CN114213838A - Flame-retardant nylon composite material with low pungent smell and preparation method and application thereof - Google Patents
Flame-retardant nylon composite material with low pungent smell and preparation method and application thereof Download PDFInfo
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- CN114213838A CN114213838A CN202111471030.7A CN202111471030A CN114213838A CN 114213838 A CN114213838 A CN 114213838A CN 202111471030 A CN202111471030 A CN 202111471030A CN 114213838 A CN114213838 A CN 114213838A
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- flame retardant
- flame
- composite material
- nylon composite
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 105
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000004677 Nylon Substances 0.000 title claims abstract description 34
- 229920001778 nylon Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 230000002195 synergetic effect Effects 0.000 claims abstract description 33
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 12
- 239000002516 radical scavenger Substances 0.000 claims abstract description 12
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003365 glass fiber Substances 0.000 claims description 15
- 229920006122 polyamide resin Polymers 0.000 claims description 13
- 239000004793 Polystyrene Substances 0.000 claims description 11
- 229920002223 polystyrene Polymers 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- -1 alcohol stearates Chemical class 0.000 claims description 7
- 229940123457 Free radical scavenger Drugs 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 abstract description 32
- 239000007789 gas Substances 0.000 abstract description 20
- 229910000042 hydrogen bromide Inorganic materials 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 5
- 229920002292 Nylon 6 Polymers 0.000 description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 230000002452 interceptive effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920006052 Chinlon® Polymers 0.000 description 2
- 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 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LXWPJAGZRHTAOO-UHFFFAOYSA-N [Sb].[Br] Chemical compound [Sb].[Br] LXWPJAGZRHTAOO-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- MBAUOPQYSQVYJV-UHFFFAOYSA-N octyl 3-[4-hydroxy-3,5-di(propan-2-yl)phenyl]propanoate Chemical compound OC1=C(C=C(C=C1C(C)C)CCC(=O)OCCCCCCCC)C(C)C MBAUOPQYSQVYJV-UHFFFAOYSA-N 0.000 description 1
- 238000013027 odor testing Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- 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
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 provides a flame-retardant nylon composite material with low pungent smell, a preparation method and application thereof, wherein a brominated flame retardant is adopted, and borate synergistic flame retardant and organic silicone synergistic flame retardant are used in a matched manner, so that generation of hydrogen bromide pungent smell gas is reduced on the premise of ensuring the flame-retardant requirement of V-0; on the other hand, the radical scavenger is adopted to delay the thermal decomposition of the material and further control the generation of volatile gas, so that the flame-retardant nylon composite material with low pungent smell is obtained, and the flame-retardant nylon composite material can be widely applied to the fields of automotive interior, water pump/water valve parts, household appliance shells and the like.
Description
Technical Field
The invention relates to the technical field of environment-friendly brominated flame-retardant nylon, and particularly relates to a flame-retardant nylon composite material with low pungent smell, and a preparation method and application thereof.
Background
The polyamide resin has excellent comprehensive properties such as mechanical property, barrier property, heat resistance, wear resistance, chemical corrosion resistance and the like, and is widely applied to the fields of machinery manufacturing industry, household appliances, electric tools, electronic appliances, transportation and the like. Polyamide 6 has certain flame retardant property, pure resin can achieve V-2 flame retardance, but a dripping ignition phenomenon exists, and after the glass fiber is added for reinforcement, due to the candle core effect of the glass fiber, the composite material can only achieve the HB flame retardant grade, so that the application field of the composite material is greatly limited. In the fields of electronics, electrical appliances, household appliances and the like, most plastic parts are in direct or indirect contact with current, so that clear flame retardant requirements, such as the V-0 flame retardant requirement of UL94, are put forward for materials.
The nylon flame-retardant modification has various schemes, common flame retardants include an environment-friendly brominated flame retardant, a halogen-free organic phosphorus flame retardant, a halogen-free red phosphorus flame retardant, an inorganic hydroxide flame retardant, a halogen-free nitrogen flame retardant and the like, and each flame retardant system has respective advantages and disadvantages and has respective suitable application fields and scenes. From the comprehensive product performance and the market application scale, the environment-friendly brominated flame-retardant system is still the most mainstream flame-retardant modification method at present. However, various flame retardants have certain odor, especially at high temperature, the odor is more obvious and even pungent, and cannot meet the environmental requirements of the material in the injection molding process, or the formed product affects the comfort in specific environments.
Among various flame retardant systems, brominated flame retardants have relatively large odor and can retard flame because the flame retardants are decomposed at high temperature to generate hydrogen bromide gas, which is a flame quencher that can capture hydrogen radicals and hydroxyl radicals generated by thermal decomposition in the matrix resin, delay chain decomposition of the matrix resin, and protect the resin. It is the generation of hydrogen bromide that causes such materials to produce a more pungent odor when burned. In a brominated flame retardant system, a brominated antimony flame retardant system (namely, a brominated flame retardant and an antimony trioxide synergistic flame retardant) has higher flame retardant efficiency, but has larger pungent smell, because the antimony trioxide synergistic flame retardant can promote more hydrogen bromide gas to be generated, at the moment, the hydrogen bromide gas is often excessive.
The current research on low odor is mainly focused on automotive interior materials, and mainly non-flame retardant polypropylene materials, and engineers and scholars have found various truly effective solutions to control the odor of materials in this field. However, in the field of flame retardant nylon, relatively few solutions have been developed for low odor, which not only manifests itself in the odor during injection molding processing, but also includes the odor generated during the placement or use of the injection molded article. Chinese patent discloses that the pungent odor of the composite material is reduced by introducing nano metal oxide having adsorption function, while a odorless ester flow modifier is preferred to obtain a composite material with low pungent odor. Chinese patent discloses that the pungent smell caused by phosphine in red phosphorus flame-retardant reinforced material is reduced by using microcapsule red phosphorus master batch and modified activated zeolite powder. Chinese patent discloses that the release of phosphine is inhibited by the addition of iron oxide, thereby reducing the pungent odor of the composite material. The prior art mainly adsorbs the generated volatile pungent smell through the adsorptive nanoparticles, and only can achieve short-term effects, and when external conditions change, such as high temperature and other conditions, the smell can still be slowly diffused, and a solution is not searched from the source. Based on the phenomenon, some injection products need to be continuously baked at high temperature, and the odor can meet the odor requirement of a terminal customer after being slowly baked, but the consumption is large.
Disclosure of Invention
The brominated polystyrene flame retardant is combined with the borate and organic silicone synergistic flame retardant to replace the existing bromine-antimony flame retardant system, so that the flame retardant requirement of V-0 can be ensured, and the generation of pungent odor gas can be reduced; on the other hand, the radical scavenger is adopted to delay the thermal decomposition of the material and further control the generation of volatile gas, thereby obtaining the flame-retardant nylon composite material with low pungent smell.
Still another object of the present invention is to provide a method for preparing a flame retardant nylon composite material with low pungent odor.
Another object of the present invention is to provide a use of a flame retardant nylon composite material with low pungent odor.
The above purpose of the invention is realized by the following technical scheme:
the flame-retardant nylon composite material with low pungent smell comprises the following components in parts by weight:
the relative viscosity of the polyamide resin is 2.0-2.8 measured at 25 ℃ in 96% concentrated sulfuric acid.
According to the invention, polyamide resin is used as a matrix, brominated polystyrene flame retardant is adopted, two synergistic flame retardants of borate synergistic flame retardant and organic silicone synergistic flame retardant are matched, and a free radical trapping agent is adopted, so that antimony synergistic flame retardant in a traditional bromine-antimony flame retardant system is avoided, and generation of pungent odor gas is reduced on the premise of ensuring the flame retardant requirement of V-0; on the other hand, the radical scavenger is adopted to delay the thermal decomposition of the material and further control the generation of volatile gas, thereby obtaining the flame-retardant nylon composite material with low pungent smell. According to the invention, by analyzing the principle of pungent odor generation in the brominated flame-retardant nylon composite material and optimizing the design in the gas generation link, the generation of pungent odor is inhibited or reduced from the source while a better flame-retardant effect is maintained, and the solution is more effective and more durable.
The relative viscosity of the polyamide resin also has a certain influence on the smell of the composite material, and when the relative viscosity is too low, the molecular weight is low, the oligomer content is high, the volatile micromolecules are high, and the smell is negatively influenced. When the relative viscosity is too high, the molecular weight of the resin is high, the melt viscosity is high during the molding process, the generated shear heat is large, and the odor is also adversely affected.
Preferably, the composition comprises the following components in parts by weight:
preferably, the mass ratio of the borate synergistic flame retardant to the organic silicone synergistic flame retardant is 2: 1-3: 1.
Preferably, the relative viscosity of the polyamide resin is 2.2-2.4.
The relative viscosity of the polyamide resin is measured according to standard ISO 307-2007 at 25 ℃ in the presence of 96% concentrated sulfuric acid.
Preferably, the polyamide resin is one or more of polyamide 6, polyamide 66, polyamide 610, polyamide 6T and polyamide 10T.
More preferably, the polyamide resin is polyamide 6.
Preferably, the weight average molecular weight Mw of the brominated polystyrene flame retardant is 5500-215000.
Preferably, the borate synergistic flame retardant is anhydrous zinc borate and/or hydrous zinc borate.
The organosilicone synergistic flame retardant is a silicone, preferably the silicone is a linear polydimethylsiloxane.
Preferably, the radical scavenger is a sterically hindered phenol and/or a derivative of a sterically hindered phenol.
Preferably, the free radical scavenger is one or more of Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1098, Irganox 1330, and Irganox 1135.
Preferably, the chopped glass fiber has the length of 1.5-6.0 mm and the diameter of 7-16 mu m.
Preferably, the chopped glass fiber has a length of 3-4.5 mm and a diameter of 8-12 μm.
Preferably, the chopped glass fiber strands are strands of A-, E-, C-, D-, S-and R-glass fibers, the fibers having a circular, oval or square cross-section.
Preferably, the lubricant is one or more of stearamides, alcohol stearates, stearates and long-chain saturated linear carboxylates.
The preparation method of the flame-retardant nylon composite material with low pungent smell comprises the following steps:
weighing polyamide resin, brominated polystyrene flame retardant, borate synergistic flame retardant, organic silicone synergistic flame retardant, free radical scavenger and lubricant according to a ratio, uniformly mixing to obtain a mixture, adding the mixture and the chopped glass fiber respectively, and carrying out melt blending.
More specifically, the raw materials (except the chopped glass fiber) are weighed according to the proportion, mixed in a high-speed mixer and then weighed. The chopped glass fibers are added separately by another metering scale from the 5 th barrel of the twin-screw extruder, and the temperature settings of the twin-screw extruder from one zone to ten zones are respectively as follows: 80 ℃, 180 ℃, 260 ℃, 250 ℃, 240 ℃ and 260 ℃.
The invention also protects the application of the flame-retardant nylon composite material with low pungent smell in preparing automobile interior trims, water pump/water valve parts or household appliance shells.
The invention also protects a nylon product which is prepared from the flame-retardant nylon composite material with low pungent smell.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the polyamide resin is used as a matrix, and the combination of two synergistic flame retardants of borate synergistic flame retardant and organic silicone synergistic flame retardant is matched, so that the generation of pungent odor gases such as hydrogen bromide and the like is reduced on the premise of ensuring the flame retardant requirement of V-0; and the radical trapping agent is also matched to delay the thermal decomposition of the material, so that the generation of volatile gas is further controlled, and the flame-retardant nylon composite material with low pungent smell is obtained, and can be widely applied to the fields of automotive interior, water pump/water valve parts, household appliance shells and the like.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The starting materials used in the following examples and comparative examples:
polyamide 6 resin a: the relative viscosity, measured at 25 ℃ in 96% concentrated sulfuric acid, was 2.38 according to ISO Standard 307-2007, PA 6M 2400, weight average molecular weight 14550, Kyoto Xinhui Mada Chinlon Co., Ltd.
Polyamide 6 resin B: according to ISO 307-2007 standard, the relative viscosity measured at 25 ℃ and 96% concentrated sulfuric acid is 2.0, PA 6M 2000, weight average molecular weight 10875, Midama Chinlon Co., Ltd.
Polyamide 6 resin C: according to ISO 307-2007 standard, the relative viscosity measured at 25 ℃ and 96% concentrated sulfuric acid is 2.8, PA6 HY2800A, weight average molecular weight 16975, Jiangsu Haiyang chemical fiber Limited.
Polyamide 66 resin D: the relative viscosity, measured at 25 ℃ in 96% concentrated sulfuric acid, was 2.38 according to ISO Standard 307-2007, the weight-average molecular weight was 13350, PA66 EPR24, Neuma group.
Polyamide 6 resin E: the relative viscosity, measured at 25 ℃ in 96% concentrated sulfuric acid, was 4.2 according to ISO Standard 307-2007, the weight-average molecular weight was 32000, PA 6B 40L, BASF CHEMICAL CO., Germany.
Brominated polystyrene flame retardant a: weight average molecular weight 5620, SAYTEX HP-5010PST, Yabao group.
Brominated polystyrene flame retardant B: weight average molecular weight 213400, BPS7010, shandongtian chemical corporation.
Brominated polystyrene flame retardant C: weight average molecular weight 285000, BPS (7010), double abundance chemical ltd.
Zinc borate synergistic flame retardant: hydrous zinc borate, HT-207, by Fine chemical Co., Ltd, Tencel.
Organosilicone synergistic flame retardant: RM4-7081, Dow Corning.
Antimony trioxide synergistic flame retardant: S-12N, commercially available.
Chopped glass fiber: the E glass fiber is commercially available, the length of the fiber is 4.5mm, the diameter of the round fiber is 11 microns, and the same brands are adopted in the following examples and comparative examples.
Radical scavenger: sterically hindered phenols, IRGANOX 1098, basf, germany.
Lubricant: the same designations are used for the alcohol stearates, the following examples and comparative examples.
Example 1
The flame-retardant nylon composite material with low pungent smell comprises the following components in parts by weight as shown in tables 1-3 below.
TABLE 1 Components and parts by weight of examples 1-7
TABLE 2 Components and parts by weight thereof of examples 8-15
TABLE 3 Components in respective proportions and parts by weight thereof
The preparation method of the flame-retardant nylon composite material with low pungent smell comprises the following steps:
the raw materials (except the chopped glass fiber) are weighed according to the proportion, mixed in a high-speed mixer and added from a scale 1. The chopped glass fiber is added separately by a metering scale 2 from the 5 th section of a screw barrel of a double-screw extruder, and the temperature settings of the double-screw extruder from a first zone to a tenth zone are respectively as follows: 80 ℃, 180 ℃, 260 ℃, 250 ℃, 240 ℃ and 260 ℃.
Performance testing
1. Test method
(1) Composite odor evaluation method 1: the method is carried out by referring to a popular automobile interior decoration odor testing method PV3900-2019, the testing judgment standard is classified into 1-6 grades, and meanwhile, the situation between the two judgment grades can occur: grade 1, no odor; grade 2, odorous, but non-interfering odor; grade 3, obvious smell, but no interfering smell; class 4, interfering odor; grade 5, strong interference smell; grade 6, unbearable odor, and grading by professional olfactors, wherein one decimal place can be reserved for each evaluation result, such as 3.5, 3.8, 4.2 and the like, and each group of samples is graded by 5 olfactors and then averaged.
Composite odor evaluation method 2: the most pungent, odoriferous gas is mainly hydrogen bromide, and therefore the odor evaluation is performed by testing the content of hydrogen bromide. The method comprises the following steps: and (3) taking the square plate with the injection size of 100 × 3mm out of the die cavity, immediately putting the square plate into a closed glassware in which a hydrogen bromide gas concentration tester (MS500 handheld hydrogen bromide gas detector) is placed in advance, standing for 2 hours, reading the numerical value on the tester, and taking an average value after each group of samples are tested for 5 points.
(2) Vertical combustion experiment: the injection molding size is (125mm multiplied by 13mm multiplied by 0.8mm) according to the requirements of UL94-2013 standard. Standard combustion bar: the test was carried out according to UL94-2013 standard, the flame was applied for the first time for 10s, the after flame time t1 was recorded, the flame time applied for the second time for 10s, the after flame time t2 and the after burn time t3 were recorded. The combustion rating criteria are given in Table 4.
TABLE 4 Combustion rating criteria
| Judging conditions | Class V-0 | Class V-1 | Class V-2 |
| After flame time for each individual sample (t1 and t2) | ≤10s | ≤30s | ≤30s |
| Total afterflame time for all test samplestf(t1+t2) | ≤50s | ≤250s | ≤250s |
| After flame and burn time for each individual sample (t2+ t3) | ≤30s | ≤60s | ≤60s |
| Whether or not to burn and supportRack | Is free of | Is free of | Is free of |
| Burning the particles orDripping objectWhether to ignite the bottom-laying absorbent cotton | Is free of | Is free of | Is provided with |
2. Test results
TABLE 5 results of Performance test of each example and comparative example
As can be seen from comparative examples 2 and 3 in Table 5, when brominated polystyrene flame retardants are added into the composite material and synergistic flame retardants are respectively and independently added, the system can not meet the V-0 flame-retardant requirement, the odor grade of the composite material is over 4.2, and the hydrogen bromide gas content is greater than 38 ppm. The V-0 flame retardance can be achieved after the synergistic flame retardant with reasonable amount and proportion is added in the comparative example 4, but the odor rating of the composite material can only reach 4.7 due to the lack of the free radical trapping agent, and the hydrogen bromide gas content is as high as 45 ppm; comparative example 5 only adds fire retardant and free radical scavenger, the composite material smell grade is better, can reach 3.3 level, the hydrogen bromide gas content is only 23ppm at the same time, but the fire-retardant grade can only reach HB level; comparative example 6 adopts the traditional antimony trioxide as the synergistic flame retardant, the pungent smell is obviously increased, the smell grade can only reach 6 grades, and the hydrogen bromide gas content is as high as 95 ppm. Comparative example 7 using high viscosity PA6 with a relative viscosity of 4.2, the composite odor rating reached only 4.2 even with the addition of the radical scavenger, and the hydrogen bromide content was high, reaching 40 ppm.
As can be seen from the examples 1-15 in the table 5, the composite material can meet the flame retardance of V-0 with the thickness of 0.8mm by introducing the non-antimony synergistic flame retardant borate and the organic silicone synergistic flame retardant. On the other hand, the thermal degradation of the material in the processing process is reduced by introducing the free radical scavenger, the generation of volatile small molecular substances is further inhibited, and the pungent odor is reduced. The odor rating of the system containing the antimony trioxide synergistic flame retardant is generally above 6, and after the improvement, the odor rating of the prepared flame-retardant nylon composite material is reduced to 3.0-4.0, and the content of hydrogen bromide gas is also obviously reduced.
In conclusion, the brominated polystyrene flame retardant, the organic silicone synergistic flame retardant, the borate synergistic flame retardant and the free radical trapping agent are introduced, so that the flame retardant effect is good, the problem that the traditional bromine/antimony flame-retardant nylon 6 composite material has high pungent smell is solved from the source, the processing environment of a factory is improved, the harm to a human body is reduced, the environment friendliness is better, the application scene of the composite material is expanded, and the requirements of fields with higher requirements on smell, such as automobile interiors, water pump/water valve parts, household appliance shells and the like, are met.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The flame-retardant nylon composite material with low pungent smell is characterized by comprising the following components in parts by weight:
the relative viscosity of the polyamide resin is 2.0-2.8 measured at 25 ℃ in 96% concentrated sulfuric acid.
2. The low pungent odor flame retardant nylon composite of claim 1, comprising the following components in parts by weight:
3. the low-pungent-smell flame-retardant nylon composite material of claim 1, wherein the mass ratio of the borate synergistic flame retardant to the organic silicone synergistic flame retardant is 2: 1-3: 1.
4. The low pungent odor flame retardant nylon composite material of claim 1, wherein the polyamide resin has a relative viscosity of 2.2-2.4 measured at 25 ℃ in 96% concentrated sulfuric acid.
5. The low pungent odor flame retardant nylon composite material of claim 1, wherein the brominated polystyrene flame retardant has a weight average molecular weight Mw of 5500 to 215000.
6. The low pungent odor flame retardant nylon composite of claim 1, wherein the radical scavenger is a sterically hindered phenol and/or a derivative of a sterically hindered phenol.
7. The low pungent odor flame retardant nylon composite material of claim 1, wherein the chopped glass fiber has a length of 1.5-6.0 mm and a diameter of 7-16 μm.
8. The low pungent odor flame retardant nylon composite of claim 1, wherein the lubricant is one or more of stearamides, alcohol stearates, long chain saturated linear carboxylates.
9. The preparation method of the low-pungent-smell flame-retardant nylon composite material of any one of claims 1 to 8 is characterized by comprising the following steps of:
the polyamide resin, the brominated polystyrene flame retardant, the borate synergistic flame retardant, the organic silicone synergistic flame retardant, the free radical scavenger and the lubricant are weighed according to a ratio, mixed uniformly to obtain a mixture, and the mixture and the chopped glass fiber are respectively added for melt blending.
10. A nylon product, which is characterized by being prepared from the low-pungent-smell flame-retardant nylon composite material as claimed in any one of claims 1 to 8.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108204A (en) * | 2009-12-24 | 2011-06-29 | 合肥杰事杰新材料有限公司 | Plastic case material for breaker and preparation method thereof |
| CN102796366A (en) * | 2011-12-08 | 2012-11-28 | 上海耐特复合材料制品有限公司 | Non-antimony flame-retardant polyamide composite material and preparation method and application thereof |
| CN102796367A (en) * | 2011-12-08 | 2012-11-28 | 上海耐特复合材料制品有限公司 | Flame-retardant nylon composite and preparation method and application thereof |
| CN108239391A (en) * | 2016-12-27 | 2018-07-03 | 上海凯赛生物技术研发中心有限公司 | A kind of light flame-retardant reinforced polyamide composition and preparation method thereof |
| CN109265990A (en) * | 2018-08-31 | 2019-01-25 | 广东圆融新材料有限公司 | High glass fire-retarding reinforced polyamide composition |
| CN109705571A (en) * | 2018-12-24 | 2019-05-03 | 金旸（厦门）新材料科技有限公司 | A kind of low-density, low smell bromine system flame-retardant reinforced nylon 66 and preparation method thereof |
| CN109705568A (en) * | 2018-11-30 | 2019-05-03 | 金旸（厦门）新材料科技有限公司 | A kind of low precipitation fire-retardant polyamide material of low smell, preparation method and application |
| CN111138851A (en) * | 2019-12-18 | 2020-05-12 | 南京聚隆科技股份有限公司 | Flame-retardant reinforced micro-foaming nylon material and preparation method thereof |
| CN112280292A (en) * | 2020-11-13 | 2021-01-29 | 江苏金发科技新材料有限公司 | High-temperature thermal-stability flame-retardant nylon 66 composite material and preparation method thereof |
| CN112552680A (en) * | 2020-12-11 | 2021-03-26 | 上海金发科技发展有限公司 | Efficient flame-retardant nylon composite material and preparation method thereof |
-
2021
- 2021-12-03 CN CN202111471030.7A patent/CN114213838B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108204A (en) * | 2009-12-24 | 2011-06-29 | 合肥杰事杰新材料有限公司 | Plastic case material for breaker and preparation method thereof |
| CN102796366A (en) * | 2011-12-08 | 2012-11-28 | 上海耐特复合材料制品有限公司 | Non-antimony flame-retardant polyamide composite material and preparation method and application thereof |
| CN102796367A (en) * | 2011-12-08 | 2012-11-28 | 上海耐特复合材料制品有限公司 | Flame-retardant nylon composite and preparation method and application thereof |
| CN108239391A (en) * | 2016-12-27 | 2018-07-03 | 上海凯赛生物技术研发中心有限公司 | A kind of light flame-retardant reinforced polyamide composition and preparation method thereof |
| CN109265990A (en) * | 2018-08-31 | 2019-01-25 | 广东圆融新材料有限公司 | High glass fire-retarding reinforced polyamide composition |
| CN109705568A (en) * | 2018-11-30 | 2019-05-03 | 金旸（厦门）新材料科技有限公司 | A kind of low precipitation fire-retardant polyamide material of low smell, preparation method and application |
| CN109705571A (en) * | 2018-12-24 | 2019-05-03 | 金旸（厦门）新材料科技有限公司 | A kind of low-density, low smell bromine system flame-retardant reinforced nylon 66 and preparation method thereof |
| CN111138851A (en) * | 2019-12-18 | 2020-05-12 | 南京聚隆科技股份有限公司 | Flame-retardant reinforced micro-foaming nylon material and preparation method thereof |
| CN112280292A (en) * | 2020-11-13 | 2021-01-29 | 江苏金发科技新材料有限公司 | High-temperature thermal-stability flame-retardant nylon 66 composite material and preparation method thereof |
| CN112552680A (en) * | 2020-12-11 | 2021-03-26 | 上海金发科技发展有限公司 | Efficient flame-retardant nylon composite material and preparation method thereof |
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