CN116426009A - Surface flame-retardant compatibilized glass fiber reinforced nylon composite material and preparation method thereof - Google Patents
Surface flame-retardant compatibilized glass fiber reinforced nylon composite material and preparation method thereof Download PDFInfo
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- CN116426009A CN116426009A CN202310236116.4A CN202310236116A CN116426009A CN 116426009 A CN116426009 A CN 116426009A CN 202310236116 A CN202310236116 A CN 202310236116A CN 116426009 A CN116426009 A CN 116426009A
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 161
- 239000003063 flame retardant Substances 0.000 title claims abstract description 155
- 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 154
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 239000004677 Nylon Substances 0.000 title claims abstract description 64
- 229920001778 nylon Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 claims description 12
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- 229920000388 Polyphosphate Polymers 0.000 claims description 9
- 239000001205 polyphosphate Substances 0.000 claims description 9
- 235000011176 polyphosphates Nutrition 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 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 claims description 5
- 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 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 3
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 claims description 3
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 3
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 2
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 29
- 238000001746 injection moulding Methods 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 9
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 41
- 229920002292 Nylon 6 Polymers 0.000 description 38
- 239000000835 fiber Substances 0.000 description 31
- 239000000203 mixture Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
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- 238000005303 weighing Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- 239000004952 Polyamide Substances 0.000 description 4
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- KTLIMPGQZDZPSB-UHFFFAOYSA-M diethylphosphinate Chemical compound CCP([O-])(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-M 0.000 description 2
- 239000011151 fibre-reinforced plastic Substances 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002743 phosphorus functional group Chemical group 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000178289 Verbascum thapsus Species 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (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 surface flame-retardant compatibilized glass fiber reinforced nylon composite material and a preparation method thereof, belongs to the technical field of preparation of modified nylon materials, and is used for solving the technical problems of 'candle core effect' caused by glass fibers and poor flame retardance and mechanical properties of the nylon composite material. Firstly, grafting an interface flame-retardant compatibilizer to the surface of glass fiber to prepare the surface flame-retardant compatibilizer glass fiber; and then mixing the prepared surface flame-retardant compatibilized glass fiber with nylon, flame retardant, auxiliary agent and the like, extruding, granulating and injection molding to prepare the flame-retardant compatibilized glass fiber reinforced nylon composite material. According to the invention, the interface flame-retardant compatibilizer is grafted on the surface of the glass fiber, so that the candle core effect is weakened, the interface effect of the glass fiber and the nylon matrix is improved, the reinforcing effect is achieved, the mechanical property and the flame-retardant property of the glass fiber reinforced nylon flame-retardant composite material are improved, and the application range is enlarged.
Description
Technical Field
The invention belongs to the technical field of preparation of modified nylon materials, and particularly relates to a surface flame-retardant compatibilized glass fiber reinforced nylon composite material and a preparation method thereof.
Background
Polyamide (PA), commonly known as Nylon (Nylon), is a common engineering plastic, has excellent properties of good molding processability, good self-lubricity, wear resistance, easy coloration and the like, and is widely applied in the fields of automobile industry, electronics and electrical, equipment manufacturing and the like. However, nylon materials have low notched impact strength, are not flame-retardant, release a large amount of heat during combustion, and are accompanied by a molten drop phenomenon, which limits the application of nylon materials, particularly in fields where fire safety is important. Flame retardant modification of nylon is therefore highly desirable to meet the need for safe use.
The addition of halogen-free flame retardant to the system is a common solution for flame retardant nylon at present. The phosphorus flame retardant comprising diethyl aluminum phosphinate and the nitrogen flame retardant comprising melamine cyanurate are widely applied to flame retardant modification of polyamide materials due to the characteristics of excellent flame retardant effect, low toxicity, low smoke, environmental friendliness and the like. However, the introduction of the additive flame retardant often leads to deterioration of the mechanical properties of the matrix resin, and cannot meet the application requirements of the matrix resin in the fields of machinery, electronics, instruments, meters and the like. Fiber reinforcement is an effective method for improving the mechanical properties of the composite material, and glass fiber is widely applied to reinforcement modification of nylon composite materials with higher cost performance. However, when the glass fiber reinforced nylon composite is exposed to heat radiation of sufficient magnitude, the matrix in the composite is softened and degraded, cracked, debonded with the glass fiber, and the like, and the matrix around the glass fiber begins to run off, and the molten matrix wets the glass fiber to provide a continuous fuel for combustion, which is the wick effect. Thus, the introduction of glass fibers presents new difficulties and challenges for flame retardance of nylon materials. In addition, uneven dispersion of the flame retardant and defects of fiber/matrix interfaces caused by compatibility problems between the inorganic fibers and the flame retardant particles and the organic matrix also deteriorate the service performance of the nylon matrix after flame retardant modification. The surface modification of GF by designing and synthesizing the flame retardant with the functions of compatibilization and interfacial flame retardance is an effective method for improving the interfacial compatibility of fibers, the flame retardant and a matrix, improving the dispersion uniformity of flame retardant particles and improving the mechanical properties of the flame retardant composite material; meanwhile, the interface flame retardant plays a role in the combustion process, a large number of carbon layers are formed on the surface of the fiber, and the adsorption, infiltration, spreading and flow of the polymer melt in the interface area can be effectively blocked, so that the candle core effect is weakened or even eliminated, the flame retardant effect of the composite material is greatly improved, and the high performance of the flame retardant reinforced nylon is realized.
Patent CN111171234a discloses a polymeric flame retardant synergistic compatibilizer. The compatilizer is a compound containing phosphorus element and having a plurality of anhydride reaction sites on a molecular chain. At the processing temperature of the polymer, polar anhydride groups can react with amino grafted on the surface of the glass fiber and the chain end groups of polymer molecules at the same time, so that the interfacial compatibility and the adhesiveness of a polymer matrix and the glass fiber are greatly improved. However, the method directly adds the compatilizer and the glass fiber into the polymer matrix, so that the compatilizer and the glass fiber are in random contact, the required addition amount of the compatilizer is higher, and the mechanical property and the flame retardant property of the glass fiber reinforced nylon composite material are improved only to a limited extent.
Disclosure of Invention
In order to overcome the technical problems of poor flame retardant property and higher additive amount of a compatibilizer in the glass fiber reinforced nylon in the prior art, the invention provides the surface flame retardant compatibilizer glass fiber reinforced nylon composite material and the preparation method thereof, and the prepared nylon composite material realizes flame retardant UL-94 (3.2 mm) V-0 grade and effectively solves the technical problems of high efficiency, halogen-free flame retardance and high performance of the fiber reinforced polymer flame retardant material; the preparation method has simple operation process, does not influence the processing technology process of the original fiber reinforced nylon composite material, and can be used for large-scale production.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of a surface flame-retardant compatibilized glass fiber reinforced nylon composite material comprises the steps of (10-30) mixing flame-retardant compatibilized glass fiber, nylon, flame retardant and antioxidant: (40-60): (1-20): (0.1-1) and uniformly mixing, extruding, granulating and injecting to obtain the flame-retardant compatibilized glass fiber reinforced nylon composite material.
The method for preparing the flame-retardant and compatibilized glass fiber reinforced nylon composite material according to claim 1, which is characterized by comprising the following steps:
(1) Soaking glass fiber in a mixed solution I consisting of a silane coupling agent and a solvent I, regulating the pH value of the solution, and carrying out silane coupling agent modification treatment to obtain silane coupling agent modified glass fiber;
(2) And (3) soaking the silane coupling agent modified glass fiber in a mixed solution II formed by the interface flame-retardant compatibilizer and the solvent II, and performing flame-retardant compatibilizer modification treatment to obtain the flame-retardant modified glass fiber.
The mass ratio of the silane coupling agent to the solvent I in the step (1) is 1: (3-5), the silane coupling agent is KH550, KH560, KH570 or KH590; the solvent I comprises the following components in percentage by mass (1-2): water and ethanol of (8-9); the temperature of the modification treatment of the silane coupling agent is 40-90 ℃ and the time is 4-8h.
In the step (2), the mixed solution II is prepared from an interface flame-retardant compatibilizer and a solvent II according to a mass ratio of 1: (70-110) preparing; the solvent II is tetrahydrofuran, diethyl ether, acetone or butanone; the temperature for the modification treatment of the flame-retardant compatibilizer is 50-80 ℃ and the time is 10-14h.
The interface flame-retardant compatibilizer is PPC, and the structural formula of the PPC is as follows:
the preparation method of the PPC comprises the following steps: first, methylene chloride (300 mL), hydroxyethyl acrylate (11.62 g,0.1 mol), and triethylamine (10.12 g,0.1 mol) were added in this order to a round-bottomed flask equipped with a constant pressure dropping funnel and a magnetic stirrer, and diphenylphosphinoyl chloride (23.66 g,0.1 mol) was slowly added dropwise under a nitrogen atmosphere at a temperature of 0℃or lower, and after the addition was completed, the reaction was carried out at room temperature for 5 to 6 hours, with the temperature maintained at 25 to 35 ℃. After the reaction, the yellow liquid was repeatedly washed with a large amount of distilled water, and after drying, the solvent in the product was removed to obtain intermediate a. Then, tetrahydrofuran (400 mL), intermediate A (31.63 g,0.1 mol), maleic anhydride (9.80 g,0.1 mol) and the like were sequentially introduced into a two-necked flask equipped with a condensing device, air remaining in the device was evacuated, and azobisisobutyronitrile (0.12 g) as a catalyst was added under a nitrogen atmosphere, and refluxed at 70 to 90℃for 12 to 24 hours to obtain a reddish-colored liquid. And (3) after removing the solvent by rotary evaporation, washing the wine red liquid by using a large amount of diethyl ether, and drying at 40-70 ℃ for 12-24 hours to obtain the product PPC. The reaction formula is as follows:
The interface flame-retardant compatibilizer is HPC, and the structural formula of the HPC is as follows:
n is an integer.
The preparation method of HPC comprises the following steps: DOPO (17.28 g,80 mmol) is firstly dissolved in 80mL of dichloromethane, carbon tetrachloride (14.76 g,96 mmol) is added, the mixture is placed in an ice bath, the temperature is reduced to 3 ℃ below zero to 5 ℃, hydroxyethyl acrylate (11.15 g,96 mmol) and triethylamine (9.70 g,96 mmol) are mixed and slowly dripped into a carbon dichloride solution of DOPO, magnetic stirring is carried out for 2h, and after dripping is finished, the mixture is transposed for reaction for 12-24h at 30 ℃ to 50 ℃. The reaction product was washed 3-8 times with water, dried and distilled to give a white viscous liquid B. Tetrahydrofuran (300 mL), intermediate B (33.01, 0.1 mol), maleic anhydride (9.80 g,0.1 mol) were then sequentially added to a two-necked flask equipped with a condensing device, the residual air in the device was removed, azobisisobutyronitrile (0.12 g) was added under nitrogen atmosphere, and reflux was carried out at 60-80℃for 12-24 hours to obtain a reddish-colored liquid. After the solvent is removed by rotary evaporation, a large amount of diethyl ether is used for washing the wine red liquid, and the product HPC is obtained after drying for 12-24 hours at the temperature of 40-60 ℃. The reaction formula is as follows:
the interface flame-retardant compatibilizer is HDOPO, and the structural formula of the HDOPO is as follows:
the preparation method of the HDOPO comprises the following steps: hydroxyethyl acrylate (6.47 g,0.55 mol), DOPO (10.00 g,0.46 mol), triethylamine (5.6 g,0.55 mol) and dichloromethane (80 mL) are sequentially added into a single-port bottle, the reaction is carried out for 12-24 hours at 30-40 ℃, the reaction liquid is extracted for 3-5 times by water, and the organic layer is taken, distilled and dried to obtain the product HDOPO. The reaction formula is as follows:
the flame retardant is one or more than two of aluminum hypophosphite (AIHP), diethyl aluminum phosphinate (ADP), melamine polyphosphate (MPP), melamine Cyanurate (MCA), ammonium polyphosphate (APP), melamine (ME) or 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof, and silane structure-containing benzoxazine, phosphorus, nitrogen, sulfur-containing halogen-free ionic liquids; the antioxidant is one or more of antioxidant 1010, antioxidant 1098 and antioxidant 1076.
The technological parameters of extrusion granulation are as follows: the extrusion temperature is 240-280 ℃, the main screw speed of extrusion is 90-130rpm, and the feeding frequency is 1-4Hz.
The invention has the beneficial effects that: the invention utilizes the synthesized interface flame-retardant compatibilizer to carry out surface modification on the glass fiber to obtain the glass fiber with the surface flame-retardant compatibilizer function, which is directly applied to the molding process of the fiber reinforced polymer composite material without changing the processing technological conditions of the original composite material. Under the condition that the dosages of the interface flame-retardant compatibilizer are the same, compared with the method of directly adding the fiber/matrix interface of the obtained composite material, the effect of grafting the interfacial flame-retardant compatibilizer on the surface of the glass fiber is obviously improved, the char forming capability of the surface of the fiber in the combustion process is obviously enhanced, the synergistic enhancement between the flame retardant property and the mechanical property of the composite material is realized, the mechanical property and the flame retardant property of the glass fiber reinforced nylon flame-retardant composite material are improved, and the application range is enlarged.
The interface flame-retardant compatibilizer synthesized by the method is simple and feasible in process, and particularly does not contain halogen elements in the adopted DOPO structure. In addition, the mechanical property and the flame retardance of the HPC and the HDOPO prepared by the invention are higher than those of the PPC when the HPC and the HDOPO are applied to the nylon composite material; the synthesized HPC shows more excellent interface increase Rong Heqi phase flame-retardant effect in the material processing process; the compatibilizer HDOPO needs only one step in the synthesis process, and the process is simpler.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a nuclear magnetic resonance hydrogen spectrum of an interface flame retardant compatibilizer PPC.
Fig. 2 is a nuclear magnetic resonance hydrogen spectrum of the interfacial flame retardant compatibilizer HPC.
Fig. 3 is a nuclear magnetic resonance hydrogen spectrum of the interfacial flame retardant compatibilizer HDOPO.
FIG. 4 shows the matrix interface bonding in the cross section of the sample after impact test; (a) PA6/GF/FR; (b) PA6/GF-HPC/FR; (c) PA6/GF-HDOPO/FR; (d) PA6/GF-PPC/FR.
FIG. 5 shows the matrix interface bonding in the cross section of the sample after impact test; (a) PA6/GF/FR/HDOPO; (b) PA6/GF-HDOPO/FR.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the surface flame-retardant compatibilized glass fiber reinforced nylon composite material comprises the following steps:
the first step, synthesizing an interface compatibilizer HPC, wherein the specific preparation steps are as follows: (1) DOPO (17.28 g,80 mmol) was dissolved in 80mL of methylene chloride, carbon tetrachloride (14.76 g,96 mmol) was added thereto, the mixture was cooled to-3℃in an ice bath, hydroxyethyl acrylate (11.15 g,96 mmol) and triethylamine (9.70 g,96 mmol) were mixed, and then slowly dropped into the DOPO carbon dichloride solution, magnetically stirred for 2 hours, and after the dropping was completed, the mixture was reacted at 30℃for 24 hours with stirring. The reaction product was washed 5 times with water, dried and evaporated to give a white viscous liquid B.
(2) Tetrahydrofuran (300 mL), intermediate B (33.01, 0.1 mol), maleic anhydride (9.80 g,0.1 mol) were sequentially added to a two-necked flask equipped with a condensing device, the remaining air in the device was evacuated, azobisisobutyronitrile (0.12 g) was added under a nitrogen atmosphere, and the mixture was refluxed at 80℃for 12 hours to obtain a reddish wine liquid. After the solvent was removed by rotary evaporation, the wine red liquid was washed with a large amount of diethyl ether and dried at 60℃for 12 hours to give HPC whose nuclear magnetic resonance hydrogen spectrum is shown in FIG. 2.
And secondly, soaking the glass fiber in a mixed solution of KH550, distilled water and ethanol, wherein 55020 parts of KH, 8 parts of distilled water and 72 parts of ethanol, adjusting the pH to 5, and reacting for 6 hours at the temperature of 80 ℃. Finally, the glass fiber treated by KH550 is washed by distilled water and dried for standby.
Third, the KH550 treated glass fiber was placed in a large beaker, and 0.6 parts of HPC and 150 parts of tetrahydrofuran were added thereto, and reacted at 60℃for 12 hours. Finally, the flame-retardant modified glass fiber is dried for later use and is marked as GF-HPC.
And fourthly, weighing 659.5 parts of nylon, 30 parts of flame-retardant modified glass fiber, 8.9 parts of diethyl aluminum phosphinate, 1.1 parts of melamine cyanurate and 10980.5 parts of antioxidant by weight. The raw materials are dried and then mixed uniformly (flame-retardant modified glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried for 12 hours at 80 ℃ and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. The flame-retardant compatibilized glass fiber reinforced nylon 6 composite material is obtained and is named as PA6/GF-HPC/FR.
Example 2
The preparation method of the surface flame-retardant compatibilized glass fiber reinforced nylon composite material comprises the following steps:
the first step, synthesizing an interface compatibilizer HDOPO, which comprises the following specific preparation steps: to a single-necked flask, hydroxyethyl acrylate (6.47 g,0.55 mol), DOPO (10.00 g,0.46 mol), triethylamine (5.6 g,0.55 mol) and methylene chloride (80 mL) were sequentially added, the mixture was reacted at 35℃for 12 hours, the reaction mixture was extracted 3 times with water, and the organic layer was distilled off and dried to give a product HDOPO having a nuclear magnetic resonance hydrogen spectrum shown in FIG. 3.
And secondly, soaking the glass fiber in a mixed solution of KH550, distilled water and ethanol, wherein 55020 parts of KH, 8 parts of distilled water and 72 parts of ethanol, adjusting the pH to 4, and reacting for 6 hours at the temperature of 80 ℃. Finally, the glass fiber treated by KH550 is washed by distilled water and dried for standby.
Third, the KH550 treated glass fiber was placed in a large beaker, and 0.6 part of HDOPO and 150 parts of tetrahydrofuran were added thereto, and reacted at 60℃for 12 hours. Finally, the flame-retardant modified glass fiber is dried for standby and is marked as GF-HDOPO.
And fourthly, weighing 659.5 parts of nylon, 30 parts of flame-retardant modified glass fiber, 8.9 parts of diethyl phosphinate, 1.1 parts of melamine cyanurate and 10980.5 parts of antioxidant according to parts by weight. The raw materials are dried and then mixed uniformly (flame-retardant modified glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried for 12 hours at 80 ℃ and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. The obtained flame-retardant compatibilized glass fiber reinforced nylon 6 composite material is named as PA6/GF-HDOPO/FR.
Example 3
The preparation method of the surface flame-retardant compatibilized glass fiber reinforced nylon composite material comprises the following steps:
the first step, synthesizing an interface compatibilizer PPC, wherein the specific preparation steps are as follows: (1) Dichloromethane (300 mL), hydroxyethyl acrylate (11.62 g,0.1 mol), triethylamine (10.12 g,0.1 mol) and diphenylphosphinoyl chloride (23.66 g,0.1 mol) were added in this order to a round-bottomed flask equipped with a constant pressure dropping funnel and a magnetic stirrer, and diphenylphosphinoyl chloride (23.66 g,0.1 mol) was slowly added dropwise under a nitrogen atmosphere at a temperature of less than 0℃and then allowed to react at room temperature for 5 to 6 hours after the addition was completed, and the temperature was maintained at 25 to 35 ℃. After the reaction, the yellow liquid was repeatedly washed with a large amount of distilled water, and after drying, the solvent in the product was removed to obtain intermediate a.
(2) Tetrahydrofuran (400 mL), intermediate A (31.63 g,0.1 mol), maleic anhydride (9.80 g,0.1 mol) were sequentially added to a two-necked flask equipped with a condensing device, the residual air in the device was removed, and the catalyst azobisisobutyronitrile (0.12 g) was added under a nitrogen atmosphere, followed by refluxing at 90℃for 24 hours to obtain a reddish-colored liquid. After the solvent is removed by rotary evaporation, a large amount of diethyl ether is used for washing the wine red liquid, and the product PPC is obtained after drying for 12 hours at 70 ℃, and the nuclear magnetic resonance hydrogen spectrum of the product PPC is shown in figure 1.
And secondly, soaking the glass fiber in a mixed solution of KH550, distilled water and ethanol, wherein 55020 parts of KH, 8 parts of distilled water and 72 parts of ethanol, adjusting the PH to 4-5, and reacting for 6 hours at the temperature of 80 ℃. Finally, the glass fiber treated by KH550 is washed by distilled water and dried for standby.
Third, the KH550 treated glass fiber was placed in a large beaker, and 0.6 parts of PPC and 150 parts of tetrahydrofuran were added thereto, and reacted at 60℃for 12 hours. Finally, the flame-retardant modified glass fiber is dried for standby and is marked as GF-PPC.
And fourthly, weighing 659.5 parts of nylon, 30 parts of flame-retardant modified glass fiber, 8.9 parts of diethyl phosphinate, 1.1 parts of melamine cyanurate and 10980.5 parts of antioxidant according to parts by weight. The raw materials are dried and then mixed uniformly (flame-retardant modified glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried for 12 hours at 80 ℃ and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. The obtained PPC flame-retardant compatibilized glass fiber reinforced nylon 6 composite material is named as PA6/GF-PPC/FR.
Example 4
The preparation method of the surface flame-retardant compatibilized glass fiber reinforced nylon composite material comprises the following steps:
in the first step, the glass fiber is soaked in a mixed solution of KH570, distilled water and ethanol, wherein 57020 parts of KH, 20 parts of distilled water and 80 parts of ethanol, the PH is regulated to 4-5, the temperature is 90 ℃, and the reaction time is 4 hours. Finally, washing the glass fiber treated by KH570 with distilled water and drying for later use.
In the second step, the KH570 treated glass fiber was placed in a large beaker, and 1 part of HPC and 110 parts of acetone were added thereto, and reacted at 80℃for 11 hours. Finally, the flame-retardant modified glass fiber is dried for standby.
And thirdly, weighing 659 parts of nylon, 30 parts of flame-retardant modified glass fiber, 8.9 parts of diethyl aluminum phosphinate, 1.1 parts of melamine polyphosphate, 10980.5 parts of antioxidant and 10760.5 parts of antioxidant 1076 in parts by weight. The raw materials are dried and then mixed uniformly (flame-retardant modified glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried for 12 hours at 80 ℃ and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. Obtaining the HPC flame-retardant compatibilized glass fiber reinforced nylon 6 composite material.
Example 5
The preparation method of the surface flame-retardant compatibilized glass fiber reinforced nylon composite material comprises the following steps:
in the first step, the glass fiber is soaked in a mixed solution of KH560, distilled water and ethanol, wherein the KH56020 parts, the distilled water 10 parts and the ethanol 50 parts, the PH is regulated to 4-5, the temperature is 40 ℃, and the reaction time is 8 hours. Finally, the glass fiber treated by KH560 is washed by distilled water and dried for standby.
In the second step, the KH560 treated glass fiber was placed in a large beaker, and 0.6 parts of HDOPO and 120 parts of diethyl ether were added thereto to react at 50℃for 10 hours. Finally, the flame-retardant modified glass fiber is dried for standby.
Thirdly, weighing 659 parts of nylon, 30 parts of flame-retardant modified glass fiber, 8.9 parts of diethyl aluminum phosphinate, 1.1 parts of melamine polyphosphate and 10101 parts of antioxidant 1010 according to parts by weight. The raw materials are dried and then mixed uniformly (flame-retardant modified glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried for 12 hours at 80 ℃ and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. Obtaining the HDOPO flame-retardant compatibilized glass fiber reinforced nylon 6 composite material.
Comparative example 1
In the first step, the glass fiber is soaked in a mixed solution of KH550, distilled water and ethanol, wherein 55020 parts of KH, 8 parts of distilled water and 72 parts of ethanol, the PH is regulated to 4-5, the temperature is 80 ℃, and the reaction time is 6 hours. Finally, the glass fiber treated by KH550 is washed by distilled water and dried for standby.
Secondly, weighing nylon 6, KH550 modified Glass Fiber (GF), diethyl aluminum phosphinate, melamine cyanurate, HPC and antioxidant 1098 according to parts by weight, wherein 659.5 parts of nylon, 29.4 parts of KH550 modified glass fiber, 8.9 parts of diethyl aluminum phosphinate, 1.1 parts of melamine cyanurate, 0.6 part of HPC and 10980.5 parts of antioxidant. The raw materials are dried and then mixed uniformly (glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried at 80 ℃ for 6 hours and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. The glass fiber reinforced nylon 6 flame-retardant composite material is obtained and is named as PA6/GF/FR/HPC.
Comparative example 2
In the first step, the glass fiber is soaked in a mixed solution of KH550, distilled water and ethanol, wherein 55020 parts of KH, 8 parts of distilled water and 72 parts of ethanol, the PH is regulated to 4-5, the temperature is 80 ℃, and the reaction time is 6 hours. Finally, the glass fiber treated by KH550 is washed by distilled water and dried for standby.
And secondly, weighing 659.5 parts of nylon, 29.4 parts of KH550 modified glass fiber, 8.9 parts of aluminum diethylphosphinate, 1.1 parts of melamine cyanurate, 0.6 part of HDOPO and 10980.5 parts of antioxidant by weight. The raw materials are dried and then mixed uniformly (glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried at 80 ℃ for 6 hours and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. The glass fiber reinforced nylon 6 flame-retardant composite material is obtained and is named as PA6/GF/FR/HDOPO.
Comparative example 3
In the first step, the glass fiber is soaked in a mixed solution of KH550, distilled water and ethanol, wherein 55020 parts of KH, 8 parts of distilled water and 72 parts of ethanol, the PH is regulated to 4-5, the temperature is 80 ℃, and the reaction time is 6 hours. Finally, the glass fiber treated by KH550 is washed by distilled water and dried for standby.
And secondly, weighing 659.5 parts of nylon, 29.4 parts of KH550 modified glass fiber, 8.9 parts of aluminum diethylphosphinate, 1.1 parts of melamine cyanurate, 0.6 part of PPC and 10980.5 parts of antioxidant by weight. The raw materials are dried and then mixed uniformly (glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried at 80 ℃ for 6 hours and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. The glass fiber reinforced nylon 6 flame-retardant composite material is obtained and is named as PA6/GF/FR/PPC.
Comparative example 4
In the first step, the glass fiber is soaked in a mixed solution of KH570, distilled water and ethanol, wherein 57020 parts of KH, 20 parts of distilled water and 80 parts of ethanol, the PH is regulated to 4-5, the temperature is 90 ℃, and the reaction time is 4 hours. Finally, washing the glass fiber treated by KH570 with distilled water and drying for later use.
Secondly, weighing 659 parts of nylon, 29.4 parts of glass fiber, 8.9 parts of diethyl aluminum phosphinate, 1.1 parts of melamine polyphosphate, 0.6 part of HPC, 10980.5 parts of antioxidant and 10760.5 parts of antioxidant 1076 by weight. The raw materials are dried and then mixed uniformly (flame-retardant modified glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried for 12 hours at 80 ℃ and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. Obtaining the HPC flame-retardant compatibilized glass fiber reinforced nylon 6 composite material.
Comparative example 5
In the first step, the glass fiber is soaked in a mixed solution of KH560, distilled water and ethanol, wherein the KH56020 parts, the distilled water 10 parts and the ethanol 50 parts, the PH is regulated to 4-5, the temperature is 40 ℃, and the reaction time is 8 hours. Finally, the glass fiber treated by KH560 is washed by distilled water and dried for standby.
Secondly, weighing 659 parts of nylon, 29.4 parts of glass fiber, 8.9 parts of diethyl aluminum phosphinate, 1.1 parts of melamine polyphosphate, 0.6 part of HDOPO and 10101 parts of antioxidant 1010 according to parts by weight. The raw materials are dried and then mixed uniformly (flame-retardant modified glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried for 12 hours at 80 ℃ and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. Obtaining the HDOPO flame-retardant compatibilized glass fiber reinforced nylon 6 composite material.
Comparative example 6
In the first step, the glass fiber is soaked in a mixed solution of KH550, distilled water and ethanol, wherein 55020 parts of KH, 8 parts of distilled water and 72 parts of ethanol, the PH is regulated to 4-5, the temperature is 80 ℃, and the reaction time is 6 hours. Finally, the glass fiber treated by KH550 is washed by distilled water and dried for standby.
And secondly, weighing nylon 6, KH550 modified glass fiber, diethyl aluminum phosphinate and an antioxidant 1098 according to parts by weight, wherein 659.5 parts of nylon, 30 parts of KH550 modified glass fiber, 8.9 parts of diethyl aluminum phosphinate, 1.1 parts of melamine cyanurate and 10980.5 parts of antioxidant. The raw materials are dried and then mixed uniformly (glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried at 80 ℃ for 6 hours and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. The glass fiber reinforced nylon 6 flame-retardant composite material is obtained and is named as PA6/GF/FR.
Comparative example 7
In the first step, the glass fiber is soaked in a mixed solution of KH560, distilled water and ethanol, wherein the KH56020 parts, the distilled water 10 parts and the ethanol 50 parts, the PH is regulated to 4-5, the temperature is 40 ℃, and the reaction time is 8 hours. Finally, the glass fiber treated by KH560 is washed by distilled water and dried for standby.
Secondly, weighing 659 parts of nylon, 30 parts of glass fiber, 8.9 parts of aluminum diethyl phosphinate, 1.1 parts of melamine polyphosphate and 10101 parts of antioxidant according to parts by weight of nylon 6, flame-retardant modified glass fiber, aluminum diethyl phosphinate, melamine polyphosphate and antioxidant 1010. The raw materials are dried and then mixed uniformly (flame-retardant modified glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried for 12 hours at 80 ℃ and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. And obtaining the glass fiber reinforced nylon 6 flame-retardant composite material.
Comparative example 8
In the first step, the glass fiber is soaked in a mixed solution of KH550, distilled water and ethanol, wherein 55020 parts of KH, 8 parts of distilled water and 72 parts of ethanol, the PH is regulated to 4-5, the temperature is 80 ℃, and the reaction time is 6 hours. Finally, the glass fiber treated by KH550 is washed by distilled water and dried for standby.
And secondly, weighing the nylon 6, the KH550 modified glass fiber and the antioxidant 1098 according to parts by weight, wherein 669.5 parts of nylon, 30 parts of KH550 modified glass fiber and 10980.5 parts of antioxidant. The raw materials are dried and then mixed uniformly (glass fiber is added from a side feeding port), then the mixture is melted, extruded and granulated, and the obtained granules are dried at 80 ℃ for 6 hours and then are injection molded by an injection molding machine. The temperatures of all sections of the extruder are 240, 245 and 245 ℃, the rotating speed of a main screw is 90r/min, and the feeding frequency is 2Hz; the temperature of each section of the injection molding machine is 240, 245 and 245 ℃. Obtaining the glass fiber reinforced nylon 6 composite material.
Test case
The amounts of the components of the composite materials prepared in examples 1 to 5 and comparative examples 1 to 8 are shown in Table 1, and the corresponding mechanical properties and flame retardant properties are shown in Table 2.
TABLE 1 glass fiber reinforced nylon 6 flame retardant composite composition table
Table 2 glass fiber reinforced nylon 6 flame retardant composite performance table
As can be seen from experimental test results (Table 2) of examples 1-5 and comparative examples 1-8, the flame retardant property and the mechanical property of the composite material are obviously improved in the examples 1-5 compared with the comparative examples 6 and 7 without the interfacial flame retardant compatibilizer modified glass fiber. Wherein the tensile strength, flexural modulus and notched impact strength of the system employing HPC (example 1) surface modified glass fibers were increased by 20.7%, 20.0%, 24.1% and 17.6%, respectively, over the system without flame retardant compatibilizer (comparative example 6). Compared with samples (examples 1, 4 and 2) in which HPC and HDOPO are directly added to a flame-retardant system (comparative examples 1, 4 and 2), the notch impact strength of the samples is respectively improved by 20.2%, 29.9% and 21.3%, which indicates that the interface flame-retardant compatibilizer directly modified glass fiber can effectively improve the interface combination between the fiber and matrix resin, and solve the problem of the deterioration of the impact performance of the composite material caused by the added flame retardant. From the interface combination and extraction conditions of the fibers and the matrix in the impact section morphology graph of the composite material in fig. 4, the extraction conditions of the fibers in the system without the flame retardant compatibilizer (comparative example 6, fig. 4 a) are more obvious, the surface of the extracted fibers is smoother, and the resin residues are less; the system with flame retardant compatibilizer (fig. 4b-d, examples 1-3) has shorter fiber extraction length and obvious resin residue on the fiber surface of the extracted part, which shows that the flame retardant compatibilizer PPC, HPC, HDOPO has excellent interfacial compatibilizer effect on PA6/GF/FR, so that the mechanical properties of the corresponding composite system (examples 1-5, comparative examples 1-5) are better than those of the system without flame retardant compatibilizer (comparative examples 6, 7). From the sectional view of the composite material obtained by adding the HDOPO surface modified glass fiber (example 2) and directly blending the HDOPO (comparative example 2) with the system in fig. 5, it can be seen that after the composite material obtained by directly carrying out surface flame retardant compatibilization modification on the fiber is damaged by external force, a large amount of resin matrix is attached to the surface of the fiber, and the fiber extraction degree is shorter than that of the directly blended system (comparative example 2), which indicates that the interface flame retardant is directly treated on the surface of the fiber, so that the interface bonding between the fiber and the matrix can be effectively improved, and the effect is the key of improving the mechanical property of the glass fiber reinforced nylon 6 flame retardant composite material.
From the results of the combustion test, the systems added with the flame retardant compatibilizer HPC and the HDOPO can pass through the UL-94 grade, the limiting oxygen index reaches more than 29%, and the flame retardant grade is achieved. In particular, the systems added with GF-HPC and GF-HDOPO (examples 1, 2 and examples 4 and 5) have the limit oxygen index value improved by more than 20.6% and the ignition time prolonged by 14.3% -44.6% by UL-94V-0 grade compared with the system without flame retardant compatibilizer (comparative example 6).
Under the existing additive amount, the flame retardant property and the mechanical property of the glass fiber reinforced composite system directly modified by HPC and HDOPO are better than those of the composite system directly blending HPC and HDOPO in the system, and the modification effect of the system containing HPC and HDOPO interface compatibilization flame retardant is better than that of the system containing PPC. This is related to the molecular structure of several interfacial compatibilizers and their dispersion in the matrix. The HPC molecular chain structure contains a plurality of anhydride groups, can be subjected to grafting reaction with amino groups on the surface of GF, and the HPC molecular chain contains phosphorus groups, anhydride groups and carboxyl groups formed after the grafting reaction can also be subjected to reaction with terminal amino groups on the PA6 chain, so that interface combination between GF and matrix PA6 is promoted. And PPC and HPC have similar interfacial compatibilization mechanisms. The phosphorus groups and hydroxyl groups in the HDOPO structure promote the interface bonding of the fiber and the matrix through the hydrogen bonding between GF and PA 6. The interfacial compatibilizer is firstly treated on the surface of the fiber, and stronger physical and chemical bonds are formed on the surface of the fiber preferentially, so that the interfacial compatibilizer can directly act on the interface between the fiber and the matrix in the subsequent processing process, and the effect is better and more obvious. When the interfacial compatibilizer is added into the matrix in a blending way, the interfacial compatibilizer has the problems of incapability of migrating to the fiber/matrix interface, uneven distribution and the like, so that the compatibilization effect of the interfacial compatibilizer is inferior to that of a sample in which the interfacial compatibilizer firstly carries out surface modification on the fiber. Under the fire environment, the PPC and the HPC can play a role in flame retardance through the cooperation of a condensed phase and a gas phase dual flame retardance mechanism and FR. At high temperature, PPC and HPC are thermally decomposed to generate PO free radicals to capture active H, OH and HOO free radicals in flame, so that the chain reaction of the combustion process is terminated, and the gas-phase flame retardant effect is achieved. HDOPO has a flame retardant mechanism similar to DOPO and is capable of releasing PO-radicals to trap active radicals in the flame reaction and thereby inhibit the combustion process. The P-C bond energy in the HPC and HDOPO structures is weaker, and compared with PPC, the HPC and the HDOPO structures are easier to decompose in advance to form new phosphate or polyphosphate to cover the surface of the combustible material, and meanwhile polyphosphoric acid, phosphorous acid, phosphoric acid and the like are generated to dehydrate and carbonize the polyamide matrix to form a crosslinked compact carbon layer, so that oxygen and heat are isolated from being transferred into the matrix, and the condensed phase flame retardant effect is achieved. When the interface flame-retardant compatibilizer acts on the fiber/matrix interface, the interface flame-retardant compatibilizer can directly promote the formation of a fiber/matrix interface carbon layer in a fire environment, reduce the surface interface energy of glass fibers, inhibit the wetting and diffusion of polymer melt on the surfaces of the fibers, thereby blocking the candlewick effect brought by the fibers and showing more excellent flame-retardant effect.
In conclusion, the flame retardant compatibilizer added in the embodiment obviously solves the flame retardant problem caused by the fiber candle core effect in the PA6/GF, improves the flame retardant property of the composite material, realizes the improvement of the mechanical property of the composite material, and further meets the performance requirements of the PA6/GF composite material in the fields of automobile parts, mechanical industry, aerospace and the like. In addition, the flame-retardant compatibilizer is adopted to modify the fiber surface, so that fiber customization production can be performed, the influence on the processing process of manufacturing the corresponding flame-retardant composite material is small, and the industrial production, popularization and application of the fiber-reinforced nylon flame-retardant composite material are facilitated.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The preparation method of the surface flame-retardant compatibilized glass fiber reinforced nylon composite material is characterized in that flame-retardant compatibilized glass fiber, nylon, flame retardant and antioxidant are mixed according to the following ratio of (10-30): (40-60): (1-20): (0.1-1) and uniformly mixing, extruding, granulating and injecting to obtain the flame-retardant compatibilized glass fiber reinforced nylon composite material.
2. The method for preparing the surface flame-retardant and compatibilized glass fiber reinforced nylon composite material according to claim 1, wherein the method for preparing the flame-retardant and compatibilized glass fiber comprises the following steps:
(1) Soaking glass fiber in a mixed solution I consisting of a silane coupling agent and a solvent I, regulating the pH value of the solution, and carrying out silane coupling agent modification treatment to obtain silane coupling agent modified glass fiber;
(2) And (3) soaking the silane coupling agent modified glass fiber in a mixed solution II formed by the interface flame-retardant compatibilizer and the solvent II, and performing flame-retardant compatibilizer modification treatment to obtain the flame-retardant compatibilizer glass fiber.
3. The method for preparing the surface flame-retardant and compatibilized glass fiber reinforced nylon composite material according to claim 2, wherein the mass ratio of the silane coupling agent to the solvent I in the step (1) is 1: (3-5), the silane coupling agent is any one of KH550, KH560, KH570 or KH590; the solvent I comprises the following components in percentage by mass (1-2): water and ethanol of (8-9); the temperature of the modification treatment of the silane coupling agent is 40-90 ℃ and the time is 4-8h.
4. The preparation method of the surface flame-retardant and compatibilized glass fiber reinforced nylon composite material according to claim 3, wherein the mixed solution II in the step (2) comprises an interface flame-retardant compatibilizer and a solvent II according to a mass ratio of 1: (70-110) preparing; the solvent II is any one of tetrahydrofuran, diethyl ether, acetone or butanone; the temperature for the modification treatment of the flame-retardant compatibilizer is 50-80 ℃ and the time is 10-14h.
5. The method for preparing a surface flame-retardant and compatibilized glass fiber reinforced nylon composite material according to any one of claims 2 to 4, wherein the interfacial flame-retardant compatibilizer is PPC, and the structural formula of PPC is:
n is an integer.
6. The method for preparing a surface flame-retardant and compatibilized glass fiber reinforced nylon composite material according to any one of claims 2 to 4, wherein the interfacial flame-retardant compatibilizer is HPC having a structural formula:
n is an integer.
7. The method for preparing a surface flame-retardant and compatibilized glass fiber reinforced nylon composite material according to any one of claims 2 to 4, wherein the interfacial flame-retardant compatibilizer is HDOPO, and the structural formula of the HDOPO is:
8. the preparation method of the surface flame-retardant compatibilized glass fiber reinforced nylon composite material according to claim 1, wherein the flame retardant is one or more than two of aluminum hypophosphite, diethyl aluminum phosphinate, melamine polyphosphate, melamine cyanurate, ammonium polyphosphate, melamine or 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof, benzoxazine containing a silane structure, or ionic liquid containing phosphorus, nitrogen and sulfur halogen-free elements; the antioxidant is one or more of antioxidant 1010, antioxidant 1098 and antioxidant 1076.
9. The method for preparing the surface flame-retardant and compatibilized glass fiber reinforced nylon composite material according to claim 1, wherein the technological parameters of extrusion granulation are as follows: the extrusion temperature is 240-280 ℃, the main screw speed of extrusion is 90-130rpm, and the feeding frequency is 1-4Hz.
10. The surface flame retardant compatibilized glass fiber reinforced nylon composite prepared by the method of any one of claims 2-9.
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| CN117603474A (en) * | 2023-12-20 | 2024-02-27 | 武汉中科先进材料科技有限公司 | Fiber-reinforced unsaturated polyester resin composite material for photovoltaic bracket and preparation method thereof |
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| CN117603474A (en) * | 2023-12-20 | 2024-02-27 | 武汉中科先进材料科技有限公司 | Fiber-reinforced unsaturated polyester resin composite material for photovoltaic bracket and preparation method thereof |
| CN117603474B (en) * | 2023-12-20 | 2024-05-31 | 武汉中科先进材料科技有限公司 | Fiber-reinforced unsaturated polyester resin composite material for photovoltaic bracket and preparation method thereof |
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