CN115449153A - Polypropylene composition, long-fiber reinforced polypropylene composite material, preparation method and application thereof, and product - Google Patents
Polypropylene composition, long-fiber reinforced polypropylene composite material, preparation method and application thereof, and product Download PDFInfo
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- CN115449153A CN115449153A CN202110643480.3A CN202110643480A CN115449153A CN 115449153 A CN115449153 A CN 115449153A CN 202110643480 A CN202110643480 A CN 202110643480A CN 115449153 A CN115449153 A CN 115449153A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 360
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 349
- -1 Polypropylene Polymers 0.000 title claims abstract description 348
- 239000000835 fiber Substances 0.000 title claims abstract description 177
- 239000002131 composite material Substances 0.000 title claims abstract description 115
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000011256 inorganic filler Substances 0.000 claims abstract description 20
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 230000014759 maintenance of location Effects 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims description 65
- 229920005989 resin Polymers 0.000 claims description 65
- 238000005470 impregnation Methods 0.000 claims description 43
- 238000001125 extrusion Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 32
- 239000003365 glass fiber Substances 0.000 claims description 29
- 238000012545 processing Methods 0.000 claims description 28
- 239000000155 melt Substances 0.000 claims description 17
- 239000000314 lubricant Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 6
- 238000005452 bending Methods 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
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002667 nucleating agent Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
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- 239000000454 talc Substances 0.000 claims description 3
- 229910052623 talc Inorganic materials 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 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 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000003733 fiber-reinforced composite Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
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- 230000003078 antioxidant effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
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- 229920001296 polysiloxane Polymers 0.000 description 8
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- 238000001746 injection moulding Methods 0.000 description 4
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- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical group C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical group C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
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- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
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- 239000011707 mineral Substances 0.000 description 1
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- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08J2323/12—Polypropene
-
- 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
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- 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
-
- 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
- C08J2423/14—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
- 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
-
- 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
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- 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
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
-
- 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
Abstract
The invention relates to the field of fiber reinforced composite materials, in particular to a polypropylene composition, a long-fiber reinforced polypropylene composite material, a preparation method and application thereof, and a product. The composition comprises: 8-50 parts of polypropylene I, 8-50 parts of polypropylene II, 20-60 parts of continuous fibers, 1-5 parts of compatibilizer, 0-30 parts of inorganic filler and 0.5-2 parts of auxiliary agent; wherein the weight ratio A of the polypropylene I to the polypropylene II satisfies the following condition: a is more than or equal to 0.16 and less than or equal to 6.25, and the number average molecular weight of the polypropylene I is not equal to that of the polypropylene II. The composition is used for preparing the long-fiber reinforced polypropylene composite material, and can effectively improve the fiber retention length, the flow property and the mechanical property of the long-fiber reinforced polypropylene composite material.
Description
Technical Field
The invention relates to the field of fiber reinforced composite materials, in particular to a polypropylene composition, a long-fiber reinforced polypropylene composite material, a preparation method and application thereof, and a product.
Background
Polypropylene is a versatile plastic with good physical-mechanical, chemical and processing properties. Due to the defects of large low-temperature brittleness, large shrinkage rate of products and the like of PP, the application and development of PP in the fields of precision, engineering materials and the like are greatly limited, glass fibers, talcum powder, mineral powder and the like are generally used for reinforcement and modification, the glass fiber reinforcement is the first choice for light weight, the cost performance is high, and the PP is widely applied to structural parts of automobiles, household appliances, electric tools and the like to replace materials such as metal, nylon and the like.
Fiber reinforced polypropylene is classified into three types of Short Fiber (SFT), long Fiber (LFT), and Continuous Fiber (CFT) reinforcement, depending on the fiber retention length. The mechanical property of the short fiber reinforced polypropylene (PP/SFT) is relatively low, and the continuous fiber reinforced polypropylene (PP/CFT) has excellent mechanical property, but the molding process is complex and the cost is high. Compared with PP/SFT, the long fiber reinforced polypropylene (PP/LFT) has better performance, and compared with PP/CFT, the PP/LFT has the characteristics of simple processing technology, low cost and the like. Accordingly, LFT reinforced thermoplastic composites are receiving increasing attention.
Long fiber reinforced polypropylene materials are currently mainly prepared by impregnation, direct injection molding and composite fiber processes. The direct injection molding method has simple production process and higher continuity, but has higher requirement on equipment; the composite fiber method has high process requirement and large equipment investment, and large-scale popularization and application are not developed. In contrast, the melt impregnation method has relatively low investment and high production efficiency, and is the most common method for producing long-fiber reinforced polypropylene materials at present.
For example, CN111138756A and CN111117062A respectively adopt a melting and dipping method to prepare long glass fiber reinforced polypropylene for products such as automobile storage battery brackets and automobile front end modules. Many studies on glass fiber reinforced polypropylene composite materials have been reported, but many studies relate to improvement of interfacial bonding strength between glass fibers and polypropylene substrates, for example, CN103589058A, CN103342858A, and CN102329448A select polar maleic anhydride grafted polypropylene and silane coupling agent as interfacial compatibilizer between GF and PP to improve interfacial bonding force between GF and PP, so as to obtain good interfacial bonding.
Along with the increase of the particle length of the long-fiber reinforced polypropylene product and the fiber retention length in the product, the integration degree of the product is continuously improved, the size of the product is increased, the structural design is more and more complicated, the design and the use requirements of the product can not be completely met by the common long-fiber reinforced polypropylene, and relatively few reports on the processing flow property of the long-fiber reinforced polypropylene product are reported at present.
At present, long-fiber reinforced polypropylene composite materials are required to have longer fiber retention length and stronger flow property and mechanical property. Accordingly, there is a need for a long fiber reinforced polypropylene composite and method suitable for providing a composite having excellent fiber retention length, flow properties, and mechanical properties at the same time.
Disclosure of Invention
The invention aims to overcome the problems of low fiber retention length, poor processing fluidity, poor mechanical property and the like of the existing long-fiber reinforced polypropylene composite material, and provides a polypropylene composition, a long-fiber reinforced polypropylene composite material, a preparation method and application thereof, and a product.
In order to achieve the above object, the present invention provides in a first aspect a polypropylene composition comprising: 8-50 parts of polypropylene I, 8-50 parts of polypropylene II, 20-60 parts of continuous fibers, 1-5 parts of compatibilizer, 0-30 parts of inorganic filler and 0.5-2 parts of auxiliary agent;
wherein the weight ratio A of the polypropylene I to the polypropylene II satisfies the following requirements: a is more than or equal to 0.16 and less than or equal to 6.25, and the number average molecular weight of the polypropylene I is not equal to that of the polypropylene II.
The invention provides a long-fiber reinforced polypropylene composite material, which is prepared from the composition provided by the first aspect.
The third aspect of the present invention provides a method for preparing a long fiber reinforced polypropylene composite material, comprising:
(1) Mixing 8-50 parts by weight of polypropylene I, 8-50 parts by weight of polypropylene II, 1-5 parts by weight of compatibilizer, 0-30 parts by weight of inorganic filler and 0.5-2 parts by weight of auxiliary agent to obtain polypropylene mixed resin;
(2) Extruding the polypropylene mixed resin to obtain a resin melt;
(3) In an extrusion impregnation die head, carrying out impregnation processing on the resin melt and 20-60 parts by weight of continuous fibers to enable the resin melt to wrap the continuous fibers so as to obtain a long fiber reinforced polypropylene composite material;
wherein the weight ratio A of the polypropylene I to the polypropylene II satisfies the following condition: a is more than or equal to 0.16 and less than or equal to 6.25, and the number average molecular weight of the polypropylene I is not equal to that of the polypropylene II.
The invention provides a long-fiber reinforced polypropylene composite material prepared by the method provided by the second aspect and/or a long-fiber reinforced polypropylene composite material prepared by the method provided by the third aspect.
The fifth aspect of the invention provides an article comprising the long fiber reinforced polypropylene composite provided by the second aspect and/or the long fiber reinforced polypropylene composite obtained by the method provided by the third aspect.
According to the technical scheme, the polypropylene I and the polypropylene II with different number average molecular weights are introduced into the polypropylene composition for compounding, particularly, the melt flow rates of the polypropylene I and the polypropylene II are further limited, and the continuous fibers, the compatibilizer, the inorganic filler and the auxiliary agent in specific weight parts are limited, so that the synergistic effect among the components in the composition can be effectively coordinated, and then the polypropylene I and the polypropylene II and the added components except the continuous fibers are extruded into uniform resin melt by a screw rod and impregnated and wrapped with the continuous fibers, so that the long-fiber reinforced polypropylene composite material with the fiber retention length increased, the flow property and the mechanical property is prepared.
The technical scheme provided by the invention can better disperse the compatibilizer, the inorganic filler and the auxiliary agent in the polypropylene I and the polypropylene II, overcomes the problem that the fluidity and the mechanical property cannot be simultaneously realized when the long-fiber reinforced polypropylene is used, and realizes that the prepared long-fiber reinforced polypropylene composite material has excellent fluidity and mechanical property.
According to the method provided by the invention, the materials are selected according to the formula components to adapt to the impregnation process, the continuous fibers are filled and processed, the reserved length of the continuous fibers in the polypropylene base material can be ensured, the reserved length of the continuous fibers in the final product can be more than 2mm, and the effect of the continuous fibers is reflected; and the compatibilizer is introduced, so that the dispersion of the continuous fibers in the polypropylene I and the polypropylene II and the synergistic effect of the continuous fibers, the inorganic filler and the auxiliary agent can be ensured, and the long fiber reinforced polypropylene composite material with the enhanced mechanical property and the enhanced flow property is provided.
The long-fiber reinforced polypropylene composite material provided by the invention is used in products, and can solve the problems of insufficient stamping die, uneven material, uneven cooling shrinkage and the like in the forming process of the products, thereby improving the value of the products and widening the application field of the products.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides in a first aspect a polypropylene composition comprising: 8-50 parts of polypropylene I, 8-50 parts of polypropylene II, 20-60 parts of continuous fibers, 1-5 parts of compatibilizer, 0-30 parts of inorganic filler and 0.5-2 parts of auxiliary agent;
wherein the weight ratio A of the polypropylene I to the polypropylene II satisfies the following condition: a is more than or equal to 0.16 and less than or equal to 6.25, and the number average molecular weight of the polypropylene I is not equal to that of the polypropylene II.
In the invention, the number average molecular weight and the weight ratio A of the polypropylene I and the polypropylene II are regulated and controlled, so that the long-fiber reinforced polypropylene composite material has excellent fluidity and mechanical property.
In some embodiments of the invention, preferably, the composition comprises: 10-46 parts of polypropylene I, 10-46 parts of polypropylene II, 30-40 parts of continuous fiber, 2-5 parts of compatibilizer, 0-30 parts of inorganic filler and 0.5-1.5 parts of auxiliary agent.
In some embodiments of the present invention, preferably, the weight ratio a of polypropylene I to polypropylene II satisfies: a is more than or equal to 0.22 and less than or equal to 4.6. The optimized weight ratio is more favorable for improving the comprehensive performance of the long-fiber reinforced polypropylene composite material.
In some embodiments of the present invention, preferably, the number average molecular weight of the polypropylene I is 10000 to 30000g/mol, preferably 20000 to 30000g/mol; the molecular weight distribution is from 1.5 to 4, preferably from 2 to 3.
In some embodiments of the present invention, preferably the polypropylene II has a number average molecular weight of 30000-100000g/mol, preferably 40000-60000g/mol; the molecular weight distribution is 2 to 4, preferably 2 to 3.
According to the invention, the number-average molecular weight of the polypropylene I is not equal to the number-average molecular weight of the polypropylene II, for example, 30000g/mol < number-average molecular weight of the polypropylene II < 100000g/mol, when the number-average molecular weight of the polypropylene I is 30000 g/mol.
In the present invention, the polypropylene I and the polypropylene II are used as a matrix in the polypropylene composition, and each of the polypropylene I and the polypropylene II is independently selected from at least one of homo-polypropylene, block co-polypropylene and random co-polypropylene.
In some embodiments of the present invention, preferably, the polypropylene I has a melt flow rate of 1000 to 3000g/10min, preferably 1500 to 3000g/10min, at 230 ℃ and a load of 2.16 kg; the melt flow rate of the polypropylene II is 50 to 300g/10min, preferably 50 to 200g/10min.
In the present invention, the melt flow rate parameter is measured in accordance with GB/T3682-2000 without specific indications.
In the present invention, there is a wide range of selection of the sources of the polypropylene I and the polypropylene II as long as the number average molecular weights and the melt flow rates (230 ℃ C. And a load of 2.16 kg) of the polypropylene I and the polypropylene II satisfy the above-mentioned limitations. In the present invention, the polypropylene I and the polypropylene II may be obtained commercially or may be prepared.
The polypropylene composition provided by the invention can be used for introducing continuous fibers into high-fluidity polypropylene, and is more favorable for improving the mechanical strength of polypropylene (polypropylene I and polypropylene II). The polypropylene composition can be used for an extrusion impregnation method, is suitable for continuous production of continuous fibers, and is beneficial to retaining the continuous fibers.
In some embodiments of the invention, preferably the continuous fibers have a linear density of 1200 to 5000tex, preferably 2000 to 4000tex; the diameter is 8-20 μm, preferably 12-15 μm.
In the present invention, the continuous fibers may be selected from a wide range as long as the continuous fibers satisfy the above physical property parameters. Preferably, the continuous fiber is selected from at least one of glass fiber, carbon fiber, basalt fiber and aramid fiber, and is preferably glass fiber.
According to the present invention, preferably, the compatibilizer is selected from modified polymers containing polar compound derivative groups and/or low molecular weight compounds having dual functionalization. The polar group of the compatibilizer with specific structural properties and the silicon hydroxyl and other structures on the surface of the fiber are adopted to form hydrogen bonds, so that the polypropylene is tightly combined with the surface of the fiber, and the mechanical property of the composite material is improved.
In some embodiments of the present invention, preferably, the compatibilizer is selected from poly (propylene-graft-polar monomers) selected from at least one of maleic anhydride, acrylic acid, methacrylic acid, methyl methacrylate, vinyl versatate, butyl acrylate, butyl methacrylate, methyl acrylate, ethyl 2-methacrylate, allyl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, and isooctyl acrylate, preferably maleic anhydride and/or glycidyl methacrylate, more preferably maleic anhydride.
In some embodiments of the present invention, it is preferred that the poly (propylene-graft-polar monomer) has a grafting ratio of polar monomer of 0.8 to 2wt%, preferably 1 to 1.5wt%.
In some embodiments of the present invention, preferably, the poly (propylene-graft-polar monomer) has a melt flow rate of 100 to 1000g/10min, preferably 100 to 600g/10min, at 230 ℃ and a load of 2.16 kg.
In a preferred embodiment of the present invention, the compatibilizer is maleic anhydride grafted polypropylene, and the grafting ratio of maleic anhydride in the maleic anhydride grafted polypropylene is 0.8-2wt%, preferably 1-1.5wt%; the melt flow rate of the maleic anhydride grafted polypropylene is 100 to 1000g/10min, preferably 100 to 600g/10min at 230 ℃ and a load of 2.16 kg.
In the present invention, the inorganic filler is intended to play a role in reducing the cost of the composite material, reducing the shrinkage rate of the article, increasing the rigidity, retarding flame, and preventing static electricity. Preferably, the inorganic filler is selected from at least one of talc, calcium carbonate, montmorillonite, carbon black, magnesium hydroxide, decabromodiphenylethane, triammonium phosphate, diammonium phosphate, ammonium polyphosphate, and antimony trioxide.
In the present invention, there is a wide range of choices for the auxiliaries. Preferably, the auxiliary agent is selected from at least one of an antioxidant, a lubricant, a light aging resistant agent, a heat stabilizer, a mold release agent and a nucleating agent, and is preferably an antioxidant and/or a lubricant.
In the present invention, there is a wide range of selection from the types of the antioxidant, lubricant, anti-aging agent, heat stabilizer, mold release agent and nucleating agent, and they may be compounds that are conventional in the art.
In one embodiment of the present invention, the antioxidant is selected from the group consisting of antioxidants 1076, namely octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; the lubricant is selected from silicones; the light aging inhibitor is selected from poly [ [6- [ (1, 3-tetramethylbutyl) amino ] -1,3, 5-triazine-2, 4-diyl ] [ (1, 3-tetramethylbutyl) amino ] -1,3, 5-triazine 2,2,6,6-tetramethyl-4-piperidyl) imino ] -1, 6-hexanediyl [ (2,2,6,6-tetramethyl-4-piperidyl) imino ] ]; the heat stabilizer is selected from distearyl pentaerythritol diphosphite; the nucleating agent is selected from dibenzylidene sorbitol.
According to a particularly preferred embodiment of the invention, the composition comprises: 8-50 parts of polypropylene I, 8-50 parts of polypropylene II, 20-60 parts of continuous fiber, 1-5 parts of compatibilizer, 0-30 parts of inorganic filler and 0.5-2 parts of auxiliary agent;
wherein the weight ratio A of the polypropylene I to the polypropylene II satisfies the following condition: a is more than or equal to 0.16 and less than or equal to 6.25, and the number average molecular weight of the polypropylene I is not equal to that of the polypropylene II;
the number average molecular weight of the polypropylene I is 10000-30000g/mol; the number average molecular weight of the polypropylene II is 30000-100000g/mol;
under the conditions of 230 ℃ and 2.16kg of load, the melt flow rate of the polypropylene I is 1000-3000g/10min, and the melt flow rate of the polypropylene II is 50-300g/10min;
the linear density of the continuous fiber is 1200-5000tex; the diameter is 8-20 μm.
In a second aspect, the present invention provides a long fiber reinforced polypropylene composite made from the composition provided in the first aspect.
According to the present invention, it is preferable that the content of the continuous fiber in the long fiber reinforced polypropylene composite is 10 to 60wt%, preferably 20 to 50wt%, based on the total weight of the long fiber reinforced polypropylene composite.
According to the present invention, preferably, the length of the long fiber reinforced polypropylene composite material is 8-15mm, preferably 8-12mm; the retention length of the continuous fibers in the long fiber reinforced polypropylene composite material is more than or equal to 2mm, and preferably 2-5mm.
According to the invention, preferably, the tensile strength of the long fiber reinforced polypropylene composite material is more than or equal to 120MPa; the bending strength is more than or equal to 180MPa; the notch impact strength is more than or equal to 25kJ/mm 2 (ii) a The flow length is more than or equal to 450mm.
In the present invention, the tensile strength parameters of the long fiber reinforced polypropylene composite are tested according to standard ISO 527-2; the bending strength parameter and the bending modulus parameter of the long-fiber reinforced polypropylene composite material are tested according to the characterization ISO 178; the notch impact strength parameter of the long fiber reinforced polypropylene composite material is tested according to the standard ISO 180/1 eA; the flow length parameters of the long fiber reinforced polypropylene composite are tested according to the helical length test method of the standard ASTM D863.
In the present invention, the bending strength parameter of the long fiber-reinforced polypropylene composite material is mainly determined by the content of the continuous fiber in the long fiber-reinforced polypropylene composite material, without specific description.
According to the present invention, the long fiber reinforced polypropylene composite material is preferably prepared from the polypropylene composition of the present invention, and can be prepared by an extrusion impregnation method.
The third aspect of the present invention provides a method for preparing a long fiber reinforced polypropylene composite material, comprising:
(1) Mixing 8-50 parts by weight of polypropylene I, 8-50 parts by weight of polypropylene II, 1-5 parts by weight of compatibilizer, 0-30 parts by weight of inorganic filler and 0.5-2 parts by weight of auxiliary agent to obtain polypropylene mixed resin;
(2) Extruding the polypropylene mixed resin to obtain a resin melt;
(3) In an extrusion impregnation die head, carrying out impregnation processing on the resin melt and 20-60 parts by weight of continuous fibers to enable the resin melt to wrap the continuous fibers so as to obtain a long fiber reinforced polypropylene composite material;
wherein the weight ratio A of the polypropylene I to the polypropylene II satisfies the following condition: a is more than or equal to 0.16 and less than or equal to 6.25, and the number average molecular weight of the polypropylene I is not equal to that of the polypropylene II.
The method provided by the invention can be used for mixing and extruding the components (the polypropylene I, the polypropylene II, the compatibilizer, the inorganic filler and the auxiliary agent) except the continuous fiber in the polypropylene composition to obtain the resin melt, and then carrying out impregnation processing on the resin melt and the continuous fiber to wrap the continuous fiber. Particularly, polypropylene I and polypropylene II with different number average molecular weights are compounded, and the mutual synergistic effect of other components can effectively improve the processing fluidity and the impregnation effect of the resin melt.
In the invention, the mixing conditions have a wide selection range, and only the polypropylene I, the polypropylene II, the compatibilizer, the inorganic filler and the auxiliary agent are uniformly mixed. Preferably, in the step (1), the mixing conditions include: the temperature is 40-80 deg.C, the time is 3-5min, and the rotation speed is 100-500rpm. The polypropylene composition is used for uniformly mixing other components except the continuous fibers in the polypropylene composition, so that the compatibilizer, the inorganic filler and the auxiliary agent are in better contact, and the polypropylene composition is favorable for better dispersion in polypropylene matrixes (polypropylene I and polypropylene II) after the continuous fibers are added.
In some embodiments of the present invention, preferably, in step (2), the extrusion processing conditions include: the temperature is 160-230 ℃, and the rotating speed is 50-200rpm. Wherein, the extrusion temperature and the rotation speed of the extruder can be used for ensuring that the polypropylene mixed resin obtained in the step (1) is well melted into a resin melt so as to be suitable for wrapping the continuous fibers.
In some embodiments of the present invention, preferably, in step (3), the temperature of the impregnation process is 230 to 280 ℃, preferably 240 to 260 ℃. Wherein, the impregnation temperature is the temperature of an extrusion impregnation die head, and the impregnation processing of the resin melt and the continuous fibers in the extrusion impregnation die head can be ensured.
In the present invention, the physical parameters and types of the polypropylene I, the polypropylene II, the compatibilizer, the inorganic filler and the auxiliary agent are defined as above, and the description of the present invention is omitted here.
In the preparation method provided by the invention, the step (3) can be used for extruding to obtain the mixture of the resin melt coated continuous fibers. And cooling the mixture to obtain the polypropylene composite material. In order to facilitate the further processing of various molded polypropylene products, the polypropylene composite material can be further cut into 8-15mm particles, preferably 8-12mm, by a granulator, and used as master batches for molding processing for later use.
The invention provides a long-fiber reinforced polypropylene composite material prepared by the method provided by the second aspect and/or a long-fiber reinforced polypropylene composite material prepared by the method provided by the third aspect.
The fifth aspect of the invention provides an article comprising the long fiber reinforced polypropylene composite provided by the second aspect and/or the long fiber reinforced polypropylene composite obtained by the method provided by the third aspect.
In some embodiments of the present invention, the article may be a composite of the long fiber reinforced polypropylene composite provided by the present invention and other materials, such as a composite of the long fiber reinforced polypropylene composite provided by the present invention and a metal; the invention also provides a long fiber reinforced polypropylene composite material.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the composition of the long fiber reinforced polypropylene composite was determined according to the amounts of the components charged.
The melt flow rate parameter is measured according to GB/T3682-2000;
the tensile strength parameters are measured according to standard ISO 527-2;
the flexural strength parameters and flexural modulus parameters were tested according to standard ISO 178;
the notched impact strength parameters were tested according to the ISO Standard 180/1 eA;
the flow length parameters were tested according to the spiral length test method of the standard ASTM D863.
Polypropylene A is commercially available from RiandBarcel corporation under the designation MF 650Y; the number average molecular weight is 2.6 ten thousand g/mol, the molecular weight distribution is 2.11, and the melt flow rate is 1800g/10min under the conditions of 230 ℃ and 2.16kg of load;
polypropylene B is commercially available from SK, korea under the designation BX 3920; the number average molecular weight is 4.4 ten thousand g/mol, the molecular weight distribution is 2.73, and the melt flow rate is 100g/10min under the conditions of 230 ℃ and 2.16kg of load;
the glass fibers were purchased from Owensconning under the designation
Commercial product of SE 4849; the linear density was 2400tex, the diameter was 17 μm;
PP-g-MAH (maleic anhydride grafted Polypropylene) is commercially available from Exxon Mobil under the trade designation PO 1020; the grafting ratio was 1% by weight, and the melt flow rate was 430g/10min (230 ℃,2.16 kg) at 230 ℃ and a load of 2.16 kg;
the silicone master batch is purchased from Beijia high polymer materials GmbH of Jining;
antioxidants were purchased from BASF corporation under the trademark B225.
The relevant performance parameters of the long fiber reinforced polypropylene composites prepared in examples 1-8 and comparative examples 1-4 are shown in Table 1.
And (3) testing conditions: drying the long fiber reinforced polypropylene composite material at 100-120 ℃ for 2-6h, testing the flow length by an injection molding machine, injection molding the dried long fiber reinforced polypropylene composite material into a test sample strip at the molding temperature of 230-280 ℃, and testing the correlation performance after the sample strip is placed for 24h under the standard curing condition.
Example 1
(1) Adding 46 parts by weight of polypropylene I (polypropylene A), 10 parts by weight of polypropylene II (polypropylene B), 3 parts by weight of compatibilizer (PO 1020), 0.5 part by weight of antioxidant (B225) and 0.5 part by weight of lubricant (silicone master batch) into a high-speed mixer, and fully mixing to obtain polypropylene mixed resin;
wherein, the mixing conditions comprise: the mixing temperature of the high-speed mixer is 60 ℃, the rotating speed of the high-speed mixer is 300rpm, and the mixing time is 4min; the weight ratio A of the polypropylene I to the polypropylene II is 4.6;
(2) Directly adding the polypropylene mixed resin into a hopper of long glass fiber extrusion and impregnation equipment, and performing extrusion processing through an extruder to obtain a resin melt;
wherein the extrusion processing conditions include: the extrusion temperature is 160-230 ℃, and the rotation speed of an extruder is 50-200rpm;
(3) Extruding the above resin melt into an impregnation die connected to an extruder head while simultaneously extruding 40 parts by weight of continuous fibers
SE 4849) is introduced into an impregnation die head through a tractor, continuous fibers are dispersed in a resin melt at the impregnation temperature of 250 ℃, the resin melt is coated with the continuous glass fibers, and the obtained mixture of the resin melt coated with the continuous glass fibers is cooled and then cut into particles to obtain the long fiber reinforced polypropylene composite material S1.
Wherein the length of the long-fiber reinforced polypropylene composite material S1 is 12mm; the content of the continuous fiber was 40wt% based on the total weight of the long fiber-reinforced polypropylene composite material S1.
Example 2
(1) Adding 33.6 parts by weight of polypropylene I (polypropylene A), 22.4 parts by weight of polypropylene II (polypropylene B), 3 parts by weight of compatibilizer (PO 1020), 0.5 part by weight of antioxidant (B225) and 0.5 part by weight of lubricant (silicone master batch) into a high-speed mixer, and fully mixing to obtain polypropylene mixed resin;
wherein, the mixing conditions comprise: the mixing temperature of the high-speed mixer is 60 ℃, the rotating speed of the high-speed mixer is 300rpm, and the mixing time is 4min; the weight ratio A of the polypropylene I to the polypropylene II is 1.5;
(2) Directly adding the polypropylene mixed resin into a hopper of long glass fiber extrusion impregnation equipment, and performing extrusion processing through an extruder to obtain a resin melt;
wherein the extrusion processing conditions include: the extrusion temperature is 160-230 ℃, and the rotating speed of an extruder is 50-200rpm;
(3) Extruding the above resin melt into an impregnation die connected to an extruder head while simultaneously extruding 40 parts by weight of continuous fibers
SE 4849) is introduced into an impregnation die head through a tractor, continuous fibers are dispersed in a resin melt at the impregnation temperature of 250 ℃, the resin melt covers the continuous glass fibers, and the obtained mixture of the resin melt covering the continuous glass fibers is cooled and cut into particles to obtain the long fiber reinforced polypropylene composite material S2.
Wherein the length of the long-fiber reinforced polypropylene composite material S2 is 12mm; the content of the continuous fiber was 40wt% based on the total weight of the long fiber-reinforced polypropylene composite material S2.
Example 3
(1) Adding 28 parts by weight of polypropylene I (polypropylene A), 28 parts by weight of polypropylene II (polypropylene B), 3 parts by weight of compatibilizer (PO 1020), 0.5 part by weight of antioxidant (B225) and 0.5 part by weight of lubricant (silicone master batch) into a high-speed mixer for fully mixing to obtain polypropylene mixed resin;
wherein, the mixing condition comprises: the mixing temperature of the high-speed mixer is 60 ℃, the rotating speed of the high-speed mixer is 300rpm, and the mixing time is 4min; the weight ratio A of the polypropylene I to the polypropylene II is 1;
(2) Directly adding the polypropylene mixed resin into a hopper of long glass fiber extrusion and impregnation equipment, and performing extrusion processing through an extruder to obtain a resin melt;
wherein the extrusion processing conditions include: the extrusion temperature is 160-230 ℃, and the rotating speed of an extruder is 50-200rpm;
(3) Extruding the resin melt into an impregnation die connected to an extruder head while simultaneously extruding 40 parts by weight of continuous fibers (b)
SE 4849) is introduced into an impregnation die head through a tractor, continuous fibers are dispersed in a resin melt at the impregnation temperature of 250 ℃, the resin melt is coated with the continuous glass fibers, and the obtained mixture of the resin melt coated with the continuous glass fibers is cooled and then cut into particles to obtain the long fiber reinforced polypropylene composite material S3.
Wherein the length of the long-fiber reinforced polypropylene composite material S3 is 12mm; the content of the continuous fiber was 40wt% based on the total weight of the long fiber-reinforced polypropylene composite S3.
Example 4
(1) Adding 22.4 parts by weight of polypropylene I (polypropylene A), 33.6 parts by weight of polypropylene II (polypropylene B), 3 parts by weight of compatibilizer (PO 1020), 0.5 part by weight of antioxidant (B225) and 0.5 part by weight of lubricant (silicone master batch) into a high-speed mixer for fully mixing to obtain polypropylene mixed resin;
wherein, the mixing conditions comprise: the mixing temperature of the high-speed mixer is 60 ℃, the rotating speed of the high-speed mixer is 300rpm, and the mixing time is 4min; the weight ratio A of the polypropylene I to the polypropylene II is 0.67;
(2) Directly adding the polypropylene mixed resin into a hopper of long glass fiber extrusion and impregnation equipment, and performing extrusion processing through an extruder to obtain a resin melt;
wherein the extrusion processing conditions include: the extrusion temperature is 160-230 ℃, and the rotation speed of an extruder is 50-200rpm;
(3) Extruding the above resin melt into an impregnation die connected to an extruder head while simultaneously extruding 40 parts by weight of continuous fibers
SE 4849) is introduced into an impregnation die head through a tractor, continuous fibers are dispersed in a resin melt at the impregnation temperature of 250 ℃, the resin melt covers the continuous glass fibers, and the obtained mixture of the resin melt covering the continuous glass fibers is cooled and cut into particles to obtain the long fiber reinforced polypropylene composite material S4.
Wherein the length of the long-fiber reinforced polypropylene composite material S4 is 12mm; the content of the continuous fiber was 40wt% based on the total weight of the long fiber-reinforced polypropylene composite S4.
Example 5
(1) Adding 11.2 parts by weight of polypropylene I (polypropylene A), 44.8 parts by weight of polypropylene II (polypropylene B), 3 parts by weight of compatibilizer (PO 1020), 0.5 part by weight of antioxidant (B225) and 0.5 part by weight of lubricant (silicone master batch) into a high-speed mixer for fully mixing to obtain polypropylene mixed resin;
wherein, the mixing conditions comprise: the mixing temperature of the high-speed mixer is 60 ℃, the rotating speed of the high-speed mixer is 300rpm, and the mixing time is 4min; the weight ratio A of the polypropylene I to the polypropylene II is 0.25;
(2) Directly adding the polypropylene mixed resin into a hopper of long glass fiber extrusion and impregnation equipment, and performing extrusion processing through an extruder to obtain a resin melt;
wherein the extrusion processing conditions include: the extrusion temperature is 160-230 ℃, and the rotating speed of an extruder is 50-200rpm;
(3) Extruding the above resin melt into an impregnation die connected to an extruder head while simultaneously extruding 40 parts by weight of continuous fibers
SE 4849) is introduced into an impregnation die head through a tractor, continuous fibers are dispersed in a resin melt at the impregnation temperature of 250 ℃, the resin melt is coated with the continuous glass fibers, and the obtained mixture of the resin melt coated with the continuous glass fibers is cooled and then cut into particles to obtain the long fiber reinforced polypropylene composite material S5.
Wherein the length of the long-fiber reinforced polypropylene composite material S5 is 12mm; the content of the continuous fiber was 40wt% based on the total weight of the long fiber-reinforced polypropylene composite S5.
Example 6
(1) Adding 33 parts by weight of polypropylene I (polypropylene A), 33 parts by weight of polypropylene II (polypropylene B), 2 parts by weight of compatibilizer (PO 1020), 0.5 part by weight of antioxidant (B225) and 0.5 part by weight of lubricant (silicone master batch) into a high-speed mixer, and fully mixing to obtain polypropylene mixed resin;
wherein, the mixing conditions comprise: the mixing temperature of the high-speed mixer is 60 ℃, the rotating speed of the high-speed mixer is 300rpm, and the mixing time is 4min; the weight ratio A of the polypropylene I to the polypropylene II is 1;
(2) Directly adding the polypropylene mixed resin into a hopper of long glass fiber extrusion and impregnation equipment, and performing extrusion processing through an extruder to obtain a resin melt;
wherein the extrusion processing conditions include: the extrusion temperature is 160-230 ℃, and the rotating speed of an extruder is 50-200rpm;
(3) Extruding the above resin melt into an impregnation die connected to an extruder head while simultaneously extruding 30 parts by weight of continuous fibers
SE 4849) is introduced into an impregnation die head through a tractor, continuous fibers are dispersed in a resin melt at the impregnation temperature of 250 ℃, the resin melt covers the continuous glass fibers, and the obtained mixture of the resin melt covering the continuous glass fibers is cooled and cut into particles to obtain the long fiber reinforced polypropylene composite material S6.
Wherein the length of the long-fiber reinforced polypropylene composite material S6 is 12mm; the content of the continuous fiber was 30wt% based on the total weight of the long fiber-reinforced polypropylene composite S6.
Example 7
The same procedures as in example 1 were carried out except that in the step (1), 46 parts by weight of the polypropylene I (polypropylene A) was replaced with 48 parts by weight of the polypropylene I (polypropylene A) and 10 parts by weight of the polypropylene II (polypropylene B) was replaced with 8 parts by weight of the polypropylene II (polypropylene B), to obtain a long fiber-reinforced polypropylene composite material S7.
Wherein the length of the long-fiber reinforced polypropylene composite material S7 is 12mm; the content of the continuous fiber was 40wt% based on the total weight of the long fiber-reinforced polypropylene composite S7.
Example 8
The same procedure as in example 1 was repeated except that, in the step (1), 10 parts by weight of talc was added and the other steps were repeated to obtain a long fiber-reinforced polypropylene composite S8.
Wherein the length of the long-fiber reinforced polypropylene composite material S8 is 12mm; the content of the continuous fiber was 36wt% based on the total weight of the long fiber-reinforced polypropylene composite S8.
Comparative example 1
The procedure of example 1 was repeated, except that in the step (1), 46 parts by weight of the polypropylene I (polypropylene A) and 10 parts by weight of the polypropylene II (polypropylene B) were replaced with 56 parts by weight of the polypropylene II (polypropylene B), to obtain a long-fiber-reinforced polypropylene composite D1.
Wherein the length of the long-fiber reinforced polypropylene composite material D1 is 12mm; the content of the continuous fiber was 40wt% based on the total weight of the long fiber-reinforced polypropylene composite material D1.
Comparative example 2
The procedure of example 1 was repeated, except that in the step (1), 46 parts by weight of the polypropylene I (polypropylene A) and 10 parts by weight of the polypropylene II (polypropylene B) were replaced with 56 parts by weight of the polypropylene I (polypropylene A), and the other steps were repeated, to obtain a long-fiber-reinforced polypropylene composite D2.
Wherein the length of the long-fiber reinforced polypropylene composite material D2 is 12mm; the content of the continuous fiber was 40wt% based on the total weight of the long fiber-reinforced polypropylene composite material D2.
Comparative example 3
The procedure is as in example 1, except that, in step (1), 46 parts by weight of polypropylene I (polypropylene A) and 10 parts by weight of polypropylene II (polypropylene A)B) Replacing 56 parts by weight of polypropylene II (polypropylene B), 40 parts by weight of continuous fiber: (
SE 4849) was replaced with 40 parts by weight of short glass fibers (ECS 13-4.5-508A; the linear density was 2400tex, the diameter was 13 μm, and the length was 4.5 mm), and the same procedure was followed to obtain a short fiber reinforced polypropylene composite D3.
Wherein the length of the short fiber reinforced polypropylene composite material D3 is 2mm; the content of the fiber was 40wt% based on the total weight of the short fiber-reinforced polypropylene composite material D3.
Comparative example 4
The same procedures as in example 1 were repeated except that in the step (1), 46 parts by weight of the polypropylene I (polypropylene A) was replaced with 50 parts by weight of the polypropylene I (polypropylene A) and 10 parts by weight of the polypropylene II (polypropylene B) was replaced with 6 parts by weight of the polypropylene II (polypropylene B), to obtain a long fiber-reinforced polypropylene composite material D4.
Wherein the length of the long fiber reinforced polypropylene composite material D4 is 12mm; the content of the continuous fiber was 40wt% based on the total weight of the long fiber-reinforced polypropylene composite material D4.
TABLE 1
From the results in table 1, it can be seen that the long fiber reinforced polypropylene composite material prepared from the polypropylene composition provided by the present invention has excellent flowability and mechanical properties, and especially by limiting the weight parts, weight ratio and number average molecular weight of polypropylene I and polypropylene II, it is more beneficial to improve the comprehensive properties of the long fiber polypropylene composite material.
Compared with example 1, the long fiber reinforced polypropylene composite material D1 prepared in comparative example 1 without adding polypropylene I has excellent mechanical properties, but the flow length parameter is obviously lower, which indicates that the processing fluidity is poor.
Compared with example 1, the long fiber reinforced polypropylene composite material D2 prepared in comparative example 2 without adding polypropylene II has excellent flow length parameters, but has obviously lower mechanical property parameters, such as tensile strength parameters and notched impact strength parameters.
Comparative example 3 the short fiber reinforced polypropylene composite material D3 prepared using short glass fibers showed excellent processing flowability as compared to example 1, but its corresponding mechanical properties were relatively poor due to the low fiber retention length.
Compared with example 1, the long fiber reinforced polypropylene composite material prepared by comparative example 4 by using polypropylene I and polypropylene II with the weight ratio A not within the limited range has excellent flow length parameters, but has obviously lower mechanical property parameters, such as lower tensile strength parameters and lower notch impact strength parameters.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A polypropylene composition, characterized in that it comprises: 8-50 parts of polypropylene I, 8-50 parts of polypropylene II, 20-60 parts of continuous fibers, 1-5 parts of compatibilizer, 0-30 parts of inorganic filler and 0.5-2 parts of auxiliary agent;
wherein the weight ratio A of the polypropylene I to the polypropylene II satisfies the following condition: a is more than or equal to 0.16 and less than or equal to 6.25, and the number average molecular weight of the polypropylene I is not equal to that of the polypropylene II.
2. The composition of claim 1, wherein the composition comprises: 10-46 parts of polypropylene I, 10-46 parts of polypropylene II, 30-40 parts of continuous fiber, 2-5 parts of compatibilizer, 0-30 parts of inorganic filler and 0.5-1.5 parts of auxiliary agent;
preferably, the weight ratio a of polypropylene I to polypropylene II satisfies: a is more than or equal to 0.22 and less than or equal to 4.6.
3. Composition according to claim 1 or 2, wherein the polypropylene I has a number average molecular weight of 10000-30000g/mol, preferably 20000-30000g/mol; a molecular weight distribution of 1.5 to 4, preferably 2 to 3;
preferably, the number average molecular weight of the polypropylene II is 30000-100000g/mol, preferably 40000-60000g/mol; a molecular weight distribution of 2 to 4, preferably 2 to 3;
preferably, the melt flow rate of the polypropylene I is 1000 to 3000g/10min, preferably 1500 to 3000g/10min, at 230 ℃ and under a load of 2.16 kg; the melt flow rate of the polypropylene II is 50 to 300g/10min, preferably 50 to 200g/10min.
4. Composition according to any one of claims 1 to 3, wherein the continuous fibres have a linear density of 1200 to 5000tex, preferably 2000 to 4000tex; the diameter is 8-20 μm, preferably 12-15 μm;
preferably, the continuous fiber is selected from at least one of glass fiber, carbon fiber, basalt fiber and aramid fiber.
5. The composition according to any one of claims 1 to 4, wherein the compatibilizer is selected from modified polymers containing polar compound derivative groups and/or low molecular weight compounds with dual functionalization;
preferably, the compatibilizer is selected from poly (propylene-graft-polar monomers) selected from at least one of maleic anhydride, acrylic acid, methacrylic acid, methyl methacrylate, vinyl versatate, butyl acrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, 2-ethyl methacrylate, allyl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, and isooctyl acrylate;
preferably, in the poly (propylene-graft-polar monomer), the grafting ratio of the polar monomer is 0.8 to 2wt%, preferably 1 to 1.5wt%;
preferably, the melt flow rate of the poly (propylene-graft-polar monomer) is 100 to 1000g/10min, preferably 100 to 600g/10min at 230 ℃ and a load of 2.16 kg.
6. The composition of any of claims 1-5, wherein the inorganic filler is selected from at least one of talc, calcium carbonate, montmorillonite, carbon black, magnesium hydroxide, decabromodiphenylethane, triammonium phosphate, diammonium phosphate, ammonium polyphosphate, and antimony trioxide;
preferably, the auxiliary agent is selected from at least one of an oxidizing agent, a lubricant, an anti-light aging agent, a heat stabilizer, a mold release agent, and a nucleating agent.
7. A long fiber reinforced polypropylene composite prepared from the composition of any one of claims 1 to 6.
8. The long fiber reinforced polypropylene composite of claim 7, wherein the continuous fiber content of the long fiber reinforced polypropylene composite is 10 to 60wt%, preferably 20 to 50wt%, based on the total weight of the long fiber reinforced polypropylene composite;
preferably, the length of the long fiber reinforced polypropylene composite material is 8-15mm, preferably 8-12mm; the retention length of the continuous fibers in the long fiber reinforced polypropylene composite material is more than or equal to 2mm, and preferably 2-5mm;
preferably, the tensile strength of the long fiber reinforced polypropylene composite material is more than or equal to 120MPa; the bending strength is more than or equal to 180MPa; the notch impact strength is more than or equal to 25kJ/mm 2 (ii) a The flow length is more than or equal to 450mm.
9. A preparation method of a long fiber reinforced polypropylene composite material is characterized by comprising the following steps:
(1) Mixing 8-50 parts by weight of polypropylene I, 8-50 parts by weight of polypropylene II, 1-5 parts by weight of compatibilizer, 0-30 parts by weight of inorganic filler and 0.5-2 parts by weight of auxiliary agent to obtain polypropylene mixed resin;
(2) Extruding the polypropylene mixed resin to obtain a resin melt;
(3) In an extrusion impregnation die head, carrying out impregnation processing on the resin melt and 20-60 parts by weight of continuous fibers to enable the resin melt to wrap the continuous fibers so as to obtain a long fiber reinforced polypropylene composite material;
wherein the weight ratio A of the polypropylene I to the polypropylene II satisfies the following condition: a is more than or equal to 0.16 and less than or equal to 6.25, and the number average molecular weight of the polypropylene I is not equal to that of the polypropylene II.
10. The method of claim 9, wherein in step (1), the mixing conditions comprise: the temperature is 40-80 ℃, the time is 3-5min, and the rotating speed is 100-500rpm;
preferably, in the step (2), the extrusion processing conditions include: the temperature is 160-230 ℃, and the rotating speed is 50-200rpm;
preferably, in step (3), the temperature of the impregnation process is 230 to 280 ℃, preferably 240 to 260 ℃.
11. Use of the long fiber reinforced polypropylene composite of claim 7 or 8 and/or the long fiber reinforced polypropylene composite produced by the method of claim 9 or 10 in articles, in particular in large articles, thin-walled articles, complex articles.
12. An article comprising the filament reinforced polypropylene composite of claim 7 or 8 and/or the filament reinforced polypropylene composite produced by the method of claim 9 or 10.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289375A (en) * | 2013-05-22 | 2013-09-11 | 江苏金发科技新材料有限公司 | Continuous glass fiber reinforced polypropylene-nylon composite material and preparation method thereof |
| CN103289194A (en) * | 2013-05-22 | 2013-09-11 | 江苏金发科技新材料有限公司 | Basalt continuous fiber reinforced polypropylene material and preparation method thereof |
| CN105623097A (en) * | 2016-03-02 | 2016-06-01 | 北京航天试验技术研究所 | Nanometer-material-compounded long-glass-fiber-reinforced polypropylene material and preparing method thereof |
| CN106243490A (en) * | 2016-07-29 | 2016-12-21 | 中广核俊尔新材料有限公司 | A kind of antistatic long glass fiber reinforced polypropylene composite material and its preparation method and application |
| CN106604961A (en) * | 2014-08-28 | 2017-04-26 | 伊奎斯塔化学有限公司 | Carbon fiber-filled thermoplastic olefinic compounds and related automotive components |
-
2021
- 2021-06-09 CN CN202110643480.3A patent/CN115449153A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289375A (en) * | 2013-05-22 | 2013-09-11 | 江苏金发科技新材料有限公司 | Continuous glass fiber reinforced polypropylene-nylon composite material and preparation method thereof |
| CN103289194A (en) * | 2013-05-22 | 2013-09-11 | 江苏金发科技新材料有限公司 | Basalt continuous fiber reinforced polypropylene material and preparation method thereof |
| CN106604961A (en) * | 2014-08-28 | 2017-04-26 | 伊奎斯塔化学有限公司 | Carbon fiber-filled thermoplastic olefinic compounds and related automotive components |
| CN105623097A (en) * | 2016-03-02 | 2016-06-01 | 北京航天试验技术研究所 | Nanometer-material-compounded long-glass-fiber-reinforced polypropylene material and preparing method thereof |
| CN106243490A (en) * | 2016-07-29 | 2016-12-21 | 中广核俊尔新材料有限公司 | A kind of antistatic long glass fiber reinforced polypropylene composite material and its preparation method and application |
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