CN116478479A - Micro-foaming polypropylene material and preparation method and application thereof - Google Patents
Micro-foaming polypropylene material and preparation method and application thereof Download PDFInfo
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- CN116478479A CN116478479A CN202310616685.1A CN202310616685A CN116478479A CN 116478479 A CN116478479 A CN 116478479A CN 202310616685 A CN202310616685 A CN 202310616685A CN 116478479 A CN116478479 A CN 116478479A
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- -1 polypropylene Polymers 0.000 title claims abstract description 117
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 114
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 114
- 238000005187 foaming Methods 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000012745 toughening agent Substances 0.000 claims abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 3
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 claims description 35
- 229920002943 EPDM rubber Polymers 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000155 melt Substances 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229920005604 random copolymer Polymers 0.000 claims description 8
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 7
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 7
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims description 7
- 229920000428 triblock copolymer Polymers 0.000 claims description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 6
- 229920001897 terpolymer Polymers 0.000 claims description 6
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000872 buffer Substances 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 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 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 239000013585 weight reducing agent Substances 0.000 abstract description 23
- 230000000052 comparative effect Effects 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 12
- 239000011148 porous material Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- IQOICMOMHUBJCM-UHFFFAOYSA-N oct-1-ene Chemical compound CCCCCCC=C.CCCCCCC=C IQOICMOMHUBJCM-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 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 group 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- BXKCRNHYYRAVPD-UHFFFAOYSA-N oct-1-ene;styrene Chemical compound CCCCCCC=C.C=CC1=CC=CC=C1 BXKCRNHYYRAVPD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/02—CO2-releasing, e.g. NaHCO3 and citric acid
-
- 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
- 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
- C08J2323/14—Copolymers of propene
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a micro-foaming polypropylene material, a preparation method and application thereof. The grouping of the micro-foaming polypropylene material comprises: polypropylene resin, compatilizer, filler, toughening agent and auxiliary agent. The micro-foaming polypropylene material has high closed porosity and weight reduction ratio after foaming, and can maintain good notch impact strength.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a micro-foaming polypropylene material and a preparation method and application thereof.
Background
The light weight of the automobile industry is a development trend, and foaming is one of the important ways of light weight, wherein polypropylene micro-foaming is favored by automobile manufacturers, and deep research and exploration are conducted on interior trim and exterior trim parts, such as an instrument desk, a door plate, an inner door handle, a seat guide rail guard plate and the like, so that important breakthrough can be brought by applying foaming materials to parts such as the instrument desk, the door plate, the inner door handle, the seat guide rail guard plate and the like.
EPP is totally called as foaming polypropylene, is produced by foaming and modifying polypropylene, has the characteristics of high hardness, light weight and energy absorption, and is widely applied to the automobile industry. EPP is a high-crystallization type composite material with excellent performance, and becomes the compression-resistant buffering heat-insulating material which is the fastest growing and most environment-friendly at present by the unique and excellent performance. For EPP, the weight reduction ratio and the closed pore rate after foaming are mainly concerned, and the higher the weight reduction ratio and the higher the closed pore rate are, the better the foaming performance is, wherein the weight reduction ratio is high, and the material cost of enterprise production can be effectively reduced. Furthermore, since EPP is often used for producing compression-buffered parts, it is also required to have good impact strength.
The Chinese patent No. CN110791015A adds melt strength regulator (ethylene-octene copolymer of 0.1-5 g/10 min) and solvent-resistance improver (ethylene-octene copolymer of 2-50 g/10 min) into injection molding grade polypropylene material, but only shows closed porosity, and does not pay attention to weight reduction effect and impact strength.
In order to solve the above problems, there has been a need for developing a foamed polypropylene having a high closed cell ratio, a high weight reduction ratio and a good impact strength.
Disclosure of Invention
The primary purpose of the invention is to overcome the problems of poor closed cell rate and weight reduction ratio of the foaming polypropylene and insufficient attention to the impact strength of the foaming polypropylene in the prior art, and provide a micro-foaming polypropylene material. The micro-foaming polypropylene material has high closed porosity and weight reduction ratio after foaming, and can maintain good notch impact strength.
The invention further aims to provide a preparation method of the micro-foaming polypropylene material.
The invention further aims to provide an application of the micro-foaming polypropylene material in preparing an automobile compression-resistant buffer part.
The above object of the present invention is achieved by the following technical solutions:
the micro-foaming polypropylene material comprises the following components in parts by weight:
the melt index of the polypropylene resin is 0.5-3 g/10min;
the compatilizer is ethylene-propylene-butyl terpolymer polypropylene grafted sodium maleate, and the grafting rate is 1.5-3%.
In the invention, the grafting rate of the ethylene-propylene-diene monomer polypropylene grafted sodium maleate refers to the mass fraction of sodium maleate in the ethylene-propylene-diene monomer polypropylene grafted sodium maleate, and the grafting rate is measured by an acid-base titration method.
In the present invention, the melt index of the polypropylene resin can be measured according to test standard ISO 1133-1/2:2012 at 230℃under 2.16kg test conditions.
The inventor of the invention discovers through researches that the micro-foaming polypropylene material obtained by matching polypropylene resin with specific melt index with specific compatilizer (ethylene propylene diene monomer (ETPP) grafted sodium maleate with specific grafting ratio) has high closed porosity and weight reduction ratio after foaming. The reason for this is: the ethylene-propylene-diene copolymer polypropylene grafted sodium maleate with specific grafting rate can endow the interface of polypropylene resin with specific melt index with firm binding force with filler, obviously improve the melt strength of the material, and is beneficial to the foaming molding of the material, thereby obviously improving the closed porosity and weight reduction ratio of the micro-foaming polypropylene material. In addition, by adding the specific compatilizer, the notch impact strength of the micro-foaming polypropylene material after foaming can be obviously improved, so that the micro-foaming polypropylene material after foaming can maintain good notch impact strength. Specifically, the weight reduction ratio of the foamed micro-foaming polypropylene material can reach more than 29.7 percent and reaches 38.1 percent at most; the closed pore rate can reach more than 94.7 percent, and the highest closed pore rate reaches 98.8 percent; the notch impact strength of the cantilever beam can be kept at 28.9KJ/m 2 The use requirement of the application scene is met, and the highest use requirement can reach 49.7KJ/m 2 。
Namely, the micro-foaming polypropylene material has high closed porosity and weight reduction ratio after foaming, and can keep good notch impact strength.
Preferably, the micro-foaming polypropylene material comprises the following components in parts by weight:
preferably, the grafting rate of the ethylene-propylene-diene monomer polypropylene grafted sodium maleate is 1.6-2.8%.
Preferably, the ethylene-propylene-diene monomer polypropylene grafted sodium maleate is prepared by the following method: mixing ethylene-propylene-diene copolymer polypropylene, sodium maleate and an antioxidant to obtain a mixture for later use; dissolving an initiator, alpha-methylstyrene and 1-octene in a solvent to obtain a mixed solution for later use; adding the mixed solution into the mixture, and carrying out melt extrusion to obtain the ethylene-propylene-diene monomer copolymer polypropylene grafted sodium maleate.
Optionally, the melt index of the ethylene-propylene-diene monomer polypropylene in the ethylene-propylene-diene monomer polypropylene grafted sodium maleate is 5-9 g/10min.
Preferably, the melt index of the ethylene-propylene-diene monomer polypropylene in the ethylene-propylene-diene monomer polypropylene grafted sodium maleate is 7-9 g/10min.
The melt index of the ethylene-propylene-diene monomer polypropylene in the ethylene-propylene-diene monomer polypropylene grafted sodium maleate is in the range, so that the obtained micro-foaming polypropylene material has higher closed porosity, weight reduction ratio and notch impact strength.
The melt index of the ethylene-propylene-diene copolymer polypropylene can be measured according to the test standard ISO 1133-1/2:2012 at 230℃under 2.16kg test conditions.
More preferably, the antioxidant is antioxidant 1010, antioxidant 168 or antioxidant DSTDP.
More preferably, the initiator is di-t-butyl peroxide.
More preferably, the ethylene-propylene-diene monomer polypropylene grafted sodium maleate comprises the following components in the preparation process: 100 parts by weight of ethylene propylene diene monomer terpolymer, 2-4 parts by weight of sodium maleate, 0.2-0.4 part by weight of antioxidant, 0.2-0.4 part by weight of initiator, 2-3 parts by weight of alpha-methyl styrene and 1-octene 1-1.5 parts by weight.
More preferably, the melt extrusion is followed by a purification step.
Specifically, the ethylene-propylene-diene monomer polypropylene grafted sodium maleate is prepared by the following method (the unit of the dosage of each component is weight part):
a) Uniformly mixing 100 parts of ethylene-propylene-diene monomer terpolymer polypropylene, 2-4 parts of sodium maleate and 0.2-0.4 part of antioxidant by a high-speed mixer, wherein the rotating speed of the high-speed mixer is 650-750 RPM, and obtaining a mixture for later use;
b) Dissolving 0.2-0.4 part of initiator di-tert-butyl peroxide (DTBP), 2-3 parts of alpha-methyl styrene (AMS) and 1-1.5 parts of 1-Octene (1-Octene) in 35-45 parts of acetone at the temperature of 35-45 ℃ to obtain a mixed solution for standby;
c) Adding the mixed solution into the mixture obtained in the step a), uniformly mixing by a high-speed mixer, and adding into a double-screw extruder for melt extrusion grafting reaction after all acetone volatilizes to obtain ethylene-propylene-diene monomer copolymer polypropylene grafted sodium maleate coarsening compound; wherein the temperature of the twin-screw extruder is 135-150 ℃;
d) Adding 1 part of ethylene-propylene-diene terpolymer polypropylene grafted sodium maleate coarser into 35-45 parts of dimethylbenzene, stirring at 70-80 ℃ until the sodium maleate coarser is completely dissolved, pouring the mixture into 60-70 parts of acetone solution while the mixture is hot to generate flocculent precipitate, washing the flocculent precipitate with acetone for 3-5 times to obtain a first purified product, and then drying the flocculent precipitate in a ventilation kitchen to constant weight; repeating the above purification for 2 times, and finally obtaining the purified ethylene-propylene-diene copolymer polypropylene grafted sodium maleate, and placing the sodium maleate in a vacuum drying oven for drying for 24 hours until the weight is constant for standby.
Fillers and toughening agents commonly used in the art can be used in the present invention without any particular limitation.
Optionally, the filler includes, but is not limited to, talc, calcium carbonate, or basic magnesium sulfate whiskers, and the like.
Alternatively, the toughening agent includes, but is not limited to, a random copolymer of styrene-octene, a random copolymer of ethylene-butene, a Metallocene Linear Low Density Polyethylene (MLLDPE), a metallocene ethylene-propylene copolymer, or a hydrogenated styrene-butadiene-styrene linear triblock copolymer (SEBS), etc.
Preferably, the toughening agent is at least one of an ethylene-butene random copolymer or a metallocene linear low density polyethylene.
The toughening agent is selected from ethylene-butene random copolymer or metallocene linear low-density polyethylene, and the obtained micro-foaming polypropylene material has higher closed-cell rate and weight reduction ratio after foaming.
Preferably, the toughening agent is a hydrogenated styrene-butadiene-styrene linear triblock copolymer.
The toughening agent is hydrogenated styrene-butadiene-styrene linear triblock copolymer, so that the obtained micro-foaming polypropylene material has higher notch impact strength besides high closed cell rate and high weight reduction ratio. In addition, the hydrogenated styrene-butadiene-styrene linear triblock copolymer is subjected to hydrogenation treatment, so that the weather resistance is outstanding, the weather resistance of the micro-foaming polypropylene material is better, and the low-temperature toughening effect is also good.
Optionally, the auxiliary agent is at least one of an antioxidant or a lubricant.
Alternatively, the antioxidants include, but are not limited to, hindered phenols or phosphites.
Optionally, the lubricant includes, but is not limited to, a stearate-based lubricant.
The preparation method of the micro-foaming polypropylene material comprises the following steps: and mixing the components, carrying out melt extrusion and granulation to obtain the micro-foaming polypropylene material.
Preferably, the melt extrusion is performed using a twin screw extruder.
More preferably, the temperature of the twin-screw extruder is 170 to 200 ℃.
The application of the micro-foaming polypropylene material in preparing the automobile compression-resistant buffer part is also in the protection scope of the invention.
Preferably, the automobile compression-resistant buffer part is an automobile seat side guard plate.
Compared with the prior art, the invention has the beneficial effects that:
the micro-foaming polypropylene material has high closed porosity and weight reduction ratio after foaming, and can maintain good notch impact strength.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples for the purpose of illustration and not limitation, and various modifications may be made within the scope of the present invention as defined by the appended claims.
The reagents selected for the examples and comparative examples of the present invention are described below:
polypropylene resin No. 1: b8101 (copolymerization, mfr=0.5 g/10 min), petrified;
polypropylene resin # 2: AS164 (copolymerization, mfr=1.2 g/10 min), singapore TPC;
polypropylene resin 3#: k8303 (copolymerization, mfr=3 g/10 min), crape;
polypropylene resin # 4: b1101 (homopolymerization, mfr=0.5 g/10 min), taiwan chemical fiber in taiwan area of our country;
polypropylene resin No. 5: EP548R (copolymerization, mfr=30 g/10 min), mesosea shell;
filler 1#: talcum powder, AH-51210 (3000 mesh Talcum powder), liaoning Ai Hai;
filler 2#: whisker, WS-1S2 (basic magnesium sulfate whisker), yingkoukang as science and technology;
filler 3#: calcium carbonate, 75T, chang omega;
toughening agent 1#: mfr=0.5 g/10min (190 ℃/2.16 kg), ethylene-octene random copolymer, 8150, dow chemical in the united states;
toughening agent # 2: mfr=0.3 g/10min (190 ℃/2.16 kg), ethylene-butene random copolymer, DF605, japan triple well chemistry;
toughening agent 3#: mfr=13G/10 min (190 ℃/2.16 kg), hydrogenated styrene-butadiene-styrene linear triblock copolymer (SEBS), model G1657, usa koteng;
toughening agent 4#: mfr=1.5 g/10min (190 ℃/2.16 kg), metallocene ethylene-propylene copolymer, vistamaxx 6102, exkesen mobil;
toughening agent 5#: mfr=1.0 g/10min (190 ℃/2.16 kg), metallocene Linear Low Density Polyethylene (MLLDPE), exeed 1018MF, exkesen mobil;
the melt index of the above toughening agent can be measured according to test standard ISO 1133-1/2:2012 at 190℃under 2.16kg test conditions.
Ethylene propylene diene monomer (ETC) terpolymer Polypropylene No. 1: f5006, mfr=6.0 g/10min (230 ℃/2.16 kg), zeolitization;
ethylene propylene diene monomer (ETC) terpolymer Polypropylene No. 2: c5608M, MFR =8.0 g/10min (230 ℃/2.16 kg), petaloid;
poly 1-butene: 509, mfr=5.5 g/10min (230 ℃/2.16 kg), liaidebarsel;
compatibilizer 1#: the preparation method comprises the following steps (the unit of the dosage of each component is weight part):
a) Uniformly mixing 100 parts of ethylene-propylene-diene copolymer polypropylene 1#, 2.0 parts of sodium maleate and 0.22 part of antioxidant by a high-speed mixer, and obtaining a mixture for later use at the rotating speed of 670RPM of the high-speed mixer;
b) Dissolving 0.22 part of initiator di-tert-butyl peroxide (DTBP), 2 parts of alpha-methyl styrene (AMS) and 1.1 parts of 1-Octene (1-Octene) in 36 parts of acetone at 36 ℃ to obtain a mixed solution for later use;
c) Adding the mixed solution into the mixture obtained in the step a), uniformly mixing by a high-speed mixer, and adding into a double-screw extruder for melt extrusion grafting reaction after all acetone volatilizes to obtain ethylene-propylene-diene monomer copolymer polypropylene grafted sodium maleate coarsening compound; wherein the temperature of the twin-screw extruder is 136 ℃;
d) Adding 1 part of ethylene-propylene-diene terpolymer polypropylene grafted sodium maleate coarser into 35 parts of dimethylbenzene, stirring at 72 ℃ until the sodium maleate coarser is completely dissolved, pouring the mixture into 62 parts of acetone solution while the mixture is hot to generate flocculent precipitate, washing the flocculent precipitate with acetone for 3 times to obtain a first purified product, and then placing the flocculent precipitate into a ventilation kitchen to be dried to constant weight; repeating the above steps for 2 times, and finally, putting the purified ethylene-propylene-diene copolymer polypropylene grafted sodium maleate into a vacuum drying oven for drying for 24 hours to constant weight, thus obtaining the compatilizer No. 1. The grafting ratio of the compatilizer 1# was 1.6%.
Compatibilizer 2#: the self-made preparation method is basically the same as that of the compatilizer 1# except that: the amount of sodium maleate was 3.0 parts. The grafting ratio of the compatilizer 2# was 2.2%.
Compatibilizer 3#: the self-made preparation method is basically the same as that of the compatilizer 1# except that: and replacing the ethylene-propylene-diene monomer copolymer polypropylene 1# with ethylene-propylene-diene monomer copolymer polypropylene 2#. The grafting ratio of the compatilizer 3# was 2.8%.
Compatibilizer 4#: the self-made preparation method is basically the same as that of the compatilizer 1# except that: the difference is that: the amount of sodium maleate was 1.5 parts. The grafting ratio of the compatilizer 4# was 0.8%.
Compatibilizer 5#: the self-made preparation method is basically the same as that of the compatilizer 1# except that: and replacing the ethylene-propylene-diene terpolymer polypropylene No. 1 with poly-1-butene to obtain the poly-1-butene grafted sodium maleate. The grafting ratio of the compatilizer 5# was 1.1%.
Antioxidant 1#: SONOX 1010, commercially available;
antioxidant 2#: SONOX 168, commercially available;
and (3) a lubricant: zinc stearate, commercially available;
foaming agent: sodium bicarbonate master batch, EE25C, japan.
The components (e.g., antioxidants, lubricants, etc.) selected for each of the parallel examples and comparative examples are the same commercially available products, unless otherwise specified.
The preparation process of the micro-foaming polypropylene material of each embodiment and the comparative example of the invention is as follows: weighing the components according to the proportion, adding the components into a high-speed mixer, stirring and blending for 4 minutes at the rotating speed of 650 revolutions per minute to obtain a premix, adding the mixed particles into a 75D co-rotating double-screw extruder, and carrying out melt extrusion, granulation, drying and cooling to obtain the micro-foaming polypropylene material. The temperature of the twin-screw extruder was 170 ℃, 200 ℃, 210 ℃, 205 ℃, 200 ℃ and 200 ℃ in order from the feeding section to the head.
And (3) uniformly mixing 100 parts by weight of the micro-foaming polypropylene material with 2 parts by weight of foaming agent, adding the mixture into an injection molding machine for foaming, and performing performance test on the mixture to obtain test bars by injection molding.
The micro-foaming polypropylene materials provided by the embodiments and the comparative examples are foamed and injection molded into test bars, and the performance is measured according to the following test method:
density: testing according to ISO 1183-1-2019; units: g/cm 3 ；
Weight reduction ratio: [ (pre-foaming density-post-foaming density)/pre-foaming density ]. Times.100%;
cell closure rate: testing according to GB 10799-2008;
notched Izod impact Strength: testing according to ISO 180-2000; units: KJ/m 2 ；
Examples 1 to 14
Examples 1-14 provide a series of micro-foamed polypropylene materials having the formulations shown in tables 1 and 2.
Table 1 formulations (parts by weight) of examples 1 to 8
Table 2 formulations (parts by weight) of examples 9 to 14
Comparative example 1
This comparative example provides a micro-foaming polypropylene material whose formulation differs from that of example 1 in that polypropylene resin # 1 and polypropylene resin # 2 are not added, but 50 parts of polypropylene resin # 5 are added.
Comparative example 2
This comparative example provides a micro-expanded polypropylene material having a formulation different from that of example 1 in that compatibilizer 1# was replaced with compatibilizer 4#.
Comparative example 3
This comparative example provides a micro-expanded polypropylene material having a formulation different from that of example 1 in that compatibilizer 1# was replaced with compatibilizer 5#.
Comparative example 4
This comparative example provides a micro-expanded polypropylene material having a formulation different from that of example 1 in that no compatibilizer # 1 was added.
The properties of the micro-expanded polypropylene materials of each of the examples and comparative examples were measured according to the above-mentioned test methods, and the test results are shown in Table 3.
TABLE 3 results of Performance test of micro-expanded Polypropylene materials of examples and comparative examples
As can be seen from Table 3, the micro-foaming polypropylene materials of examples 1 to 14 have a high weight reduction ratio and a high closed porosity after foaming, wherein the weight reduction ratio can reach 29.7% or more and reaches 38.1% at most; the closed pore rate can reach more than 94.7 percent, and the highest closed pore rate reaches 98.8 percent; and the notch impact strength of the cantilever beam of the micro-foaming polypropylene material can be kept at 28.9KJ/m 2 The use requirement of the application scene is met, and the maximum use requirement reaches 49.7KJ/m 2 . The above shows that the micro-foaming polypropylene material of the invention has high closed porosity and weight reduction ratio after foamingAnd good notched impact strength can be maintained.
The melt index of the polypropylene resin added in the comparative example 1 is not proper, and the weight reduction ratio and the closed pore rate of the micro-foaming polypropylene material after foaming are obviously lower; the grafting rate of the compatilizer 4# added in the comparative example 2 is too low, the weight reduction ratio and the closed cell rate of the micro-foaming polypropylene material after foaming are also low, and particularly the closed cell rate is low; the compatilizer added in the comparative example 3 is sodium poly-1-butene grafted and grafted maleate, and the weight reduction ratio and the closed pore ratio of the micro-foaming polypropylene material after foaming are low; comparative example 4, in which no specific compatibilizer of the present invention was added, had significantly lower weight loss ratio and lower closed cell ratio after foaming of the micro-foamed polypropylene material.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The micro-foaming polypropylene material is characterized by comprising the following components in parts by weight:
the melt index of the polypropylene resin is 0.5-3 g/10min;
the compatilizer is ethylene-propylene-butyl terpolymer polypropylene grafted sodium maleate, and the grafting rate is 1.5-3%.
2. The micro-foaming polypropylene material according to claim 1, wherein the micro-foaming polypropylene material comprises the following components in parts by weight:
3. the micro-foaming polypropylene material according to claim 1, wherein the ethylene-propylene-diene monomer polypropylene grafted sodium maleate is prepared by the following method: mixing ethylene-propylene-diene copolymer polypropylene, sodium maleate and an antioxidant to obtain a mixture for later use; dissolving an initiator, alpha-methylstyrene and 1-octene in a solvent to obtain a mixed solution for later use; adding the mixed solution into the mixture, and carrying out melt extrusion to obtain the ethylene-propylene-diene monomer copolymer polypropylene grafted sodium maleate.
4. The micro-foaming polypropylene material according to claim 1, wherein the melt index of the ethylene-propylene-diene monomer polypropylene in the ethylene-propylene-diene monomer polypropylene grafted sodium maleate is 5-9 g/10min.
5. The micro-foaming polypropylene material according to claim 1, wherein the filler is at least one of talcum powder, calcium carbonate or basic magnesium sulfate whisker.
6. The micro-expanded polypropylene material according to claim 1, wherein the toughening agent is at least one of an ethylene-octene random copolymer, an ethylene-butene random copolymer, a metallocene linear low density polyethylene, a metallocene ethylene-propylene copolymer or a hydrogenated styrene-butadiene-styrene linear triblock copolymer.
7. The micro-expanded polypropylene material according to claim 6, wherein the toughening agent is a hydrogenated styrene-butadiene-styrene linear triblock copolymer.
8. The micro-foaming polypropylene material according to claim 1, wherein the auxiliary agent is at least one of an antioxidant or a lubricant.
9. The method for preparing the micro-foaming polypropylene material according to any one of claims 1 to 8, which is characterized by comprising the following steps: and mixing the components, carrying out melt extrusion and granulation to obtain the micro-foaming polypropylene material.
10. Use of the micro-foaming polypropylene material according to any one of claims 1 to 8 for preparing an automobile compression-resistant buffer part.
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