Shanghai sparkling chemical auxiliary agent company Limited.
The silane coupling agent is a silane coupling agent KH-570 which is purchased from Anhui silicon treasure.
The weight ratio of the silane coupling agent KH-570 to the calcium stearate is 1: 0.8.
the second aspect of the invention provides a preparation method of the flame-retardant bio-based polyamide material, which comprises the following steps: (1) mixing the bio-based polyamide in a high-speed mixer at the rotating speed of 450r/min for 5min to obtain a mixed material A; mixing the flame retardant, the filler and the auxiliary agent in a high-speed mixer at the rotating speed of 450r/min for 5min to obtain a mixed material B; (2) adding the mixed materials A and B into a screw extruder, wherein the temperature of the screw extruder is as follows from a main feeding section to a die head: extruding at 160 deg.C, 210 deg.C, 230 deg.C, 250 deg.C, 260 deg.C, 265 deg.C and 270 deg.C, and with a twin-screw rotation speed of 200 rpm.
Evaluation of Performance
1. Mechanical properties: the flame retardant bio-based polyamide materials provided in the examples and comparative examples were tested for tensile strength, flexural strength, breaking strength according to ISO527-2:1993, ISO178:2001, ISO527-2:1993, respectively, and the results are shown in table 1.
2. Toughness: the flame retardant bio-based polyamide materials provided in the examples and comparative examples were tested for notched izod impact strength and unnotched impact strength according to ISO180:2001, with the results shown in table 1.
3. Flame retardancy: the flame retardant bio-based polyamide materials provided in the examples and comparative examples were tested for flame retardant performance according to UL94, and the results are shown in table 1.
TABLE 1 Performance characterization test
As can be seen from the performance characterization test results in Table 1, the flame-retardant bio-based polyamide material provided by the invention has high flame-retardant performance, and also has good toughness and mechanical strength.
Claims (10)
1. The flame-retardant bio-based polyamide material is characterized by comprising the following components in parts by weight: 60-80 parts of bio-based polyamide, 10-20 parts of flame retardant, 1-20 parts of filler, 2-8 parts of compatibilizer and 1-10 parts of auxiliary agent.
2. The flame retardant bio-based polyamide material of claim 1, wherein said bio-based polyamide is polymerized from pentanediamine and a dibasic acid.
3. The flame retardant bio-based polyamide material of claim 2, wherein said pentanediamine is biologically prepared from bio-based raw materials; the dibasic acid is at least one of oxalic acid, terephthalic acid, isophthalic acid, dodecanoic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, undecanedioic acid, octadecanedioic acid and maleic acid.
4. The flame retardant bio-based polyamide material of claim 1, wherein the flame retardant is hypophosphite, melamine cyanurate.
5. The flame retardant bio-based polyamide material of claim 4, wherein said hypophosphite salt is at least one of dimethyl hypophosphite, ethyl methyl hypophosphite, diethyl hypophosphite, methyl n-propyl hypophosphite, methane di (methyl hypophosphite) salt, benzene-1, 4- (dimethyl hypophosphite) salt, methyl phenyl hypophosphite, diphenyl hypophosphite.
6. The flame retardant bio-based polyamide material of claim 1, wherein the filler is at least one of kaolin, diatomaceous earth, glass fiber, halloysite nanotubes, fumed silica, calcium carbonate, nano alumina, and titanium dioxide.
7. The flame retardant biobased polyamide material of claim 1, wherein the compatibilizer is at least one of a maleic anhydride grafted polyolefin elastomer, a maleic anhydride grafted polyethylene, a maleic anhydride grafted polyolefin elastomer, a maleic anhydride grafted ethylene propylene diene monomer, a maleic anhydride grafted ethylene vinyl acetate, a maleic anhydride grafted ethylene butadiene styrene copolymer, a methyl methacrylate ethyl acrylate, a methyl methacrylate butadiene styrene terpolymer.
8. The flame retardant bio-based polyamide material according to claim 1 or 4, wherein the auxiliary agent is a silane coupling agent, a lubricant.
9. The flame retardant bio-based polyamide material of claim 8, wherein the lubricant is at least one of N, N' -ethylene bis stearamide, oxidized polyethylene wax, polyethylene vinyl acetate wax, pentaerythritol stearate, montanate, oleamide, erucamide, calcium stearate, sodium stearate, barium stearate, calcium stearate.
10. A method for preparing a flame retardant bio-based polyamide material according to any one of claims 1 to 9, characterized by comprising the steps of: (1) mixing the bio-based polyamide and the compatibilizer in a high-speed mixer at the rotating speed of 400-500r/min for 4-6min to obtain a mixed material A; mixing the flame retardant, the filler and the auxiliary agent in a high-speed mixer at the rotating speed of 400-500r/min for 4-6min to obtain a mixed material B; (2) adding the mixed materials A and B into a screw extruder, wherein the temperature of the screw extruder is as follows from a main feeding section to a die head: 150-170 ℃, 200-220 ℃, 220-240 ℃, 240-260 ℃, 250-270 ℃ and 260-280 ℃, and the double-screw rotation speed is 100-300rpm, thereby obtaining the composite material.
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