CN115418049B - 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 68
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 62
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 47
- 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 13
- 239000012745 toughening agent Substances 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims description 18
- 239000000806 elastomer Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 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
- 238000001125 extrusion Methods 0.000 claims description 6
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 6
- 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
- 239000000155 melt Substances 0.000 claims description 4
- 238000000034 method Methods 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
- 238000012661 block copolymerization Methods 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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 compound 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
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 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
- 239000007787 solid Substances 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
- 239000008096 xylene Substances 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
- 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
- 239000005060 rubber Substances 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
- 238000012360 testing method Methods 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
- 239000000539 dimer Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 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
- 239000004035 construction material Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 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
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 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
- 239000000126 substance 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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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% -23% of inorganic filler master batch; 3% -20% 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 with good physical and mechanical properties, chemical properties and processability, and therefore, polypropylene has a wide range of applications in construction materials, electric tools, automobiles, household appliances materials, etc. For wider applications, polypropylene is often modified, such as talc filled, calcium carbonate filled, glass fiber reinforced, and the like.
However, with the development of the automobile industry, the light weight, high performance and low cost of automobile plastic parts are the main trend of current development. Taking talcum powder modified polypropylene composite material as an example, the material is generally applied to parts with complex structures and larger sizes, such as bumpers, door panels, tail door outer panels and the like, and the weight of a single piece is 3-6 kg. In order to achieve the effect of light weight of parts, a method of reducing the wall thickness of a finished product is often adopted, but the reduction of the wall thickness of the finished product can lead to the reduction of mechanical properties, and the combination of the large shrinkage rate of polypropylene and brittleness at low temperature can lead to limited use. Therefore, in order to achieve the purpose of weight reduction, it is necessary to ensure the balance between the rigidity and toughness of the low-density material.
The Chinese patent application number 201310740894.3 discloses a high-modulus ultrahigh impact polypropylene composite material and a preparation method thereof, wherein an ethylene-butene copolymer is used as a toughening agent, and superfine talcum powder is used as a filler to improve the rigidity, so that the effect of rigidity and toughness balance is achieved. However, the embodiments of the patent all adopt higher filler proportion, and the rigidity can be improved, but the density of the material is still high, and the requirement of light weight cannot be met.
The Chinese patent application number 201810989480.7 discloses a low-density high-rigidity polypropylene material and a preparation method thereof, talcum powder which has high sheet integrity and large length-diameter ratio and is modified by silane auxiliary agents is used as filling, and a stiffening nucleating agent is matched to ensure that the material has the characteristics of high rigidity, high toughness and high flow under lower density. But the impact strength of the material can only reach about 35KJ/m 2, and the use of the product under the high impact working condition can not be satisfied.
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 invention aims at realizing the following scheme:
the modified polypropylene material with low density, high rigidity and high impact comprises the following components in percentage by weight:
the polypropylene is a mixture of homo-polypropylene and block-copolymerized polypropylene with the mass ratio of 1:9-6:4.
The melt flow rate of the homo-polypropylene is 20-100 g/10min, and the flexural modulus is 1500-2200 MPa; the melt flow rate of the block copolymerized 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 copolymerized polypropylene is 20-40%, the EPR is soluble in xylene at 20-35 ℃, the intrinsic viscosity eta in decalin is 3-5.5 dL/g, and the particle size 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 inorganic filler with a silane coupling agent.
The silane coupling agent is one or more of an amino silane coupling agent, an epoxy silane coupling agent and an acyloxy silane coupling agent.
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 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 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 bisstearic acid amide and N, N' -ethylene bisstearic 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 material and extruding by a single screw 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; and mixing the materials, extruding by double screws, and preparing 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 auxiliary antioxidant is selected from phosphite antioxidants.
Compared with the prior art, the invention has the following beneficial effects:
(1) Compared with the traditional modified high-rigidity high-impact polypropylene formula, the low-density high-rigidity high-impact modified polypropylene material comprises high-rigidity polypropylene and block-copolymerized polypropylene, wherein the high-rigidity polypropylene is favorable for maintaining the flexural modulus, the dimer EPR content, the intrinsic viscosity and the disperse phase particle size in the preferable block-copolymerized polypropylene are more favorable for improving the notch impact strength of the modified material, and the low-viscosity low-Tg POE can enable the modified material to maintain good notch impact strength at low temperature;
(2) Compared with the traditional modified high-rigidity high-impact polypropylene formula, the low-density high-rigidity high-impact modified polypropylene material of the invention adopts the propenyl elastomer as a carrier in the inorganic filler master batch, thereby enhancing the compatibility between polypropylene and a toughening agent, enhancing the interfacial effect between polypropylene and the toughening agent, and improving the flexural modulus of the modified material while keeping the toughness;
(3) Compared with the traditional modified high-rigidity high-impact polypropylene formula, the low-density high-rigidity high-impact modified polypropylene material provided by the invention adopts the polyethylene nucleating agent to refine the crystal phase grain size in the dimer EPR phase of the block copolymerization polypropylene, so that the flexural modulus of the modified material is improved without affecting 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 present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Preparation example 1 preparation of inorganic filler masterbatch
The preparation of the inorganic filler master batch comprises the following steps:
(1) Preparing modified inorganic filler: diluting KH-550 silane coupling agent with ethanol and water (KH 550: water: ethanol=15:10:75), stirring in a stirrer for 5-10 min, pouring inorganic filler into the stirrer after hydrolysis is completed, stirring at high speed to uniformly disperse KH550, filtering, and drying at 110 ℃ in a vacuum oven to obtain coupling agent modified inorganic filler;
(2) Preparing inorganic filler master batches: adding the components into an internal mixer according to the weight percentage of the masterbatch formula in the table 1 for banburying, and then pouring into a single screw extruder for granulating to obtain inorganic filler masterbatch; 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 masterbatch formulation (weight percent)
Wherein:
The propylene-based elastomer is: propylene-butene copolymer elastomer TAFMER XM-7070S, mfR3.0g/10min at 190℃and 2.16kg, manufactured by Mitsui chemical Co., ltd;
The inorganic filler is as follows: jetfine3CA is talcum powder, D50 is about 1.0 μm, whiteness is more than or equal to 94, and Imerrys is produced.
Comparative preparation example 1
Comparative preparation 1 differs from preparation 1 in that the propylene-based elastomer (propylene-butene copolymer elastomer TAFMER XM-7070S) was replaced with a toughening agent ENGAGE 8842.
Examples 1 to 6
Examples 1-6 provide a method for preparing a modified polypropylene material with low density, high rigidity and high impact, which specifically comprises the following steps:
the inorganic filler master batch and the rest components prepared in the preparation example are added into a high-speed mixer according to the weight percentage of each component in the table 2, and after being fully mixed, the mixture is placed into a double-screw extruder, the rotating speed is controlled at 600rpm, the temperature is controlled at 190-220 ℃, and the low-density high-rigidity modified polypropylene material is prepared by extrusion granulation.
The contents of the respective raw material components of the low-density high-rigidity high-impact modified polypropylene materials described in examples 1 to 6 are shown in Table 2.
Table 2 weight percent of each component
Wherein:
Homo-polypropylene: HX3900 high-crystalline homo-polypropylene, MFR65g/10min at 230 ℃, 2.16KG, flexural modulus 210MPa, SK chemical production;
The block copolymerized polypropylene has a propylene homopolymer matrix phase and an EPR disperse 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, MFR0.5g/10min at 190 ℃, tg of-58 ℃, DOW production;
Nucleating agent: hyperform HPN-20E polyethylene nucleating agent, manufactured by Meldrum;
millad 3988 polypropylene nucleator, produced by Meldrum;
an antioxidant: 168 phosphite antioxidant, BASF; IRGANOX 1010 hindered phenol antioxidant, BASF;
And (3) a lubricant: EBS ethylene bis stearamide Japanese flower king production.
Comparative examples 1 to 6
Comparative examples 1 to 6 were prepared in the same manner as in example 1, and the components and contents are shown in Table 3.
Table 3 comparative examples weight percent of each component
Wherein:
EP548R block-copolymerized polypropylene, lyondellBasell;
Hifax EP246P block copolymer polypropylene, polyMirae.
Comparative example 1 differs from example 1 in that the nucleating agent is Millad 3988;
comparative example 2 differs from example 3 in that the propylene-based elastomer in the inorganic filler masterbatch was replaced with a toughening agent ENGAGE 8842;
comparative example 3 differs from example 3 in that the block copolymerized polypropylene is EP548R;
comparative example 4 differs from example 6 in that the block copolymerized polypropylene is EP246P;
comparative example 5 differs from example 1 in that the ratio of HX3900 to A2 is 1:18;
Comparative example 6 differs from example 1 in that the ratio of HX3900 to A2 is 4:1.
Performance testing
The test criteria are as follows:
density: tested according to the ISO1183 standard;
ash content: tested according to ISO3451 standard;
Tensile strength: according to ISO527 standard;
Flexural modulus: tested according to ISO178 standard;
Notched Izod impact strength: tested according to the ISO180 standard.
Table 4 test results for examples and comparative examples
According to the analysis of test results, the larger the intrinsic viscosity of the rubber phase EPR is, the higher the molecular weight of the EPR is, the better the mechanical property of the rubber phase EPR 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 lines and shear bands can be effectively initiated, and the toughening of the system is improved.
The physical properties of the products of examples 1 to 6 all reach a density of less than or equal to 1.0g/cm 3, a flexural modulus of 1500 to 1900MPa, a normal temperature notched impact strength of more than or equal to 50KJ/m 2, and a low temperature (-30 ℃) notched impact strength of more than or equal to 5KJ/m 2, while the comparative examples do not reach the effects of low density, high rigidity and high impact without using the optimized EPR phase block copolymerized polypropylene, the compatibilized toughening agent propylene-based elastomer and the polyethylene nucleating agent.
The notched impact strength of the product of comparative example 1, although reaching 42.2KJ/m 2, was only 1420MPa;
the product of comparative example 2 has a notched impact strength of 50.2KJ/m 2, but a flexural modulus of 1350MPa only;
the product of comparative example 3 has a flexural modulus of 1700MPa, but the notched impact strength is only 30.5KJ/m 2, and the low-temperature notched impact strength is only 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 notched impact was also only 4.1KJ/m 2;
the product of comparative example 5 has a flexural modulus of only 1230MPa, although the notched impact strength reaches 62.3KJ/m 2;
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 notched impact was also only 2.9KJ/m 2.
In conclusion, the polypropylene material prepared by the method 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 describes specific embodiments of the present application. It is to be understood that the application is not limited to the particular embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the application. The embodiments of the application and the features of the embodiments may be combined with each other arbitrarily without conflict.
Claims (6)
1. The modified polypropylene material with low density, high rigidity and high impact is characterized by comprising the following components in percentage by weight:
The polypropylene is a mixture of homo-polypropylene and block-copolymerized polypropylene with the mass ratio of 1:9-6:4;
the melt flow rate of the homo-polypropylene is 20-100 g/10min, and the flexural modulus is 1500-2200 MPa; the melt flow rate of the block copolymerized 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 copolymerized polypropylene is 20-40%, the EPR is soluble in xylene at 20-35 ℃, the intrinsic viscosity eta in decalin is 3-5.5 dL/g, and the particle size is 0.5-3 mu m;
the inorganic filler master batch is prepared from the following raw materials in percentage by weight:
19-34.8% of propenyl elastomer;
65% -80% of modified inorganic filler;
0.1 to 0.5 percent of antioxidant;
0.1 to 0.5 percent of lubricant;
the modified inorganic filler is obtained by treating inorganic filler with a silane coupling agent.
2. The modified polypropylene material with low density, high rigidity and high impact according to claim 1, 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;
3. The modified polypropylene material with low density, high rigidity and high impact according to claim 1, wherein the toughening agent is one or more of POE, POP, SEBS, EPDM, SBS, TPU and silicone rubber.
4. The low density, high stiffness and high impact modified polypropylene material of claim 1, wherein the nucleating agent is a polyolefin nucleating agent.
5. The modified polypropylene material with low density, high rigidity and high impact according to claim 1, wherein 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.
6. A method for preparing the modified polypropylene material with low density, high rigidity and high impact according to any one of claims 1 to 5, comprising 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 extruding the material after banburying 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; the materials are mixed and then extruded by a screw rod 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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