CN114058116A - Polypropylene composite material and preparation method thereof - Google Patents
Polypropylene composite material and preparation method thereof Download PDFInfo
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- CN114058116A CN114058116A CN202111265374.2A CN202111265374A CN114058116A CN 114058116 A CN114058116 A CN 114058116A CN 202111265374 A CN202111265374 A CN 202111265374A CN 114058116 A CN114058116 A CN 114058116A
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- -1 Polypropylene Polymers 0.000 title claims abstract description 94
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 93
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 76
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 38
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 29
- 229920002689 polyvinyl acetate Polymers 0.000 claims abstract description 23
- 239000011118 polyvinyl acetate Substances 0.000 claims abstract description 23
- 239000012745 toughening agent Substances 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000010008 shearing Methods 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000004611 light stabiliser Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group 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 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- 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
- C08K2201/004—Additives being defined by their length
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a polypropylene composite material and a preparation method thereof, wherein the polypropylene composite material is prepared from 70-85 parts of polypropylene resin, 5-15 parts of a toughening agent, 5-15 parts of basic magnesium sulfate whisker, 1-5 parts of polyvinyl acetate, 0.2 part of an initiator and 0.8 part of other auxiliary agents in parts by weight. According to the invention, a small amount of basic magnesium sulfate whiskers are added into the polypropylene resin, and the basic magnesium sulfate whiskers have lower density and have a needle-shaped structure, so that the rigidity of the polypropylene material can be better enhanced; and then, adding high molecular weight polyvinyl acetate, introducing polar groups on the polypropylene molecular chain, and simultaneously adjusting screw combinations among all zones of the extruder to ensure that the basic magnesium sulfate whiskers are uniformly dispersed and anchored on the polypropylene molecular chain.
Description
Technical Field
The invention belongs to the technical field of high-molecular material modification, and particularly relates to a polypropylene composite material and a preparation method thereof.
Background
Polypropylene (PP for short) is a general thermoplastic resin, has the advantages of low density, low price, easy processing and forming, wide sources and the like, and is widely applied to the markets of automobiles, household appliances and the like. However, pure polypropylene materials have poor balance of rigidity and toughness and poor weather resistance, and therefore, polypropylene resins need to be modified.
With the continuous development of the automobile industry and the like, various major host plants are pursuing polypropylene composite materials with higher performance. The current and future trends are that the wall thickness of automobile parts is thinner and thinner, which requires the material to have higher fluidity, higher rigidity and toughness, and puts higher requirements on the polypropylene resin modification technology. The existing polypropylene modification technology is mostly limited to simple blending, melting and extruding of polypropylene resin, a toughening agent, mineral filling and other components, and the prepared modified polypropylene material has certain mechanical properties, can basically meet the requirements of traditional automobile parts, but cannot adapt to the future development trend.
Chinese patent publication No. CN 107868183 a discloses that acrylic acid-2-hydroxyethyl ester is grafted on a polypropylene molecular chain to improve the performance of polypropylene, and acrylic acid-2-hydroxyethyl ester is a low molecular weight liquid compound, and is volatile in a high temperature extrusion process in an extruder, and meanwhile, unreacted acrylic acid-2-hydroxyethyl ester monomer remains in polypropylene, which has a large influence on the material performance, and the finally prepared polypropylene compound has a low performance. Chinese patent publication No. CN 101070417 a discloses that maleic anhydride, styrene, and acrylic acid are grafted on a polypropylene molecular chain to increase the surface polarity of polypropylene, and the same maleic anhydride, styrene, and acrylic acid are all low molecular weight liquid monomers, which have strong volatility, and a large amount of volatile components in the extrusion process will reduce the grafting ratio, and meanwhile, the residual monomers in the final material will affect the performance of the material.
Disclosure of Invention
In view of the above, the present invention provides a polypropylene composite material and a preparation method thereof, so as to solve the problems proposed in the background art, the method provided by the present invention is different from the traditional polypropylene modification technology, mainly starting from the combination between polypropylene resin and mineral filling, high molecular weight polyvinyl acetate is added, polar groups are introduced on polypropylene molecular chains, and meanwhile, the screw combination among all the regions is adjusted, so that basic magnesium sulfate whiskers are uniformly dispersed and "anchored" on the polypropylene molecular chains. When the product is subjected to external force, the basic magnesium sulfate whisker can not be separated from the polypropylene molecular chain, so that the external force resistance of the product is greatly improved. The prepared polypropylene composite material has excellent mechanical property and can be well suitable for interior and exterior decorative parts of automobiles and the like.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a polypropylene composite material, which is prepared from 55-90 parts of polypropylene resin, 1-20 parts of toughening agent, 1-20 parts of basic magnesium sulfate whisker, 1-5 parts of polyvinyl acetate, 0.1-0.3 part of initiator and 0.5-3 parts of other auxiliary agents in parts by weight.
As a further scheme of the invention: the melt flow rate of the polypropylene resin is (1-100) g/10min under the conditions of 230 ℃ and 2.16kg, the flexural modulus is more than or equal to 1200MPa, and the notched impact strength of a cantilever beam is more than or equal to 5KJ/m2。
As a further scheme of the invention: the toughening agent is an ethylene-octene copolymer, and the density of the ethylene-octene copolymer is 0.86-0.90g/cm3The melt flow rate under the conditions of 190 ℃ and 2.16kg was (0.5-5) g/10 min.
As a further scheme of the invention: the length of the basic magnesium sulfate whisker is 10-60 mu m, preferably 30-60 mu m, and the length-diameter ratio is more than 30. The longer the length of the basic magnesium sulfate whisker, the larger the length-diameter ratio, and the better the polypropylene can be reinforced.
As a further scheme of the invention: the polyvinyl acetate has the number average molecular weight of 12000-25000, wherein the content of the vinyl acetate is 10-30%.
As a further scheme of the invention: the initiator is dicumyl peroxide, and the purity of the initiator is at least chemical purity.
As a further scheme of the invention: the other auxiliary agents comprise at least one of an antioxidant, a light stabilizer, a lubricant and a pigment. The antioxidant, the light stabilizer, the lubricant and the pigment are all conventional additives in the field and are not particularly limited, for example, the antioxidant comprises a main antioxidant and an auxiliary antioxidant, the main antioxidant can be a hindered phenol antioxidant, the auxiliary antioxidant can be a phosphite antioxidant, and the antioxidants can be used independently or in combination; the light stabilizer may be a hindered amine light stabilizer; the lubricant can be selected from zinc stearate, calcium stearate and polyethylene wax, and can be used alone or in combination; the pigment can be selected from carbon black and the like, and the material can be dyed into different colors according to different requirements. Since they are all known auxiliaries, they are not described in detail here.
In another aspect of the present invention, a preparation method of the polypropylene composite material is provided, which includes the following steps:
weighing polypropylene resin, polyvinyl acetate, an initiator and other auxiliaries according to the parts by weight, and fully mixing to obtain a uniform mixed material;
adding the mixed material from a main feeding port of a double-screw extruder; weighing the toughening agent according to the weight part and adding the toughening agent from a first side feeding port of a double-screw extruder; and weighing the dried basic magnesium sulfate whiskers according to the parts by weight, adding the basic magnesium sulfate whiskers from a second side feeding port, and carrying out melt blending, extrusion and granulation to obtain the polypropylene composite material.
Further: the temperature of each zone of the double-screw extruder is as follows in sequence: the first zone is 200-fold at 210 ℃, the second zone is 200-fold at 210 ℃, the third zone is 200-fold at 210 ℃, the fourth zone is 200-fold at 210 ℃, the fifth zone is 180-fold at 200 ℃, the sixth zone is 180-fold at 200 ℃, the seventh zone is 180-fold at 200 ℃, the eighth zone is 180-fold at 200 ℃, the ninth zone is 180-fold at 200 ℃ and the tenth zone is 180-fold at 200 ℃; the rotating speed of the screw is 300-600 r/min, and the vacuum degree is-0.06 to-0.1 MPa;
further: a main feeding port and a first side feeding port of the double-screw extruder adopt a strongly dispersed screw combination and at least comprise 2 ZME thread blocks; a screw combination with strong shearing and strong dispersion is adopted between the first side feed opening and the second side feed opening, and at least comprises 2 ZME thread blocks and 3 90-degree shear blocks; and a screw combination with weak shearing and strong dispersion is adopted between the second-side feed opening and the machine head, at least 3 ZME thread blocks are contained, and no more than 2 90-degree shearing blocks are adopted.
The invention also provides application of the polypropylene composite material in preparation of interior and exterior automotive parts, and light-weight and thin-walled automotive parts such as door panels, bumpers and the like can be prepared.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, a small amount of dried basic magnesium sulfate whiskers are added into the polypropylene resin, and the basic magnesium sulfate whiskers have lower density and have a needle-shaped structure, so that the rigidity of the polypropylene material can be better enhanced; and then, adding high molecular weight polyvinyl acetate, introducing polar groups on the polypropylene molecular chain, and simultaneously adjusting screw combinations among all zones of the extruder to ensure that the basic magnesium sulfate whiskers are uniformly dispersed and anchored on the polypropylene molecular chain. When the product is subjected to external force, the basic magnesium sulfate whisker can not be separated from the polypropylene molecular chain, so that the external force resistance of the product is greatly improved. The prepared polypropylene composite material has excellent mechanical property and can be well suitable for interior and exterior decorative parts of automobiles and the like. The basic magnesium sulfate whisker can prevent powder agglomeration after being dried, and is easy to feed.
Specifically, between the main feeding port and the first side feeding port, the initiator is heated to generate free radicals which attack tertiary hydrogen on polypropylene and polyvinyl acetate, so that the reaction between the polypropylene and the polyvinyl acetate is initiated, polar groups (ester groups) are introduced on the polypropylene molecular chain and can generate an anchoring effect with the polar groups on the surface of the basic magnesium sulfate whiskers, and the basic magnesium sulfate whiskers are tightly adsorbed on the polypropylene molecular chain. The toughening agent is uniformly dispersed in the polypropylene composite material, so that the mechanical property of the material is enhanced.
The reaction mechanism of the present invention is as follows:
the preparation method provided by the invention improves the screw combination mode of the conventional double-screw extruder, adopts a strong dispersion mode in the screw combination between the main feeding port and the first side feeding port, can ensure that the polyvinyl acetate is better dispersed in the polypropylene, the dicumyl peroxide is heated and decomposed to generate free radicals, the polypropylene and the polyvinyl acetate are initiated to generate a grafting reaction, and polar groups are introduced to the polypropylene molecular chain, so that the adsorption effect can be generated with the polar groups on the surface of the basic magnesium sulfate whisker.
The mode of strong shearing and strong dispersion is adopted between the first side feeding port and the second side feeding port, so that the toughening agent can be uniformly distributed in the polypropylene resin, a 'sea-island' structure is mainly formed, the toughness of the polypropylene can be improved to a great extent, and energy can be better absorbed when the polypropylene resin is impacted by external force. The second side feeding and the machine head adopt a weak shearing strong dispersion mode, the strong dispersion mainly ensures that the basic magnesium sulfate whisker is uniformly dispersed in the polypropylene and is uniformly anchored on a polypropylene molecular chain, and the basic magnesium sulfate whisker cannot be separated from the polypropylene molecular chain when external force is applied; the weak shearing mainly ensures that the basic magnesium sulfate whisker has larger length-diameter ratio, thereby being capable of better reinforcing the polypropylene and better resisting external force so as to prevent a workpiece from deforming.
The polyvinyl acetate mainly plays a role of a bridge, one end of the polyvinyl acetate is connected with a polypropylene molecular chain, and the other end of the polyvinyl acetate provides a polar group (ester group) which interacts with the polar group on the surface of the basic magnesium sulfate whisker, so that the polypropylene and the basic magnesium sulfate whisker have better binding force.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the specific embodiments illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The following examples and comparative examples employ the following raw material specific information:
the polypropylene resin is selected from polypropylene copolymer with melt index of 1-100 g/10min (230 deg.C)2.16Kg), the flexural modulus is more than or equal to 1200MPa, and the impact strength of a cantilever beam notch is more than or equal to 5KJ/m2EP508N, available from landification;
polyvinyl acetate (PVAc) with a number average molecular weight of 12000-25000, wherein the weight portion of the polyvinyl acetate is 10-30%, and the mark is 420, and is produced by DuPont Dow or Korea Letian chemical;
the toughening agent is an elastomer ethylene-octene copolymer with the density of 0.86-0.90g/cm3The melt index is (0.5-5) g/10min (190 ℃, 2.16Kg), and is the brand 8842, available from Dow chemical or Korea SK;
the initiator is dicumyl peroxide, has the purity of chemical purity and is produced from Shanghai Gaoqiao petrifaction;
basic magnesium sulfate whisker, length of 10-60 microns, length-diameter ratio > 30, brand WS-3D, produced from Yingkowski;
the main antioxidant is tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester with the brand number of 1010, produced by Pasteur Germany;
the auxiliary antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite, brand 168, available from basf, germany;
the light stabilizer is 2- (2' -hydroxy-3 ',5' -bis (a, a-dimethylbenzyl) phenyl) benzotriazole with the trade name UV-P, produced by Pasteur Germany;
the lubricant is zinc stearate, grade AV300, produced in Dongguan Hanwei;
the pigment is carbon black, a commercially available product.
All materials are conventional and common products sold in the market.
It is understood that the above raw material reagents are only examples of some specific embodiments of the present invention, so as to make the technical scheme of the present invention more clear, and do not represent that the present invention can only adopt the above reagents, particularly, the scope of the claims is subject to. In addition, "parts" described in examples and comparative examples mean parts by weight unless otherwise specified.
Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.
In the following examples 1-7 and comparative examples 1-6, the components were weighed according to table 1, and the polypropylene resin, polyvinyl acetate, initiator and other additives were added to a high-speed stirrer and stirred for 3-5min to obtain a uniform mixed material; putting the basic magnesium sulfate whisker into an oven for drying, wherein the temperature of the oven is 80-100 ℃, and the time is 2-4 h;
adding the mixed material from a main feeding port of a double-screw extruder; the toughening agent is added from a first side feeding port of the double-screw extruder; and adding the basic magnesium sulfate whisker/talcum powder from a second side feeding port, and carrying out melt blending, extrusion and granulation to obtain the polypropylene composite material.
The double-screw rotating speed of the double-screw extruder is 500 r/min, and the extrusion temperature is as follows: the first zone is 200-fold at 210 ℃, the second zone is 200-fold at 210 ℃, the third zone is 200-fold at 210 ℃, the fourth zone is 200-fold at 210 ℃, the fifth zone is 180-fold at 200 ℃, the sixth zone is 180-fold at 200 ℃, the seventh zone is 180-fold at 200 ℃, the eighth zone is 180-fold at 200 ℃, the ninth zone is 180-fold at 200 ℃ and the tenth zone is 180-fold at 200 ℃; the vacuum degree is-0.06-0.1 MPa; the screw combinations were arranged as per table 2.
TABLE 1 component ratios for the preparation of composites in the examples and comparative examples
TABLE 2 twin-screw extruder screw combinations in examples 1-7 and comparative examples 1-6
The polypropylene composites obtained in examples 1 to 7 and comparative examples 1 to 6 were subjected to density, tensile strength, flexural modulus, impact strength, and melt flow rate, respectively, and the results of the measured physical properties are shown in Table 3.
TABLE 3 test results of Properties of Polypropylene composite in examples 1 to 7 and comparative examples 1 to 6
The test conditions in table 3 are specifically: the environmental temperature is (23 +/-2) ° C, the environmental humidity is (50 +/-5)%, and all samples are placed under the environment for 24h for testing; the test method is as follows:
1. impact strength of polypropylene composite: carrying out cantilever beam impact test according to the experimental method of GB/T1843, wherein the sample size is 80 multiplied by 10 multiplied by (4.0 +/-0.2) mm, and the A-shaped gap is formed;
2. tensile strength of polypropylene composite: carrying out a tensile test according to an experimental method of GB/T1040.2-2006, carrying out 1A type injection molding on a sample strip, wherein the experimental speed is 50 mm/min;
3. flexural modulus of polypropylene composite: bending test is carried out according to the test method of GB/T9341-2008, the size of a sample strip is 80 multiplied by 10 multiplied by (4.0 +/-0.2) mm, the test speed is 2mm/min, and the support span is 64 mm;
4. melt flow rate of polypropylene composite: carrying out a melt flow rate test according to the experimental method of GB/3682-2000, wherein the experimental temperature is 230 ℃, and the load is 2.16 Kg;
5. density of polypropylene composite: density tests were carried out according to the experimental method of GB/T1033.1-2008.
And (4) analyzing results:
from Table 3, it can be seen that the amount of basic magnesium sulfate whiskers is in positive correlation with the flexural modulus of the polypropylene composite material in examples 1 to 7; after polyvinyl acetate and an initiator are added, the flexural modulus of the material is greatly increased, and the anchoring effect is generated between the polypropylene molecular chain and basic magnesium sulfate whisker after polar groups are introduced; when the amount of the toughening agent is less, the impact strength of the material is too low, and when the amount is more, the flexural modulus of the material is lower.
Compared with the comparative example 1, in the embodiment 4, after the screw dispersion between the main feeding port and the first side feeding port is weakened, the flexural modulus of the material is also greatly reduced, because the polyvinyl acetate and the polypropylene are not fully mixed due to the weakened screw dispersion, so that the polar groups on the polypropylene molecular chain are not uniformly distributed, and finally, the basic magnesium sulfate whiskers are not uniformly adsorbed on the polypropylene molecular chain.
Compared with the comparative examples 2 to 3, when the screw dispersion between the first side feed opening and the second side feed opening is weakened, the impact performance of the material is reduced because the toughening agent is not uniformly dispersed in the polypropylene, so that the toughening agent is agglomerated, and the toughening efficiency is reduced; when the screw shear between the first side feed opening and the second side feed opening is weakened, the impact performance of the material is also reduced because the toughening agent does not form a sea-island structure through strong shear, so that the impact performance of the final material is reduced.
Compared with the comparative examples 4 and 5, when the shearing between the second side feeding opening and the machine head is strengthened, the flexural modulus of the material is reduced, because the basic magnesium sulfate whiskers are sheared due to strong shearing, the length-diameter ratio is reduced, and the strengthening capability is reduced; when the dispersion between the second side feeding opening and the machine head is weakened, the flexural modulus of the material is also reduced because the basic magnesium sulfate whiskers are not dispersed and are agglomerated, and finally the flexural modulus of the material is reduced.
Compared with the comparative example 6, when the basic magnesium sulfate whisker is replaced by the talcum powder, the flexural modulus of the material is reduced sharply because the basic magnesium sulfate whisker has a needle-shaped structure, and the talcum powder has a lamellar structure, and the reinforcing capability of the needle-shaped structure on polypropylene is far higher than that of the lamellar structure.
Although the present description is described in terms of embodiments, not every embodiment includes only a single embodiment, and such description is for clarity only, and those skilled in the art should be able to integrate the description as a whole, and the embodiments can be appropriately combined to form other embodiments as will be understood by those skilled in the art.
Therefore, the above description is only a preferred embodiment of the present application, and is not intended to limit the scope of the present application; all changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (10)
1. The polypropylene composite material is characterized by being prepared from 70-85 parts of polypropylene resin, 5-15 parts of toughening agent, 5-15 parts of basic magnesium sulfate whisker, 1-5 parts of polyvinyl acetate, 0.2 part of initiator and 0.8 part of other auxiliary agent in parts by weight.
2. The polypropylene composite according to claim 1, wherein the polypropylene resin has a melt flow rate of (1 to 100) g/10min at 230 ℃ under 2.16 kg.
3. The polypropylene composite of claim 1, wherein the toughening agent is an ethylene-octene copolymer having a density of 0.86-0.90g/cm3The melt flow rate under the conditions of 190 ℃ and 2.16kg was (0.5-5) g/10 min.
4. The polypropylene composite material according to claim 1, wherein the basic magnesium sulfate whiskers have a length of 10-60 μm and an aspect ratio of > 30.
5. The polypropylene composite of claim 1, wherein the polyvinyl acetate has a number average molecular weight of 12000-25000, and a vinyl acetate content of 10-30%.
6. The polypropylene composite of claim 1, wherein the initiator is dicumyl peroxide.
7. The polypropylene composite of claim 1, wherein the other additives comprise at least one of antioxidants, light stabilizers, lubricants and pigments.
8. A method for preparing a polypropylene composite according to any one of claims 1 to 7, comprising the steps of:
weighing polypropylene resin, polyvinyl acetate, an initiator and other auxiliaries according to the parts by weight, and fully mixing to obtain a uniform mixed material;
adding the mixed material from a main feeding port of a double-screw extruder; weighing the toughening agent according to the weight part and adding the toughening agent from a first side feeding port of a double-screw extruder; and weighing the dried basic magnesium sulfate whiskers according to the parts by weight, adding the basic magnesium sulfate whiskers from a second side feeding port, and carrying out melt blending, extrusion and granulation to obtain the polypropylene composite material.
9. The method of claim 8, wherein:
the temperature of each zone of the double-screw extruder is as follows in sequence: the first zone is 200-fold at 210 ℃, the second zone is 200-fold at 210 ℃, the third zone is 200-fold at 210 ℃, the fourth zone is 200-fold at 210 ℃, the fifth zone is 180-fold at 200 ℃, the sixth zone is 180-fold at 200 ℃, the seventh zone is 180-fold at 200 ℃, the eighth zone is 180-fold at 200 ℃, the ninth zone is 180-fold at 200 ℃ and the tenth zone is 180-fold at 200 ℃; the rotating speed of the screw is 300-600 r/min, and the vacuum degree is-0.06 to-0.1 MPa;
a main feeding port and a first side feeding port of the double-screw extruder adopt a strongly dispersed screw combination and at least comprise 2 ZME thread blocks; a screw combination with strong shearing and strong dispersion is adopted between the first side feed opening and the second side feed opening, and at least comprises 2 ZME thread blocks and 3 90-degree shear blocks; and a screw combination with weak shearing and strong dispersion is adopted between the second-side feed opening and the machine head, at least 3 ZME thread blocks are contained, and no more than 2 90-degree shearing blocks are adopted.
10. Use of the polypropylene composite according to any one of claims 1 to 7 for the manufacture of interior and exterior automotive trim parts.
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