CN115558205A - Polypropylene composite material with low linear expansion coefficient and preparation method thereof - Google Patents
Polypropylene composite material with low linear expansion coefficient and preparation method thereof Download PDFInfo
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- CN115558205A CN115558205A CN202211280984.4A CN202211280984A CN115558205A CN 115558205 A CN115558205 A CN 115558205A CN 202211280984 A CN202211280984 A CN 202211280984A CN 115558205 A CN115558205 A CN 115558205A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 132
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 126
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- -1 Polypropylene Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000002667 nucleating agent Substances 0.000 claims abstract description 23
- 239000011256 inorganic filler Substances 0.000 claims abstract description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 19
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 19
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 18
- 239000012745 toughening agent Substances 0.000 claims abstract description 15
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 84
- 238000000034 method Methods 0.000 claims description 20
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 13
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 8
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- 239000010456 wollastonite Substances 0.000 claims description 8
- 229910052882 wollastonite Inorganic materials 0.000 claims description 8
- 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 claims description 7
- 239000000835 fiber Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 5
- 239000000600 sorbitol Substances 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 229920002292 Nylon 6 Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims 1
- 229920005629 polypropylene homopolymer Polymers 0.000 claims 1
- 239000002121 nanofiber Substances 0.000 abstract description 20
- 238000011065 in-situ storage Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 description 15
- 239000008187 granular material Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001410 Microfiber Polymers 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000003658 microfiber Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XOSXWYQMOYSSKB-UHFFFAOYSA-M disodium;4-[4-[(4-amino-3-methyl-5-sulfophenyl)-[4-(4-sulfonatophenyl)azaniumylidenecyclohexa-2,5-dien-1-ylidene]methyl]anilino]benzenesulfonate Chemical compound [Na+].[Na+].OS(=O)(=O)C1=C(N)C(C)=CC(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)=C1 XOSXWYQMOYSSKB-UHFFFAOYSA-M 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a low linear expansion coefficient polypropylene composite material and a preparation method thereof, and the raw material formula comprises the following components in percentage by weight: 43% -82% of polypropylene (PP) resin; 10 to 25 percent of thermoplastic fiber-forming resin; compatilizer 2% >, E6 percent; 5 to 20 percent of toughening agent; 0 to 25 percent of superfine inorganic filler; 0.1 to 0.3 percent of PP nucleating agent; 0.9 to 1.7 percent of processing aid. The PP composite material has an in-situ micro-nano fiber forming structure, and the density is lower than 1.20g/cm 3 . The invention can make the interface compatibility of polypropylene and micro-nano fiber better, further improve the strength and dimensional stability of the composite material, and can be applied to large-scale parts in the field of automobiles. The added superfine inorganic filler is reduced, the density of the PP composite material is greatly reduced, and the PP composite material has good comprehensive properties such as surface effect and strength and conforms to the development trend of light weight of the current automobile parts.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a low-linear-expansion-coefficient polypropylene composite material and a preparation method thereof.
Background
Compared with other general thermoplastic plastics, the polypropylene (PP) has the advantages of low density, excellent processing performance, environmental protection, no toxicity, easy recovery and the like. Meanwhile, the modified PP composite material has the advantages of low-temperature impact resistance, aging resistance and the like, so that the modified PP composite material is widely applied to the fields of automobiles, household appliances and the like. However, since PP is a highly crystalline polymer material, some shrinkage behaviors often occur during injection molding and using processes of products, and the problems of large linear expansion Coefficient (CLTE) and poor dimensional stability exist, and especially when PP is used for large-sized products in the automobile field, such as bumpers, door panels, instrument panels and the like, the assembly requirements of the products are often difficult to meet.
At present, the main methods for reducing the linear expansion coefficient of PP materials are: the production is carried out by adding inorganic filler, ethylene/octene copolymer (POE), nucleating agent and the like. However, to achieve a lower linear expansion coefficient, a large amount of inorganic filler and POE are required to be added, which not only causes a sharp increase in density of the PP composite material and a decrease in overall properties, but also causes an increase in material cost. There is also a method of preparing a PP composite material having a low linear expansion coefficient by adding glass fiber, and the composite material prepared by the method has a poor surface effect and is not suitable for products having high requirements on surface quality, such as automobile interior and exterior.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the polypropylene composite material with the low linear expansion coefficient and the preparation method thereof.
The invention provides a polypropylene composite material with a low linear expansion coefficient, which comprises the following raw materials in percentage by weight:
the density of the polypropylene composite material with the low linear expansion coefficient is lower than 1.20g/cm 3 。
Preferably, the PP resin is one or more of homopolymerized polypropylene and copolymerized polypropylene, and the crystallinity of the PP resin is more than or equal to 38%.
Preferably, the thermoplastic fiber-forming resin is one or more of polyethylene terephthalate, polybutylene terephthalate, polycaprolactam and polyhexamethylene adipamide.
Preferably, the compatilizer is one or more of polypropylene grafted maleic anhydride and polypropylene grafted glycidyl methacrylate.
Preferably, the toughening agent is one or more of ethylene/butylene copolymer and ethylene/octene copolymer, and the toughening agent Mooney viscosity is not higher than 20MU.
Preferably, the superfine inorganic filler is one or more of talcum powder, wollastonite and calcium sulfate whiskers, wherein the mesh number of the talcum powder and the wollastonite is more than 2500 meshes, the diameter of the calcium sulfate whiskers is not more than 5 mu m, and the length-diameter ratio of the calcium sulfate whiskers is 5-40.
Preferably, the PP nucleating agent is one or more of aryl phosphate nucleating agent and sorbitol nucleating agent.
Preferably, the low linear expansion coefficient polypropylene composite material has a TD linear expansion coefficient of less than or equal to 40 μm/m DEG C, and/or an MD linear expansion coefficient of less than or equal to 50 μm/m DEG C.
The invention provides a PP composite material with low linear expansion coefficient, which is prepared by 43-82% of polypropylene (PP) resin, 10-25% of thermoplastic fiber-forming resin, 2-6% of compatilizer, 5-20% of toughening agent, 0.1-0.3% of PP nucleating agent, 0.9-1.7% of processing aid and other raw materials. The PP composite material has an in-situ micro-nano fiber forming structure, and the density is lower than 1.20g/cm 3 . The compatilizer is higher in addition amount, so that the interfacial compatibility between the PP and the micro-nano fiber is better, the strength and the dimensional stability of the composite material are further improved, and the composite material can be applied to large-sized parts in the automobile field, for example, the TD linear expansion coefficient is less than or equal to 40 micrometers/(m DEG C), and the MD linear expansion coefficient is less than or equal to 50 micrometers/(m DEG C). Meanwhile, the added superfine inorganic filler is reduced in amount, the density of the PP composite material is greatly reduced, and the PP composite material has good comprehensive properties such as surface effect and strength and conforms to the development trend of light weight of automobile parts at present.
The invention provides a preparation method of the polypropylene composite material with low linear expansion coefficient, which comprises the following steps:
s1, weighing PP resin, thermoplastic fiber forming resin, a toughening agent, superfine inorganic filler, a PP nucleating agent and a processing aid according to a weight ratio, and mixing and stirring to obtain a mixed material;
and S2, adding a compatilizer through a side feeding device by using a double-screw extruder with the length-diameter ratio of more than or equal to 36 or a three-screw extruder with the length-diameter ratio of more than or equal to 15 on the mixed material obtained in the step S1, extruding the mixed material at the temperature which is higher than the melting temperature of PP and lower than the melting temperature of thermoplastic fiber-forming resin, drawing strips, cooling and granulating to obtain the low-linear-expansion-coefficient polypropylene composite material.
Preferably, the compatilizer is added through a special low-speed side feeding device, and the addition amount is controlled to be less than 10%.
In the traditional in-situ fiber forming research, the compatilizer is added by directly feeding and extruding the raw materials and the compatilizer after the compatilizer is mixed with the raw materials and the like through a main feeding port, and the dosage of the compatilizer added by the method is limited. The dosage is too small, and the compatibility of the PP and the micro-nano fiber interface is poor; if the amount is too large, the micro-nanofibers will be inhibited from being produced due to too high interfacial compatibility.
Compared with the prior art, the PP composite material with the low linear expansion coefficient and the preparation method thereof provided by the invention are unique, and the micro-nano fiber with a certain length-diameter ratio formed in the extrusion process can be directly utilized to control the linear expansion coefficient of the PP material, so that the dimensional stability is improved. Furthermore, the invention changes the adding mode of the compatilizer by a special low-speed side feeding device, so that the dispersed phase is mixed with the compatilizer after forming primary micro-fiber through a certain shearing action in the melting section of the extruder, the blocking effect of the compatilizer on the generation of micro-nano fiber can be greatly reduced, the adding amount of the compatilizer is improved, the interfacial compatibility of PP and the micro-nano fiber is better, and the strength and the dimensional stability of the obtained composite material are further improved. Experiments show that the TD linear expansion coefficient of the PP composite material prepared by the invention is less than or equal to 40 mu m/(m.DEG C), and the MD linear expansion coefficient is less than or equal to 50 mu m/(m.DEG C), so that the PP composite material can be applied to large-sized parts in the automobile field. Meanwhile, the PP composite material with the low linear expansion coefficient has the advantages of low density, good surface effect, strength and other excellent comprehensive properties, simple and convenient preparation method and contribution to application.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a polypropylene composite material with a low linear expansion coefficient, which comprises the following raw materials in percentage by weight:
the density of the polypropylene composite material with the low linear expansion coefficient is lower than 1.20g/cm 3 。
The PP composite material with the low linear expansion coefficient is prepared by an in-situ micro-nano fiber forming method in the material extrusion process, and has the advantages of low density, better surface effect, excellent comprehensive performance and the like. The invention also changes the adding mode of the compatilizer, increases the dosage of the compatilizer which can be added, simultaneously can greatly reduce the barrier effect of the compatilizer on the generation of micro-nano fiber, and is beneficial to being applied to the fields of light-weight interior and exterior trim of automobiles and the like.
The raw materials for preparing the polypropylene composite material comprise 43-82% of PP resin, and specifically 44-66% by mass. The PP resin is preferably one or more blends of high crystallinity, high melt flow rate homo-or co-polypropylene. Preferably, the crystallinity of the PP resin is not less than 38%, the melt flow rate is not less than 30g/10min (GB/T3682.1-2017, 230 ℃,2.16 kg), and the melt flow rate of the PP resin is not more than 120g/10min.
In the embodiment of the invention, the raw material formula comprises 10-25% of thermoplastic fiber-forming resin, for example, 10%, 15%, 18%, 20%, 25% and the like. The main principle of the invention is to adopt a method for forming micro-nano fiber in situ, and utilize the micro-nano fiber formed in the extrusion process to control the linear expansion coefficient of the PP modified material.
In-situ fiber forming refers to the in-situ formation of a reinforced fiber structure in the processing process, which is generally realized by carrying out extrusion molding, injection molding and other processing on polymer blend melt to promote components forming a dispersed phase to form microfibers with diameters much smaller than the diameters of macroscopic fibers in situ in a matrix; the thermoplastic fiber-forming resin is used for participating in forming a thermoplastic resin with a micro-nano fiber structure (micro-nano scale fiber form). Among the raw material resins described in the examples of the present invention, the thermoplastic fiber-forming resin has a relatively high melting temperature (the melting temperature generally ranges from 220 ℃ to 270 ℃), and specifically includes one or more of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycaprolactam (PA 6) and polyhexamethylene adipamide (PA 66), for example, one of PET, PBT and PA 66. In the examples of the present invention, the thermoplastic fiber-forming resin is substantially free of moisture and may be dried using commercially available resin raw materials.
The raw material formula of the invention comprises 2-6% of compatilizer and 5-20% of toughening agent by weight percentage. The compatilizer is one or more of polypropylene grafted maleic anhydride (PP-g-MAH) and polypropylene grafted glycidyl methacrylate (PP-g-GMA), the grafting rate is 0.6-1.0%, and the addition amount can be 2.5-5%. The invention improves the addition amount of the compatilizer in the product, and the formed micro-nano fiber greatly reduces the linear expansion coefficient of the PP material, is beneficial to improving the strength, the dimensional stability and the like of the composite material, and can be applied to large-scale parts in the field of automobiles.
In a specific embodiment of the invention, the toughening agent is one or a mixture of two of ethylene/butene copolymer and ethylene/octene copolymer; the toughening agent is preferably added in a proportion of 5-16%, and the Mooney viscosity is not higher than 20MU (ASTM D1646).
And the raw material formula comprises 0-25% of superfine inorganic filler, and the superfine inorganic filler generally has a mesh number of more than or equal to 2500 meshes, or has a diameter of less than or equal to 5 mu m. Some embodiments use 5-20% inorganic filler in the range of 2500 mesh to 5000 mesh, and some embodiments may not add inorganic filler. The added superfine inorganic filler is reduced in dosage, and the lower density of the PP composite material is favorably ensured.
In the preferred embodiment of the invention, the superfine inorganic filler is one or more of talcum powder, wollastonite and calcium sulfate whisker which are mixed, and the mesh number can be 2500 meshes, 5000 meshes, or the diameter is less than or equal to 5 μm (the general parameters of the calcium sulfate whisker are the diameter and the length-diameter ratio). The main component of the talcum powder is hydrous magnesium silicate; wollastonite is a triclinic, fine plate crystal, and the aggregate is in a radial or fibrous form. The calcium sulfate whisker is a needle-shaped fiber sub-nanometer material which grows in a single crystal form and has the chemical formula of CaSO 4 。
The PP composite material prepared by the embodiment of the invention comprises the following raw materials in percentage by mass: 0.1 to 0.3 percent of PP nucleating agent and 0.9 to 1.7 percent of processing aid, and the sum of the proportion of all materials is 100 percent. The PP nucleating agent is preferably one or more of aryl phosphate nucleating agent and sorbitol nucleating agent. Aryl phosphate nucleating agents, such as bis [2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate ] aluminium hydroxy salt. Sorbitol-based nucleating agents, such as [1,3, 2, 4-bis (p-methylbenzylidene) sorbitol. The processing aid is a chemical aid for processing the filling modified polymer material, which is well known to those skilled in the art, and is a commercially available raw material substance. Illustratively, the processing aids mainly include phenolic heat stabilizers (antioxidant 1010 or antioxidant 1076), phosphite heat stabilizers (antioxidant 168), lubricants (ethylene bis stearamide EBS or polyethylene wax), white oil; antioxidant 1010: antioxidant 168: EBS: white oil =1 to 2:2 to 4:4 to 5:2 to 5 mass ratio.
In the present invention, the density of the low linear expansion coefficient polypropylene composite material is lower than 1.20g/cm 3 E.g. 1.00-1.17g/cm 3 In the meantime. According to ISO 11359-2, the TD linear expansion coefficient of the low linear expansion coefficient polypropylene composite material is less than or equal to 40 μm/m DEG C, and/or the MD linear expansion coefficient is less than or equal to 50 μm/m DEG C. The density of the composite material is lower than that of a PP material with a low linear expansion coefficient in the current market, and the composite material conforms to the development trend of current automobile lightweight application products.
The embodiment of the present invention provides a preparation method of the polypropylene composite material with low linear expansion coefficient as described above, including the following steps:
s1, weighing PP resin, thermoplastic fiber-forming resin, a toughening agent, superfine inorganic filler, a PP nucleating agent and a processing aid according to a weight ratio, and mixing and stirring to obtain a mixed material;
and S2, adding the compatilizer into the mixed material obtained in the step S1 through a double-screw extruder with the length-diameter ratio of more than or equal to 36 or a three-screw extruder with the length-diameter ratio of more than or equal to 15 by a side feeding device, and extruding at the temperature higher than the melting temperature of PP and lower than the melting temperature of thermoplastic fiber-forming resin to obtain the polypropylene composite material with the low linear expansion coefficient.
In a preferred embodiment of the present invention, the composite material is prepared by the following specific steps:
1) Placing the thermoplastic fiber-forming resin in a vacuum drying oven at 110-120 ℃, and drying for 5-6 hours;
2) Weighing the PP resin, the dried thermoplastic fiber-forming resin in the step 1), the toughening agent, the superfine inorganic filler, the PP nucleating agent and the processing aid according to the mass ratio, placing the mixture into a high-speed mixer, mixing for 3-5 min at normal temperature, and fully and uniformly stirring to obtain a uniformly mixed material;
3) Adding the compatilizer through a side feeding device by a double-screw extruder with the length-diameter ratio (L/D) being more than or equal to 36 or a three-screw extruder with the length-diameter ratio (L/D) being more than or equal to 15 to the mixed material obtained in the step 2), and extruding the mixed material at the temperature (T2) which is higher than the melting temperature (T1) of PP and lower than the melting temperature (T2) of the thermoplastic fiber-forming resin, namely T2 is more than the processing temperature and is more than T1; and then drawing strips, cooling by a cold water tank below 5 ℃, and pelletizing by a pelletizer to obtain the low-expansion-coefficient PP composite material.
The material composition content of the embodiment of the invention is as described above, and the mixed material is extruded and granulated by a screw, wherein the compatilizer is added by a side feeding device. Some embodiments use a twin screw extrusion apparatus with L/D ≥ 36, and other embodiments use a three screw extrusion apparatus with L/D ≥ 15; processing according to a certain zone temperature (generally divided into nine zones), wherein the head temperature is preferably 210-260 ℃, the rotating speed of a screw main machine can be 350-450 rpm, drawing strips are cooled by a cold water tank, cut into granules by a granulator, and the granules are cooled to room temperature to prepare the low-linear expansion coefficient polypropylene composite material.
In the preferred embodiment of the present application, the compatibilizer is added by a special low-speed side feeding device, and the addition amount is controlled to be less than 10%. In order to realize low-speed side feeding, firstly, a frequency converter with 750W of original configuration is changed into 1500W by changing a frequency converter with larger power, and secondly, a motor with larger speed reduction ratio is changed, and the motor with the speed reduction ratio of 23; other low speed side feeding modes can also be adopted.
In the preparation method of the PP composite material with the low linear expansion coefficient, provided by the embodiment of the invention, the linear expansion coefficient of the PP material is controlled by directly utilizing micro-nano fibers with a certain length-diameter ratio formed in the extrusion process, so that the dimensional stability is improved; and the addition amount of the compatilizer is increased through a special low-speed side feeding device, so that the interfacial compatibility of PP and micro-nano fiber is better, and the strength and the dimensional stability of the material are further improved. Meanwhile, the amount of the added inorganic filler is reduced, the density of the material is greatly reduced, and the development trend of light weight of the automobile at present is met.
The following examples and comparative examples are given to further illustrate the low linear expansion coefficient polypropylene composite of the present invention and the preparation method thereof, but the present invention is not limited to the following examples. Wherein the PP resin is homo-or co-polypropylene with high crystallinity and high melt flow rate; the crystallinity of PP resin is more than or equal to 38 percent, and the melt flow rate is more than or equal to 30g/10min. The superfine inorganic filler has mesh number not less than 2500 mesh, or diameter not more than 5 micron. The thermoplastic fiber-forming resin in the raw material has a higher melting temperature; toughening agent ethylene/butylene, ethylene/octene copolymer, its Mooney viscosity is not higher than 20MU; the PP nucleating agent is one of aryl phosphate nucleating agent or sorbitol nucleating agent; the processing aids include lubricants, antioxidants, and the like.
The main raw materials and sources are as follows:
specification and model of material manufacturer
PP Korea SK BX3900 (melt flow rate 60g/10min, ASTM D-1238)
PBT China blue Star 1100A (melting temperature 225 deg.C)
PET Large glossy polyester chip (melting temperature 260 ℃ C.)
PA66 Martha EPR27 (melting temperature 256 ℃ C.)
Toughening agent Korea SK 875L (Mooney viscosity 8 MU)/8613L (Mooney viscosity 3 MU)
Talcum powder Aihai CP250 (5000 mesh)
Wollastonite southern wollastonite XYNFW-SW5 (2500 meshes)
Calcium sulfate whisker Shanghai Fengyu NP-S04-S (1-5 μm)
Nucleating agent Shanxi chemical industry TMP-6
PP-g-MAH Shenyang four-dimensional SWJ-1B (grafting ratio 0.6% -08%)
PP-g-GMA Guangzhou east gold PPG-2321 (grafting rate ≈ 1%)
Antioxidant basf 1010
Antioxidant basf 168
Lubricant Indonesia EBS
White oil commercially available
Antioxidant 1010: antioxidant 168: EBS: white oil =1 to 2:2 to 4:4 to 5:2 to 5 mass ratio
The main parameters of the double-screw extruder are as follows: TDS-35C/600-22-40 of Nanjing noda, the diameter of a screw is 35.6mm, and the length-diameter ratio is 40; the three-screw extruder has the main parameters: zhongxing innovation 3ME-35, screw diameter 35mm, length-diameter ratio 36; main parameters of the side feeder: motor reduction ratio 50, power 750W, and inverter power 1500W.
Example 1
1) Firstly, putting the PBT raw material in a vacuum drying oven at 120 ℃ for drying for 5 hours;
2) Weighing the materials according to the following material ratio, respectively placing the materials into a high-speed mixer, and mixing for 3-5 min at normal temperature to obtain a mixed material;
3) Granulating the mixed material by a double-screw extruder (the length-diameter ratio L/D is more than or equal to 36), adding 3% of PP-g-GMA (the mass fraction is the percentage of the total mass of the mixed material in the step 2, and the same below) into a side feeding device, and processing the mixed material by the following steps: the temperature of the first zone is 170 +/-5 ℃, the temperature of the second zone is 185 +/-5 ℃, the temperature of the third zone is 205 +/-5 ℃, the temperature of the fourth zone is 210 +/-5 ℃, the temperature of the fifth zone is 200 +/-5 ℃, the temperature of the sixth zone is 210 +/-5 ℃, the temperature of the seventh zone is 210 +/-5 ℃, the temperature of the eighth zone is 200 +/-5 ℃, the temperature of the ninth zone is 210 +/-5 ℃, the temperature of a machine head is 215 +/-5 ℃, the rotating speed of a screw main machine is 350-450 rpm, a brace is cooled by a cold water tank below 5 ℃, a granulator is granulated, and granules are cooled to room temperature, so that the low-linear expansion coefficient polypropylene composite material is obtained.
Example 2
1) Putting the PA66 raw material into a vacuum drying oven at 120 ℃ for drying for 5 hours;
2) Weighing the materials according to the following material ratio, respectively placing the materials into a high-speed mixer, and mixing for 3-5 min at normal temperature to obtain a mixed material;
3) Granulating the mixed material by a double-screw extruder (the length-diameter ratio L/D is more than or equal to 36), adding 3% PP-g-MAH into a side feeding device, and processing the mixture by the following steps: the temperature of the first zone is 170 +/-5 ℃, the temperature of the second zone is 190 +/-5 ℃, the temperature of the third zone is 230 +/-5 ℃, the temperature of the fourth zone is 245 +/-5 ℃, the temperature of the fifth zone is 220 +/-5 ℃, the temperature of the sixth zone is 235 +/-5 ℃, the temperature of the seventh zone is 245 +/-5 ℃, the temperature of the eighth zone is 240 +/-5 ℃, the temperature of the ninth zone is 245 +/-5 ℃, the temperature of a machine head is 250 +/-5 ℃, the rotating speed of a screw main machine is 350-450 rpm, a brace is cooled by a cold water tank below 5 ℃, a granulator is granulated, and granules are cooled to room temperature, so that the low-linear expansion coefficient polypropylene composite material is obtained.
Example 3
1) Putting the PA66 raw material into a vacuum drying oven at 120 ℃ for drying for 5 hours;
2) Weighing the materials according to the following material ratio, respectively placing the materials into a high-speed mixer, and mixing for 3-5 min at normal temperature to obtain a mixed material;
3) Granulating the mixed material by a three-screw extruder (the length-diameter ratio L/D is more than or equal to 15), adding 4% of PP-g-MAH into a side feeding device, and processing the mixed material by the following steps: the temperature of the first zone is 170 +/-5 ℃, the temperature of the second zone is 190 +/-5 ℃, the temperature of the third zone is 230 +/-5 ℃, the temperature of the fourth zone is 245 +/-5 ℃, the temperature of the fifth zone is 220 +/-5 ℃, the temperature of the sixth zone is 235 +/-5 ℃, the temperature of the seventh zone is 245 +/-5 ℃, the temperature of the eighth zone is 240 +/-5 ℃, the temperature of the ninth zone is 245 +/-5 ℃, the temperature of a machine head is 250 +/-5 ℃, the rotating speed of a screw main machine is 350-450 rpm, a brace is cooled by a cold water tank below 5 ℃, a granulator is granulated, and granules are cooled to room temperature, so that the low-linear expansion coefficient polypropylene composite material is obtained.
Example 4
1) Firstly, putting a PET raw material into a vacuum drying oven at 120 ℃ for drying for 5 hours;
2) Weighing the materials according to the following material ratio, respectively placing the materials into a high-speed mixer, and mixing for 3-5 min at normal temperature to obtain a mixed material;
3) Granulating the mixed material by a three-screw extruder (the length-diameter ratio L/D is more than or equal to 15), adding 2.5 percent PP-g-GMA into a side feeding device, and processing the mixed material by the following steps: the temperature of the first zone is 170 +/-5 ℃, the temperature of the second zone is 225 +/-5 ℃, the temperature of the third zone is 245 +/-5 ℃, the temperature of the fourth zone is 245 +/-5 ℃, the temperature of the fifth zone is 225 +/-5 ℃, the temperature of the sixth zone is 250 +/-5 ℃, the temperature of the seventh zone is 250 +/-5 ℃, the temperature of the eighth zone is 240 +/-5 ℃, the temperature of the ninth zone is 250 +/-5 ℃, the temperature of the machine head is 255 +/-5 ℃, the rotating speed of a main screw is 350-450 rpm, a brace is cooled by a cold water tank below 5 ℃, a granulator is granulated, and granules are cooled to room temperature, so that the low-linear expansion coefficient polypropylene composite material is obtained.
Example 5
1) Firstly, putting a PET raw material into a vacuum drying oven at 120 ℃ for drying for 5 hours;
2) Weighing the materials according to the following material ratio, respectively placing the materials into a high-speed mixer, and mixing for 3-5 min at normal temperature to obtain a mixed material;
3) Granulating the mixed material by a double-screw extruder (the length-diameter ratio L/D is more than or equal to 36), adding 4.5 percent of PP-g-GMA into a side feeding device, and processing the mixed material by the following steps: the temperature of the first zone is 170 +/-5 ℃, the temperature of the second zone is 225 +/-5 ℃, the temperature of the third zone is 245 +/-5 ℃, the temperature of the fourth zone is 245 +/-5 ℃, the temperature of the fifth zone is 225 +/-5 ℃, the temperature of the sixth zone is 250 +/-5 ℃, the temperature of the seventh zone is 250 +/-5 ℃, the temperature of the eighth zone is 240 +/-5 ℃, the temperature of the ninth zone is 250 +/-5 ℃, the temperature of the machine head is 255 +/-5 ℃, the rotating speed of a main screw is 350-450 rpm, a brace is cooled by a cold water tank below 5 ℃, a granulator is granulated, and granules are cooled to room temperature, so that the low-linear expansion coefficient polypropylene composite material is obtained.
Example 6
1) Firstly, putting the PBT raw material in a vacuum drying oven at 120 ℃ for drying for 5 hours;
2) Weighing the materials according to the following material ratio, respectively placing the materials into a high-speed mixer, and mixing for 3-5 min at normal temperature to obtain a mixed material;
3) Granulating the mixed material by a double-screw extruder (the length-diameter ratio L/D is more than or equal to 36), adding 4.5 percent PP-g-GMA into a side feeding device, and processing the mixed material by the following steps: the temperature of the first zone is 170 +/-5 ℃, the temperature of the second zone is 185 +/-5 ℃, the temperature of the third zone is 205 +/-5 ℃, the temperature of the fourth zone is 210 +/-5 ℃, the temperature of the fifth zone is 200 +/-5 ℃, the temperature of the sixth zone is 210 +/-5 ℃, the temperature of the seventh zone is 210 +/-5 ℃, the temperature of the eighth zone is 200 +/-5 ℃, the temperature of the ninth zone is 210 +/-5 ℃, the temperature of the head is 215 +/-5 ℃, the rotation speed of a screw main machine is 350-450 rpm, a brace is cooled by a cold water tank below 5 ℃, a granulator is used for granulating, and granules are cooled to room temperature, so that the low-linear expansion coefficient polypropylene composite material is obtained.
Comparative example 1
1) Weighing the materials according to the following material ratio, respectively placing the materials into a high-speed mixer, and mixing for 3-5 min at normal temperature to obtain a mixed material;
2) Granulating the mixed material by a three-screw extruder, wherein the processing technology comprises the following steps: the temperature of the first zone is 170 +/-5 ℃, the temperature of the second zone is 185 +/-5 ℃, the temperature of the third zone is 195 +/-5 ℃, the temperature of the fourth zone is 200 +/-5 ℃, the temperature of the fifth zone is 190 +/-5 ℃, the temperature of the sixth zone is 200 +/-5 ℃, the temperature of the seventh zone is 200 +/-5 ℃, the temperature of the eighth zone is 190 +/-5 ℃, the temperature of the ninth zone is 195 +/-5 ℃, the temperature of the machine head is 200 +/-5 ℃, the rotating speed of a screw main machine is 350-450 rpm, the bracing wire is cooled by a cold water tank, the granules are cut by a granulator, and the granules are cooled to room temperature, thus obtaining the polypropylene composite material.
Comparative example 2
1) Weighing the materials according to the following material ratio, respectively placing the materials into a high-speed mixer, and mixing for 3-5 min at normal temperature to obtain a mixed material;
2) Granulating the mixed material by a double-screw extruder, wherein the processing technology comprises the following steps: the temperature of the first zone is 170 +/-5 ℃, the temperature of the second zone is 185 +/-5 ℃, the temperature of the third zone is 195 +/-5 ℃, the temperature of the fourth zone is 200 +/-5 ℃, the temperature of the fifth zone is 190 +/-5 ℃, the temperature of the sixth zone is 200 +/-5 ℃, the temperature of the seventh zone is 200 +/-5 ℃, the temperature of the eighth zone is 190 +/-5 ℃, the temperature of the ninth zone is 195 +/-5 ℃, the temperature of the machine head is 200 +/-5 ℃, the rotation speed of a screw main machine is 350-450 rpm, the bracing wire is cooled by a cold water tank, the granules are cut by a granulator, and the granules are cooled to room temperature, so that the polypropylene composite material is obtained.
Comparative example 3
1) Weighing the materials according to the following material ratio, respectively placing the materials into a high-speed mixer, and mixing for 3-5 min at normal temperature to obtain a mixed material;
2) Granulating the mixture by a double-screw extruder, wherein the processing technology comprises the following steps: the temperature of the first zone is 170 +/-5 ℃, the temperature of the second zone is 185 +/-5 ℃, the temperature of the third zone is 195 +/-5 ℃, the temperature of the fourth zone is 200 +/-5 ℃, the temperature of the fifth zone is 190 +/-5 ℃, the temperature of the sixth zone is 200 +/-5 ℃, the temperature of the seventh zone is 200 +/-5 ℃, the temperature of the eighth zone is 190 +/-5 ℃, the temperature of the ninth zone is 195 +/-5 ℃, the temperature of the machine head is 200 +/-5 ℃, the rotating speed of a screw main machine is 350-450 rpm, the bracing wire is cooled by a cold water tank, the granules are cut by a granulator, and the granules are cooled to room temperature, thus obtaining the polypropylene composite material.
The modified PP composite material prepared in the comparative example and the embodiment is tested for linear expansion coefficient, density and mechanical property, and the formula of the raw materials and the test results are respectively shown in the following table:
TABLE 1 formulation for preparing PP composite according to inventive and comparative examples
TABLE 2 Performance test results of PP composites prepared by inventive and comparative examples
Note: the density test standard GB 1033 is full name: test of GB/T1033.1-2008 non-foamed Plastic Density part 1 impregnation method, hydrometer method and titration method
ISO 11359-2 full name: ISO 11359-2-1999 thermomechanical analysis of plastics (TMA) part 2: measurement of coefficient of linear thermal expansion and glass transition temperature
Compared with a comparative example, the low-linear-expansion-coefficient PP composite material prepared by the embodiment of the invention has the advantages that the linear expansion coefficient and the material density are both greatly reduced, the TD linear expansion coefficient is less than or equal to 40 mu m/(m DEG C), the MD linear expansion coefficient is less than or equal to 50 mu m/(m DEG C), and the material strength is also greatly improved.
The density of the PP material with low expansion coefficient on the market is basically not lower than 1.17g/cm 3 (ii) a The linear expansion coefficient is generally between 30 and 50 μm/m.DEG.C (the linear expansion coefficient of ordinary filled PP is between 80 and 100 μm/m.DEG.C.). The linear expansion coefficient of the material of the embodiment of the invention is similar to that of the material on the market, and the main innovation points comprise that: the first method is to prepare PP with low linear expansion coefficient by in-situ forming micro-nano fiberThe density of the prepared PP with the low linear expansion coefficient is lower than that of the PP in the market, and the addition mode of the compatilizer is changed in the microfiber forming method, so that the using amount of the compatilizer is increased, and the addition amount is larger than that in the prior art (the addition amount of the compatilizer is properly increased, so that the performance of the material can be improved).
From the above examples, the preparation method described in the embodiments of the present invention is: mixing the raw materials except the compatilizer, adding the mixture into a double-screw extruder with the length-diameter ratio (L/D) being more than or equal to 36 or a three-screw extruder with the length-diameter ratio (L/D) being more than or equal to 15, simultaneously adding the compatilizer through a special low-speed side feeding device, and carrying out extrusion, drawing strips, cooling and granulating at a certain temperature to prepare the modified PP product. The method is unique, and the micro-nano fiber with a certain length-diameter ratio formed in the extrusion process is directly utilized to control the linear expansion coefficient of the PP material, so that the dimensional stability is improved; the interface compatibility of PP and the micro-nano fiber is better, and the strength and the dimensional stability of the material are further improved; the density of the material is greatly reduced, and the development trend of light weight of the automobile at present is met.
In summary, the preferred embodiments of the present invention are described, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The polypropylene composite material with the low linear expansion coefficient is characterized by comprising the following raw materials in percentage by weight:
the density of the polypropylene composite material with the low linear expansion coefficient is lower than 1.20g/cm 3 。
2. The polypropylene composite material with low linear expansion coefficient as claimed in claim 1, wherein the PP resin is one or more of homo-polypropylene and co-polypropylene, and the crystallinity of the PP resin is not less than 38%.
3. The low coefficient of linear expansion polypropylene composite of claim 1, wherein the thermoplastic fiber-forming resin is one or more of polyethylene terephthalate, polybutylene terephthalate, polycaprolactam, and polyhexamethylene adipamide.
4. The low coefficient of linear expansion polypropylene composite of claim 1, wherein the compatibilizer is one or more of polypropylene grafted maleic anhydride and polypropylene grafted glycidyl methacrylate.
5. The polypropylene composite with a low linear expansion coefficient as claimed in claim 1, wherein the toughening agent is one or more of ethylene/butene copolymer and ethylene/octene copolymer, and Mooney viscosity of the toughening agent is not higher than 20MU.
6. The polypropylene composite material with the low linear expansion coefficient as claimed in claim 1, wherein the PP nucleating agent is one or more of aryl phosphate nucleating agents and sorbitol nucleating agents.
7. The polypropylene composite material with low linear expansion coefficient as claimed in claim 1, wherein the ultrafine inorganic filler is one or more of talcum powder, wollastonite and calcium sulfate whisker, wherein the mesh number of the talcum powder and the wollastonite is more than 2500 meshes, the diameter of the calcium sulfate whisker is not more than 5 μm, and the length-diameter ratio is 5-40.
8. The low coefficient of linear expansion polypropylene composite according to any one of claims 1 to 7, wherein the low coefficient of linear expansion polypropylene composite has a TD coefficient of linear expansion of 40 μm/m ° C or less and/or an MD coefficient of linear expansion of 50 μm/m ° C or less.
9. The method for preparing a low coefficient of linear expansion polypropylene composite according to any one of claims 1 to 8, comprising the steps of:
s1, weighing PP resin, thermoplastic fiber forming resin, a toughening agent, superfine inorganic filler, a PP nucleating agent and a processing aid according to a weight ratio, and mixing and stirring to obtain a mixed material;
and S2, adding the compatilizer into the mixed material obtained in the step S1 through a double-screw extruder with the length-diameter ratio of more than or equal to 36 or a three-screw extruder with the length-diameter ratio of more than or equal to 15 by a side feeding device, and extruding at the temperature higher than the melting temperature of PP and lower than the melting temperature of thermoplastic fiber-forming resin to obtain the polypropylene composite material with the low linear expansion coefficient.
10. The method for preparing the anti-static agent, according to claim 9, wherein the compatilizer is added through a special low-speed side feeding device, and the addition amount is controlled to be less than 10%.
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