CN106750263B - A kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material - Google Patents
A kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material Download PDFInfo
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- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims abstract description 16
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011265 semifinished product Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 7
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 241001502050 Acis Species 0.000 claims abstract description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000006837 decompression Effects 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 150000002148 esters Chemical class 0.000 claims abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 229920000881 Modified starch Polymers 0.000 claims description 2
- 239000004368 Modified starch Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019426 modified starch Nutrition 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- -1 pentaerythritol esters compound Chemical class 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims 1
- 239000012948 isocyanate Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 239000003063 flame retardant Substances 0.000 abstract description 10
- 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 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 244000178289 Verbascum thapsus Species 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
Abstract
The invention belongs to the preparation technical fields of organic high molecular compound, disclose a kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material, successively the following steps are included: 1), by caprolactam being melted at 75-150 DEG C, modifying agent is added and hydrolyzes 3.5-5h, modifying agent is positive one of esters of silicon acis, silicate or orthosilicic acid；2) molar ratio of, addition melamine and cyanuric acid progress prepolymerization in situ, melamine and cyanuric acid is 1:1, and reaction temperature is 180-260 DEG C, reaction pressure 0.6-1.5Mpa, reaction time 1-5h；3) 200-280 DEG C, is raised the temperature to, vacuumizes and carries out decompression polycondensation, reaction time 1-5h；4) molecular weight regulator, is added, the reaction was continued 1-3h obtains semi-finished product；5), that semi-finished product are cooling, broken, washing and drying process, obtain finished product.The preparation method of halogen-free flameproof super-toughened nylon 6 composite material provided by the invention solves the bad technical problem of nylon 6 composite material poor compatibility, flame retardant effect that existing preparation method prepares.
Description
Technical field
The invention belongs to the preparation technical fields of organic high molecular compound, and in particular to a kind of halogen-free flameproof super-toughened nylon
The preparation method of 6 composite materials.
Background technique
Nylon 6 is polycaprolactam, and also referred to as PA6 is translucent or opaque creamy white crystals shape, has that density is low, draws
Stretch bending strength and notch impact strength be big, the advantages that thermal decomposition temperature and high fusing point, especially have good wearability, from
Lubricity and solvent resistance are widely used in fields such as machinery, traffic, national defence, and become very important work
One of engineering plastics.
Currently, the application range of PA6 increasingly increases with the appearance of a large amount of functionalization product, and it uses ring
Border is also increasingly harsher, is often applied in the environment such as inflammable, explosive, corrosion and high humidity, this just proposes the performance of PA6
Higher requirement, especially anti-flammability.In order to meet the needs of market, the anti-flammability of PA6 is improved, people are in the mistake for preparing PA6
Cheng Zhong joined some additional processing steps, and the preferable PA6 of relatively common in the prior art and effect will be the preparation method comprises the following steps: will
Caprolactam carries out ring opening hydrolysis, polymerization, adds fire retardant blending, and the two is uniformly mixed to get resistance is arrived using extruder
Combustion property nylon 6 material.
However, the PA6 prepared by the above method, compatibility is poor between fire retardant and matrix, and flame retardant effect is bad,
The PA6 is subjected to the experiment of UL-94 vertical combustion, obtaining its flame retardant rating at most also can only achieve V-1, all full in many fields
Foot not corresponding requirement.
Summary of the invention
The invention is intended to provide a kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material, existing preparation side is solved
The bad technical problem of nylon 6 composite material poor compatibility that method is prepared, flame retardant effect.
The preparation method of one of this programme halogen-free flameproof super-toughened nylon 6 composite material, successively the following steps are included:
1) caprolactam of 90-100 mass parts is melted at 75-150 DEG C, 0.4-0.8 mass is added at such a temperature
Part modifying agent hydrolyze 3.5-5h, modifying agent is positive one of esters of silicon acis, silicate or orthosilicic acid；
2) molar ratio of, addition melamine and cyanuric acid progress prepolymerization in situ, melamine and cyanuric acid is 1:1,
The sum of the two mass parts are 4-8 parts, and reaction temperature is 180-260 DEG C, reaction pressure 0.6-1.5Mpa, reaction time 1-
5h；
3) 200-280 DEG C, is raised the temperature to, vacuumizes and carries out decompression polycondensation, reaction time 1-5h；
4) molecular weight regulator of 0.1-0.3 mass parts, is added, the reaction was continued 1-3h obtains semi-finished product；
5), that semi-finished product are cooling, broken, washing and drying process, obtain finished product.
Preparation method in using the above scheme:
In step 1), modifying agent hydrolyzes at 75-150 DEG C generates silica.
In step 2), equimolar melamine and cyanuric acid pass through self-assembling reaction in the solution and generate a kind of supermolecule
Compound while MCA, MCA have planar extension structure, also has the layer structure along C crystallographic axis longitudinal growth.In fire ring
In border, when temperature is close to 350 DEG C, MCA distillation absorbs a large amount of heat, and degradation occurs and generates MA and CA, and CA can promote PA6
Main chain is degraded into oligomer and is detached from high-temperature area in the form of molten drop, and most of heat is taken away；With the further raising of temperature,
MA and CA degrade, and generate nitrogen, the inert gases such as ammonia, take away amount of heat and effectively reduce the oxygen in air and contain
Amount, so as to play fire-retardant effect.
In step 3), the by-product that can be reduced in polymerization reaction is vacuumized, increases the degree of polymerization of product.
In step 4), the molecular weight of the adjustable product of molecular weight regulator is added, keeps molecular weight distribution more uniform.
The silica generated in step 1) is under conditions of temperature is 180-260 DEG C, pressure is 0.6-1.5Mpa, molten
Melt and synthesizes MCA-SiO in caprolactam2Nucleocapsid structure is scattered in molten caprolactam, in-situ preparation reinforced phase, then is carried out
Polymerization forms polymer.MCA-SiO2In nucleocapsid structure, MCA is kernel, SiO2For shell, MCA coating modification, SiO are realized2
Shell can control MCA partial size, on the one hand fine MCA enables MCA spread more evenly across in the base, on the other hand forms
Good interfacial effect enhances the compatibility of MCA and matrix, improves the mechanical performance of PA6, high degree is reduced because of fire retardant
Addition and to PA6 mechanical performance generate influence.In addition, SiO2Shell plays the role of enhancing PA6 intensity, and MCA is as interior
Core and be present in SiO2Interior of shell can play and inhibit SiO2The effect of " the candle wick effect " that generates, that is, avoiding MCA is enhancing
In 6 system of nylon due to the problem of MCA flame retardant property declines caused by " candle wick effect ", the two is cleverly combined,
Not only the intensity of PA6 had been enhanced, but also has improved the flame retardant property of PA6.
Further, the vacuum degree vacuumized in the step 3) is 0.06~0.1Mpa.
Further, the temperature reacted in the step 1) is 100-120 DEG C, and the time of hydrolysis is 4h.This reaction condition effect
Fruit is more preferable, is convenient for SiO2Generation.
Further, reaction temperature is 200-220 DEG C in the step 2), reaction time 3h.The condition is more advantageous to
MCA-SiO2The formation of nucleocapsid structure.
Further, temperature is increased to 220-240 DEG C in the step 3), reaction time 3h.The condition is more conducive to polymerize
The progress of reaction.
Further, the molecular weight regulator in the step 4) includes isocyanuric acid three-glycidyl ester, glycerol, 2,4- first
Phenylene diisocyanate, hexamethylene diisocyanate, how one or more of diisocyanate.
Further, carbon forming agent is additionally added in the step 4).For PA6 in burning situation, carbon forming agent can form insulation carbon-coating,
To prevent heat transmitting.
Further, the carbon forming agent is pentaerythrite, in pentaerythritol esters compound, dipentaerythritol, modified starch
One or more.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail:
Each technological parameter of embodiment one to embodiment six is as shown in table 1:
Table 1
A kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material of the present invention is illustrated by taking embodiment one as an example,
Successively the following steps are included:
1) caprolactam of 2500g is melted at 100 DEG C, then 12.5g teos hydrolysis is added at such a temperature
4h generates silica；
2) 200 DEG C, are raised the temperature to, controlling the pressure in reaction kettle is 1Mpa, is added into the fusant in step 1)
Enter 81.6g melamine and 87.6g cyanuric acid, stirs, in-situ preparation MCA-SiO2Nucleocapsid structure, and prepolymerization is carried out, it reacts
3h；
3) 220 DEG C, are raised the temperature to, being evacuated to its internal vacuum degree to reaction kettle is 0.08MPa, is carried out in oneself
The depressurization condensation reaction of amide, reaction time 3h；
4) isocyanuric acid three-glycidyl ester of 3g, is added, the reaction was continued 2h obtains semi-finished product；
5), semi-finished product are successively carried out to natural cooling, broken, washing and be dried, it is multiple to obtain halogen-free flameproof super-toughened nylon 6
Condensation material finished product.
Embodiment two to embodiment five each technological parameter that the difference is that only in table 1.
Experiment:
Comparative example one is to comparative example three:
Modifying agent of the embodiment one into embodiment three is replaced with into hexamethylene diamine and adipic acid, remaining is remained unchanged,
Replaced embodiment one to embodiment three is respectively comparative example one to comparative example three.
Comparative example four:
Caprolactam is subjected to ring opening hydrolysis, after polymerization, melamine polyphosphate is added and is uniformly mixed, using being extruded into
The method of type combines the two, obtains anti-flammability nylon 6 material.
Comparative example five:
Nylon 6 material is obtained after caprolactam is carried out ring opening hydrolysis, polymerization.
Comparative example six replaces the technological parameter of step 2) in embodiment one to comparative example nine respectively are as follows:
Comparative example six: 175 DEG C of reaction temperature, reaction pressure 1MPa；
Comparative example seven: 265 DEG C of reaction temperature, reaction pressure 1MPa；
Comparative example eight: 200 DEG C of reaction temperature, reaction pressure 0.58MPa；
Comparative example nine: 265 DEG C of reaction temperature, reaction pressure 1.52MPa；
Remaining is the same as example 1.
Embodiment one to embodiment five, comparative example one to comparative example nine are under equal conditions tested for the property, as a result
It is as shown in table 2:
Table 2
It can be obtained by table 2, nylon 6 composite material intensity prepared by the present invention is high, good flame retardation effect.
For those skilled in the art, without departing from the inventive concept of the premise, several changes can also be made
Shape and improvement, these also should be considered as protection scope of the present invention, these all will not influence the effect and patent that the present invention is implemented
Practicability.
Claims (7)
1. a kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material, which is characterized in that successively the following steps are included:
1) caprolactam of 90-100 mass parts is melted at 75-150 DEG C, 0.4-0.8 mass parts are added at such a temperature
Modifying agent hydrolyzes 3.5-5h, and modifying agent is positive one of esters of silicon acis, silicate or orthosilicic acid；
2) molar ratio of, addition melamine and cyanuric acid progress prepolymerization in situ, melamine and cyanuric acid is 1:1, the two
The sum of mass parts are 4-8 parts, and reaction temperature is 180-260 DEG C, reaction pressure 0.6-1.5MPa, reaction time 1-5h；
3) 200-280 DEG C, is raised the temperature to, vacuumizes and carries out decompression polycondensation, reaction time 1-5h；
4) molecular weight regulator of 0.1-0.3 mass parts, is added, the reaction was continued 1-3h obtains semi-finished product；
5), that semi-finished product are cooling, broken, washing and drying process, obtain finished product；Molecular weight regulator in the step 4) includes
Isocyanuric acid three-glycidyl ester, glycerol, 2,4- toluene di-isocyanate(TDI), hexamethylene diisocyanate, naphthalene diisocyanate
One or more of.
2. a kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material according to claim 1, which is characterized in that
The vacuum degree vacuumized in the step 3) is 0.06~0.1MPa.
3. a kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material according to claim 1 or 2, feature exist
In the temperature reacted in the step 1) is 100-120 DEG C, and the time of hydrolysis is 4h.
4. a kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material according to claim 1 or 2, feature exist
In reaction temperature is 200-220 DEG C in the step 2), reaction time 3h.
5. a kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material according to claim 4, which is characterized in that
Temperature is increased to 220-240 DEG C in the step 3), reaction time 3h.
6. a kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material, feature described according to claim 1 or 2 or 5
It is, is additionally added carbon forming agent in the step 4).
7. a kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material according to claim 6, which is characterized in that
The carbon forming agent is one or more of pentaerythrite, pentaerythritol esters compound, dipentaerythritol, modified starch.
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| CN201611031407.6A CN106750263B (en) | 2016-11-22 | 2016-11-22 | A kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material |
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| CN201611031407.6A CN106750263B (en) | 2016-11-22 | 2016-11-22 | A kind of preparation method of halogen-free flameproof super-toughened nylon 6 composite material |
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