CN117264325B - A polypropylene composite material and preparation method thereof - Google Patents
A polypropylene composite material and preparation method thereof Download PDFInfo
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- CN117264325B CN117264325B CN202311430855.3A CN202311430855A CN117264325B CN 117264325 B CN117264325 B CN 117264325B CN 202311430855 A CN202311430855 A CN 202311430855A CN 117264325 B CN117264325 B CN 117264325B
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- -1 polypropylene Polymers 0.000 title claims abstract description 58
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 54
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 54
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 67
- 239000000843 powder Substances 0.000 claims abstract description 46
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims abstract description 41
- 229910000077 silane Inorganic materials 0.000 claims description 40
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 39
- 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 31
- 238000000034 method Methods 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012745 toughening agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 22
- 230000008961 swelling Effects 0.000 abstract description 21
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 68
- 230000000052 comparative effect Effects 0.000 description 25
- 230000000694 effects Effects 0.000 description 14
- 244000025254 Cannabis sativa Species 0.000 description 11
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 11
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 11
- 235000009120 camo Nutrition 0.000 description 11
- 235000005607 chanvre indien Nutrition 0.000 description 11
- 239000011487 hemp Substances 0.000 description 11
- 239000010445 mica Substances 0.000 description 11
- 229910052618 mica group Inorganic materials 0.000 description 11
- 229920002678 cellulose Polymers 0.000 description 10
- 239000001913 cellulose Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 238000002955 isolation Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000010705 motor oil Substances 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229920005606 polypropylene copolymer Polymers 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 244000077995 Coix lacryma jobi Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 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
- C08L23/14—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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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
本发明公开了一种聚丙烯复合材料及其制备方法，属于高分子材料技术领域，该产品通过特定的硅烷改性纳米纤维素与合成云母粉的搭配协同作用，可以大幅度提升产品的耐溶剂溶胀性，同时产品的组分分散性优异，外观不会受到影响，表面无明显麻点或流痕。The invention discloses a polypropylene composite material and a preparation method thereof, belonging to the technical field of polymer materials. The product can greatly improve the solvent swelling resistance of the product through the synergistic effect of the combination of specific silane-modified nanocellulose and synthetic mica powder. At the same time, the product has excellent component dispersibility, the appearance will not be affected, and there is no obvious pitting or flow mark on the surface.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polypropylene composite material and a preparation method thereof.
Background
In the automobile industry, some parts such as instrument decorative plates, outer bumpers, shell protection sleeves and the like are all made of plastics, and polypropylene materials are the highest in use frequency.
However, since automobile parts are exposed to organic reagents such as engine oil for a long time, a polypropylene material for preparing the parts is required to have a certain solvent swelling resistance, but with functionalization and generalization of automobile products, the swelling resistance of the existing polypropylene material cannot meet market demands gradually, especially in some engineering vehicle fields, and the solvent resistance of the automobile parts is required to be more than 200 hours.
In the prior art, the solvent resistance improvement scheme for the polypropylene material generally introduces partial solvent stabilizer into the product so as to control the matrix resin to inhibit the penetration of the product after the solvent contacts, but the solvent swelling resistance of the existing product is still poor, and meanwhile, the introduction of the modifier can lead to the reduction of the dispersibility of the whole component, finally, the appearance of the product is greatly influenced, and the application range is greatly limited.
Disclosure of Invention
Based on the defects existing in the prior art, the invention aims to provide the polypropylene composite material, and the product can greatly improve the solvent swelling resistance of the product through the collocation synergistic effect of specific silane modified nanocellulose and synthetic mica powder, meanwhile, the component dispersibility of the product is excellent, the appearance is not influenced, and obvious pits or flow marks are not generated on the surface.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the polypropylene composite material comprises the following components in parts by weight:
50-90 parts of polypropylene resin, 3-15 parts of toughening agent, 5-25 parts of talcum powder, 1-2 parts of silane modified nano cellulose, 2-5 parts of synthetic mica powder and 0.1-2.5 parts of processing aid.
Preferably, the polypropylene composite material comprises the following components in parts by weight:
60-80 parts of polypropylene resin, 5-10 parts of toughening agent, 10-20 parts of talcum powder, 1-2 parts of silane modified nano cellulose, 2-5 parts of synthetic mica powder and 0.1-2.5 parts of processing aid.
Preferably, in the polypropylene composite material, the mass percent of the polypropylene resin is not less than 60wt%.
The existing polypropylene composite material generally adopts an elastomer component with higher oil absorption to improve the solvent swelling resistance effect of the product, but the method can reduce the comprehensive performance of the product, and finally the function of the product is influenced. In order to overcome the defects of the existing product, the nano-sized macromolecular polysaccharide such as cellulose is matched with the synthetic mica powder to serve as a key component, the nano-sized cellulose can be easily combined with the synthetic mica powder based on silane groups loaded on the surface after silane modification, and a lamellar overlapping barrier network is automatically formed on the surface layer of the matrix polypropylene resin.
On the other hand, due to the lamellar structure of the synthetic mica powder, the size of cellulose is required to reach the nanometer level to be effectively dispersed among gaps of the mica powder, and after the experiments of the inventor, the inventor finds that when the cellulose in the product is only at the micrometer level, the product is difficult to realize the solvent swelling resistance effect, meanwhile, unlike the natural mica powder, the synthetic mica powder has higher hardness and toughness, so the structural stability is good, the lamellar structure cannot be damaged due to the processing process of the product, and the same technical effect cannot be achieved if the synthetic mica powder is replaced by the natural mica powder.
Preferably, the synthetic mica powder is fluorophlogopite powder, and the melting point is 1370-1380 ℃.
Preferably, the mass ratio of the silane modified nanocellulose to the synthetic mica powder is (1:2) - (2:5).
In the polypropylene composite material, compared with polypropylene resin and talcum powder serving as a filler, the addition amount of silane modified nanocellulose and synthetic mica powder is small, and the main reason is that excessive addition of the silane modified nanocellulose and the synthetic mica powder also causes appearance problems of products, and under the condition that the total addition amount of the silane modified nanocellulose and the synthetic mica powder is fixed, the quality ratio of the silane modified nanocellulose and the synthetic mica powder is better in comprehensive performance under the above range through screening.
Preferably, the diameter of the silane modified nanocellulose is more than 95% and the length of the silane modified nanocellulose is more than 95% and more than 30-2000 nm;
More preferably, the silane modified nanocellulose has a diameter of 10-30 nm of more than 95% and a length of 100-500 nm of more than 95%.
The diameter and the length of the silane modified nanocellulose are detected by a particle size detector.
In the invention, the diameter and length range of the silane modified nanocellulose is limited to more than 95% of the whole material, and the other range of the diameter and length materials are ignored by the person skilled in the art, and the diameter and length range can be considered as the range of the whole silane modified nanocellulose.
In the polypropylene composite material, the silane modified nanocellulose has the main functions of a binding agent and a gap filler of a mica sheet in a self-built barrier network, so that the silane modified nanocellulose with different sizes has certain difference in application effect, and the solvent swelling resistance effect of the product is better when the type in the preferred range is adopted as a product component through screening.
Preferably, the silicon element mass content of the silane modified nanocellulose is 10-12 ppm.
The silicon element mass content of the silane modified nanocellulose is obtained by IPC detection.
More preferably, the silane modified nanocellulose is obtained by mixing and dispersing nanocellulose and a silane coupling agent.
More preferably, the mass ratio of the silane coupling agent to the nanocellulose in the silane-modified nanocellulose is (0.5-1.5): 100.
More preferably, the silane coupling agent comprises at least one of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane and gamma-methacryloxypropyl siloxane.
The inventor experiments show that the nano cellulose has rich surface groups, so that the compatibility of the nano cellulose in the polypropylene matrix resin can be effectively realized by modifying the nano cellulose by adopting the conventional common multi-type silane coupling agents.
Preferably, the average sheet diameter of the synthetic mica powder is 20-80 mu m.
More preferably, the average plate diameter of the synthetic mica powder is 30-60 μm.
More preferably, the average plate diameter of the synthetic mica powder is in the range of one or any two of 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm.
The particle diameter of the synthetic mica powder is obtained by testing with a particle size tester.
As described above, the synthetic mica powder in the technical scheme of the invention is a key component for forming the barrier structure, but the larger the sheet diameter of the component is, the better, and experiments show that when the sheet diameter of the synthetic mica powder is preferably in the range of 30-60 mu m, the better the comprehensive performance of the product is.
Preferably, the polypropylene resin is a copolymerized polypropylene.
More preferably, the melt flow rate of the polypropylene copolymer resin is 1-100 g/10min at 230 ℃ under a load of 2.16kg according to ISO 1133-2011.
More preferably, the melt flow rate of the polypropylene copolymer resin is 10-50 g/10min at 230 ℃ under a load of 2.16kg according to ISO 1133-2011.
More preferably, the polypropylene copolymer resin has a melt flow rate of one or any two of 10g/10min, 15g/10min, 20g/10min, 25g/10min, 30g/10min, 35g/10min, 40g/10min, 45g/10min, 50g/10min under a load of 2.16kg at 230℃according to ISO 1133-2011.
Preferably, the mesh number of the talcum powder is more than or equal to 1000 meshes.
Preferably, the talc has a mesh number in the range of one or any two of 1000 mesh, 1250 mesh, 2000 mesh, 3000 mesh, 3500 mesh, 4000 mesh, 5000 mesh, 6000 mesh, 7000 mesh and 8000 mesh.
More preferably, the mesh number of the talcum powder is 1250-3500 mesh.
In the polypropylene composite material, talcum powder serves as a main filler, but the talcum powder can be also brought into a self-built isolation protection network layer formed by a product, so that when the mesh number of the talcum powder is more than or equal to 1000 meshes and the particle size is smaller, the talcum powder can effectively assist silane modified nanocellulose to better fill gaps of the isolation network, and the isolation effect of the talcum powder on a solvent is better.
In addition, experiments by the inventor prove that each talcum powder can be used for preparing products by taking the existing commercial brands as raw materials based on actual use requirements, or a commercial product can be purchased in advance and then used after being screened by particles, and the performances of the products prepared by talcum powder of the same mesh number and talcum powder of different models or sources are basically the same through comparison by the inventor, so that in the product system disclosed by the invention, the properties of the talcum powder except the mesh number have no influence on the performances of the products concerned by the invention.
Preferably, the toughening agent is at least one of an ethylene/octene copolymer, an ethylene/butene copolymer, and an ethylene/propylene copolymer.
More preferably, the toughening agent has a melt index of 1-20 g/10min at 230 ℃ under a load of 2.16kg according to ISO 1133-2011.
Preferably, the processing aid comprises at least one of an antioxidant and a lubricant.
More preferably, the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.
More preferably, the antioxidant is a mixture of hindered phenol antioxidants and phosphite antioxidants according to the ratio of (0.8-1.2).
More preferably, the lubricant is at least one of a silicone lubricant and a wax lubricant.
Based on the needs of actual products, the person skilled in the art can properly introduce some components commonly introduced into some polypropylene composite materials without affecting the product performance, such as antioxidants for improving the ageing resistance of the product, lubricants for improving the processing performance of the product, and the like, and further can also introduce components for improving the processing dispersibility of the product, such as a dispersing agent, wherein the dispersing agent can be at least one of polyol ester and fatty alcohol ester.
Another object of the present invention is to provide a method for preparing the polypropylene composite material, comprising the steps of:
And after uniformly mixing the components, carrying out melt extrusion granulation in a double-screw extruder to obtain the swelling-resistant polypropylene composite material.
The preparation method of the polypropylene composite material has simple operation steps and can realize industrialized mass production.
Preferably, the temperature interval of the double-screw extruder is 160-240 ℃, and the screw rotating speed is 400-600 r/min.
The invention also aims to provide application of the polypropylene composite material in preparing automobile parts.
Preferably, the automotive component comprises a separator.
The polypropylene composite material is based on a specific self-built isolation network, can effectively prevent the erosion of organic solvents such as engine oil and the like on parts when being applied to automobile parts, has extremely low permeation and precipitation efficiency of the organic solvents in the product, can achieve time consumption of precipitation for more than 200 hours, and has good appearance and no obvious defects.
The polypropylene composite material and the preparation method thereof have the beneficial effects that the product can greatly improve the solvent swelling resistance of the product through the collocation synergistic effect of the specific silane modified nanocellulose and the synthetic mica powder, meanwhile, the component dispersibility of the product is excellent, the appearance is not influenced, and no obvious pits or flow marks exist on the surface.
Detailed Description
The present invention will be further described with reference to specific examples and comparative examples for better illustrating the objects, technical solutions and advantages of the present invention, and the object of the present invention is to be understood in detail, not to limit the present invention. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments involved in the practice of the present invention are common reagents and instruments unless otherwise specified.
It should be noted that, in the specific embodiment of the present technical solution, the synthetic mica is fluorophlogopite, the melting point is 1370-1380 ℃, the main components of the natural mica are muscovite and phlogopite, the melting point is less than or equal to 900 ℃, and the synthetic mica and the natural mica are not limited by the literal description of the synthetic mica and the natural mica, and the differences are not repeated here.
Examples 1 to 16
In one embodiment of the polypropylene composite material and the application thereof, the composition of the polypropylene composite material is shown in table 1.
The preparation method of the polypropylene composite material comprises the following steps:
And (3) uniformly mixing all the components in the formula by a high-speed mixer, and sending the mixture into a double-screw extruder from a main feeding port for melt blending extrusion and pelleting to obtain the polypropylene composite material.
When the components are subjected to melt blending extrusion, the temperature zone of the twin-screw extruder is set to be 165-175 ℃ in a first zone, 185-195 ℃ in a second zone, 205-215 ℃ in a third zone, 205-215 ℃ in a fourth zone, 215-225 ℃ in a fifth zone, 215-225 ℃ in a sixth zone, 225-235 ℃ in a seventh zone, 225-235 ℃ in an eighth zone, 225-235 ℃ in a ninth zone, the screw speed is 500rpm, and the screw length-diameter ratio is 40:1.
Comparative examples 1 to 9
The comparative examples differ from the examples only in the kinds and proportions of the components, as shown in Table 2.
Among the components described in each example and comparative example,
The polypropylene resin 1 is Zhenhai for refining to produce M30RHC, the copolymerized polypropylene has a melt flow rate of 26g/10min under the load of 2.16kg at 230 ℃ according to ISO 1133;
the polypropylene resin 2 is Zhenhai for refining to produce Z30S, and the melt flow rate of the copolymerized polypropylene under the load of 2.16kg at 230 ℃ according to ISO 1133 is 25g/10min;
The toughening agent 1 is POE 7447 produced by Dow chemical production, and the ethylene/octene copolymer has a melt index of 5g/10min under the load of 2.16kg at 230 ℃ according to ISO 1133;
The toughening agent 2 is POE 7467 produced by Dow chemical production, and the ethylene/butene copolymer has a melt index of 1.5g/10min under the load of 2.16kg at 230 ℃ according to ISO 1133;
the talcum powder 1 is TYT-777A produced by North sea group, and is 3000 mesh talcum powder;
the talcum powder 2 is talcum powder of 2000 meshes produced by Guangxi Longwei and having TY 90-7-C;
the talcum powder 3 is talcum powder of ultra 5,5000 meshes produced by coix seed Ai Hai;
the talcum powder 4 is TYT-8875B,1000 mesh talcum powder produced by North sea group;
The nanocellulose 1 is a product produced by Wuhan Kangqiong, the diameter of the nanocellulose is 10-30 nm and accounts for more than 95%, and the length of the nanocellulose is 100-500 nm and accounts for more than 95%;
The nanocellulose 2 is a product produced by the Wuhan Kangqiong, the diameter of the nanocellulose is 2-10 nm and accounts for more than 95%, and the length of the nanocellulose is 30-100 nm and accounts for more than 95%;
the nanocellulose 3 is a product produced by the Wuhan Kangqiong, the diameter of the nanocellulose is 40-80 nm, the nanocellulose accounts for more than 95%, the length of the nanocellulose is 0.5-2 um, and the nanocellulose accounts for more than 95%;
the cellulose is a product produced by Wuhank's Michaelis-co, the diameter of the cellulose is 0.2-0.5 mu m and accounts for more than 95%, and the length of the cellulose is 2-5 mu m and accounts for more than 95%;
The silane coupling agent 1 is KH-550, gamma-aminopropyl triethoxy siloxane produced by Nanjing dawn.
The silane coupling agent 2 is KH570, gamma-methacryloxypropyl siloxane produced by Nanjing dawn.
The silane modified nano cellulose 1 is prepared by a self-control method, wherein the self-control method is to mix and stir the nano cellulose 1 and the silane coupling agent 1 for 2min according to the mass ratio of 100:1 until the nano cellulose is uniformly obtained, and the silicon mass content is 10ppm;
the silane modified nano cellulose 2 is prepared by a self-control method, wherein the self-control method is to mix and stir the nano cellulose 2 and the silane coupling agent 1 according to the mass ratio of 100:1 for 2min until the nano cellulose is uniformly obtained, and the silicon mass content is 11ppm;
The silane modified nano cellulose 3 is prepared by a self-control method, wherein the self-control method is to mix and stir the nano cellulose 3 and the silane coupling agent 1 according to the mass ratio of 100:1 for 2min until the mixture is uniform, and the silicon mass content is 11ppm;
The silane modified nano cellulose 4 is prepared by a self-control method, wherein the self-control method is to mix and stir nano cellulose 1 and a silane coupling agent 2 according to a mass ratio of 100:1 for 2min until the mixture is uniform, and the silicon mass content is 12ppm;
the silane modified cellulose is prepared by a self-control method, wherein the self-control method comprises the steps of mixing and stirring cellulose and a silane coupling agent 1 according to a mass ratio of 100:1 for 2min until the mixture is uniform, and the silicon mass content is 10ppm;
The silane modified talcum powder is prepared by a self-control method, wherein talcum powder 3 and silane coupling agent 1 are mixed and stirred for 2min according to the mass ratio of 100:1 until the silane modified talcum powder is uniformly obtained, and the silicon mass content is 11ppm;
the synthetic mica powder 1 is produced by Suzhou Shenwei, and the average sheet diameter is 40 mu m, the synthetic mica powder 2 is produced by Suzhou Shenwei, and the average sheet diameter is 80 mu m;
The synthetic mica powder 3 is a product produced by Suzhou Shenwei, and the average sheet diameter is 20 mu m;
the synthetic mica powder 4 is a product produced by Suzhou Shenwei, and the average sheet diameter is 50 mu m;
The natural mica powder is produced by Jiangmen Jingda, and the average sheet diameter is 30 mu m;
the antioxidant is a mixture of a commercially available hindered phenol antioxidant and a commercially available phosphite antioxidant according to a mass ratio of 1:1;
The lubricant is commercially available national polyfluoro production lubricant MSA-255;
The raw materials of the components used in each of the examples and comparative examples of the present invention were all commercially available raw materials unless otherwise specified, and the raw materials of the components used in each of the parallel experiments were all the same.
The reverse test shows that the mesh number of talcum powder and the average sheet diameter of synthetic mica powder in each product are not basically changed before and after processing (the change rate of single product is lower than 5%), so that the sizes of talcum powder and synthetic mica powder before and after processing are not changed. Similarly, the size of the silane modified nanocellulose in the product after modification and processing is almost the same as the diameter and length of the nanocellulose starting material, so the nanocellulose size in the product can be considered to be the same as the starting material.
TABLE 1
TABLE 2
In order to verify the performance of the polypropylene composite material of the present invention, the following performance tests were performed on the products prepared in each example and comparative example, and specific steps are as follows:
(1) Solvent swelling resistance test the products of each example and comparative example were cut into 100X 100mm size panels, 5mL of organic solvent was dropped onto the panels with a dropper, then placed in a 100℃oven for 240 hours, removed for cooling to room temperature, wiped clean with clean cotton cloth, and the panels were evaluated for changes in the location of the organic solvent by comparison, and the evaluation ratings were as described below. Meanwhile, whether a solvent is separated out from the back surface is observed, the separation time is recorded, and the swelling resistance of the sample is evaluated in two aspects, wherein the organic solvent used in the experiment is engine oil.
Positive rating criteria were:
1, the oil stain at the experimental part can be wiped off, the color is not changed, and the gray level is 5;
2, the oil stain at the experimental part can be wiped off, the color is slightly changed, and the gray level is 4/5;
3, the oil stain at the experimental part can be wiped off, the color is obviously changed, and the gray level is 4;
4, the oil stain at the experimental part can be wiped off, the color is greatly changed, and the gray level is 3/4;
5, the oil stain at the experimental part can not be completely wiped off, most of the oil stain is permeated into the sample plate, the color is greatly changed, and the gray level is 3;
and 6, the oil stains at the experimental part can not be wiped off, and basically all the oil stains are permeated into the sample plate.
(2) Appearance test the products of each example and comparative example were cut into 100X 100mm templates, and whether the surface of the template had obvious flow marks was observed, and the pits appearing on the surface were counted, followed by classification, and a higher level indicated a poorer appearance.
The grading criteria are:
1 grade, 0.1mm of hemp points are less than 10, and no hemp points are more than 0.1mm
2 Grade, wherein the number of 0.1mm hemp points is more than or equal to 10, the number of 0.2mm hemp points is less than 10, and no hemp points are more than 0.2 mm;
3 grade, wherein the number of 0.2mm hemp points is more than or equal to 10, the number of 0.3mm hemp points is less than 10, and no hemp points are more than 0.3 mm;
4 grade, wherein the number of 0.3mm hemp points is more than or equal to 10, the number of 0.4mm hemp points is less than 10, and no hemp points are more than 0.4 mm;
the test results are shown in tables 3 and 4.
TABLE 3 Table 3
TABLE 4 Table 4
| Test item | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 |
| Grade of front swelling | 5 | 3 | 4 | 3 | 2 | 3 | 3 | 4 | 3 |
| Back side precipitation time (h) | 24 | 109 | 153 | 180 | 210 | 162 | 168 | 135 | 153 |
| Whether or not there is a flow mark | Without any means for | Without any means for | Without any means for | Has the following components | Has the following components | Has the following components | Without any means for | Without any means for | Without any means for |
| Appearance grade | 1 | 2 | 1 | 2 | 2 | 3 | 1 | 1 | 1 |
As can be seen from tables 3 and 4, compared with the product of comparative example 1 without any modified component, the polypropylene composite material of the present invention can still reach 3 levels and below after the front surface is soaked in the organic solvent for 240 hours in the solvent-resistant swelling test process, and meanwhile, the precipitation time of the back surface solvent can reach 180 hours or above, on the other hand, the product has good appearance, can maintain 2 levels and below, can maintain the appearance level at a lower level, has a small number of pits, and has no obvious flow marks, which indicates that the isolation structure formed based on the specific silane modified nanocellulose and the synthetic mica powder can effectively inhibit the swelling erosion of the solvent, and meanwhile, can not significantly influence the appearance of the product. In the polypropylene composite material of the present invention, according to examples 1 and 5 to 7, it is known that, in addition to silane modified nanocellulose and synthetic mica powder, the size of talc powder as a filler also has a certain influence on the swelling resistance of the product, when the mesh number of the product is large, as shown in example 4, the compactness of the product filled in the insulation network is low, the swelling resistance of the product is reduced compared with the products of examples 1 and 5, and the size of talc powder in the product of example 6 is too small, so that aggregation is easy, the solvent swelling resistance and appearance effect of the product are low, and in combination, the effect is optimal when the mesh number of talc powder is 1250 to 3500 mesh. The size of the silane modified nanocellulose and the size of the synthetic mica powder which are key components also influence the performance of the product, and when the diameter of the silane modified nanocellulose in the product is more than 95% and the length is 100-500 nm and more than 95% as shown in examples 1, 8-10 and 11-12, and the average sheet diameter of the synthetic mica powder is in the range of 30-60 μm, the comprehensive performance of the product is optimal. On the other hand, when the total amount of the two components is fixed and the ratio of the two components is changed, as shown in embodiment 1and embodiment 13 to 15, when the mass ratio of the two components is maintained in the range of (1:2) to (2:5), the two components can exert the best collocation effect, and the performance of the formed isolated network structure is best. In contrast, in the products of comparative examples 2 and 3, the silane-modified nanocellulose and the synthetic mica powder are added alone as the modifying components, and the swelling resistance of the product is improved to a certain extent compared with that of the product of comparative example 1, wherein the improvement effect of the silane-modified nanocellulose on the solvent precipitation on the back of the product is not ideal, but the front grade is improved to 3, and the synthetic mica powder alone has the opposite trend, which means that the silane-modified nanocellulose and the synthetic mica powder are used together necessarily, so that the whole solvent swelling resistance of the product can be synergistically improved. However, both cannot be added excessively, and if it is added excessively, as shown in comparative examples 4 and 5, the barrier network coverage tends to be deteriorated due to the agglomeration effect, and the appearance effect of the product tends to be deteriorated. In addition, as can be seen from comparative example 6, the nanocellulose is directly introduced into the polypropylene composite material of the invention without being modified by silane, which may have the problem of insufficient compatibility, so that the product cannot form an expected isolation network, meanwhile, cellulose can be effectively dispersed in a lamellar structure of mica powder only under the nano size to play a role in leak repairing, if the size is too large, the performance of the product is poor as shown in comparative example 7, and as a filler of the lamellar structure, not any modified component can be qualified, as shown in comparative example 8, talcum powder with smaller size is adopted to replace nanocellulose to synthesize mica powder through modification matching, and the solvent swelling resistance effect of the product is not ideal. As a main material of the insulation structure, it is required to have high thermal stability and strength, and the natural mica powder used in comparative example 9 does not have the corresponding properties, so that the desired effect cannot be achieved even though the material has a lamellar structure as well, after being used for preparing the polypropylene composite material of the present invention.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. The polypropylene composite material is characterized by comprising the following components in parts by weight:
50-90 parts of polypropylene resin, 3-15 parts of toughening agent, 5-25 parts of talcum powder, 1-2 parts of silane modified nano cellulose, 2-5 parts of synthetic mica powder and 0.1-2.5 parts of processing aid;
The polypropylene resin is copolymerized polypropylene, the melt flow rate of the copolymerized polypropylene resin is 1-100 g/10min under the conditions of 230 ℃ and 2.16kg load according to ISO 1133-2011, the mesh number of talcum powder is more than or equal to 1000 meshes, the diameter of the silane modified nanocellulose is more than 95% in 2-80 nm, the length of the silane modified nanocellulose is more than 95% in 30-2000 nm, the average plate diameter of the synthetic mica powder is 20-80 mu m, and the toughening agent is at least one of ethylene/octene copolymer and ethylene/butene copolymer;
the silane modified nanocellulose is obtained by mixing and dispersing nanocellulose and a silane coupling agent, wherein the silane coupling agent comprises at least one of gamma-aminopropyl triethoxysilane, gamma-glycidol ether oxypropyl trimethoxy silane and gamma-methacryloxypropyl siloxane.
2. The polypropylene composite material according to claim 1, wherein the mass ratio of the silane modified nanocellulose to the synthetic mica powder is (1:2) - (2:5).
3. The polypropylene composite of claim 1, wherein the processing aid comprises at least one of an antioxidant and a lubricant.
4. A method for preparing a polypropylene composite material according to any one of claims 1 to 3, comprising the steps of:
and after uniformly mixing the components, carrying out melt extrusion granulation in a double-screw extruder to obtain the polypropylene composite material.
5. The use of the polypropylene composite material according to any one of claims 1 to 3 for the production of automotive parts.
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