CN115418049A - Low-density high-rigidity high-impact modified polypropylene material and preparation method thereof - Google Patents
Low-density high-rigidity high-impact modified polypropylene material and preparation method thereof Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 71
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 70
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 70
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000011256 inorganic filler Substances 0.000 claims abstract description 30
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 30
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 239000002667 nucleating agent Substances 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 229920001971 elastomer Polymers 0.000 claims description 19
- 238000012661 block copolymerization Methods 0.000 claims description 15
- 239000000806 elastomer Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical class NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000004945 silicone rubber Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 19
- 238000012360 testing method Methods 0.000 description 8
- 239000005060 rubber Substances 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- XXHCQZDUJDEPSX-KNCHESJLSA-L calcium;(1s,2r)-cyclohexane-1,2-dicarboxylate Chemical compound [Ca+2].[O-]C(=O)[C@H]1CCCC[C@H]1C([O-])=O XXHCQZDUJDEPSX-KNCHESJLSA-L 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 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
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a low-density high-rigidity high-impact modified polypropylene material and a preparation method thereof, wherein the polypropylene material comprises the following components in percentage by weight: 54.9 to 83.75 percent of polypropylene composition; 13 to 23 percent of inorganic filler master batch; 3 to 20 percent of toughening agent; 0.05 to 0.6 percent of nucleating agent; 0.1 to 0.5 percent of antioxidant; 0.1 to 1 percent of lubricant. The polypropylene material prepared by the invention maintains toughness, improves the flexural modulus of the modified material, improves the impact strength of the modified material, and can still maintain good impact strength in a low-temperature environment.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a low-density high-rigidity high-impact modified polypropylene material and a preparation method thereof.
Background
Polypropylene (PP) is a semi-crystalline thermoplastic plastic with good physical and mechanical properties, chemical properties and processability, and thus, polypropylene has wide applications in the fields of building engineering materials, electric tools, automobile and household appliance materials, and the like. For wider applications, polypropylene is often modified, for example talc filled, calcium carbonate filled, glass fiber reinforced, etc.
However, with the development of the automobile industry, the weight reduction, high performance and low cost of the plastic parts of automobiles become the main trend of the current development. Taking the talcum powder modified polypropylene composite material as an example, the material is generally applied to products with complex structures and larger sizes, such as bumpers, door panels, tail door outer plates and the like, and the weight of a single piece is 3-6 kg. In order to achieve the effect of lightening parts, a method of reducing the wall thickness of a part is often adopted, but the reduction of the wall thickness of the part can cause the reduction of mechanical properties, and the polypropylene has larger shrinkage rate and brittleness at low temperature, so that the use is limited. Therefore, in order to achieve weight reduction, it is necessary to ensure a balance between rigidity and toughness of the low-density material.
The Chinese invention patent with the application number of 201310740894.3 discloses a high-modulus ultrahigh-impact polypropylene composite material and a preparation method thereof, wherein ethylene-butylene copolymer is used as a toughening agent, and superfine talcum powder is used as a filler to improve rigidity, so that the effect of rigidity and toughness balance is achieved. However, the embodiments of this patent all adopt a higher filler proportion, and although the rigidity can be improved, the density of the material is still high, and the requirement of light weight cannot be met.
Chinese patent with application number 201810989480.7 discloses a low-density and high-rigidity polypropylene material and a preparation method thereof, wherein talcum powder which is high in sheet integrity and large in length-diameter ratio and is modified by a silane auxiliary agent is used as filling, and a rigidity-increasing nucleating agent is matched to ensure that the material is made into a materialHas the characteristics of high rigidity, high toughness and high fluidity under lower density. But the impact strength of the material can only reach 35KJ/m 2 Left and right, the use of the product under high impact conditions cannot be met.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a low-density high-rigidity high-impact modified polypropylene material and a preparation method thereof.
The purpose of the invention is realized by the following scheme:
a low-density high-rigidity high-impact modified polypropylene material comprises the following components in percentage by weight:
the polypropylene is a mixture of homo-polypropylene and block co-polypropylene with a mass ratio of 1.
The flow rate of the homopolymerized polypropylene melt is 20-100 g/10min, and the flexural modulus is 1500 MPa-2200 MPa; the melt flow rate of the block copolymerization polypropylene is 10-40 g/10min, and the weight average molecular weight is 200000-300000.
The ethylene content in the block copolymerization polypropylene is 5-30%; the EPR content in the block copolymerization polypropylene is 20-40%, the block copolymerization polypropylene is soluble in dimethylbenzene at 20-35 ℃, the intrinsic viscosity eta of the block copolymerization polypropylene in decalin is 3-5.5 dL/g, and the particle size of the block copolymerization polypropylene is 0.5-3 mu m.
The carrier in the inorganic filler master batch is a propylene-based elastomer, and the monomer copolymerized with propylene is preferably one or more of ethylene, butene, hexene and octene.
The inorganic filler master batch is prepared from the following raw materials in percentage by weight:
the modified inorganic filler is obtained by treating an inorganic filler with a silane coupling agent.
The silane coupling agent is one or more of amino silane coupling agent, epoxy silane coupling agent and acyloxy silane coupling agent.
The inorganic filler is one or more of wollastonite, mica, talcum powder, crystal whisker and montmorillonite, and the particle size of the inorganic filler is 0.5-5.0 mu m;
the toughening agent is one or more of POE, POP, SEBS, EPDM, SBS, TPU and silicon rubber.
The toughening agent is preferably POE.
The nucleating agent is a polyolefin nucleating agent.
The lubricant is one or more of fatty acid salt, fatty acid amide, silane polymer, solid paraffin, liquid paraffin, calcium stearate, zinc stearate, stearic acid amide, silicone powder, methylene bis-stearic acid amide and N, N' -ethylene bis-stearic acid amide.
The preparation method of the low-density high-rigidity high-impact modified polypropylene material comprises the following steps:
step one, preparing materials according to parts by weight: 19-34.8% of propenyl elastomer, 65-80% of modified inorganic filler, 0.1-0.5% of antioxidant and 0.1-0.5% of lubricant, and carrying out banburying on the materials and then carrying out single-screw extrusion to obtain inorganic filler master batch;
step two, preparing materials according to parts by weight: 54.9 to 83.75 percent of polypropylene composition, 13 to 23 percent of inorganic filler master batch, 3 to 20 percent of toughening agent, 0.05 to 0.6 percent of nucleating agent, 0.1 to 0.5 percent of antioxidant and 0.1 to 1.0 percent of lubricant; the materials are mixed and then extruded by double screws to prepare the low-density high-rigidity high-impact modified polypropylene material.
In the first step, the banburying temperature is 160-180 ℃, the temperature of each section of the single-screw extruder is 170-190 ℃, and the extrusion rotating speed is 300-500rpm
And in the second step, the extrusion temperature of the double-screw extruder is 190-220 ℃, and the extrusion rotating speed is 400-800 rpm.
The antioxidant comprises a main antioxidant and an auxiliary antioxidant; wherein the primary antioxidant is selected from hindered phenol antioxidants; the secondary antioxidant is selected from phosphite antioxidants.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with the traditional formula of modified high-rigidity high-impact polypropylene, the polypropylene composition comprises the high-rigidity polypropylene and the block copolymerization polypropylene, wherein the high-rigidity polypropylene is favorable for keeping the flexural modulus, the preferable block copolymerization polypropylene has the dimer EPR content, the intrinsic viscosity and the dispersed phase particle size, and the notch impact strength of the modified material is improved;
(2) Compared with the traditional formula of modified high-rigidity high-impact polypropylene, the low-density high-rigidity high-impact modified polypropylene material has the advantages that the compatibility between polypropylene and a toughening agent is enhanced due to the fact that the inorganic filler master batch adopts the propenyl elastomer as the carrier, so that the mutual interface effect is enhanced, and the bending modulus of the modified material is improved while the toughness is maintained;
(3) Compared with the traditional formula of modified high-rigidity high-impact polypropylene, the low-density high-rigidity high-impact modified polypropylene material disclosed by the invention has the advantages that the polyethylene nucleating agent is adopted, so that the crystal grain size of a crystalline phase in a dimer EPR phase of block copolymer polypropylene can be refined, and the flexural modulus of the modified material is improved without influencing the notch impact strength.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
Preparation example 1Preparation of inorganic filler masterbatch
The preparation method of the inorganic filler master batch comprises the following steps:
(1) Preparing a modified inorganic filler: diluting a KH-550 silane coupling agent with ethanol and water (KH 550: water: ethanol =15: 75, stirring in a stirrer for 5-10 minutes, after hydrolysis is completed, pouring the inorganic filler into the stirrer, stirring at high speed to uniformly disperse KH550, then performing suction filtration, and drying in a vacuum oven at 110 ℃ to obtain a coupling agent-modified inorganic filler;
(2) Preparing inorganic filler master batch: adding the components into an internal mixer for internal mixing according to the weight percentage of the master batch formula in the table 1, and then pouring the mixture into a single-screw extruder for granulation to obtain inorganic filler master batches; the temperature of the internal mixer is 160-180 ℃, the temperature of each section of the single-screw extruder is 170-190 ℃, and the rotating speed of the single-screw extruder is as follows: 500rpm.
TABLE 1 Master batch formulation (weight percent)
Wherein:
the propylene-based elastomer is: propylene-butene copolymer elastomer TAFMER XM-7070S, MFR3.0g/10min at 190 ℃ under 2.16kg, produced by Mitsui chemical Co., ltd;
the inorganic filler is: jetfine3CA is talcum powder, D50 is about 1.0 mu m, whiteness is more than or equal to 94, and the product is Imerys.
Comparative preparation example 1
Comparative preparation example 1 differs from preparation example 1 in that the propylene-based elastomer (propylene-butene copolymer elastomer TAFMER XM-7070S) is replaced with a toughening agent ENGAGE 8842.
Examples 1 to 6
Examples 1-6 provide a method for preparing a low density, high stiffness, high impact modified polypropylene material, comprising the steps of:
adding the inorganic filler master batch and the rest components prepared in the preparation example into a high-speed mixer according to the weight percentage of the components in the table 2, fully mixing, placing the mixture into a double-screw extruder, controlling the rotating speed to be 600rpm and the temperature to be 190-220 ℃, and performing extrusion granulation to obtain the low-density high-rigidity high-impact modified polypropylene material.
The raw material component contents of the low density high stiffness high impact modified polypropylene materials described in examples 1-6 are shown in Table 2.
TABLE 2 weight percentages of the components
Wherein:
homo-polypropylene: HX3900 high-crystalline homo-polypropylene, MFR65g/10min at 230 ℃ under 2.16KG, flexural modulus 2100MPa, SK chemical production;
the block copolymerization polypropylene has a propylene homopolymer matrix phase and an EPR dispersed phase;
a1 has: MFR20g/10min, weight average molecular weight 22 ten thousand, ethylene content 15%, EPR content 30wt%, intrinsic viscosity [ eta ]4.5dL/g, rubber phase particle size 1.1 μm;
a2 has: MFR25g/10min, weight average molecular weight 23 ten thousand, ethylene content 14%, EPR content 35wt%, intrinsic viscosity [ eta ]4.1dL/g, rubber phase particle size 1.2 μm;
a3 has: MFR30g/10min, weight average molecular weight 24 ten thousand, ethylene content 13%, EPR content 35wt%, intrinsic viscosity [ eta ]3.2dL/g, rubber phase particle size 1.3 μm;
toughening agent: ENGAGE 8842 ethylene-octene elastomer, density 0.857g/cm 3 At 190 ℃ and 2.16kg, MFR0.5g/10min, tg of-58 ℃ and DOW production;
nucleating agent: a Hyperform HPN-20E polyethylene nucleating agent, produced by Milliken;
millad 3988 polypropylene nucleating agent, produced by Milliken;
antioxidant:
168 phosphite ester antioxidant, manufactured by BASF; IRGANOX 1010 hindered phenol antioxidant, manufactured by BASF;
lubricant: EBS ethylene bis stearamide produced by Japan Kao.
Comparative examples 1 to 6
Comparative examples 1-6 were prepared in the same manner as example 1, with the components and amounts shown in Table 3.
Table 3 comparative examples the weight percentages of the components
Wherein:
EP548R block copolypropylene, produced by LyondellBasell;
hifax EP246P block copolypropylene, produced by PolyMirae.
Comparative example 1 differs from example 1 in that the nucleating agent was Millad 3988;
comparative example 2 differs from example 3 in that the propylene-based elastomer in the inorganic filler masterbatch was replaced with toughening agent ENGAGE 8842;
comparative example 3 differs from example 3 in that the block co-polypropylene is EP548R;
comparative example 4 differs from example 6 in that the block co-polypropylene is EP246P;
comparative example 5 differs from example 1 in that the ratio of HX3900 and A2 is 1;
comparative example 6 differs from example 1 in that the ratio of HX3900 and A2 is 4.
Performance test
The test criteria were as follows:
density: testing according to ISO1183 standard;
ash content: testing according to ISO3451 standard;
tensile strength: testing according to ISO527 standard;
flexural modulus: testing according to ISO178 standard;
notched Izod impact strength: testing according to ISO180 standard.
TABLE 4 test results of examples and comparative examples
According to analysis of test results, the larger the intrinsic viscosity number of the rubber phase EPR is, the higher the molecular weight of the rubber phase EPR is, the better the mechanical property of the rubber phase is, the larger the contribution to the rigidity of the system is, the smaller the particle size of the rubber phase is, the better the dispersion is, the generation of silver streaks and shear bands can be effectively initiated, and the toughening and the improvement of the system are facilitated.
The physical properties of the products of examples 1 to 6 all reached a density of 1.0g/cm or less 3 Flexural modulus of 1500-1900 MPa, normal temperature notch impact strength not less than 50KJ/m 2 And the low-temperature (-30 ℃) notch impact strength is more than or equal to 5KJ/m 2 In the case of the comparative example, the effects of low density, high rigidity and high impact strength are not achieved under the condition that the optimized EPR phase block copolymerization polypropylene, the compatibilization-assisting toughening agent propylene-based elastomer and the polyethylene nucleating agent are not used.
Although the notched impact strength of the product of comparative example 1 reached 42.2KJ/m 2 But the flexural modulus is only 1420MPa;
although the notched impact strength of the product of comparative example 2 reached 50.2KJ/m 2 But the flexural modulus is only 1350MPa;
the product of comparative example 3 had a flexural modulus of 1700MPa, but the notched impact strength was only 30.5KJ/m 2 And the low-temperature notch impact only reaches 3.2KJ/m 2 ；
The flexural modulus of the product of comparative example 4 reached 1650MPa, but the notched impact strength was only 44.5KJ/m 2 And the low-temperature notch impact only reaches 4.1KJ/m 2 ；
Although the notched impact strength of the product of comparative example 5 reached 62.3KJ/m 2 But the flexural modulus is only 1230MPa;
the flexural modulus of the product of comparative example 6 reached 1690MPa, but the notched impact strength was only 26.4KJ/m 2 And the low-temperature notch impact only reaches 2.9KJ/m 2 。
In conclusion, the polypropylene material prepared by the invention maintains toughness, improves the flexural modulus of the modified material, improves the impact strength of the modified material, and can still maintain good impact strength in a low-temperature environment.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. A low-density high-rigidity high-impact modified polypropylene material is characterized by comprising the following components in percentage by weight:
the polypropylene is a mixture of homo-polypropylene and block co-polypropylene with a mass ratio of 1.
2. The low-density high-rigidity high-impact modified polypropylene material as claimed in claim 1, wherein the melt flow rate of the homo-polypropylene is 20-100 g/10min, and the flexural modulus is 1500 MPa-2200 MPa; the melt flow rate of the block copolymerization polypropylene is 10-40 g/10min, and the weight average molecular weight is 200000-300000.
3. The low-density high-rigidity high-impact modified polypropylene material as claimed in claim 1, wherein the ethylene content in the block copolymer polypropylene is 5-30%; the EPR content in the block copolymerization polypropylene is 20-40%, the block copolymerization polypropylene is soluble in dimethylbenzene at 20-35 ℃, the intrinsic viscosity eta of the block copolymerization polypropylene in decalin is 3-5.5 dL/g, and the particle size of the block copolymerization polypropylene is 0.5-3 mu m.
4. The low-density high-rigidity high-impact modified polypropylene material according to claim 1, wherein the inorganic filler masterbatch is prepared from the following raw materials in percentage by weight:
19 to 34.8 percent of propenyl elastomer;
65 to 80 percent of modified inorganic filler;
0.1 to 0.5 percent of antioxidant;
0.1 to 0.5 percent of lubricant.
5. The low-density high-rigidity high-impact modified polypropylene material according to claim 4, wherein the modified inorganic filler is obtained by treating an inorganic filler with a silane coupling agent.
6. The low-density high-rigidity high-impact modified polypropylene material as claimed in claim 5, wherein the inorganic filler is one or more of wollastonite, mica, talcum powder, whisker and montmorillonite, and the particle size of the inorganic filler is 0.5-5.0 μm.
7. The low-density high-rigidity high-impact modified polypropylene material as claimed in claim 1, wherein the toughening agent is one or more of POE, POP, SEBS, EPDM, SBS, TPU and silicone rubber.
8. The low density high stiffness high impact modified polypropylene material according to claim 1, wherein the nucleating agent is a polyolefin nucleating agent.
9. The low density high stiffness high impact modified polypropylene material according to claim 1, wherein the lubricant is one or more of fatty acid salts, fatty acid amides, silane polymers, paraffin wax, liquid paraffin, calcium stearate, zinc stearate, stearic acid amides, silicone powder, methylene bis stearic acid amides, N' -ethylene bis stearic acid amides.
10. A method for preparing a low density high rigidity high impact modified polypropylene material according to any one of claims 4 to 9, comprising the steps of:
step one, preparing materials according to parts by weight: 19-34.8% of propenyl elastomer, 65-80% of modified inorganic filler, 0.1-0.5% of antioxidant and 0.1-0.5% of lubricant, and the materials are banburied and then extruded to obtain inorganic filler master batch; the banburying temperature is 160-180 ℃, the temperature of each section of the single-screw extruder is 170-190 ℃, and the extrusion rotating speed is 300-500rpm;
step two, preparing materials according to parts by weight: 54.9 to 83.75 percent of polypropylene composition, 13 to 23 percent of inorganic filler master batch, 3 to 20 percent of toughening agent, 0.05 to 0.6 percent of nucleating agent, 0.1 to 0.5 percent of antioxidant and 0.1 to 1.0 percent of lubricant; mixing the materials and extruding the mixture by a screw to prepare the low-density high-rigidity high-impact modified polypropylene material; the temperature of each section of the double-screw extruder is 190-220 ℃, and the extrusion rotating speed is 400-800 rpm.
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