CN108165002A - MCA fire-retardant Nylon 66 composite materials and preparation method thereof - Google Patents
MCA fire-retardant Nylon 66 composite materials and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 103
- 229920002302 Nylon 6,6 Polymers 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims 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 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 15
- 239000004677 Nylon Substances 0.000 claims abstract description 14
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 229920001778 nylon Polymers 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 13
- -1 carboxylic acid compound Chemical class 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002885 octadecanoids Chemical class 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 235000021355 Stearic acid Nutrition 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims 1
- 239000008117 stearic acid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000001125 extrusion Methods 0.000 abstract 1
- 239000012757 flame retardant agent Substances 0.000 abstract 1
- 238000005469 granulation Methods 0.000 abstract 1
- 230000003179 granulation Effects 0.000 abstract 1
- 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 39
- 238000012360 testing method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 10
- 229920000742 Cotton Polymers 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- BDJRBEYXGGNYIS-UHFFFAOYSA-N azelaic acid group Chemical group C(CCCCCCCC(=O)O)(=O)O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920006395 saturated elastomer Polymers 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
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 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
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical class [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of MCA fire-retardant Nylon 66s composite material and preparation method thereof, using nylon66 fiber as resin matrix, using the common MCA fire retardants in market, with reference to C8‑C18Long carbon chain unitary unsaturated carboxylic acid compound and C8‑C18At least one of Long carbon chain binary unsaturated carboxylic acid compound makes composite material reach stable V0 flame retardant ratings for fire-retardant stabilizer system, it is by 68 94 parts by weight of PA66 resins, 6 30 parts by weight of MCA fire retardants, 0.2 0.4 parts by weight of antioxidant, 0.2 0.6 parts by weight of lubricant and 0.2 1.0 parts by weight of fire-retardant stabilizer are by carrying out melting extrusion, granulation is prepared, it uses common MCA fire retardants that can obtain the flame-retardant PA 66 materials of V0 grades, and MCA flame retardant agent contents can be down to 6wt%, material preparation process is simple, it is at low cost, available for electronic apparatus, field of connectors, especially wire connection terminal field.
Description
Technical field
The invention belongs to polyhexamethylene adipamide (PA66) technical field of modification, more particularly to a kind of MCA fire-retardant Nylon 66s
Composite material and preparation method thereof, available for electronic apparatus, field of connectors, especially wire connection terminal field.
Background technology
Polyamide is excellent with excellent mechanical performance, barrier property, heat resistance, wearability, resistant to chemical etching etc.
Comprehensive performance, be widely used in the fields such as machinery manufacturing industry, electric tool, electronic apparatus and communications and transportation.But due to PA66
Resin can only achieve V-2 flame retardant ratings, and molten drop object easily causes secondary burning of igniting in combustion process, causes the fire of bigger,
Significantly limited so as to cause its application field, especially in industry/automotive electronics appliance field, these products are direct or indirect
Power utilization environment is contacted, electric leakage, short circuit, electric arc etc. easily cause fire in circuit.Therefore, in practical applications, many PA66
Product be required to carry out it is flame-retardant modified, to reach as defined in UL the requirement of V-0 fire-protection ratings.Nitrogenated flame retardant MCA has green ring
Protect, smoke density is low, excellent electrical properties, density are light, easy coloring, it is cost-effective the advantages that, be widely used in the fire-retardant of nylon66 fiber and change
In property, modified product is widely used in connector, low-voltage electrical apparatus, contactor, ordinary appliances housing etc..
MCA nitrogen contents are high, and flame retarding efficiency is high, and additive amount only needs 6wt.% fire-retardant etc. with regard to PA66 systems can be made to reach V-0
Grade.But tradition MCA flame-retardant PA 66 materials, in combustion test, molten drop heat content is high, otherwise it is melted during drippage with band flame
Drop directly ignite absorbent cotton or without flame form molten drop with high thermal ignition absorbent cotton, material flame retardant test result is caused to reach
Less than the V0 ranks in UL standards or stable V0 flame retardant ratings are not achieved, fluctuation is especially big.Foreign patent
JP2016155924 (A), can be with system along with the surfactant of polyalcohol esters by by the MCA interworkings of different-grain diameter
Reach stable V0 flame retardant ratings, but different-grain diameter MCA needs to obtain by special synthesis technology, usability is by a fixed limit
System.103408750 A of Chinese patent CN add in melamine cyanurate (MCA) as resistance in monomer of polyamide polymerization process
Fire agent, Nano-meter SiO_22It is synergistic flame retardant with metal oxide, in-situ polymerization prepares Flameproof polyamide, although the method can be made
Standby fire-retardant stabilization and excellent in mechanical performance composite material, but be not suitable for large-scale industrial production.Chinese patent
CN101679743A is matrix in polyamide, and melamine cyanurate is fire retardant, by adding in surfactant, i.e., comprising extremely
More than one few polyalkylene polyol aliphatic esters can obtain the MCA flame-retardant polyamide composite materials of V0 flame retardant ratings, but this
MCA additive amounts are very high in method, can seriously affect the mechanical property for material of resuming a session, especially toughness of material.
Invention content
In order to solve the above technical problems, the present invention provides a kind of MCA fire-retardant Nylon 66s composite material and preparation method thereof,
The composite material can reach stable V0 flame retardant ratings, and either fire retardant source or the preparation side of the composite material
Method, it is relatively simple, it is very suitable for industrialized production.
The technical scheme is that：
The invention discloses a kind of MCA fire-retardant Nylon 66s composite material, the composite material is by following by weight each
Component is prepared：68-94 parts of PA66 resins, 6-30 parts of MCA fire retardants, 0.2-0.4 parts of antioxidant, 0.2-0.6 parts of lubricant
With fire-retardant stabilizer 0.2-1.0 parts.
Wherein, the fire-retardant stabilizer is C8-C18Long carbon chain unitary unsaturated carboxylic acid compound and C8-C18Long carbon chain binary is satisfied
At least one of with carboxylic acid compound, and the fire-retardant stabilizer is preferably azelaic acid, decanedioic acid, dodecanedicarboxylic acid, ten
At least one of three carbon dicarboxylic acids, 15 carbon dicarboxylic acids and octadecanoid acid.
Wherein, the PA66 resin terminal groups content meets formula：1.5<X<2.5, wherein end carboxyl contains in X=PA66 resins
Amount/terminal amino group content, and the viscosity of the PA66 resins is 130-220ml/g, the assay method of the viscosity is according to ISO
307-2007 standard tests.
Wherein, the MCA fire retardants are melamine cyanurate, the content of remaining melamine in the MCA fire retardants
Less than 0.04wt.%, the content of remaining cyanuric acid is 0.01-0.2wt.%, and the average grain diameter D50 of the MCA fire retardants is 2.0-
8.0 μm, average grain diameter is to test gained using Malvern particle size analyzer, and the pH value of the MCA fire retardants is 5.0-6.0,
PH value assay method is using titration measuring.
Wherein, the antioxidant is at least one in Hinered phenols antioxidant, amine antioxidants and phosphoric acid ester antioxidant
Kind.
Wherein, the lubricant is stearic amide series lubricant agent, Solsperse 2000 ester lubricant and stearates moisten
At least one of lubrication prescription.
The invention also discloses a kind of preparation method of above-mentioned MCA fire-retardant Nylon 66s composite material, which includes
Following step：
(1) weigh 65-93 parts by weight PA66 resins, 6-30 parts by weight MCA fire retardants, 0.2-0.4 parts by weight antioxidant,
0.2-0.6 parts by weight lubricant, the fire-retardant stabilizer of 0.2-1.0 parts by weight, and above-mentioned each component is put into mixing machine and is total to
It mixes until uniformly, obtaining pre-composition；
(2) melting mixing, and extruding pelletization will be carried out in gained pre-composition input double screw extruder in step (1), obtained
To MCA flame-retardant PA 66 composite materials；The screw slenderness ratio of wherein described double screw extruder is (40-48):1, barrel temperature is
260-270 DEG C, screw speed 300-450rpm.
The method have the benefit that：MCA fire-retardant Nylon 66s composite material of the present invention is using nylon66 fiber as resin
Matrix, using the common MCA fire retardants in market, with reference to C8-C18Long carbon chain unitary unsaturated carboxylic acid compound and C8-C18Long carbon chain two
At least one of first unsaturated carboxylic acid compound can obtain the flame-retardant PA 66 product of stable V0 grades for fire-retardant stabilizer, be not required to
Special controlling is carried out to the form of MCA fire retardants or special cladding etc. reason is carried out to it, by the MCA for adding low ratio
Fire retardant is the composite material that can obtain flame retardant property and good mechanical properties, can not only reduce fire retardant in itself to material
Negative effect, as toughness of material reduce, fire retardant be used for a long time process be precipitated the problems such as, and preparation method simple possible, into
This is low.
Specific embodiment
In order to better understand the technological means of the present invention, and can be implemented in accordance with the contents of the specification, below
In conjunction with specific embodiments and comparative example, the specific embodiment of the present invention is described in further detail, following embodiment
For illustrating the present invention, but the scope of the present invention is not limited to, be especially not limited to used in following specific embodiments
Each component raw material model.
Used each component raw material are as follows：
PA66 resins：PA66EP-158, Zhejiang Hua Feng groups；
MCA fire retardants：MCA fire retardant -1, Shouguang WeiDong Chemical Co., Ltd.；
MCA fire retardant -2, Sichuan fine chemistry industry；
Antioxidant：N, N'- be bis--(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine
(IRGANOX1098), BASF；
Lubricant：Ethylene bis stearic acid amide, lubricant-EBS HI-LUBE, South Korea's cell；
Fire-retardant stabilizer：Azelaic acid (No. CAS:123-99-9), it is commercially available；
Decanedioic acid (No. CAS:111-20-6), it is commercially available；
Dodecanedicarboxylic acid (No. CAS:693-23-2), it is commercially available；
Octadecanoid acid (No. CAS:57-11-4), it is commercially available.
According in specific embodiment 1-9 described in table 1 and table 2 comparative example A-D be formulated dosage weigh respectively PA66 resins,
MCA fire retardants, antioxidant, lubricant and fire-retardant stabilizer, and above-mentioned each component is put into mixing machine and carries out mixing until
It is even, obtain pre-composition；Then gained pre-composition is put into double screw extruder and carries out melting mixing, and extruding pelletization, obtained
Flame-retardant PA 66 composite material；Wherein the screw slenderness ratio of double screw extruder is (40-48):1, barrel temperature is 260-270 DEG C,
Screw speed is 300-450rpm.
1 specific embodiment 1-9 each component dosage (units of table：kg)
2 comparative example A's-D each component dosage (units of table：kg)
The MCA fire-retardant Nylon 66 composite materials that gained is prepared in above-mentioned specific embodiment 1-9 and comparative example A-D are hindered
Performance test is fired, testing standard is strictly provided with reference to UL94, specific as follows：
According to " the flammable of plastic material is tested, and the regulation of UL94 " carries out flammable test.Based on burn rate, extinguish
Whether time, the ability for resisting drippage and dropping ignite absorbent cotton, to obtain flame retardant rating.For the sample of test：Ruler
It is very little for 125mm length × 13mm width × be not more than 13mm thickness batten, the present invention be selected as in the thickness of sample tested
0.8mm.According to the UL94 regulations, and based on the test result obtained for five samples, material flame retardant rating can be classified
For (UL94-HB)：V0, V1, V2,5VA and/or 5VB；But in the present invention, only the flame retardant rating of material is classified as：V0、V1
And V2, and the criteria for classification of each flame retardant rating such as table 3：
3 UL94 flame retardant rating criteria for classifications of table
| Judge condition | V-0 grades | V-1 grades | V-2 grades |
| The residual flame time (t1 and t2) of each individually sample | ≤10s | ≤30s | ≤30s |
| All total residual flame times tf (t1+t2) of test sample | ≤50s | ≤250s | ≤250s |
| The residual flame of each individually sample adds the remaining bright time (t2+t3) | ≤30s | ≤60s | ≤60s |
| Whether burn and support | Nothing | Nothing | Nothing |
| Whether burning particles or dropping light shop fixtures absorbent cotton | Nothing | Nothing | Have |
The fire-retardant performance of MCA fire-retardant Nylon 66 composite materials that above-mentioned specific embodiment 1-9 and comparative example A-D prepares gained is surveyed
The result of examination is referring to shown in table 4-16.
4 embodiment of table, 1 flame retardant test result
5 embodiment of table, 2 flame retardant test result
6 embodiment of table, 3 flame retardant test result
7 embodiment of table, 4 flame retardant test result
8 embodiment of table, 5 flame retardant test result
9 embodiment of table, 6 flame retardant test result
10 embodiment of table, 7 flame retardant test result
11 embodiment of table, 8 flame retardant test result
12 embodiment of table, 9 flame retardant test result
13 comparative example of table, 1 flame retardant test result
14 comparative example of table, 2 flame retardant test result
15 comparative example of table, 3 flame retardant test result
16 comparative example of table, 4 flame retardant test result
It is compared by embodiment 1-9 it can be found that adding the binary saturated carboxylic acid of certain carbon atom number or unitary saturation carboxylic
Acid can make MCA flame-retardant PA 66 systems reach stable V-0 flame retardant ratings, and no matter MCA changes of contents is in 6wt.%-30wt.%,
Or difference MCA types are satisfied by this phenomenon.The system of end plus fire-retardant stabilizer it can be seen from comparative example A-D, system are equal
It will appear drippage Ignition phenomenon, V0 grades as defined in UL be not achieved so as to cause the flame retardant rating of material.The above results are by this
What the mechanism of invention determined：MCA fire retardants belong to for fire-retardant nylon and reach fire-retardant mesh with condensed phase, gas phase collective effect
, i.e., MCA fire retardants decompose after 350 DEG C or so distillations absorb heat and generate melamine and cyanuric acid.Then melamine
It decomposes and generates ammonia, N2, the inert gases such as NO, dilution oxygen concentration.The PA66 degradations of cyanuric acid catalysis simultaneously, PA66 is decomposed into
Oligomer, then speeded away combustion zone in the form of generating molten drop, and then shifts amount of heat to outside.The present invention passes through
The addition regulation binary saturated carboxylic acid of carbon atom number or unitary saturated carboxylic acid accelerate decomposition speed of the nylon under high temperature fused state
Rate promotes the generation of molten drop, and decomposite the cyanuric acid come with MCA accelerates PA66 to degrade jointly, quickly forms tiny molten drop, takes away
Heat leaves combustion zone, while in descent with air heat exchange occurs rapidly for tiny molten drop, is melted when reaching absorbent cotton
Drop heat content substantially reduces, and the absorbent cotton that ignites is not enough to, so as to achieve the effect that stable V0 is fire-retardant.
The above is only the preferred embodiment of the present invention, is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of MCA fire-retardant Nylon 66s composite material, which is characterized in that be prepared by following each components by weight：
68-94 parts of PA66 resins, 6-30 parts of MCA fire retardants, 0.2-0.4 parts of antioxidant, 0.2-0.6 parts of lubricant and fire-retardant stabilizer
0.2-1.0 parts；Wherein, the fire-retardant stabilizer is C8-C18Long carbon chain unitary unsaturated carboxylic acid compound and C8-C18Long carbon chain binary
At least one of unsaturated carboxylic acid compound.
2. MCA fire-retardant Nylon 66s composite material according to claim 1, it is characterised in that：The fire-retardant stabilizer is nonyl
At least one of diacid, decanedioic acid, dodecanedicarboxylic acid, tridecanyldicarboxylic acid, 15 carbon dicarboxylic acids and octadecanoid acid.
3. MCA fire-retardant Nylon 66s composite material according to claim 1, it is characterised in that：The PA66 resin terminal groups contain
Amount meets formula：1.5<X<2.5, wherein content of carboxyl end group/terminal amino group content in X=PA66 resins, and the PA66 resins
Viscosity is 130-220ml/g.
4. MCA fire-retardant Nylon 66s composite material according to claim 1, it is characterised in that：It is remaining in the MCA fire retardants
The content of melamine is less than 0.04wt.%, and the content of remaining cyanuric acid is 0.01-0.2wt.%, which is averaged
Grain size D50 is 2.0-8.0 μm, and the pH value of the MCA fire retardants is 5.0-6.0.
5. MCA fire-retardant Nylon 66s composite material according to claim 1, it is characterised in that：The antioxidant is hindered phenol
At least one of kind antioxidant, amine antioxidants and phosphoric acid ester antioxidant.
6. MCA fire-retardant Nylon 66s composite material according to claim 1, it is characterised in that：The lubricant is stearic acid
At least one of amide series lubricant agent, Solsperse 2000 ester lubricant and stearate series lubricant agent.
7. a kind of preparation method of MCA fire-retardant Nylon 66 composite materials described in claim 1-6, it is characterised in that：Including under
State step：
(1) 65-93 parts by weight PA66 resins, 6-30 parts by weight MCA fire retardants, 0.2-0.4 parts by weight antioxidant, 0.2- are weighed
0.6 parts by weight lubricant, the fire-retardant stabilizer of 0.2-1.0 parts by weight, and above-mentioned each component is put into mixing machine and be blended directly
To uniform, pre-composition is obtained；
(2) melting mixing, and extruding pelletization will be carried out in gained pre-composition input double screw extruder in step (1), obtains MCA
Flame-retardant PA 66 composite material；The screw slenderness ratio of wherein described double screw extruder is (40-48):1, barrel temperature is 260-
270 DEG C, screw speed 300-450rpm.
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| CN201711422446.3A CN108165002A (en) | 2017-12-25 | 2017-12-25 | MCA fire-retardant Nylon 66 composite materials and preparation method thereof |
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| CN201711422446.3A CN108165002A (en) | 2017-12-25 | 2017-12-25 | MCA fire-retardant Nylon 66 composite materials and preparation method thereof |
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| CN109467925A (en) * | 2018-11-29 | 2019-03-15 | 上海金发科技发展有限公司 | A kind of halogen-free flame-retardant nylon composite materials that wet and heat ageing resistant is precipitated |
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| CN113524623A (en) * | 2021-06-01 | 2021-10-22 | 金旸（厦门）新材料科技有限公司 | Method for improving impact performance of MCA flame-retardant PA66 |
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| CN109517380A (en) * | 2018-11-29 | 2019-03-26 | 上海金发科技发展有限公司 | A kind of halogen-free flame-retardant reinforced nylon composite material that wet and heat ageing resistant is precipitated |
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| CN114381116B (en) * | 2022-02-17 | 2024-03-19 | 上海金发科技发展有限公司 | Halogen-free flame-retardant polyamide composite material and preparation method and application thereof |
| CN114381116A (en) * | 2022-02-17 | 2022-04-22 | 上海金发科技发展有限公司 | Halogen-free flame-retardant polyamide composite material and preparation method and application thereof |
| CN117777715A (en) * | 2023-12-26 | 2024-03-29 | 天津金发新材料有限公司 | Heat-resistant polyamide composite material and preparation method and application thereof |
| CN118126521A (en) * | 2024-03-29 | 2024-06-04 | 金发科技股份有限公司 | Flame-retardant polyamide composite material and preparation method and application thereof |
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Application publication date: 20180615 |