CN116285116A - High-melt-strength long glass fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
High-melt-strength long glass fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- CN116285116A CN116285116A CN202211738973.6A CN202211738973A CN116285116A CN 116285116 A CN116285116 A CN 116285116A CN 202211738973 A CN202211738973 A CN 202211738973A CN 116285116 A CN116285116 A CN 116285116A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 107
- -1 polypropylene Polymers 0.000 title claims abstract description 106
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 105
- 239000003365 glass fiber Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 40
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 37
- 239000004970 Chain extender Substances 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 14
- 239000007924 injection Substances 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 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 claims description 2
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000012856 weighed raw material Substances 0.000 claims description 2
- 238000005187 foaming Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000000155 melt Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 102200017650 rs28383586 Human genes 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 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
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/14—Copolymers of propene
-
- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
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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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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Abstract
The invention discloses a high-melt-strength long glass fiber reinforced polypropylene composite material and a preparation method thereof. The high-melt-strength long glass fiber reinforced polypropylene composite material comprises the following components in parts by weight: 40-80 parts of polypropylene resin, 20-60 parts of continuous glass fiber, 1-5 parts of compatilizer, 0.1-3 parts of branched chain extender, 0.1-1 part of chain segment stabilizing auxiliary agent and 0.1-1 part of auxiliary stabilizing auxiliary agent. The invention also discloses a preparation method of the high-melt-strength long glass fiber reinforced polypropylene composite material, which increases a long-branch chain structure through a branch chain extender, and reduces the degradation of polypropylene and maintains the stability of a chain segment by directly bonding a chain segment stabilizing auxiliary agent to a polypropylene main chain in the production process. The invention relates to a high-melt-strength long glass fiber reinforced polypropylene composite material which has high melt strength and can be used for chemical foaming.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a high-melt-strength long glass fiber reinforced polypropylene composite material and a preparation method thereof.
Background
The long glass fiber reinforced polypropylene material has good mechanical property and dimensional stability, and is widely applied to the fields of automobiles, household appliances and the like to replace metal or engineering plastics for manufacturing structural members. In the field of automobile parts, long glass fiber reinforced polypropylene materials are often used for manufacturing large parts with requirements on mechanical properties of materials, such as main and auxiliary instrument boards, front end frames, skylight frameworks, tail door inner plates and the like. The automobile industry is also faced with huge energy saving and emission reduction pressure, and the weight reduction of parts by physical foaming and chemical foaming becomes a popular research direction in the current automobile industry. However, the matrix polypropylene molecular chain of the long glass fiber reinforced polypropylene material is of a linear structure, and when the temperature exceeds the melting point, the melt strength of the long glass fiber reinforced polypropylene material is rapidly reduced, so that in the foaming process of the long glass fiber reinforced polypropylene melt, bubbles are influenced by tensile stress in the growth stage to generate cracking and collapse, and the part has the defects of uneven internal cells, concave surface and the like. Therefore, how to improve the melt strength of the long glass fiber reinforced polypropylene material has important significance for future application in the automobile field.
The melt strength of the long glass fiber reinforced polypropylene material is mainly started from the aspect of improving the melt strength of a polypropylene matrix. At present, there are three main approaches to improving the melt strength of polypropylene: high-energy ray irradiation method, in-situ polymerization method and reactive extrusion method.
The high-energy ray irradiation method is a method for improving the melt strength of polypropylene by generating free radicals through high-energy ray irradiation and introducing a long-chain branched chain structure to a polypropylene main chain. Patent CN201210070775.7 discloses a method for preparing high melt strength polypropylene by heat treatment by irradiating twin screw extrusion pelletized particles with high energy electron rays. The high melt strength polypropylene prepared by the method has controllable structure, no peculiar smell of products and green and pollution-free processing process. However, the high-energy electron beam irradiation equipment has high investment, heat treatment is needed after irradiation, the operation steps are more, the working procedures are complex, and the industrial production difficulty is high.
The in-situ polymerization method is a method for directly synthesizing long-branched polypropylene by utilizing a catalyst to carry out grafting reaction in the polymerization process. Patent CN201810417286.1 discloses an industrial-grade method for preparing high melt strength polypropylene by in-situ one-step direct polymerization in a polymerization kettle of a batch liquid phase bulk polymerization process. The high melt strength polypropylene prepared by the method has higher foaming multiplying power and is suitable for a foaming process. However, the in-situ polymerization method has higher difficulty and high operation precision requirement, and is suitable for enterprises producing polypropylene raw materials.
Reactive extrusion is a process for improving the melt strength of a material by blending modification. The reactive extrusion method has the advantages of small equipment investment and simple operation process, and is suitable for large-scale industrial production. Patent CN101768242 discloses a method for preparing high melt strength polypropylene by grafting reaction of diene as grafting monomer with polypropylene melt. The high melt strength polypropylene prepared by the method has certain melt strength, larger stretching ratio and excellent melt ductility. However, the introduction of the diene monomer to graft with polypropylene requires the use of an initiator, the actual grafting efficiency is poor in controllability, the production temperature is lower than 250 ℃, and the method is not suitable for long glass fiber reinforced polypropylene materials. Patent CN110804135 discloses a method for preparing polypropylene with high melt strength by adopting a double bond-containing linear polymer through the processes of pre-crosslinking, pre-dispersing and reactive grafting of raw materials, but the method dehydrogenates a polypropylene molecular chain through an initiator to generate free radicals, which obviously causes a large amount of small molecular volatile matters to be generated, finally affects the odor and emission of materials, and the materials cannot meet the odor and emission requirements of the automotive industry on interior materials, so that the use of the materials in automotive interiors is limited.
Disclosure of Invention
In order to overcome the defects of the prior art, a high-quality material is developed for solving the problem that uneven foaming or foam collapse easily occurs when long glass fiber reinforced polypropylene composite material is subjected to chemical foaming. The invention provides a high-melt-strength long glass fiber reinforced polypropylene composite material.
The technical scheme adopted for solving the technical problems is as follows:
the high-melt-strength long glass fiber reinforced polypropylene composite material consists of the following raw materials in parts by weight: 40-80 parts of polypropylene resin, 20-60 parts of continuous glass fiber, 1-5 parts of compatilizer, 0.1-3 parts of branched chain extender, 0.1-1 part of chain segment stabilizing auxiliary agent and 0.1-1 part of auxiliary stabilizing auxiliary agent.
Wherein,,
the polypropylene is formed by blending copolymer polypropylene and homopolymerized polypropylene, wherein the copolymer polypropylene accounts for 65 percent, and the homopolymerized polypropylene accounts for 35 percent.
The continuous glass fiber is one or the combination of two of Mount Taishan glass fiber TCR738-2400 continuous glass fiber, chongqing International 4305PM-2400 continuous glass fiber or European style Kening SE4805-2400 continuous glass fiber.
The compatilizer is one or the combination of two of MAH-g-PP, MAH-g-POE or MAH-g-PS.
The branched chain extender is one or the combination of two of hyperbranched polyamide, hyperbranched polyester or hyperbranched polyurethane acrylate.
The chain segment stabilizing auxiliary agent is a reactive hindered phenol antioxidant Luchemao-R300.
The auxiliary stabilizing auxiliary agent is one or the combination of two of phosphite antioxidant 168 or thioester antioxidant DSTP.
The preparation method of the high-melt-strength long glass fiber reinforced polypropylene composite material comprises the following steps:
1): weighing raw materials of polypropylene resin, a compatilizer, a branched chain extender, a chain segment stabilizing auxiliary agent and an auxiliary stabilizing auxiliary agent according to the weight ratio, putting the weighed raw materials into a high-speed mixer for uniform mixing, and then entering an impregnating tank through a double-screw extruder;
2): the continuous glass fiber is subjected to bracing, cooling, granulating and drying treatment after passing through the dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
The invention adopts the technical scheme, and the obtained beneficial effects are as follows:
the invention adopts hyperbranched polyamide as a branched chain extender to introduce highly branched macromolecular chain segments into polypropylene molecular chain segments so as to obviously improve the melt strength of the long glass fiber reinforced polypropylene material, and adopts a reactive hindered phenol antioxidant as a chain segment stabilizing auxiliary agent to bond to a polypropylene main chain in the reaction extrusion process so as to prevent the macromolecular chain segments introduced by the branched chain extender from being broken or the polypropylene from being degraded, maintain the lasting stability of the final polypropylene chain segments, ensure the stable improvement of the melt strength of the final long glass fiber reinforced polypropylene material, ensure that the long glass fiber reinforced polypropylene material is suitable for a chemical foaming molding process, and simultaneously ensure that the mechanical property of the long glass fiber reinforced polypropylene material is basically unchanged.
Detailed Description
The technical scheme of the invention is further described below with reference to specific examples.
The product used in the embodiment of the invention is as follows:
PP-1, exxon Mobil, PP7555;
PP-2, sea-weight petrochemical, M60T;
continuous glass fiber: mount Taishan glass fiber, TCR738-2400;
and (3) a compatilizer: maleic anhydride grafted polypropylene;
branched chain extender: branchings of martial arts, HPN202;
segment stabilizer: elFatochem, luchemao-R300;
auxiliary stabilizer 1: phosphite antioxidants, basf, 168;
auxiliary stabilizer 2: thioester antioxidants, basf, DSTP, germany
Embodiments of the invention are as follows:
example 1:
1): weighing 74.9 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 0.5 part of branched chain extender, 0.2 part of chain segment stabilizing auxiliary agent and 0.4 part of auxiliary stabilizing auxiliary agent, stirring and mixing uniformly in a high-speed machine, and then entering an impregnation tank through a double-screw extruder;
2): carrying out bracing, cooling, granulating and drying treatment on 20 parts by weight of continuous glass fiber passing through a dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Example 2:
1): weighing 74.4 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 1 part of branched chain extender, 0.2 part of chain segment stabilizing auxiliary agent and 0.4 part of auxiliary stabilizing auxiliary agent, uniformly stirring and mixing in a high-speed machine, and then entering an impregnation tank through a double-screw extruder;
2): carrying out bracing, cooling, granulating and drying treatment on 20 parts by weight of continuous glass fiber passing through a dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Example 3:
1): weighing 73.9 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 1.5 parts of branched chain extender, 0.2 part of chain segment stabilizing auxiliary agent and 0.4 part of auxiliary stabilizing auxiliary agent, stirring and mixing uniformly in a high-speed machine, and then entering an impregnation tank through a double-screw extruder;
2): carrying out bracing, cooling, granulating and drying treatment on 20 parts by weight of continuous glass fiber passing through a dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Example 4:
1): weighing 73.4 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 2 parts of branched chain extender, 0.2 part of chain segment stabilizing auxiliary agent and 0.4 part of auxiliary stabilizing auxiliary agent, uniformly stirring and mixing in a high-speed machine, and then entering an impregnation tank through a double-screw extruder;
2): carrying out bracing, cooling, granulating and drying treatment on 20 parts by weight of continuous glass fiber passing through a dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Example 5:
1): weighing 74.2 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 1 part of branched chain extender, 0.4 part of chain segment stabilizing auxiliary agent and 0.4 part of auxiliary stabilizing auxiliary agent, uniformly stirring and mixing in a high-speed machine, and then entering an impregnation tank through a double-screw extruder;
2): carrying out bracing, cooling, granulating and drying treatment on 20 parts by weight of continuous glass fiber passing through a dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Example 6:
1): weighing 73.8 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 1.5 parts of branched chain extender, 0.4 part of chain segment stabilizing auxiliary agent and 0.4 part of auxiliary stabilizing auxiliary agent, stirring and mixing uniformly in a high-speed machine, and then entering an impregnation tank through a double-screw extruder;
2): carrying out bracing, cooling, granulating and drying treatment on 20 parts by weight of continuous glass fiber passing through a dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Example 7:
1): weighing 73 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 2 parts of branched chain extender, 0.6 part of chain segment stabilizing auxiliary agent and 0.4 part of auxiliary stabilizing auxiliary agent, uniformly stirring and mixing in a high-speed machine, and then entering an impregnation tank through a double-screw extruder;
2): carrying out bracing, cooling, granulating and drying treatment on 20 parts by weight of continuous glass fiber passing through a dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Example 8:
1): weighing 63.5 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 1.5 parts of branched chain extender, 0.6 part of chain segment stabilizing auxiliary agent and 0.4 part of auxiliary stabilizing auxiliary agent, stirring and mixing uniformly in a high-speed machine, and then entering an impregnation tank through a double-screw extruder;
2): 30 parts by weight of continuous glass fiber is subjected to bracing, cooling, granulating and drying treatment after passing through a dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Comparative example 1:
1): weighing 75.4 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 0.2 part of chain segment stabilizing auxiliary agent and 0.4 part of auxiliary stabilizing auxiliary agent, stirring and uniformly mixing in a high-speed machine, and then entering an impregnating tank through a double-screw extruder;
2): and (3) carrying out bracing, cooling, granulating and drying treatment on 20 parts by weight of continuous glass fiber passing through the dipping tank.
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Comparative example 2:
1): weighing 74.6 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 1 part of branched chain extender and 0.4 part of auxiliary stabilizing auxiliary agent, stirring and uniformly mixing in a high-speed machine, and then entering an impregnating tank through a double-screw extruder;
2): the continuous glass fiber with the weight ratio of 20 parts is subjected to bracing, cooling, granulating and drying treatment after passing through a dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Comparative example 3:
1): weighing 73.6 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 2 parts of branched chain extender and 0.4 part of auxiliary stabilizing auxiliary agent, stirring and uniformly mixing in a high-speed machine, and then entering an impregnating tank through a double-screw extruder;
2): the continuous glass fiber with the weight ratio of 20 parts is subjected to bracing, cooling, granulating and drying treatment after passing through a dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Comparative example 4:
1): weighing 64.6 parts of raw material polypropylene resin according to the weight ratio, and drying by a baking oven; adding 4 parts of compatilizer, 1 part of branched chain extender and 0.4 part of auxiliary stabilizing auxiliary agent, stirring and uniformly mixing in a high-speed machine, and then entering an impregnating tank through a double-screw extruder;
2): 30 parts of continuous glass fiber in weight ratio is subjected to bracing, cooling, granulating and drying treatment after passing through a dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
Material melt strength and mechanical properties comparison:
carrying out melt strength test by using RHEOTens type polymer melt tensile rheometer; tensile strength and flexural strength were tested by a universal material tester.
The results of the sample testing are shown in Table 1:
table 1 sample test results
| Test sample | Melt Strength (cN) | Tensile Strength (MPa) | Flexural Strength (MPa) |
| Example 1 | 14 | 84.2 | 114.1 |
| Example 2 | 20 | 83.6 | 112.7 |
| Example 3 | 28 | 81.8 | 113.1 |
| Example 4 | 32 | 81.3 | 112.5 |
| Example 5 | 31 | 84.9 | 113.8 |
| Example 6 | 36 | 84.1 | 112.9 |
| Example 7 | 49 | 85.7 | 115.2 |
| Example 8 | 47 | 113.5 | 154.9 |
| Comparative example 1 | 9 | 86.1 | 114.7 |
| Comparative example 2 | 12 | 74.4 | 98.2 |
| Comparative example 3 | 23 | 72.7 | 101.5 |
| Comparative example 4 | 17 | 103.1 | 134.4 |
From the above examples and comparative examples, it can be seen that the high melt strength long glass fiber reinforced polypropylene composite of the present invention is a composite material having high melt strength and excellent mechanical properties. The data comparison according to table 1 shows that the addition of the branched chain extender can significantly improve the melt strength of the long glass fiber reinforced polypropylene material, such as comparative example 1 (long glass fiber reinforced polypropylene composite material with 20% glass fiber content without the branched chain extender), which has a melt strength far lower than that of example 4 (high melt strength long glass fiber reinforced polypropylene composite material with 20% glass fiber content with 2 parts of branched chain extender added); according to the data in table 1, for example 7 (a high melt strength long glass fiber reinforced polypropylene composite material with 20% glass fiber content added with 2 parts of branched chain extender and 0.6 part of chain segment stabilizing additive), the melt strength and mechanical properties of the long glass fiber reinforced polypropylene composite material are obviously better than those of comparative example 3 (a long glass fiber reinforced polypropylene composite material with 20% glass fiber content added with 2 parts of branched chain extender), which shows that the chain segment stabilizing additive can generate a synergistic effect with the branched chain extender, and the addition of the chain segment stabilizing additive can better improve the melt strength of the long glass fiber reinforced polypropylene material, and meanwhile, the mechanical properties of the prepared high melt strength long glass fiber reinforced polypropylene composite material can be kept unchanged basically. The preparation method of the high-melt-strength long glass fiber reinforced polypropylene composite material is simple to operate, can ensure that the long glass fiber reinforced polypropylene composite material has excellent melt strength and simultaneously has basically unchanged mechanical properties, and is suitable for industrial production and application.
Claims (8)
1. The high-melt-strength long glass fiber reinforced polypropylene composite material is characterized by comprising the following raw materials in parts by weight: 40-80 parts of polypropylene resin, 20-60 parts of continuous glass fiber, 1-5 parts of compatilizer, 0.1-3 parts of branched chain extender, 0.1-1 part of chain segment stabilizing auxiliary agent and 0.1-1 part of auxiliary stabilizing auxiliary agent.
2. The high melt strength long glass fiber reinforced polypropylene composite of claim 1, wherein: the polypropylene is formed by blending copolymer polypropylene and homopolymerized polypropylene, wherein the copolymer polypropylene accounts for 65 percent, and the homopolymerized polypropylene accounts for 35 percent.
3. The high melt strength long glass fiber reinforced polypropylene composite of claim 1, wherein: the continuous glass fiber is one or the combination of two of Mount Taishan glass fiber TCR738-2400 continuous glass fiber, chongqing International 4305PM-2400 continuous glass fiber or European style Kening SE4805-2400 continuous glass fiber.
4. The high melt strength long glass fiber reinforced polypropylene composite of claim 1, wherein: the compatilizer is one or the combination of two of MAH-g-PP, MAH-g-POE or MAH-g-PS.
5. The high melt strength long glass fiber reinforced polypropylene composite of claim 1, wherein: the branched chain extender is one or the combination of two of hyperbranched polyamide, hyperbranched polyester or hyperbranched polyurethane acrylate.
6. The high melt strength long glass fiber reinforced polypropylene composite of claim 1, wherein: the chain segment stabilizing auxiliary agent is a reactive hindered phenol antioxidant Luchemao-R300.
7. The high melt strength long glass fiber reinforced polypropylene composite of claim 1, wherein: the auxiliary stabilizing auxiliary agent is one or the combination of two of phosphite antioxidant 168 or thioester antioxidant DSTP.
8. The method for preparing a high melt strength long glass fiber reinforced polypropylene composite material according to any one of claims 1 to 7, comprising the steps of:
1): weighing raw materials of polypropylene resin, a compatilizer, a branched chain extender, a chain segment stabilizing auxiliary agent and an auxiliary stabilizing auxiliary agent according to the weight ratio, putting the weighed raw materials into a high-speed mixer for uniform mixing, and then entering an impregnating tank through a double-screw extruder;
2): the continuous glass fiber is subjected to bracing, cooling, granulating and drying treatment after passing through the dipping tank;
3): and (5) taking the long glass fiber reinforced polypropylene material obtained in the step (2) to be injection molded into ISO standard sample bars for standby.
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| CN106995550A (en) * | 2016-01-26 | 2017-08-01 | 合肥杰事杰新材料股份有限公司 | A kind of ultrabranching polyamide modified polypropylene composite material and preparation method thereof |
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| Title |
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| 刘慧杰;梁博;鞠猛;: "聚丙烯抗氧剂的作用机理及发展趋势", 辽宁化工, no. 10, 20 October 2008 (2008-10-20), pages 688 - 691 * |
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