CN110483991A - A kind of halogen-free flameproof biology base nylon and preparation method thereof - Google Patents
A kind of halogen-free flameproof biology base nylon and preparation method thereof Download PDFInfo
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- CN110483991A CN110483991A CN201910759212.0A CN201910759212A CN110483991A CN 110483991 A CN110483991 A CN 110483991A CN 201910759212 A CN201910759212 A CN 201910759212A CN 110483991 A CN110483991 A CN 110483991A
- Authority
- CN
- China
- Prior art keywords
- halogen
- biology base
- base nylon
- mixture
- free flameproof
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- 239000004677 Nylon Substances 0.000 title claims abstract description 156
- 229920001778 nylon Polymers 0.000 title claims abstract description 156
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003063 flame retardant Substances 0.000 claims abstract description 118
- -1 phosphorus nitrogen Chemical compound 0.000 claims abstract description 58
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 230000003078 antioxidant Effects 0.000 claims abstract description 40
- 239000007822 coupling agent Substances 0.000 claims abstract description 31
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 28
- 239000010439 graphite Substances 0.000 claims abstract description 28
- 239000011256 inorganic filler Substances 0.000 claims abstract description 26
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 19
- 239000004917 carbon fiber Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims description 171
- 239000002131 composite material Substances 0.000 claims description 49
- 238000002156 mixing Methods 0.000 claims description 37
- 238000010792 warming Methods 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 31
- 229910052736 halogen Inorganic materials 0.000 claims description 31
- 150000002367 halogens Chemical class 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 238000001125 extrusion Methods 0.000 claims description 22
- 239000004971 Cross linker Substances 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N Ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 13
- 229920001276 Ammonium polyphosphate Polymers 0.000 claims description 13
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 13
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-Aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N Glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 12
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 150000007974 melamines Chemical class 0.000 claims description 12
- AQSJGOWTSHOLKH-UHFFFAOYSA-N Phosphite Chemical compound [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 11
- 239000004698 Polyethylene (PE) Substances 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- 239000004005 microsphere Substances 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 229960000935 Dehydrated Alcohol Drugs 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000009775 high-speed stirring Methods 0.000 claims description 10
- 239000010445 mica Substances 0.000 claims description 10
- 229910052618 mica group Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000005453 pelletization Methods 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000003801 milling Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 6
- 238000006011 modification reaction Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 abstract description 9
- 239000004033 plastic Substances 0.000 abstract description 9
- 238000004140 cleaning Methods 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 5
- 239000000314 lubricant Substances 0.000 description 21
- WSEFPKKOUNRCAJ-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;octadecanoic acid Chemical compound OCC(CO)(CO)CO.CCCCCCCCCCCCCCCCCC(O)=O WSEFPKKOUNRCAJ-UHFFFAOYSA-N 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 7
- 150000001718 carbodiimides Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005452 bending Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N Melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 3
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000004432 carbon atoms Chemical group C* 0.000 description 3
- 230000003247 decreasing Effects 0.000 description 3
- 238000011031 large scale production Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CWSZBVAUYPTXTG-UHFFFAOYSA-N 5-[6-[[3,4-dihydroxy-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxymethyl]-3,4-dihydroxy-5-[4-hydroxy-3-(2-hydroxyethoxy)-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxyoxan-2-yl]oxy-6-(hydroxymethyl)-2-methyloxane-3,4-diol Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OCCO)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 CWSZBVAUYPTXTG-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N Adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K Aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N Di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- SKRDXYBATCVEMS-UHFFFAOYSA-N Isopropyl nitrite Chemical compound CC(C)ON=O SKRDXYBATCVEMS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- YVKMMZAFUFUAAX-UHFFFAOYSA-N aluminum;tetrahydrate Chemical compound O.O.O.O.[Al] YVKMMZAFUFUAAX-UHFFFAOYSA-N 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000002708 enhancing Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000002195 synergetic Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UDOWTRCREXBYQS-UHFFFAOYSA-N CC[Ca]CC Chemical compound CC[Ca]CC UDOWTRCREXBYQS-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N Cyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N Diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N Phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000003712 anti-aging Effects 0.000 description 1
- 230000003026 anti-oxygenic Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229940064002 calcium hypophosphite Drugs 0.000 description 1
- 229910001382 calcium hypophosphite Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002153 concerted Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001808 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000003009 desulfurizing Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001050 lubricating Effects 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003000 nontoxic Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000002829 reduced Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000979 retarding Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention relates to technical field of biological materials, more particularly to a kind of halogen-free flameproof biology base nylon and preparation method thereof, the raw material including such as parts by weight: 1-4 parts of carbon fiber, 1-5 parts of antioxidant, 4-8 parts of coupling agent, 2-4 parts of expanded graphite, 40-60 parts of biology base nylon, 0.05-2 parts of plasticized modifier, 20-40 parts of halogen-free flame retardants and 8-16 parts of modified inorganic filler.Halogen-free flameproof biology base nylon in the present invention uses biological Geordie for matrix, halogen-free flame retardants, modified inorganic filler and toughener based on phosphorus nitrogen system is added biology base nylon is filled to come, cooperate carbon fiber and expanded graphite simultaneously, make halogen-free flameproof biology base nylon obtained that there is excellent anti-flammability, intensity and dimensional stability, it has been well positioned to meet the performance requirement of engineering plastics, extend the use scope of the halogen-free flameproof biology base nylon, the halogen-free flameproof biology base nylon also has clean and environmental protection, and reproducible feature simultaneously.
Description
Technical field
The present invention relates to technical field of biological materials, and in particular to a kind of halogen-free flameproof biology base nylon and its preparation side
Method.
Background technique
Nylon is a kind of excellent engineering plastics, have excellent mechanical performance, heat resistance, wearability, self-lubrication and
Good processability, application occupy first of five large-engineering plastic cement, are widely used the relevant industries such as automobile, household electrical appliances, toy
In.With making rapid progress for science and technology, requirement of the people to material is more and more harsher, and the requirement to Flame Retardancy energy and environmental protection is got over
Come higher.Traditional halogenated flame retardant is due to toxic, using being restricted.
Halogen-free flame retardants includes: inorganic, halogen-free flame retardants, phosphorus flame retardant, silicon-series five-retardant and phosphorus-nitrogen containing flame retardant.But
It is that these fire retardants cut both ways, such as: inorganic fire retardants is cheap, but additional amount is excessive, therefore the performance of plastics is difficult to
Received；Phosphorus flame retardant, the product of production have biggish migration and are limited by the color of raw material, and use scope is smaller；Separately
Outer silicon-series five-retardant, it is expensive, and product is not very mature, so phosphorus-nitrogen containing flame retardant is answered by most engineers
With.But phosphorus-nitrogen containing flame retardant additional amount is also more, while being affected by temperature larger, less stable, so exploitation new material
Performance and the defect for evading material are necessary.It is developed aluminum diethylphosphinate on the basis of phosphorus flame retardant and contains
Nitrogen combustion inhibitor nylon material is used in compounding using aluminum diethylphosphinate and organic nitrogen-containing synergist, is added in nylon material
It is prepared for fire-retardant nylon material, wherein not only due to the usage amount of aluminum diethylphosphinate is at high cost greatly, and wherein addition has
Machine nitrogenous flame ratardant keeps its flame retarding efficiency insufficient, and thermal stability is not good enough, and is easy to produce molten drop in burning, is unable to satisfy work
Industry requirement.
Summary of the invention
In order to overcome shortcoming and defect existing in the prior art, it is raw that the purpose of the present invention is to provide a kind of halogen-free flameproofs
Object Geordie dragon, the halogen-free flameproof biology base nylon use biological Geordie for matrix, halogen-free flame retardants of the addition based on phosphorus nitrogen system,
Modified inorganic filler and toughener are filled biology base nylon, while cooperating carbon fiber and expanded graphite, make nothing obtained
The fire-retardant biology base nylon of halogen has excellent anti-flammability, intensity and dimensional stability, has been well positioned to meet the property of engineering plastics
It can require, extend the use scope of the halogen-free flameproof biology base nylon, while the halogen-free flameproof biology base nylon also has cleaning
Environmental protection, and reproducible feature.
Another object of the present invention is to provide a kind of halogen-free flameproof biology base nylon and preparation method, the preparation method
Easy to operate, easy to control, high production efficiency, production cost is low, while using the biology base nylon of low viscosity, is squeezing material
Process has good mobility out, is conducive to abundant mixing, and halogen-free flameproof biology base nylon obtained has excellent mechanics strong
Degree, dimensional stability and the feature of environmental protection, while meeting the fire-retardant need of the industries such as sufficient electronic apparatus, rail traffic, automotive material
Performance requirement applies also for being mass produced.
The purpose of the invention is achieved by the following technical solution: a kind of halogen-free flameproof biology base nylon, including such as parts by weight
Raw material:
Every part of halogen-free flame retardants is that ammonium polyphosphate, melamine salt, diethyl hypophosphites and modified Halogen are multiple
Close at least two in fire retardant.More preferably, the halogen-free flame retardants is by ammonium polyphosphate, melamine salt, diethyl
Base hypophosphites and modified Halogenless composite fire retardant are 0.4-0.8:0.6-1.0:0.1-0.5:0.8-1.2 composition according to weight ratio
Mixture；More preferably, the melamine salt be in melamine cyanurate zinc and melamine cyanurate calcium extremely
Few one kind, the diethyl hypophosphites are at least one of diethyl zinc hypophosphite and diethyl calcium hypophosphite；It is more excellent
Choosing, the expanded graphite is the crystalline flake graphite after desulfurization goes out, and the crystalline flake graphite coefficient of expansion is 500-1500 times.
Halogen-free flameproof biology base nylon in the present invention uses biological Geordie for matrix, and the Halogen based on phosphorus nitrogen system is added
Fire retardant, modified inorganic filler and toughener are filled biology base nylon to come, while cooperating carbon fiber and expanded graphite, make
Halogen-free flameproof biology base nylon obtained has excellent anti-flammability, intensity and dimensional stability, has been well positioned to meet engineering
The performance requirement of plastics extends the use scope of the halogen-free flameproof biology base nylon, while the halogen-free flameproof biology base nylon is also
With clean and environmental protection, and reproducible feature.Carbon fiber therein has the mechanical strength and impact resilience of superelevation, due to carbon fiber
Have with the compound material of biology base nylon light and strong, light and rigid, high temperature resistant, corrosion-resistant, endurance, structure size stability are good
And design it is good, have the features such as large area is integrally formed；The crystalline flake graphite have excellent flexibility, compression resilience,
The characteristics such as adsorptivity, ecological environment harmony, biocompatibility, radiation resistance, can the present invention in biology base nylon it is compound
Enhance compression resilience, flexibility and the ageing resistance that halogen-free flameproof biology base nylon is made.And in used halogen-free flame retardants
Ammonium polyphosphate be a kind of function admirable non-halogen fire retardant, high polymerization degree is practically insoluble in water, has highly effective flame-retardant, environment
Friendly feature, raw smoke is extremely low when burning, does not generate hydrogen halides；And melamine cyanurate used can make halogen-free flameproof raw
The flame retardant effect of object Geordie dragon reaches UL94V-0, and particularly suitable for biology base nylon PA56, melamine cyanurate cannot be single
It is solely used in fire-retardant enhancement engineering plastics, when use will be with ammonium polyphosphate, diethyl hypophosphites and modified Halogen composite flame-proof
Agent shares, and melamine cyanurate and phosphorus flame retardant have good synergistic effect, and it is raw can be obviously improved obtained halogen-free flameproof
The flame retardant effect of object Geordie dragon, the trimeric-cyanamide cyanurate fire-retardant effect is good, and dosage is few, nontoxic, smoke amount is few and biology base
Phenomena such as nylon intermiscibility is good, influences on mechanical performance small, is not susceptible to sticking to mould in processing, foaming and frosting；Diethyl time phosphorus
Hydrochlorate is used as the outstanding halogen-free flame retardants of engineered biological Geordie dragon, and diethyl hypophosphites is in biology base nylon composite materials
Show excellent performance.
Preferably, every part of modified Halogenless composite fire retardant includes the raw material of following parts by weight:
The polynary amine crosslinker is at least one of triethanolamine and carbodiimides.
The modified Halogenless composite fire retardant is worth by the following method:
1) according to parts by weight, it is equal that stirring in reaction unit is added in melamine pyrophosphate and diethyl hypo-aluminum orthophosphate
It is even, then dehydrated alcohol is slowly added to, and be warming up to 40-60 DEG C of stirring 10-20min, mixture A is obtained, it is spare；
2) polynary amine crosslinker and alkyl orthophosphate salt are added in mixture A, are warming up to 60-80 DEG C of vacuum dehydration reaction
2-4h obtains mixture B, spare；
3) phenol is added in mixture B, is warming up to 70-90 DEG C, stirred with the rate of 200-400r/min, react 20-
40min, moves to the dry 4-6h of condition in drying device at 120-160 DEG C after reaction, and cooling, milling obtains the modification
Halogenless composite fire retardant.
Modified Halogenless composite fire retardant used using above-mentioned raw materials and method by being made in the present invention, modification nothing obtained
Halogen composite flame-retardant agent alkyl orthophosphate salt and phenol collaboration improve the high thermal stability of modified Halogenless composite fire retardant, in diethyl
Base hypo-aluminum orthophosphate and melamine pyrophosphate, which cooperate with, is added polynary amine crosslinker and dehydrated alcohol adds in compound flame-retardant system
After heat is blended, the modification Halogenless composite fire retardant with high thermal stability is made, has overcome the thermostabilization of existing flame-retardant system
Property difference defect.And temperature when needing strict control vacuum dehydration to react in the step 2) for preparing modified Halogenless composite fire retardant
Degree is 60-80 DEG C, will lead to vaporization phenomenon if temperature is excessively high, is unfavorable for the progress of dehydration, unfavorable if temperature is too low
The progress of mixture A dehydration in polynary amine crosslinker, alkyl orthophosphate salt and step 1), and then influence that modified nothing is made
Thermal stability, processing fluidity and the dispersibility of halogen composite flame-retardant agent, it is obtained that can be obviously improved with biology base nylon compound tense
Processing fluidity, dispersibility and the flame retardant property of halogen-free flameproof biology base nylon, while dimensional stability and ring can also be promoted
Guarantor property.
Preferably, every part of biology base nylon is at least two in PA56, PA66, PA610, PA6 and PA1012；More
To be preferred, it according to weight ratio is 0.8-1.2:0.4-0.8:0.6-1.0 group that the biology base nylon, which is PA56, PA66 and PA6,
At mixture.Every part of antioxidant is to be according to weight ratio by phosphite antioxidant, antioxidant 1010 and irgasfos 168
The mixture of 0.8-1.2:0.4-0.8:0.6-1.0 composition.
PA56 employed in biology base nylon is closed by penta diamino of biology base and petroleum base adipic acid monomer in the present invention
At the PA56 of synthesis has rate of drying fastly and excellent hydroscopic fast-drying, passes through collaboration PA56, PA66 and PA6 in the present invention
Respectively excellent performance changes the previous halogen-free flame retardants feature weak with the compound rear intensity of single creature Geordie dragon；And it is described
Irgasfos 168 employed in antioxidant can be effectively prevented thermal oxidative degradation of biology base nylon during long-term ageing,
It is also simultaneously a kind of efficient processing stabilizers, resistance to discoloration of halogen-free flameproof biology base nylon under the conditions of high temperature process can be improved
Property, while irgasfos 168 provides and is easier compatible ester functional groups with biology base nylon and halogen-free flame retardants, realizes efficient
It is compatible；Antioxidant 1010 has brilliant antioxygenic property to biology base nylon, and antioxidant 1010 can be effectively prevented obtained Halogen
Thermal oxidative degradation of fire-retardant biology base nylon during long-term ageing, and then extend and halogen-free flameproof biology base is made in the present invention
The service life of nylon；Phosphite antioxidant is the auxiliary antioxidant of antioxidant 1010 and irgasfos 168, phosphite ester antioxygen
Agent is most important to the inhibition of aging, and the present invention passes through the aforementioned proportion of strict control three, and three can be cooperateed with respectively excellent
Performance enhancement antioxidant antioxidant effect.
Preferably, every part of coupling agent is by gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl three
Methoxy silane and phthalate ester coupling agent are according to the mixture that weight ratio is that 0.6-1.0:0.4-0.8:0.8-1.2 is formed.Every part
It according to weight ratio is 0.4-0.8:0.6- that the plasticized modifier, which is by glycidyl methacrylate and polyethylene toughener,
The mixture of 1.0 compositions.
Gamma-aminopropyl-triethoxy-silane used and biology base nylon and inorganic filler, enhance it in coupling agent of the present invention
Caking property improves the performances such as mechanical, water-fast, anti-aging of product；And γ-glycidyl ether oxygen propyl trimethoxy silicane and phthalein
Sour coupling modifier biology base nylon can not only improve the processability of the halogen-free flameproof biology base nylon products of filling auxiliary packing
Can, and it can be obviously improved the physical mechanical property of product, make the reduction of product water absorption rate, oil absorption is reduced, auxiliary packing
Disperse even equal；And glycidyl methacrylate used in plasticized modifier is macromolecular toughening agent, and it is fine to be used as ethoxy
The reactive diluent of element is tieed up, glycidyl methacrylate is reacted with the end group of hydroxyethyl cellulose can be bright by interfacial reaction
The aobvious compatibility for improving hydroxyethyl cellulose and being blended with polyolefin elastomer molecule, further promotes biology base nylon and Halogen resistance
Fire compound, every mechanical performance of enhanced biological Geordie dragon of agent；Polyethylene toughener can be mixed with biology base nylon takes out grain, increases
The tough dose of impact strength for improving it under the premise of not influencing biology base nylon physical property itself with biology base nylon, toughness are drawn
Stretch intensity, resistance to tortuosity, winter resistance, alleviation expands with heat and contract with cold, and reduces cost.
Preferably, every part of modified inorganic filler be by the modified mica of phthalate ester coupling agent, glass microsphere and
The mixture of at least two compositions in graphene oxide.The halogen-free flameproof biology base nylon further includes 0.05-1 parts of lubricant,
The lubricant is by pentaerythritol stearate and silicone powder according to the mixing that weight ratio is that 0.4-0.8:0.8-1.2 is formed
Object.
Modified glass microsphere used can improve the physical machine of biology base nylon product in modified inorganic filler of the present invention
Tool performance can be such that the hardness and elastic modulus of material greatly increases, and the ability of rigidity and stress damping also increases, and is modified
The implantation of the carboxylic ions of graphene oxide afterwards can make the active functional group in grapheme material surface, to increase substantially
Cell and the biological respinse activity of biology base nylon, in addition the connection between the carbon atom inside graphene oxide is very flexible, when
Apply external force when graphene oxide, the meeting bending deformation of carbon atom face, so that carbon atom need not be rearranged to adapt to external force, from
And stable structure is kept, it is filled out in the present invention by the excellent properties of synergistic oxidation graphene, micarex microballoon three come reinforcement
Biology base nylon is filled, halogen-free flameproof biology base nylon properties obtained are further improved.And employed in lubricant
Pentaerythritol stearate rises in biology base nylon and halogen-free flame retardants recombination process moulds solution and lubricating action, and silicone powder energy
The processing performance that halogen-free flameproof biology base nylon is made and the dispersibility for improving auxiliary packing are effectively promoted, in addition also has and improves
The product smooth feeling of biology base nylon, wearability, ageing-resistant and impact resistance, at the same can also with state modified Halogen composite flame-proof
The alkyl orthophosphate salt that agent contains is blended, and can polymerize with biology base nylon base-material and concerted reaction occurs for halogen-free flame retardants,
The generation for improving the mutual infiltration promotion carbon-coating of biology base nylon base-material and halogen-free flame retardants, it is raw further to improve halogen-free flameproof
Object Geordie dragon flame retardant property.
A kind of preparation method of halogen-free flameproof biology base nylon, includes the following steps:
S1, according to parts by weight, after mixing evenly by halogen-free flame retardants, biology base nylon, expanded graphite and mix lubricant
It is added and is heated to 50-80 DEG C in drying device and is dried in vacuo 2-4h, be cooled to room temperature to obtain mixture A, it is spare；
S2, plasticized modifier, carbon fiber and modified inorganic filler are added in mixture A obtained in step S1, and turned
It moves in high-speed stirring apparatus and 20-40min is stirred with 4000-8000r/min rate, obtain mixture B, it is spare；
S3, antioxidant and coupling agent are added in mixture B obtained in step S2, and it is equal to be warming up to 40-60 DEG C of stirring
It is even, the extruding pelletization that heats up is transferred in Double-screw extrusion device, it is finally that particle obtained is dry under the conditions of 60-80 DEG C
Obtain the halogen-free flameproof biology base nylon；One area's temperature of the Double-screw extrusion device is 250-260 DEG C when granulation,
Two area's temperature are 240-250 DEG C, and three area's temperature are 220-240 DEG C, and four area's temperature are 210-230 DEG C, screw speed 200-
500r/min。
Heretofore described halogen-free flameproof biology base nylon is made by using the above method, using made from the above method
Halogen-free flameproof biology base nylon is matrix by using biological Geordie, and the halogen-free flame retardants based on phosphorus nitrogen system is added, is modified nothing
Machine filler and toughener are filled biology base nylon to come, while cooperating carbon fiber and expanded graphite, make Halogen resistance obtained
Firing biology base nylon has excellent anti-flammability, intensity and dimensional stability, and the performance for being well positioned to meet engineering plastics is wanted
It asks, extends the use scope of the halogen-free flameproof biology base nylon, while the halogen-free flameproof biology base nylon also has clean and environmental protection,
And reproducible feature.And the preparation method is easy to operate, easy to control, high production efficiency, production cost is low, is suitable for big rule
Mould production.Wanting the drying temperature in strict control step S1 during the preparation process is 50-80 DEG C, will lead to life if temperature is excessively high
Object Geordie dragon partial inactivation, inhibits lubricant compound to the lubrication of biology base nylon and halogen-free flame retardants instead, if temperature mistake
It is low, dry demand is not achieved；And the stirring rate when step S2 needs strict control to stir is 4000-8000r/min, if
Sufficiently dividing between each auxiliary agent is not achieved in dispersion between the excessively high each auxiliary agent unfavorable instead of stirring rate if stirring rate is too low
It dissipates, is unfavorable for modified inorganic and fills out filling with carbon fiber to biology base nylon；And want in step s3 strict control antioxidant and
Temperature when mixture B is added in coupling agent is 40-60 DEG C, because antioxidant and coupling agent play the best of effect in the present invention
Active temperature overlay region is 40-60 DEG C, the too low excessively high maximum effect that can not all play the two of temperature, while also needing strict control
The temperature of four humidity provinces of Double-screw extrusion device when granulation makes final silicon halogen-free flameproof biology base nylon obtained
The properties of material are best.
The beneficial effects of the present invention are: the halogen-free flameproof biology base nylon in the present invention uses biological Geordie for matrix,
Halogen-free flame retardants, modified inorganic filler and toughener based on phosphorus nitrogen system is added to be filled biology base nylon, matches simultaneously
Carbon fiber and expanded graphite are closed, makes halogen-free flameproof biology base nylon obtained that there is excellent anti-flammability, intensity and dimensionally stable
Property, it has been well positioned to meet the performance requirement of engineering plastics, has extended the use scope of the halogen-free flameproof biology base nylon, simultaneously should
Halogen-free flameproof biology base nylon also has clean and environmental protection, and reproducible feature.
The preparation method of halogen-free flameproof biology base nylon is easy to operate in the present invention, easy to control, high production efficiency, production
It is at low cost, while using the biology base nylon of low viscosity, make material that there is good mobility in extrusion process, is conducive to sufficiently
Mixing, halogen-free flameproof biology base nylon obtained has excellent mechanical strength, dimensional stability and the feature of environmental protection, while meeting foot
The performance requirement of the fire-retardant needs of the industries such as electronic apparatus, rail traffic, automotive material, applies also for being mass produced.
Specific embodiment
For the ease of the understanding of those skilled in the art, below with reference to embodiment, the present invention is further illustrated, real
The content that the mode of applying refers to not is limitation of the invention.
Embodiment 1
A kind of halogen-free flameproof biology base nylon, the raw material including such as parts by weight:
The crystalline flake graphite coefficient of expansion is 500 times.
Every part of halogen-free flame retardants is by ammonium polyphosphate, melamine salt, diethyl hypophosphites and modified Halogen
Composite flame-retardant agent is according to the mixture that weight ratio is that 0.4:0.6:0.1:0.8 is formed.
Every part of modified Halogenless composite fire retardant includes the raw material of following parts by weight:
The polynary amine crosslinker is by triethanolamine and carbodiimides according to the mixing that weight ratio is that 0.8:0.4 is formed
Object.
The modified Halogenless composite fire retardant is worth by the following method:
1) according to parts by weight, it is equal that stirring in reaction unit is added in melamine pyrophosphate and diethyl hypo-aluminum orthophosphate
It is even, then dehydrated alcohol is slowly added to, and be warming up to 40 DEG C of stirring 10min, mixture A is obtained, it is spare；
2) polynary amine crosslinker and alkyl orthophosphate salt are added in mixture A, are warming up to 60 DEG C of vacuum dehydration reaction 2h,
Mixture B is obtained, it is spare；
3) phenol is added in mixture B, is warming up to 70 DEG C, stirred with the rate of 200r/min, react 20min, reaction
After move to the dry 4h of condition in drying device at 120 DEG C, cooling, milling obtains the modified Halogenless composite fire retardant.
Every part of biology base nylon is PA56, PA66 and PA6 according to the mixing that weight ratio is that 0.8:0.4:0.6 is formed
Object.
Every part of antioxidant is to be according to weight ratio by phosphite antioxidant, antioxidant 1010 and irgasfos 168
The mixture of 0.8:0.4:0.6 composition.
Every part of coupling agent is by gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicon
Alkane and phthalate ester are according to the mixture that weight ratio is that 0.6:0.4:0.8 is formed.
Every part of plasticized modifier is to be according to weight ratio by glycidyl methacrylate and polyethylene toughener
The mixture of 0.4:0.6 composition.
Every part of modified inorganic filler be by glass microsphere, graphene oxide and mica according to weight ratio be 1.2:0.4:
The mixture of 0.8 composition.
The lubricant is by pentaerythritol stearate and silicone powder according to the mixing that weight ratio is that 0.4:0.8 is formed
Object.
The preparation method of the halogen-free flameproof biology base nylon, includes the following steps:
S1, according to parts by weight, after mixing evenly by halogen-free flame retardants, biology base nylon, expanded graphite and mix lubricant
It is added and is heated to 50 DEG C in drying device and is dried in vacuo 2h, be cooled to room temperature to obtain mixture A, it is spare；
S2, plasticized modifier, carbon fiber and modified inorganic filler are added in mixture A obtained in step S1, and turned
It moves in high-speed stirring apparatus and 20min is stirred with 4000r/min rate, obtain mixture B, it is spare；
S3, antioxidant and coupling agent are added in mixture B obtained in step S2, and are warming up to 40 DEG C and stir evenly,
The extruding pelletization that heats up is transferred in Double-screw extrusion device, finally by particle obtained drying to obtain under the conditions of 60 DEG C
The halogen-free flameproof biology base nylon；One area's temperature of the Double-screw extrusion device is 250 DEG C when granulation, and two area's temperature are
240 DEG C, three area's temperature are 220 DEG C, and four area's temperature are 210 DEG C, screw speed 200r/min.
Embodiment 2
A kind of halogen-free flameproof biology base nylon, the raw material including such as parts by weight:
The crystalline flake graphite coefficient of expansion is 750 times.
Every part of halogen-free flame retardants is by ammonium polyphosphate, melamine salt, diethyl hypophosphites and modified Halogen
Composite flame-retardant agent is according to the mixture that weight ratio is that 0.5:0.7:0.2:0.9 is formed.
Every part of modified Halogenless composite fire retardant includes the raw material of following parts by weight:
The polynary amine crosslinker is by triethanolamine and carbodiimides according to the mixing that weight ratio is that 0.9:0.5 is formed
Object.
The modified Halogenless composite fire retardant is worth by the following method:
1) according to parts by weight, it is equal that stirring in reaction unit is added in melamine pyrophosphate and diethyl hypo-aluminum orthophosphate
It is even, then dehydrated alcohol is slowly added to, and be warming up to 45 DEG C of stirring 13min, mixture A is obtained, it is spare；
2) polynary amine crosslinker and alkyl orthophosphate salt are added in mixture A, are warming up to 65 DEG C of vacuum dehydration reactions
2.5h obtains mixture B, spare；
3) phenol is added in mixture B, is warming up to 75 DEG C, stirred with the rate of 250r/min, react 25min, reaction
After move to the dry 4.5h of condition in drying device at 130 DEG C, cooling, milling obtains the modified Halogen composite flame-proof
Agent.
Every part of biology base nylon is PA56, PA66 and PA6 according to the mixing that weight ratio is that 0.9:0.5:0.7 is formed
Object.
Every part of antioxidant is to be according to weight ratio by phosphite antioxidant, antioxidant 1010 and irgasfos 168
The mixture of 0.9:0.5:0.7 composition.
Every part of coupling agent is by gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicon
Alkane and phthalate ester are according to the mixture that weight ratio is that 07:0.5:0.9 is formed.
Every part of plasticized modifier is to be according to weight ratio by glycidyl methacrylate and polyethylene toughener
The mixture of 0.5:0.7 composition.
Every part of modified inorganic filler be by glass microsphere, graphene oxide and mica according to weight ratio be 1.3:0.5:
The mixture of 0.9 composition.
The lubricant is by pentaerythritol stearate and silicone powder according to the mixing that weight ratio is that 0.5:0.9 is formed
Object.
The preparation method of the halogen-free flameproof biology base nylon, includes the following steps:
S1, according to parts by weight, after mixing evenly by halogen-free flame retardants, biology base nylon, expanded graphite and mix lubricant
It is added and is heated to 55 DEG C in drying device and is dried in vacuo 2.5h, be cooled to room temperature to obtain mixture A, it is spare；
S2, plasticized modifier, carbon fiber and modified inorganic filler are added in mixture A obtained in step S1, and turned
It moves in high-speed stirring apparatus and 25min is stirred with 5000r/min rate, obtain mixture B, it is spare；
S3, antioxidant and coupling agent are added in mixture B obtained in step S2, and are warming up to 45 DEG C and stir evenly,
The extruding pelletization that heats up is transferred in Double-screw extrusion device, finally by particle obtained drying to obtain under the conditions of 65 DEG C
The halogen-free flameproof biology base nylon；One area's temperature of the Double-screw extrusion device is 253 DEG C when granulation, and two area's temperature are
243 DEG C, three area's temperature are 225 DEG C, and four area's temperature are 215 DEG C, screw speed 275r/min.
Embodiment 3
A kind of halogen-free flameproof biology base nylon, the raw material including such as parts by weight:
The crystalline flake graphite coefficient of expansion is 1000 times.
Every part of halogen-free flame retardants is by ammonium polyphosphate, melamine salt, diethyl hypophosphites and modified Halogen
Composite flame-retardant agent is according to the mixture that weight ratio is that 0.6:0.8:0.3:1.0 is formed.
Every part of modified Halogenless composite fire retardant includes the raw material of following parts by weight:
The polynary amine crosslinker is by triethanolamine and carbodiimides according to the mixing that weight ratio is that 1.0:0.6 is formed
Object.
The modified Halogenless composite fire retardant is worth by the following method:
1) according to parts by weight, it is equal that stirring in reaction unit is added in melamine pyrophosphate and diethyl hypo-aluminum orthophosphate
It is even, then dehydrated alcohol is slowly added to, and be warming up to 50 DEG C of stirring 15min, mixture A is obtained, it is spare；
2) polynary amine crosslinker and alkyl orthophosphate salt are added in mixture A, are warming up to 70 DEG C of vacuum dehydration reaction 3h,
Mixture B is obtained, it is spare；
3) phenol is added in mixture B, is warming up to 80 DEG C, stirred with the rate of 300r/min, react 30min, reaction
After move to the dry 5h of condition in drying device at 140 DEG C, cooling, milling obtains the modified Halogenless composite fire retardant.
Every part of biology base nylon is PA56, PA66 and PA6 according to the mixing that weight ratio is that 01.0:0.6:0.8 is formed
Object.
Every part of antioxidant is to be according to weight ratio by phosphite antioxidant, antioxidant 1010 and irgasfos 168
1.0:0.6:0.8 the mixture of composition.
Every part of coupling agent is by gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicon
Alkane and phthalate ester are according to the mixture that weight ratio is that 0.8:0.6:1.0 is formed.
Every part of plasticized modifier is to be according to weight ratio by glycidyl methacrylate and polyethylene toughener
The mixture of 0.6:0.8 composition.
Every part of modified inorganic filler be by glass microsphere, graphene oxide and mica according to weight ratio be 1.4:0.6:
The mixture of 1.0 compositions.
The lubricant is by pentaerythritol stearate and silicone powder according to the mixing that weight ratio is that 0.6:1.0 is formed
Object.
The preparation method of the halogen-free flameproof biology base nylon, includes the following steps:
S1, according to parts by weight, after mixing evenly by halogen-free flame retardants, biology base nylon, expanded graphite and mix lubricant
It is added and is heated to 60 DEG C in drying device and is dried in vacuo 3h, be cooled to room temperature to obtain mixture A, it is spare；
S2, plasticized modifier, carbon fiber and modified inorganic filler are added in mixture A obtained in step S1, and turned
It moves in high-speed stirring apparatus and 30min is stirred with 6000r/min rate, obtain mixture B, it is spare；
S3, antioxidant and coupling agent are added in mixture B obtained in step S2, and are warming up to 50 DEG C and stir evenly,
The extruding pelletization that heats up is transferred in Double-screw extrusion device, finally by particle obtained drying to obtain under the conditions of 70 DEG C
The halogen-free flameproof biology base nylon；One area's temperature of the Double-screw extrusion device is 255 DEG C when granulation, and two area's temperature are
245 DEG C, three area's temperature are 230 DEG C, and four area's temperature are 220 DEG C, screw speed 350r/min.
Embodiment 4
A kind of halogen-free flameproof biology base nylon, the raw material including such as parts by weight:
The crystalline flake graphite coefficient of expansion is 1250 times.
Every part of halogen-free flame retardants is by ammonium polyphosphate, melamine salt, diethyl hypophosphites and modified Halogen
Composite flame-retardant agent is according to the mixture that weight ratio is that 0.7:0.9:0.4:1.1 is formed.
Every part of modified Halogenless composite fire retardant includes the raw material of following parts by weight:
The polynary amine crosslinker is by triethanolamine and carbodiimides according to the mixing that weight ratio is that 1.1:0.7 is formed
Object.
The modified Halogenless composite fire retardant is worth by the following method:
1) according to parts by weight, it is equal that stirring in reaction unit is added in melamine pyrophosphate and diethyl hypo-aluminum orthophosphate
It is even, then dehydrated alcohol is slowly added to, and be warming up to 55 DEG C of stirring 18min, mixture A is obtained, it is spare；
2) polynary amine crosslinker and alkyl orthophosphate salt are added in mixture A, are warming up to 75 DEG C of vacuum dehydration reactions
3.5h obtains mixture B, spare；
3) phenol is added in mixture B, is warming up to 85 DEG C, stirred with the rate of 350r/min, react 35min, reaction
After move to the dry 5.5h of condition in drying device at 150 DEG C, cooling, milling obtains the modified Halogen composite flame-proof
Agent.
Every part of biology base nylon is PA56, PA66 and PA6 according to the mixing that weight ratio is that 1.1:0.7:0.9 is formed
Object.
Every part of antioxidant is to be according to weight ratio by phosphite antioxidant, antioxidant 1010 and irgasfos 168
1.1:0.7:0.9 the mixture of composition.
Every part of coupling agent is by gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicon
Alkane and phthalate ester are according to the mixture that weight ratio is that 0.9:0.7:1.1 is formed.
Every part of plasticized modifier is to be according to weight ratio by glycidyl methacrylate and polyethylene toughener
The mixture of 0.7:0.9 composition.
Every part of modified inorganic filler be by glass microsphere, graphene oxide and mica according to weight ratio be 1.5:0.7:
The mixture of 1.1 compositions.
The lubricant is by pentaerythritol stearate and silicone powder according to the mixing that weight ratio is that 0.7:1.1 is formed
Object.
The preparation method of the halogen-free flameproof biology base nylon, includes the following steps:
S1, according to parts by weight, after mixing evenly by halogen-free flame retardants, biology base nylon, expanded graphite and mix lubricant
It is added and is heated to 65 DEG C in drying device and is dried in vacuo 3.5h, be cooled to room temperature to obtain mixture A, it is spare；
S2, plasticized modifier, carbon fiber and modified inorganic filler are added in mixture A obtained in step S1, and turned
It moves in high-speed stirring apparatus and 35min is stirred with 7000r/min rate, obtain mixture B, it is spare；
S3, antioxidant and coupling agent are added in mixture B obtained in step S2, and are warming up to 55 DEG C and stir evenly,
The extruding pelletization that heats up is transferred in Double-screw extrusion device, finally by particle obtained drying to obtain under the conditions of 75 DEG C
The halogen-free flameproof biology base nylon；One area's temperature of the Double-screw extrusion device is 258 DEG C when granulation, and two area's temperature are
248 DEG C, three area's temperature are 235 DEG C, and four area's temperature are 225 DEG C, screw speed 430r/min.
Embodiment 5
A kind of halogen-free flameproof biology base nylon, the raw material including such as parts by weight:
The crystalline flake graphite coefficient of expansion is 1500 times.
Every part of halogen-free flame retardants is by ammonium polyphosphate, melamine salt, diethyl hypophosphites and modified Halogen
Composite flame-retardant agent is according to the mixture that weight ratio is that 0.8:1.0:0.5:1.2 is formed.
Every part of modified Halogenless composite fire retardant includes the raw material of following parts by weight:
The polynary amine crosslinker is by triethanolamine and carbodiimides according to the mixing that weight ratio is that .2:0.8 is formed
Object.
The modified Halogenless composite fire retardant is worth by the following method:
1) according to parts by weight, it is equal that stirring in reaction unit is added in melamine pyrophosphate and diethyl hypo-aluminum orthophosphate
It is even, then dehydrated alcohol is slowly added to, and be warming up to 60 DEG C of stirring 20min, mixture A is obtained, it is spare；
2) polynary amine crosslinker and alkyl orthophosphate salt are added in mixture A, are warming up to 80 DEG C of vacuum dehydration reaction 4h,
Mixture B is obtained, it is spare；
3) phenol is added in mixture B, is warming up to 90 DEG C, stirred with the rate of 400r/min, react 20-40min, instead
The dry 6h of condition in drying device at 160 DEG C is moved to after answering, cooling, milling obtains the modified Halogen composite flame-proof
Agent.
Every part of biology base nylon is PA56, PA66 and PA6 according to the mixing that weight ratio is that 1.2:0.8:1.0 is formed
Object.
Every part of antioxidant is to be according to weight ratio by phosphite antioxidant, antioxidant 1010 and irgasfos 168
1.2:0.8:1.0 the mixture of composition.
Every part of coupling agent is by gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicon
Alkane and phthalate ester are according to the mixture that weight ratio is that 1.0:0.8:1.2 is formed.
Every part of plasticized modifier is to be according to weight ratio by glycidyl methacrylate and polyethylene toughener
The mixture of 0.8:1.0 composition.
Every part of modified inorganic filler be by glass microsphere, graphene oxide and mica according to weight ratio be 1.6:0.8:
1.2 the mixture of composition.
The lubricant is by pentaerythritol stearate and silicone powder according to the mixing that weight ratio is that 0.8:1.2 is formed
Object.
The preparation method of the halogen-free flameproof biology base nylon, includes the following steps:
S1, according to parts by weight, after mixing evenly by halogen-free flame retardants, biology base nylon, expanded graphite and mix lubricant
It is added and is heated to 80 DEG C in drying device and is dried in vacuo 4h, be cooled to room temperature to obtain mixture A, it is spare；
S2, plasticized modifier, carbon fiber and modified inorganic filler are added in mixture A obtained in step S1, and turned
It moves in high-speed stirring apparatus and 40min is stirred with 8000r/min rate, obtain mixture B, it is spare；
S3, antioxidant and coupling agent are added in mixture B obtained in step S2, and are warming up to 60 DEG C and stir evenly,
The extruding pelletization that heats up is transferred in Double-screw extrusion device, finally by particle obtained drying to obtain under the conditions of 80 DEG C
The halogen-free flameproof biology base nylon；One area's temperature of the Double-screw extrusion device is 260 DEG C when granulation, and two area's temperature are
250 DEG C, three area's temperature are 240 DEG C, and four area's temperature are 230 DEG C, screw speed 500r/min.
Comparative example 1
A kind of halogen-free flameproof biology base nylon, the raw material including such as parts by weight:
The crystalline flake graphite coefficient of expansion is 500 times.
Every part of halogen-free flame retardants is by ammonium polyphosphate, melamine salt, diethyl hypophosphites and aluminium hydroxide
It is the mixture of 0.4:0.6:0.1:0.8 composition according to weight ratio.
Every part of biology base nylon is PA56, PA66 and PA6 according to the mixing that weight ratio is that 0.8:0.4:0.6 is formed
Object.
Every part of antioxidant is to be according to weight ratio by phosphite antioxidant, antioxidant 1010 and irgasfos 168
The mixture of 0.8:0.4:0.6 composition.
Every part of coupling agent is by gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicon
Alkane and phthalate ester are according to the mixture that weight ratio is that 0.6:0.4:0.8 is formed.
Every part of plasticized modifier is to be according to weight ratio by glycidyl methacrylate and polyethylene toughener
The mixture of 0.4:0.6 composition.
Every part of modified inorganic filler be by glass microsphere, graphene oxide and mica according to weight ratio be 1.2:0.4:
The mixture of 0.8 composition.
The lubricant is by pentaerythritol stearate and silicone powder according to the mixing that weight ratio is that 0.4:0.8 is formed
Object.
The preparation method of the halogen-free flameproof biology base nylon, includes the following steps:
S1, according to parts by weight, after mixing evenly by halogen-free flame retardants, biology base nylon, expanded graphite and mix lubricant
It is added and is heated to 50 DEG C in drying device and is dried in vacuo 2h, be cooled to room temperature to obtain mixture A, it is spare；
S2, plasticized modifier, carbon fiber and modified inorganic filler are added in mixture A obtained in step S1, and turned
It moves in high-speed stirring apparatus and 20min is stirred with 4000r/min rate, obtain mixture B, it is spare；
S3, antioxidant and coupling agent are added in mixture B obtained in step S2, and are warming up to 40 DEG C and stir evenly,
The extruding pelletization that heats up is transferred in Double-screw extrusion device, finally by particle obtained drying to obtain under the conditions of 60 DEG C
The halogen-free flameproof biology base nylon；One area's temperature of the Double-screw extrusion device is 250 DEG C when granulation, and two area's temperature are
240 DEG C, three area's temperature are 220 DEG C, and four area's temperature are 210 DEG C, screw speed 200r/min.
Comparative example 2
A kind of halogen-free flameproof biology base nylon, the raw material including such as parts by weight:
The crystalline flake graphite coefficient of expansion is 1000 times.
Every part of halogen-free flame retardants is by ammonium polyphosphate, melamine salt, diethyl hypophosphites and modified Halogen
Composite flame-retardant agent is according to the mixture that weight ratio is that 0.6:0.8:0.3:1.0 is formed.
Every part of modified Halogenless composite fire retardant includes the raw material of following parts by weight:
The modified Halogenless composite fire retardant is worth by the following method:
1) according to parts by weight, it is equal that stirring in reaction unit is added in melamine pyrophosphate and diethyl hypo-aluminum orthophosphate
It is even, then dehydrated alcohol is slowly added to, and be warming up to 50 DEG C of stirring 15min, mixture A is obtained, it is spare；
2) di-tert-butyl peroxide and alkyl orthophosphate salt are added in mixture A, it is anti-is warming up to 70 DEG C of vacuum dehydrations
3h is answered, mixture B is obtained, it is spare；
3) phenol is added in mixture B, is warming up to 80 DEG C, stirred with the rate of 300r/min, react 30min, reaction
After move to the dry 5h of condition in drying device at 140 DEG C, cooling, milling obtains the modified Halogenless composite fire retardant.
Every part of biology base nylon is PA56, PA66 and PA6 according to the mixing that weight ratio is that 01.0:0.6:0.8 is formed
Object.
Every part of antioxidant is to be according to weight ratio by phosphite antioxidant, antioxidant 1010 and irgasfos 168
1.0:0.6:0.8 the mixture of composition.
Every part of coupling agent is by gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicon
Alkane and phthalate ester are according to the mixture that weight ratio is that 0.8:0.6:1.0 is formed.
Every part of plasticized modifier is to be according to weight ratio by glycidyl methacrylate and polyethylene toughener
The mixture of 0.6:0.8 composition.
Every part of modified inorganic filler be by glass microsphere, graphene oxide and mica according to weight ratio be 1.4:0.6:
The mixture of 1.0 compositions.
The lubricant is by pentaerythritol stearate and silicone powder according to the mixing that weight ratio is that 0.6:1.0 is formed
Object.
The preparation method of the halogen-free flameproof biology base nylon, includes the following steps:
S1, according to parts by weight, after mixing evenly by halogen-free flame retardants, biology base nylon, expanded graphite and mix lubricant
It is added and is heated to 60 DEG C in drying device and is dried in vacuo 3h, be cooled to room temperature to obtain mixture A, it is spare；
S2, plasticized modifier, carbon fiber and modified inorganic filler are added in mixture A obtained in step S1, and turned
It moves in high-speed stirring apparatus and 30min is stirred with 6000r/min rate, obtain mixture B, it is spare；
S3, antioxidant and coupling agent are added in mixture B obtained in step S2, and are warming up to 50 DEG C and stir evenly,
The extruding pelletization that heats up is transferred in Double-screw extrusion device, finally by particle obtained drying to obtain under the conditions of 70 DEG C
The halogen-free flameproof biology base nylon；One area's temperature of the Double-screw extrusion device is 255 DEG C when granulation, and two area's temperature are
245 DEG C, three area's temperature are 230 DEG C, and four area's temperature are 220 DEG C, screw speed 350r/min.
Comparative example 3
A kind of halogen-free flameproof biology base nylon, the raw material including such as parts by weight:
The crystalline flake graphite coefficient of expansion is 1500 times.
Every part of halogen-free flame retardants is by ammonium polyphosphate, melamine salt, diethyl hypophosphites and modified Halogen
Composite flame-retardant agent is according to the mixture that weight ratio is that 0.8:1.0:0.5:1.2 is formed.
Every part of modified Halogenless composite fire retardant includes the raw material of following parts by weight:
The polynary amine crosslinker is by triethanolamine and carbodiimides according to the mixing that weight ratio is that 1.2:0.8 is formed
Object.
The modified Halogenless composite fire retardant is worth by the following method:
1) according to parts by weight, it is equal that stirring in reaction unit is added in melamine pyrophosphate and diethyl hypo-aluminum orthophosphate
It is even, then dehydrated alcohol is slowly added to, and be warming up to 60 DEG C of stirring 20min, mixture A is obtained, it is spare；
2) polynary amine crosslinker and alkyl orthophosphate salt are added in mixture A, are warming up to 80 DEG C of vacuum dehydration reaction 4h,
Mixture B is obtained, it is spare；
3) phenol is added in mixture B, is warming up to 90 DEG C, stirred with the rate of 400r/min, react 20-40min, instead
The dry 6h of condition in drying device at 160 DEG C is moved to after answering, cooling, milling obtains the modified Halogen composite flame-proof
Agent.
Every part of biology base nylon is PA56, PA66 and PA6 according to the mixing that weight ratio is that 1.2:0.8:1.0 is formed
Object.
Every part of antioxidant is to be according to weight ratio by phosphite antioxidant, antioxidant 1010 and irgasfos 168
1.2:0.8:1.0 the mixture of composition.
It according to weight ratio is 0.8:1.2 group that every part of coupling agent, which is by three isopropyl ester of aluminic acid and silane coupling agent KH-540,
At mixture.
Every part of plasticized modifier is to be according to weight ratio by glycidyl methacrylate and polyethylene toughener
The mixture of 0.8:1.0 composition.
Every part of modified inorganic filler be by glass microsphere, graphene oxide and mica according to weight ratio be 1.6:0.8:
The mixture of 1.2 compositions.
The lubricant is by pentaerythritol stearate and silicone powder according to the mixing that weight ratio is that 0.8:1.2 is formed
Object.
The preparation method of the halogen-free flameproof biology base nylon, includes the following steps:
S1, according to parts by weight, after mixing evenly by halogen-free flame retardants, biology base nylon, expanded graphite and mix lubricant
It is added and is heated to 80 DEG C in drying device and is dried in vacuo 4h, be cooled to room temperature to obtain mixture A, it is spare；
S2, plasticized modifier, carbon fiber and modified inorganic filler are added in mixture A obtained in step S1, and turned
It moves in high-speed stirring apparatus and 40min is stirred with 8000r/min rate, obtain mixture B, it is spare；
S3, antioxidant and coupling agent are added in mixture B obtained in step S2, and are warming up to 60 DEG C and stir evenly,
The extruding pelletization that heats up is transferred in Double-screw extrusion device, finally by particle obtained drying to obtain under the conditions of 80 DEG C
The halogen-free flameproof biology base nylon；One area's temperature of the Double-screw extrusion device is 260 DEG C when granulation, and two area's temperature are
250 DEG C, three area's temperature are 240 DEG C, and four area's temperature are 230 DEG C, screw speed 500r/min.
Halogen-free flameproof biology base nylon items physical property obtained in specific embodiment 1-5 and comparative example 1-3 is carried out respectively
Detection, the results are shown in Table 1.
Table 1
From the above results, in 1-5 of the embodiment of the present invention halogen-free flameproof biology base nylon obtained every mechanicalness
Can be superior, flame retardant rating, tensile strength, bending strength and the impact strength and elongation at break of halogen-free flameproof biology base nylon have
It is obviously improved, while also there is halogen-free flameproof biology base nylon excellent degradability to be good for the environment regeneration.
Compared with Example 1, it is hindered with aluminium hydroxide instead of Halogen in comparative example 1 when preparing the fire-retardant biology base nylon of halogen
The modification Halogenless composite fire retardant in agent is fired, every physical property measurement, analysis hair are carried out to halogen-free flameproof biology base nylon obtained
Tensile strength, bending strength, impact strength and the elongation at break relative reduction of this existing halogen-free flameproof biology base nylon, anti-flammability
It can be remarkably decreased；Illustrate to add modified nothing in present invention halogen-free flame retardants used when preparing silicon systems halogen-free flameproof biology base nylon
Halogen composite flame-retardant agent can optimize every mechanical performance of obtained halogen-free flameproof biology base nylon, especially flame retardant property, make to be made
Halogen-free flameproof biology base nylon have it is excellent it is fire-retardant, heat resistance, engineering properties is tough, chemical resistance, impact resistance and ruler
Very little stabilization is suitble to large-scale production.
Compared with Example 3, it is replaced when preparing the fire-retardant biology base nylon of halogen with di-tert-butyl peroxide in comparative example 2
Polynary amine crosslinker in modified Halogenless composite fire retardant, utilizes halogen-free flameproof made from modified Halogenless composite fire retardant
Biology base nylon carries out every physical property measurement, and analysis finds the tensile strength of this halogen-free flameproof biology base nylon, bending strength, punching
Hit intensity and elongation at break relative reduction, flame retardant property are remarkably decreased；Illustrate that the present invention is preparing halogen-free flameproof biology Geordie
Polynary amine crosslinker is added when imperial in modified Halogenless composite fire retardant used to be made, can optimize obtained modification Halogen composite flame-proof
Agent, and then be conducive to be promoted every mechanical performance of obtained halogen-free flameproof biology base nylon, especially flame retardant property, make obtained
Halogen-free flameproof biology base nylon have it is excellent it is fire-retardant, heat resistance, engineering properties is tough, chemical resistance, impact resistance and size
Stablize, is suitble to large-scale production.
Compared with Example 5, even with three isopropyl ester of aluminic acid and silane when preparing the fire-retardant biology base nylon of halogen in comparative example 3
Join the mixing coupling agent of agent KH-540 composition instead of gamma-aminopropyl-triethoxy-silane, the γ-glycidol ether in coupling agent
Oxygen propyl trimethoxy silicane and phthalate ester hinder Halogen obtained according to the mixture that weight ratio is that 1.0:0.8:1.2 is formed
Fire biology base nylon and carry out every physical property measurement, analysis find the tensile strength of this halogen-free flameproof biology base nylon, bending strength,
Impact strength and elongation at break relative reduction, flame retardant rating are remarkably decreased, and flame retardant property is declined slightly；Illustrate that the present invention is making
Coupling agent selection gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen used when standby silicon systems halogen-free flameproof biology base nylon
The mixture of propyl trimethoxy silicane and phthalate ester according to weight ratio for 1.0:0.8:1.2 composition can optimize obtained halogen-free flameproof
Every mechanical performance of biology base nylon, especially tensile strength, bending strength, impact strength and elongation at break, make to be made
Halogen-free flameproof biology base nylon have it is excellent it is fire-retardant, heat resistance, engineering properties is tough, chemical resistance, impact resistance and ruler
Very little stabilization is suitble to large-scale production.
Above-described embodiment is the preferable implementation of the present invention, and in addition to this, the present invention can be realized with other way, In
Do not depart under the premise of present inventive concept it is any obviously replace it is within the scope of the present invention.
Claims (10)
1. a kind of halogen-free flameproof biology base nylon, it is characterised in that: the raw material including such as parts by weight:
2. a kind of halogen-free flameproof biology base nylon according to claim 1, it is characterised in that: every part of halogen-free flame retardants
For at least two in ammonium polyphosphate, melamine salt, diethyl hypophosphites and modified Halogenless composite fire retardant.
3. a kind of halogen-free flameproof biology base nylon according to claim 2, it is characterised in that: every part of modified Halogen is multiple
Close the raw material that fire retardant includes following parts by weight:
4. a kind of halogen-free flameproof biology base nylon according to claim 3, it is characterised in that: the modified compound resistance of Halogen
Combustion agent is worth by the following method:
1) according to parts by weight, melamine pyrophosphate and diethyl hypo-aluminum orthophosphate is added in reaction unit and stirred evenly, then
Dehydrated alcohol is slowly added to, and is warming up to 40-60 DEG C of stirring 10-20min, obtains mixture A, it is spare；
2) polynary amine crosslinker and alkyl orthophosphate salt are added in mixture A, are warming up to 60-80 DEG C of vacuum dehydration reaction 2-
4h obtains mixture B, spare；
3) phenol is added in mixture B, is warming up to 70-90 DEG C, stirred with the rate of 200-400r/min, react 20-
40min, moves to the dry 4-6h of condition in drying device at 120-160 DEG C after reaction, and cooling, milling obtains the modification
Halogenless composite fire retardant.
5. a kind of halogen-free flameproof biology base nylon according to claim 1, it is characterised in that: every part of biology base nylon
For at least two in PA56, PA66, PA610, PA6 and PA1012.
6. a kind of halogen-free flameproof biology base nylon according to claim 1, it is characterised in that: every part of antioxidant be by
Phosphite antioxidant, antioxidant 1010 and irgasfos 168 are 0.8-1.2:0.4-0.8:0.6-1.0 composition according to weight ratio
Mixture.
7. a kind of halogen-free flameproof biology base nylon according to claim 1, it is characterised in that: every part of coupling agent be by
Gamma-aminopropyl-triethoxy-silane, γ-glycidyl ether oxygen propyl trimethoxy silicane and phthalate ester coupling agent are according to weight ratio
For the mixture of 0.6-1.0:0.4-0.8:0.8-1.2 composition.
8. a kind of halogen-free flameproof biology base nylon according to claim 1, it is characterised in that: every part of plasticized modifier
By glycidyl methacrylate and polyethylene toughener according to the mixing that weight ratio is that 0.4-0.8:0.6-1.0 is formed
Object.
9. a kind of halogen-free flameproof biology base nylon according to claim 1, it is characterised in that: every part of modified inorganic is filled out
Material is the mixing for passing through at least two compositions in the modified mica of phthalate ester coupling agent, glass microsphere and graphene oxide
Object.
10. a kind of preparation method of the halogen-free flameproof biology base nylon as described in claim 1-9 any one, it is characterised in that:
Include the following steps:
S1, according to parts by weight, drying device is added after halogen-free flame retardants, biology base nylon and expanded graphite are mixed evenly
In be heated to 50-80 DEG C and be dried in vacuo 2-4h, be cooled to room temperature to obtain mixture A, it is spare；
S2, plasticized modifier, carbon fiber and modified inorganic filler are added in mixture A obtained in step S1, and are transferred to
20-40min is stirred with 4000-8000r/min rate in high-speed stirring apparatus, obtains mixture B, it is spare；
S3, antioxidant and coupling agent are added in mixture B obtained in step S2, and are warming up to 40-60 DEG C and stir evenly, then
It is transferred in Double-screw extrusion device the extruding pelletization that heats up, is finally drying to obtain particle obtained under the conditions of 60-80 DEG C
To the halogen-free flameproof biology base nylon；One area's temperature of the Double-screw extrusion device is 250-260 DEG C when granulation, 2nd area
Temperature is 240-250 DEG C, and three area's temperature are 220-240 DEG C, and four area's temperature are 210-230 DEG C, screw speed 200-500r/
min。
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| CN112778754A (en) * | 2021-01-28 | 2021-05-11 | 浙江工业大学 | Preparation method of antistatic flame-retardant nylon 6 composite material |
| CN113045889A (en) * | 2021-04-12 | 2021-06-29 | 苏州润佳高分子材料有限公司 | Halogen-free flame-retardant nylon |
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