CN111269490A - High-rigidity flame-retardant polypropylene alloy material and preparation method thereof - Google Patents
High-rigidity flame-retardant polypropylene alloy material and preparation method thereof Download PDFInfo
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- CN111269490A CN111269490A CN202010127313.9A CN202010127313A CN111269490A CN 111269490 A CN111269490 A CN 111269490A CN 202010127313 A CN202010127313 A CN 202010127313A CN 111269490 A CN111269490 A CN 111269490A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 61
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 59
- 239000003063 flame retardant Substances 0.000 title claims abstract description 54
- -1 polypropylene Polymers 0.000 title claims abstract description 46
- 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 38
- 239000000956 alloy Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000003365 glass fiber Substances 0.000 claims description 27
- 239000007822 coupling agent Substances 0.000 claims description 21
- 239000003431 cross linking reagent Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 16
- 239000003607 modifier Substances 0.000 claims description 15
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 15
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 14
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical group [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000005007 epoxy-phenolic resin Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000005357 flat glass Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229920006305 unsaturated polyester Polymers 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 15
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 14
- 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 14
- PYCBFXMWPVRTCC-UHFFFAOYSA-N ammonium metaphosphate Chemical compound N.OP(=O)=O PYCBFXMWPVRTCC-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 14
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 13
- 238000011056 performance test Methods 0.000 description 13
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002131 composite material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 2
- 229910001125 Pa alloy Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000005501 phase interface Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- MYOXMAQGEINAEF-UHFFFAOYSA-N [C].N1=NN=CC=C1 Chemical compound [C].N1=NN=CC=C1 MYOXMAQGEINAEF-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research 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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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 relates to a high-rigidity flame-retardant polypropylene alloy material and a preparation method thereof. The invention has the advantages of high strength, high modulus, environmental protection, flame retardance, low water absorption and the like, meets the requirements of high-performance miniaturization and environmental protection of electronic and electrical materials, has simple and convenient processing technology and has wide application prospect.
Description
Technical Field
The invention belongs to the field of alloy materials, and particularly relates to a high-rigidity flame-retardant polypropylene alloy material and a preparation method thereof.
Background
The polypropylene (PP) has the advantages of low density, low cost, excellent processability, excellent physical properties and the like, is widely applied to various industries such as household appliances, automobiles, garden tools and the like, and the application of the flame-retardant modified polypropylene material in the fields of building electricians, power supply peripheries and the like is gradually expanded by virtue of the advantages of the flame-retardant modified polypropylene material in CTI, ball pressure temperature and the like. At present, along with the development of the industry, electronic and electrical related equipment gradually develops towards high-performance miniaturization, and higher requirements are put forward on the comprehensive performance of materials. Therefore, how to prepare the modified polypropylene material with flame retardant and high strength and modulus properties is one of the important research directions in the industry at present.
Polyamide (PA) as an important engineering plastic has excellent mechanical property and heat-resistant stability, and a PP/PA6 alloy material can integrate the advantages of two materials, but PP and PA are a typical thermodynamic incompatible system, the phase interface tension is high, the phase interface adhesion is small, and conventional organic compatilizers such as PP grafted maleic anhydride and PP grafted dibutyl maleate have a certain compatibilization effect on the composite system, but the effect is still not ideal.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-rigidity flame-retardant polypropylene alloy material and a preparation method thereof, which further improve the strength modulus and realize high performance on the premise that the polypropylene alloy material meets the flame-retardant requirement.
The invention provides a high-rigidity flame-retardant polypropylene alloy material which comprises the following components in parts by weight:
the polypropylene is one or two of homo-polypropylene and co-polypropylene, and the melt flow rate is between 1 and 60g/10min under the test condition of 230 ℃/2.16 kg.
The polyamide is one or more of PA6, PA66 and PA 1010. Preferably PA 6.
The glass fiber is one or more of long glass fiber, short glass fiber, continuous glass fiber, low dielectric glass fiber and flat glass fiber.
The halogen-free flame retardant is a phosphorus-nitrogen intumescent flame retardant, and specifically is a mixture of two or three of polyphosphate, ammonium metaphosphate, triazine charring agent and encapsulated melamine cyanurate.
The compatilizer is one or more of PP grafted maleic anhydride, POE grafted maleic anhydride and PP grafted dibutyl maleate.
The micro-crosslinking agent is one or more of epoxy resin, phenolic resin and unsaturated polyester.
The modified inorganic nano filler is one or more of organic amine modified nano montmorillonite, modified wollastonite and organic modified nano silicon dioxide.
The coupling agent is one or more of an aminosilane coupling agent, an aluminum titanate coupling agent and a titanate coupling agent.
The flow modifier is one or two of hydroxyl-terminated hyperbranched polyester and carboxyl-terminated hyperbranched polyester.
The other auxiliary agents comprise a lubricant and/or an antioxidant.
The lubricant is one or more of erucamide, oleamide, EBS amides, PE wax and stearate.
The antioxidant is one or more of antioxidant 1010 (pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) ], antioxidant 168 (tris (2, 4-di-tert-butylphenyl) phosphite), antioxidant 1790(1,3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H,3H,5H) -trione), and antioxidant 412S (pentaerythritol tetrakis 3-lauryl thiopropionate).
The invention provides a preparation method of a high-rigidity flame-retardant polypropylene alloy material, which comprises the following steps:
the raw materials are weighed according to the proportion and uniformly mixed, wherein the glass fiber is fed on one side, and the mixture is extruded, pulled into strips and cut into particles by a double-screw extruder to obtain the high-rigidity flame-retardant polypropylene alloy material.
Advantageous effects
(1) The modified inorganic nano filler is adopted, so that the compatibility problem of the PP/PA alloy can be effectively improved, and the mechanical property of a composite system can be remarkably improved; on the other hand, a micro-crosslinking agent is added into the composite system, a crosslinking network can be formed at the interface, and the two phases penetrate each other, so that the interface structure is stable, and the compatibilization enhancing effect is achieved; in addition, the montmorillonite has obvious synergistic flame retardant effect in a halogen-free flame retardant system;
(2) the invention has excellent mechanical property and flame retardant property, the tensile strength can reach 110-2The flame retardant rating is V-0(UL94, 1.6 mm);
(3) according to the invention, through process adjustment, PP/PA forms a bicontinuous phase, the water absorption of the PA is effectively reduced by the barrier effect of the PP, and the stable usability of the material in a damp and hot environment is ensured;
(4) the invention has the advantages of high strength, high modulus, environmental protection, flame retardance, low water absorption and the like, meets the requirements of high-performance miniaturization and environmental protection of electronic and electrical materials, has simple and convenient processing technology and has wide application prospect.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Polypropylene: the melt flow rate of the homopolymerized polypropylene is between 1 and 60g/10min under the test condition of 230 ℃/2.16 kg.
Polyamide: PA6 resin.
Glass fiber: and (3) chopped glass fibers.
Halogen-free flame retardant: ammonium metaphosphate and triazine carbon forming agent with the mass ratio of 4: 1.
A compatilizer: PP-g-MAH.
Micro-crosslinking agent: and (3) epoxy resin.
Modified inorganic nanofiller: organic amine modified nano montmorillonite.
Coupling agent: an aminosilane coupling agent.
Flow modifier: hyper C100.
Antioxidant: an antioxidant 1010;
an antioxidant 168.
Lubricant: erucamide. (all the above raw materials are commercially available products)
Example 1
After 22 parts of polypropylene resin, 20 parts of PA6 resin, 22 parts of halogen-free flame retardant (ammonium metaphosphate: triazine charring agent: 4:1), 5 parts of PP-g-MAH, 1 part of micro-crosslinking agent, 0.5 part of organic amine modified nano montmorillonite, 0.2 part of aminosilane coupling agent, 0.2 part of flow modifier, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.3 part of erucamide are uniformly mixed, the mixture is added into a main feeding port of a double-screw extruder, 30 parts of chopped glass fiber is poured into a side feeding port at the rear end of the double-screw extruder, the temperature of the extruder is controlled between 220 ℃ and 240 ℃, and the mixture is subjected to bracing, cooling and dicing to obtain the high-rigidity flame-retardant polypropylene alloy material. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Example 2
After uniformly mixing 21 parts of polypropylene resin, 20 parts of PA6 resin, 22 parts of halogen-free flame retardant (ammonium metaphosphate: triazine charring agent: 4:1), 5 parts of PP-g-MAH, 2 parts of micro-crosslinking agent, 0.5 part of organic amine modified nano montmorillonite, 0.2 part of aminosilane coupling agent, 0.2 part of flow modifier, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.3 part of erucamide, adding the mixture into a main feeding port of a double-screw extruder, pouring 30 parts of chopped glass fiber into a side feeding port at the rear end of the double-screw extruder, controlling the temperature of the extruder to be between 220 ℃ and 240 ℃, and carrying out bracing, cooling and then cutting into granules to obtain the high-rigidity flame-retardant polypropylene alloy material. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Example 3
20 parts of polypropylene resin, 20 parts of PA6 resin, 22 parts of halogen-free flame retardant (ammonium metaphosphate: triazine charring agent: 4:1), 5 parts of PP-g-MAH, 3 parts of micro-crosslinking agent, 0.5 part of organic amine modified nano montmorillonite, 0.2 part of aminosilane coupling agent, 0.2 part of flow modifier, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.3 part of erucamide are uniformly mixed and then added into a main feeding port of a double-screw extruder, 30 parts of chopped glass fiber is poured into a side feeding port at the rear end of the double-screw extruder, the temperature of the extruder is controlled between 220 ℃ and 240 ℃, and the chopped glass fiber is pulled, cooled and cut into granules to obtain the high-rigidity flame-retardant polypropylene alloy material. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Example 4
22 parts of polypropylene resin, 20 parts of PA6 resin, 22 parts of halogen-free flame retardant (ammonium metaphosphate: triazine charring agent: 4:1), 5 parts of PP-g-MAH, 1 part of micro-crosslinking agent, 1 part of organic amine modified nano montmorillonite, 0.2 part of aminosilane coupling agent, 0.2 part of flow modifier, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.3 part of erucamide are uniformly mixed, then added into a main feeding port of a double-screw extruder, 30 parts of chopped glass fiber is poured into a side feeding port at the rear end of the double-screw extruder, the temperature of the extruder is controlled between 220 ℃ and 240 ℃, and the mixture is subjected to bracing, cooling and then cutting into granules to obtain the high-rigidity flame-retardant polypropylene alloy material. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Example 5
22 parts of polypropylene resin, 20 parts of PA6 resin, 22 parts of halogen-free flame retardant (ammonium metaphosphate: triazine charring agent: 4:1), 5 parts of PP-g-MAH, 1 part of micro-crosslinking agent, 3 parts of organic amine modified nano montmorillonite, 0.2 part of aminosilane coupling agent, 0.2 part of flow modifier, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.3 part of erucamide are uniformly mixed, then added into a main feeding port of a double-screw extruder, 30 parts of chopped glass fiber is poured into a side feeding port at the rear end of the double-screw extruder, the temperature of the extruder is controlled between 220 ℃ and 240 ℃, and the mixture is subjected to bracing, cooling and then cutting into granules to obtain the high-rigidity flame-retardant polypropylene alloy material. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Example 6
23 parts of polypropylene resin, 22 parts of PA6 resin, 19 parts of halogen-free flame retardant (ammonium metaphosphate: triazine charring agent: 4:1), 5 parts of PP-g-MAH, 1 part of micro-crosslinking agent, 3 parts of organic amine modified nano montmorillonite, 0.2 part of aminosilane coupling agent, 0.2 part of flow modifier, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.3 part of erucamide are uniformly mixed, then added into a main feeding port of a double-screw extruder, 30 parts of chopped glass fiber is poured into a side feeding port at the rear end of the double-screw extruder, the temperature of the extruder is controlled between 220 ℃ and 240 ℃, and the mixture is subjected to bracing, cooling and then cutting into granules to obtain the high-rigidity flame-retardant polypropylene alloy material. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Example 7
After 32 parts of polypropylene resin, 20 parts of PA6 resin, 22 parts of halogen-free flame retardant (ammonium metaphosphate: triazine charring agent: 4:1), 5 parts of PP-g-MAH, 1 part of micro-crosslinking agent, 0.5 part of organic amine modified nano montmorillonite, 0.2 part of aminosilane coupling agent, 0.2 part of flow modifier, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.3 part of erucamide are uniformly mixed, the mixture is added into a main feeding port of a double-screw extruder, 20 parts of chopped glass fiber is poured into a side feeding port at the rear end of the double-screw extruder, the temperature of the extruder is controlled between 220 ℃ and 240 ℃, and the mixture is subjected to bracing, cooling and dicing to obtain the high-rigidity flame-retardant polypropylene alloy material. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Comparative example 1
Uniformly mixing 42 parts of polypropylene resin, 22 parts of a halogen-free flame retardant (ammonium metaphosphate: triazine charring agent is 4:1), 5 parts of PP-g-MAH, 1 part of a micro-crosslinking agent, 0.5 part of organic amine modified nano-montmorillonite, 0.2 part of an aminosilane coupling agent, 0.2 part of a flow modifier, 0.1 part of an antioxidant 1010, 0.2 part of an antioxidant 168 and 0.3 part of erucamide, adding the mixture into a main feeding port of a double-screw extruder, pouring 30 parts of chopped glass fibers into a side feeding port at the rear end of the double-screw extruder, controlling the temperature of the extruder to be between 220 ℃ and 240 ℃, bracing, cooling and then pelletizing to obtain the high-rigidity flame-retardant polypropylene alloy material. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Comparative example 2
After 23 parts of polypropylene resin, 20 parts of PA6 resin, 22 parts of halogen-free flame retardant (ammonium metaphosphate: triazine charring agent: 4:1), 5 parts of PP-g-MAH, 0.5 part of organic amine modified nano montmorillonite, 0.2 part of aminosilane coupling agent, 0.2 part of flow modifier, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.3 part of erucamide are uniformly mixed, a main feeding port of a double-screw extruder is added, 30 parts of chopped glass fiber is poured into a side feeding port at the rear end of the double-screw extruder, the temperature of the extruder is controlled between 220 ℃ and 240 ℃, and the chopped polypropylene alloy material with high rigidity is obtained by carrying out bracing, cooling and then carrying out granulation. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Comparative example 3
After uniformly mixing 23 parts of polypropylene resin, 20 parts of PA6 resin, 22 parts of halogen-free flame retardant (ammonium metaphosphate: triazine charring agent: 4:1), 5 parts of PP-g-MAH, 0.2 part of aminosilane coupling agent, 0.2 part of flow modifier, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.3 part of erucamide, adding the mixture into a main feeding port of a double-screw extruder, pouring 30 parts of chopped glass fiber into a side feeding port at the rear end of the double-screw extruder, controlling the temperature of the extruder to be between 220 and 240 ℃, and carrying out bracing, cooling and granulating to obtain the high-rigidity flame-retardant polypropylene alloy material. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Comparative example 4
After 22 parts of polypropylene resin, 20 parts of PA6 resin, 22 parts of halogen-free flame retardant (ammonium metaphosphate: triazine char forming agent: 4:1), 5 parts of PP-g-MAH, 1 part of micro-crosslinking agent, 0.2 part of silane coupling agent, 0.2 part of flow modifier, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.3 part of erucamide are uniformly mixed, a main feeding port of a double-screw extruder is added, 30 parts of chopped glass fiber is poured into a side feeding port at the rear end of the double-screw extruder, the temperature of the extruder is controlled between 220 ℃ and 240 ℃, and the mixture is subjected to bracing, cooling and then grain cutting to obtain the high-rigidity flame-retardant polypropylene alloy material. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Comparative example 5
43 parts of PA6 resin, 22 parts of halogen-free flame retardant (ammonium metaphosphate: triazine charring agent is 4:1), 5 parts of PP-g-MAH, 0.2 part of aminosilane coupling agent, 0.2 part of flow modifier, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.3 part of erucamide are uniformly mixed, then the mixture is added into a main feeding port of a double-screw extruder, 30 parts of chopped glass fiber is poured into a side feeding port at the rear end of the double-screw extruder, the temperature of the extruder is controlled between 220 ℃ and 240 ℃, and the mixture is subjected to bracing, cooling and then pelleting to obtain the high-rigidity flame-retardant polypropylene alloy material. The material is injection molded into products within the range of 220 ℃ and 250 ℃, and the relevant performance test results of the products are shown in Table 1.
Table 1 results of performance test of examples and comparative examples
As can be seen from Table 1, the high-rigidity flame-retardant polypropylene alloy designed by the invention has excellent mechanical properties and flame retardant properties. As can be seen from the comparison of the data of the example 1 and the comparative example 1, after the polyamide is introduced into the flame-retardant reinforced polypropylene system, the tensile strength is improved by more than 30 percent and reaches 128MPa, the flexural modulus is improved by nearly 1000MPa, and the flame-retardant grade of a 1.6mm sample strip is kept at the influence of V-0. Compared with the comparative example 5, the water absorption of the PP/PA alloy material is greatly reduced compared with that of the reinforced polyamide, so that the stable use of the material in a damp and hot environment is ensured. As can be seen from the comparison of the data of the examples 1 to 3 and the comparative examples 2 to 3, after the micro-crosslinking agent is added, the comprehensive mechanical property of the system is remarkably improved, a crosslinking network is formed at an interface of the crosslinking system, and the two phases are mutually penetrated, so that the interface structure is stable, and the compatibilization enhancing effect is achieved. As can be seen from the comparison of the data of the examples 3-5 and the comparative examples 3-4, the addition of the nano montmorillonite has the function of enhancing and toughening, and the tensile and impact resistance of the composite material are improved, wherein the tensile strength is improved by 30MPa, and the modulus is improved by nearly 1000 MPa. It can be seen from the data of example 6 that the addition of the nano-montmorillonite can suitably reduce the amount of the flame retardant and still ensure the realization of the V-0 flame retardant rating.
Therefore, by combining the above embodiments, it can be seen that the mechanical properties of the composite material can be effectively improved by introducing the polyamide into the flame-retardant reinforced polypropylene system, and the V-0 of a 1.6mm sample strip is realized, and meanwhile, the water absorption rate is significantly reduced, and the use stability of the material in a damp and hot environment is ensured. The addition of the micro-crosslinking agent and the organic modified inorganic nano-filler enhances the comprehensive performance of the composite system through the interface effect, and the micro-crosslinking agent and the organic modified inorganic nano-filler have good synergistic effect.
Claims (10)
1. A high-rigidity flame-retardant polypropylene alloy material is characterized in that: the paint comprises the following components in parts by weight:
2. the alloy material of claim 1, wherein: the polypropylene is one or two of homo-polypropylene and co-polypropylene, and the melt flow rate is between 1 and 60g/10min under the test condition of 230 ℃/2.16 kg.
3. The alloy material of claim 1, wherein: the polyamide is one or more of PA6, PA66 and PA 1010.
4. The alloy material of claim 1, wherein: the glass fiber is one or more of long glass fiber, short glass fiber, continuous glass fiber, low dielectric glass fiber and flat glass fiber; the halogen-free flame retardant is a phosphorus-nitrogen intumescent flame retardant.
5. The alloy material of claim 1, wherein: the compatilizer is one or more of PP grafted maleic anhydride, POE grafted maleic anhydride and PP grafted dibutyl maleate.
6. The alloy material of claim 1, wherein: the micro-crosslinking agent is one or more of epoxy resin, phenolic resin and unsaturated polyester.
7. The alloy material of claim 1, wherein: the modified inorganic nano filler is one or more of organic amine modified nano montmorillonite, modified wollastonite and organic modified nano silicon dioxide.
8. The alloy material of claim 1, wherein: the coupling agent is one or more of an aminosilane coupling agent, an aluminum titanate coupling agent and a titanate coupling agent; the flow modifier is one or two of hydroxyl-terminated hyperbranched polyester and carboxyl-terminated hyperbranched polyester.
9. The alloy material of claim 1, wherein: the other auxiliary agents comprise a lubricant and/or an antioxidant.
10. A method for preparing the high-rigidity flame-retardant polypropylene alloy material according to claim 1, comprising the following steps:
the raw materials are weighed according to the proportion and uniformly mixed, wherein the glass fiber is fed on one side, and the mixture is extruded, pulled into strips and cut into particles by a double-screw extruder to obtain the high-rigidity flame-retardant polypropylene alloy material.
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| WO2022135250A1 (en) * | 2020-12-21 | 2022-06-30 | 金发科技股份有限公司 | Alloy material having ceramicized surface, preparation method therefor and application thereof |
| CN115490954A (en) * | 2022-08-29 | 2022-12-20 | 湖北合聚新材料有限公司 | Polypropylene composite material and preparation method and application thereof |
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