CN108059770B - Inorganic filler modifier, modified inorganic filler, preparation method and application of inorganic filler modifier and modified inorganic filler, polypropylene composite material and preparation method of polypropylene composite material - Google Patents
Inorganic filler modifier, modified inorganic filler, preparation method and application of inorganic filler modifier and modified inorganic filler, polypropylene composite material and preparation method of polypropylene composite material Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 85
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 79
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 78
- 239000011256 inorganic filler Substances 0.000 title claims abstract description 65
- 229910003475 inorganic filler Inorganic materials 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003607 modifier Substances 0.000 title abstract description 8
- 239000002667 nucleating agent Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 20
- 229920001971 elastomer Polymers 0.000 claims abstract description 11
- 239000000806 elastomer Substances 0.000 claims abstract description 10
- 239000000454 talc Substances 0.000 claims abstract description 7
- 229910052623 talc Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 25
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical group 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 21
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 19
- 239000007822 coupling agent Substances 0.000 claims description 18
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 18
- 239000012752 auxiliary agent Substances 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 12
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical group [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 11
- 239000008116 calcium stearate Substances 0.000 claims description 11
- 235000013539 calcium stearate Nutrition 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 229920000578 graft copolymer Polymers 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 235000012222 talc Nutrition 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000008040 ionic compounds Chemical class 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 238000007580 dry-mixing Methods 0.000 claims description 2
- 239000004611 light stabiliser Substances 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- 238000004381 surface treatment Methods 0.000 abstract description 4
- 239000003365 glass fiber Substances 0.000 abstract description 3
- 230000006911 nucleation Effects 0.000 abstract description 3
- 238000010899 nucleation Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 description 13
- 238000011056 performance test Methods 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 229920005604 random copolymer Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 6
- 238000003889 chemical engineering Methods 0.000 description 6
- 229920006351 engineering plastic Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000012745 toughening agent Substances 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 102220040412 rs587778307 Human genes 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 240000003421 Dianthus chinensis Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand 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
- 239000011976 maleic acid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the field of polymeric materials, and particularly provides an inorganic filler modifier, which comprises the following components in part by weight: the composite material comprises an interfacial compatibilizer and a beta nucleating agent, wherein the weight ratio of the beta nucleating agent to the interfacial compatibilizer is 0.04-2: 1. The invention provides a modified inorganic filler and a preparation method and application thereof, wherein the method comprises the following steps: the inorganic filler, the interfacial compatibilizer and the beta nucleating agent are uniformly mixed, wherein the inorganic filler is glass fiber and/or talc. The invention provides a polypropylene composite material and a preparation method thereof. In the invention, on the basis of the traditional rigidity-toughness balanced polypropylene technology, the toughness of a formula system, a rigid particle surface treatment technology and an interface compatibilization technology are improved by a surface nucleation technology and an optimized elastomer combination technology, and the compatibility and the bonding force of inorganic rigid particles and resin are improved, so that the rigidity of the formula system is improved.
Description
Technical Field
The invention relates to an inorganic filler modifier, a modified inorganic filler, a preparation method and application thereof, a polypropylene composite material and a preparation method thereof.
Background
As one of the traditional 5-inch general-purpose plastics, polypropylene has the advantages of low price, low density, high temperature resistance, chemical corrosion resistance, easiness in processing and the like, is widely applied, but has the obvious defects of high brittleness and low notch impact strength, and limits the further expansion of the application field.
In order to improve the toughness of polypropylene, a large amount of plasticizer or elastomer is usually added into a formula system for modification, but the addition of either plasticizer or elastomer tends to reduce the rigidity and heat resistance, while the improvement of the rigidity of polypropylene mainly comprises the addition of high-rigidity inorganic filler into the formula system, but the addition of a large amount of inorganic filler tends to reduce the elongation at break and the notch impact strength due to the low interfacial bonding force between the inorganic filler and the polypropylene.
CN104592630A discloses a polypropylene compound with low-temperature toughness and rigidity-toughness balance and a preparation method thereof, which improves the notch impact strength of a sample to 66.0KJ/m by adding normal-temperature and low-temperature impact modifiers2However, the Young's modulus in bending is 100MPa or less.
CN102311583A discloses a method for preparing rigidity-toughness balanced polypropylene, which comprises combining a plurality of polypropylene resins, processing talcum powder by a coupling agent, and modifying the impact resistance by a toughening agent, wherein the rigidity of the composition reaches about 2500MPa, but the corresponding impact strength is only 14.1KJ/m2。
CN104592628A improves the rigidity and toughness balance of the system by adding a cross-linking agent and an auxiliary cross-linking agent system, the flexural modulus of the composition is 1510MPa, and the notch impact strength is 43KJ/m2And the introduction of the cross-linking agent system influences the processing, the elongation at break and other properties of the formula system.
In the prior art, a toughening agent is adopted to improve the toughness of a system, and inorganic rigid particles are a common method for preparing a high-rigidity and high-toughness polypropylene composition to improve the rigidity of the system. In the disclosed technology, whether the toughening agent is used for improving toughness or the inorganic rigid particles are added for improving rigidity, the corresponding addition amount is large, and the high rigidity and toughness balance is difficult to realize simply by adjusting the proportion among the polypropylene matrix, the toughening agent and the inorganic rigid particles.
From the prior art, the flexural modulus of the high-rigidity high-toughness polypropylene composition is basically below 2000MPa, most of the high-rigidity high-toughness polypropylene composition is below 1500MPa, and the notch impact strength is 40KJ/m2Most of them are below 30KJ/m2It is difficult to further improve the rigidity/toughness balance of the product.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a modified inorganic filler capable of improving the rigidity and toughness of a polypropylene material.
To achieve the foregoing object, according to a first aspect of the present invention, there is provided an inorganic filler modifier comprising: the composite material comprises an interfacial compatibilizer and a beta nucleating agent, wherein the weight ratio of the beta nucleating agent to the interfacial compatibilizer is 0.04-2: 1.
According to a second aspect of the present invention, there is provided a process for the preparation of a modified inorganic filler, which process comprises: the inorganic filler, the interfacial compatibilizer and the beta nucleating agent are uniformly mixed, wherein the inorganic filler is glass fiber and/or talc.
According to a third aspect of the present invention, there is provided a modified inorganic filler produced by the production method according to the present invention.
According to a fourth aspect of the present invention there is provided the use of a modified inorganic filler according to the present invention as a polymer additive.
According to a fifth aspect of the present invention, there is provided a polypropylene composite comprising: a first component and a second component; wherein the first component comprises: (A) polypropylene, (B) a polyolefin elastomer, (D) optionally a compatibilizer, (E) optionally a coupling agent, (F) optionally an auxiliary agent; wherein the second component comprises: (C) a modified inorganic filler; the modified inorganic filler includes the modified inorganic filler of the present invention.
According to a sixth aspect of the present invention, there is provided a method for preparing the polypropylene composite material of the present invention, wherein the method comprises: carrying out melt extrusion, drying and granulation on a first component and a second component, wherein the first component comprises: (A) polypropylene, (B) a polyolefin elastomer, (D) optionally a compatibilizer, (E) optionally a coupling agent, (F) optionally an auxiliary agent; wherein the second component comprises: (C) a modified inorganic filler; the modified inorganic filler includes the modified inorganic filler of the present invention.
In the invention, based on the inorganic filler, the surface treatment is carried out by adopting the technologies of interface crystallization, interface compatibilization and the like, so that compact interface transverse crystals and beta crystals are formed on the surface of the filler, the bonding strength of the filler and the resin interface is improved, and the mechanical property of the composite material is obviously improved.
In the invention, on the basis of the traditional rigidity-toughness balanced polypropylene technology, the toughness of a formula system, a rigid particle surface treatment technology and an interface compatibilization technology are improved by a surface nucleation technology and an optimized elastomer combination technology, and the compatibility and the bonding force of inorganic rigid particles and resin are improved, so that the rigidity of the formula system is improved.
In the preferred embodiment of the invention, through the pre-mixing treatment process and the melt extrusion process, on the basis of high filler content, the toughness of the polypropylene composite material is improved, the problem that the rigidity and the toughness of the polypropylene composite material are simultaneously improved is successfully solved, the high-rigidity high-toughness polypropylene composite material is prepared, and the application field of the high-rigidity high-toughness polypropylene composition is further widened.
The polypropylene composite material has high rigidity and high toughness, and can simultaneously meet the requirements that the flexural modulus is more than or equal to 2000MPa, and the notch impact strength is more than or equal to 50KJ/m2The elongation at break is more than or equal to 200 percent. However, the prior art does not disclose a method for simultaneously satisfying the conditions that the flexural modulus is more than or equal to 2000MPa, and the notch impact strength is more than or equal to 50KJ/m2The high rigidity and high toughness polypropylene composite material with the breaking elongation rate of more than or equal to 200 percent and the report of the preparation method thereof.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the percentages refer to weight percentages and the parts refer to parts by weight. All operations are carried out at normal temperature and pressure unless otherwise specified.
The invention provides an inorganic filler modifier, which comprises the following components in part by weight: the composite material comprises an interfacial compatibilizer and a beta nucleating agent, wherein the weight ratio of the beta nucleating agent to the interfacial compatibilizer is 0.04-2: 1.
According to the invention, the weight ratio of the beta nucleating agent to the interfacial compatibilizer is preferably 0.2 to 0.5: 1.
According to the present invention, the β nucleating agent refers to a substance that can act as a heterogeneous nucleus during polyolefin crystallization, and aims to change the crystallization behavior of the resin, and has the effects of increasing the crystallization rate, the crystallinity and the β crystal conversion rate, and the selection range of the kind is wide, and commonly used β nucleating agents can be used in the present invention.
In the invention, the types of the rare earth organic complex and the aromatic amide compound are selected from a wide selection range and can be selected conventionally, for example, the rare earth organic complex is one or more of organic fused heterocyclic ring compounds, fused ring compounds, aliphatic carboxylic acids and derivatives thereof, aromatic carboxylic acids and derivatives thereof or other types of ligands and lanthanides of rare earth elements, wherein the complexes are composed of rare earth elements such as lanthanum, cerium, praseodymium, neodymium, yttrium and the like.
In the present invention, it is preferable that the aromatic amide compound is one or more of 2, 6-benzenedicarboxylic acid cyclohexanamide and/or terephthalic acid cyclohexanamide.
In the examples of the present invention, the β nucleating agent is exemplified by rare earth organic complex WBG-II (widely weilinna functional materials ltd).
In the invention, the interfacial compatibilizer refers to a polymer or small molecule system which increases the compatibility between polymer blend components and strengthens the interfacial adhesion between polymers, and aims to improve the dispersity of a filler in a resin system and improve the interfacial compatibility of the filler and a PP resin, and the selectable range is wide, and according to the invention, the interfacial compatibilizer is preferably selected from a polar monomer graft polymer and/or a silane coupling agent, preferably a mixture of the polar monomer graft polymer and the silane coupling agent, more preferably the weight ratio of the silane coupling agent to the polar monomer graft polymer is 0.1-10:1, and more preferably 0.3-4: 1.
In the present invention, the selectable range of the polar monomer is wide, and for the present invention, it is preferable that the polar monomer is one or more selected from the group consisting of acid anhydride, carboxylic acid and its derivative, amine-based compound, hydroxyl compound, epoxy compound, and ionic compound.
According to the invention, the anhydride is, for example, one or more of methacrylic anhydride, maleic anhydride and itaconic anhydride.
According to the invention, the carboxylic acid and its derivatives are, for example, one or more of acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid.
According to the present invention, the amine-based compound is one or more of a primary amine-and secondary amine-containing compound.
According to the present invention, the hydroxyl compound is one or more of hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
According to the present invention, the epoxide is one or more of phenyl glycidyl ether and ethylene oxide.
According to the invention, the ionic compound is one or more of a sulfonate, a carboxylate, a phosphate and a quaternary ammonium salt.
According to the present invention, the silane coupling agent is one or more of an aminosilane coupling agent and an epoxysilane coupling agent.
According to the invention, the polar monomer graft polymer is maleic anhydride grafted polypropylene.
According to a preferred embodiment of the invention, the compatibilizer is a mixture of a silane coupling agent and maleic anhydride grafted polypropylene (MAH-PP).
According to the invention, the grafting ratio of the maleic anhydride grafted polypropylene is 1-5%.
The object of the present invention can be achieved by the use of the aforementioned modifier-modified inorganic filler of the present invention, which provides, according to a preferred embodiment of the present invention, a process for producing a modified inorganic filler, comprising: the inorganic filler, the interfacial compatibilizer and the beta nucleating agent are uniformly mixed, wherein the inorganic filler is glass fiber and/or talc.
According to the process of the present invention, the weight ratio of beta nucleating agent to interfacial compatibilizer is preferably 0.04 to 2:1, preferably 0.2 to 0.5: 1.
The types of the beta nucleating agent and the interfacial compatibilizer according to the method of the present invention have been described in detail above and will not be described herein again.
According to the method of the invention, the inorganic filler is preferably talcum powder, more preferably the talcum powder is talcum powder with high length-diameter ratio, more preferably the talcum powder has the length-diameter ratio of more than or equal to 15, preferably the length-diameter ratio of more than or equal to 30, and the mesh number is 2000-8000 meshes, preferably 3000-5000 meshes.
According to the method of the present invention, preferably the step of mixing comprises: the first mixing and the second mixing are carried out successively, the rotational speed of the second mixing being higher than the rotational speed of the first mixing.
According to a preferred embodiment of the invention, the rotational speed of the first mixing is 10-100rpm and the rotational speed of the second mixing is 100-1000 rpm.
According to a preferred embodiment of the invention, the time of the first mixing and the time of the second mixing are each 3-5 min.
According to a preferred embodiment of the invention, the temperature of the first mixing and the temperature of the second mixing are each 60 to 120 ℃.
According to the method of the present invention, the total amount of the interfacial compatibilizer and the beta nucleating agent is preferably 3 to 15 parts, preferably 6 to 10 parts, relative to 100 parts of the amount of the inorganic filler.
The invention provides a modified inorganic filler prepared by the preparation method.
The invention provides the use of the modified inorganic filler of the invention as a polymer additive.
The invention provides a polypropylene composite material, which comprises the following components: a first component and a second component;
wherein the first component comprises: (A) polypropylene, (B) a polyolefin elastomer, (D) optionally a compatibilizer, (E) optionally a coupling agent, (F) optionally an auxiliary agent;
wherein the second component comprises: (C) a modified inorganic filler; the modified inorganic filler includes the modified inorganic filler of the present invention.
According to the invention, the polypropylene composite material has excellent rigidity, the bending strength is tested according to the standard ISO 178, and the bending modulus is more than or equal to 2000 MPa; has excellent toughness, and the notch impact strength is tested according to the standard ISO 179/1eA and is more than or equal to 50KJ/m2(ii) a Has excellent deformation resistance, and the elongation at break is more than or equal to 200 percent according to the test of standard ISO 527-2.
According to a preferred embodiment of the invention, the material comprises, by weight: 60-80 parts of a first component and 20-60 parts of a second component.
According to a preferred embodiment of the present invention, wherein the first component comprises by weight: (A) 40-70 parts of polypropylene, preferably 45-60 parts; (B) 5-20 parts of polyolefin elastomer, preferably 10-15 parts; (D) 0.5-6 parts of optional compatibilizer, preferably 1-5 parts; (E) 0.3-3 parts of optional coupling agent, preferably 0.5-1.5 parts; (F) optional auxiliaries: 0.2 to 5 parts, preferably 0.3 to 1.5 parts.
According to a more preferred embodiment of the present invention, 2 or less component (A)/component (B) or less 14, more preferably 3 or less component (A)/component (B) or less 6 on a weight basis.
According to the invention, there are no special requirements on the polypropylene of component (A), and for the purposes of the present invention, it is preferred that the polypropylene of component (A) has a melt flow rate of 5g/10min or less, preferably 3g/10min or less.
According to the present invention, it is preferred that the polypropylene of component (A) is selected from one or more of homo polypropylene, block co-polypropylene and random co-polypropylene. Specifically, for example, one or more of homopolypropylene L5E89, random copolymer polypropylene C4220 and block copolymer polypropylene BA 212E.
According to the present invention, the kind of the polyolefin elastomer of the component (B) is not particularly limited, which means that the polyolefin is a high-performance polyolefin product exhibiting rubber elasticity at normal temperature, having characteristics of small density, large bending, high low-temperature impact resistance, easy processing, etc., and in view of the present invention, one or more selected from the group consisting of an ethylene-based elastomer such as an ethylene-octene copolymer and a propylene-based elastomer are preferable. Specifically, for example, one or more of POE, OBC, and PBE.
According to the present invention, the compatibilizer of component (D) is preferably a maleic anhydride grafted polypropylene, and for the purposes of the present invention, the melt flow rate of the maleic anhydride grafted polypropylene is preferably from 10 to 400g/10min, more preferably from 50 to 200g/10min, and the grafting rate of the maleic anhydride is more preferably from 0.8 to 2%, preferably from 1 to 1.5%.
According to the present invention, the maleic anhydride-grafted polypropylene is preferably in the form of powder having a mesh size of 10 to 200 mesh, more preferably 30 to 100 mesh.
According to the present invention, the kind of the coupling agent of component (E) is not particularly limited, and any coupling agent commonly used in the art may be used in the present invention, and for the present invention, one or more selected from titanate coupling agents and silane coupling agents are preferable, and silane coupling agents are more preferable.
According to the present invention, the kind of the auxiliary agent of component (F) is not particularly limited, and any auxiliary agent commonly used in the art may be used in the present invention, and in the present invention, one or more of a lubricant, an antioxidant, a light stabilizer, a nucleating agent and a pigment is preferably included, and the lubricant is preferably calcium stearate.
In the present invention, the antioxidant is, for example, B225 obtained by compounding a primary antioxidant and a secondary antioxidant in a ratio of 1:1, and the amount thereof is, for example, 0.2 to 1.5 parts, preferably 0.3 to 0.5 part.
The invention provides a preparation method of the polypropylene composite material, wherein the method comprises the following steps: carrying out melt extrusion, drying and granulation on a first component and a second component, wherein the first component comprises: (A) polypropylene, (B) a polyolefin elastomer, (D) optionally a compatibilizer, (E) optionally a coupling agent, (F) optionally an auxiliary agent; wherein the second component comprises: (C) a modified inorganic filler; the modified inorganic filler includes the modified inorganic filler of the present invention.
According to a preferred embodiment of the present invention, the melt extrusion conditions include: the temperature is 180 ℃ and 280 ℃, the rotating speed is 50-500rpm, and the material retention time is 1-10 min.
According to a preferred embodiment of the present invention, a method for preparing a polypropylene composite comprises:
(1) putting (A) polypropylene, (B) polyolefin elastomer, (D) optional compatibilizer, (E) optional coupling agent and (F) optional auxiliary agent into a high-speed mixer for dry mixing for 3-5min, and putting the mixture into a main feeding bin of a double-screw extruder for standby after uniform mixing; adding the modified inorganic filler (C) into a side feeding port of a double-screw extruder;
(2) and melting, extruding, air-drying and granulating the main feeding bin material and the side feeding port material through a double-screw extruder to obtain the composite material.
According to a preferred embodiment of the invention, the temperature of the main machine is 150-.
The polypropylene composite material has excellent rigidity and bending strength according to the standard ISO 178 testThe flexural modulus is more than or equal to 2000 MPa; has excellent toughness, and the notch impact strength is tested according to the standard ISO 179/1eA and is more than or equal to 50KJ/m2(ii) a Has excellent deformation resistance, and the elongation at break is more than or equal to 200 percent according to the test of standard ISO 527-2.
The preparation method of the polypropylene composite material provided by the invention improves the toughness of a formula system, the surface treatment technology of rigid particles and the interface compatibilization technology by a surface nucleation technology and an optimized elastomer combination technology on the basis of the traditional rigidity-toughness balanced polypropylene technology, and improves the compatibility and the bonding force of inorganic rigid particles and resin, thereby improving the rigidity of the formula system. According to the invention, through a pre-mixing treatment process and a melt extrusion process, the toughness of the polypropylene composite material is improved on the basis of high filler content, the problem that the rigidity and the toughness of the polypropylene composite material are improved at the same time is successfully solved, the high-rigidity high-toughness polypropylene composite material is prepared, and the application field of the high-rigidity high-toughness polypropylene composite material is further widened.
Example 1
Mixing 100 parts of pulvis Talci (brand)
3CA, France IMERYS company), 1.5 parts of MAH-PP powder (100 meshes, grafting ratio of 1.0%), 1.2 parts of beta nucleating agent (WBG-II, Guangdong Weilinna functional material Co., Ltd.) and 1.5 parts of silane coupling agent (KH-570, Kyoho chemical Co., Ltd.) were placed in a high-speed mixer with heating function (temperature set at 80 ℃) and mixed at medium and low speeds (rotating speed of 50rpm, the other examples and comparative examples are the same) for 3min and at high speeds (rotating speed of 200rpm, the other examples and comparative examples are the same) for 5min, and after uniform mixing, (C) modified talc was obtained and 29 parts of the modified talc were transferred to the side feed port of the twin-screw extruder;
26 parts of homopolypropylene (PPH, L5E89, MI (3.0 g/10min, 2.16kg, 230 ℃), 30 parts of propylene random copolymer (PPR, C4220, MI (0.5 g/10min, 2.16kg, 230 ℃), 14 parts of ethylene-octene copolymer (POE, 8150, MI (0.5 g/10min, 2.16kg, 190 ℃) and 1 part of auxiliary agent (0.5 part of calcium stearate, Shijia Yongfeng chemical engineering plastics auxiliary agent factory, 0.5 part of antioxidant B225, BASF company) are put into a high-speed mixer to be dry-mixed for 3min, and 71 parts of the mixture is transferred to a main feeding port of a double-screw extruder after being uniformly mixed;
and (3) after the materials are metered and added through a main feed and a side feed of a double-screw extruder (the processing temperature is 150-.
The performance test result of the high-rigidity high-toughness polypropylene composite material is as follows: flexural modulus 2025MPa, notched impact strength 69.4KJ/m2The elongation at break was 297%.
Example 2
Mixing 100 parts of pulvis Talci (brand)
3CA, France IMERYS company), 1.8 parts of MAH-PP powder (100 meshes, the grafting ratio is 1.0 percent), 0.6 part of beta nucleating agent (WBG-II, Guangdong Weilinna functional material Co., Ltd.) and 1.8 parts of silane coupling agent (KH-570, Dow Shaoxing chemical Co., Ltd.) are placed in a high-speed mixer with a heating function (the temperature is set at 90 ℃) to be mixed at a low speed for 3min, the mixture is mixed at a high speed for 5min, and after the mixture is uniform, the (C) modified talcum powder is obtained and transferred to a side feeding port of a double-screw extruder by 34 parts;
putting 15 parts of homopolypropylene (PPH, L5E89, MI 3.0g/10min, 2.16kg, 230 ℃), 15 parts of propylene random copolymer (PPR, C4220, MI 0.5g/10min, 2.16kg, 230 ℃), 20 parts of propylene block copolymer (PPB, BA212E, MI 0.3g/10min, 2.16kg, 230 ℃), 15 parts of ethylene-octene copolymer (POE, 8150, 0.5g/10min, 2.16kg, 190 ℃) and 1 part of auxiliary agent (0.7 part of lubricant calcium stearate, Shijiazhu Yongfeng chemical engineering plastics auxiliary agent factory, 0.3 part of antioxidant B225, BASF company) into a high-speed mixer for 3min, and transferring 66 parts to the main feeding port of the twin-screw extruder after mixing uniformly;
and (3) after the materials are metered and added through a main feed and a side feed of a double-screw extruder (the processing temperature is 150-240 ℃, the rotating speed of a main machine is 200rpm), carrying out melt extrusion, air drying and granulation, thus obtaining the polypropylene composite material with high rigidity and toughness balance.
The performance test result of the high-rigidity high-toughness polypropylene composite material is as follows: flexural modulus 2078MPa, notched impact strength 64.9KJ/m2The elongation at break was 274%.
Example 3
Mixing 100 parts of pulvis Talci (brand)
3CA, France IMERYS company), 1.5 parts of MAH-PP powder (100 meshes, the grafting ratio is 1.0 percent), 1.2 parts of beta nucleating agent (WBG-II, Guangdong Weilinna functional material Co., Ltd.) and 1.5 parts of silane coupling agent (KH-570, Dow Shaoxing chemical Co., Ltd.) are placed in a high-speed mixer with a heating function (the temperature is set at 80 ℃) to be mixed at a low speed for 3min, the mixture is mixed at a high speed for 5min, and after the mixture is uniform, modified talcum powder (C) is obtained and 29 parts of the modified talcum powder are transferred to a side feeding port of a double-screw extruder;
24 parts of homopolypropylene (PPH, L5E89, MI 3.0g/10min, 2.16kg, 230 ℃), 36 parts of a propylene block copolymer (PPB, BA212E, MI 0.3g/10min, 2.16kg, 230 ℃), 6 parts of an ethylene-octene copolymer (POE, 8150, MI 0.5g/10min, 2.16kg, 190 ℃) and 4 parts of a propylene-based elastomer (PBE, 6102, MI 3.0g/10min, 2.16kg, 230 ℃), 1 part of an auxiliary (0.5 part of calcium stearate as a lubricant, guchi seifeng chemical auxiliary factory, 0.5 part of an antioxidant B225, BASF) were put into a high-speed mixer to be dry-blended for 3min, and after being uniformly blended, 71 parts were transferred to the main feed port of a twin-screw extruder;
the materials are added in a metered manner through the main feed and the side feed of a double-screw extruder (the processing temperature is 150-.
The performance test result of the high-rigidity high-toughness polypropylene composite material is as follows: flexural modulus 2537MPa, notched impact strength 53.4KJ/m2The elongation at break was 211%.
Example 4
Mixing 100 parts of pulvis Talci (brand)
3CA, France IMERYS company), 1.8 parts of MAH-PP powder (100 meshes, the grafting ratio is 1.0 percent), 0.6 part of beta nucleating agent (WBG-II, Guangdong Weilinna functional material Co., Ltd.) and 1.8 parts of silane coupling agent (KH-570, Dow Shaoxing chemical Co., Ltd.) are placed in a high-speed mixer with a heating function (the temperature is set at 90 ℃) to be mixed at a low speed for 3min, the mixture is mixed at a high speed for 5min, and after the mixture is uniform, the (C) post-treatment talcum powder is obtained and transferred to a side feeding port of a double-screw extruder by 34 parts;
placing 17.5 parts of homopolypropylene (PPH, T30S, MI 3.0g/10min, 2.16kg, 230 ℃), 17.5 parts of propylene random copolymer (PPR, C4220, MI 0.5g/10min, 2.16kg, 230 ℃), 15 parts of propylene block copolymer (PPB, H2483, MI 0.3g/10min, 2.16kg, 230 ℃), 15 parts of ethylene-octene copolymer (POE, 8150, MI 0.5g/10min, 2.16kg, 190 ℃), 1 part of adjuvant (0.7 part of lubricant calcium stearate, shizhu Yongfu chemical plastics adjuvant plant, 0.3 part of antioxidant B225, BASF company) into a high-speed mixer for 3min, and transferring 66 parts to the main feed port of the twin-screw extruder after mixing uniformly;
and (3) after the materials are metered and added through a main feed and a side feed of a double-screw extruder (the processing temperature is 160-.
The performance test result of the high-rigidity high-toughness polypropylene composite material is as follows: the flexural modulus is 2200MPa, and the notched impact strength is 55.9KJ/m2The elongation at break was 233%.
Table 1 raw material formulation and performance test results of each example
Comparative example 1
Mixing 29 parts of talcum powder (brand)
3CA, IMERYS, France) in a twin screw extruderA side feeding port for discharging;
30 parts of homopolypropylene (PPH, T30S, MI is 3.0g/10min, 2.16kg, 230 ℃), 36 parts of propylene block copolymer (PPB, BA212E, MI is 0.3g/10min, 2.16kg, 230 ℃), 4 parts of ethylene-octene copolymer (POE, 8150, MI is 0.5g/10min, 2.16kg, 190 ℃), 1 part of auxiliary agent (0.5 part of lubricant calcium stearate, Shijia Yongfeng chemical engineering plastics auxiliary agent factory, 0.5 part of antioxidant B225, BASF company) are put into a high-speed twin-screw mixer to be dry-mixed for 3min, and 71 parts of the mixture is transferred to a main feeding port after being uniformly mixed;
and (3) after the materials are metered and added through a main feed and a side feed of a double-screw extruder (the processing temperature is 160-220 ℃, the rotating speed of a main machine is 300rpm), carrying out melt extrusion, air drying and granulation, and obtaining the high-rigidity high-toughness polypropylene composite material.
The performance test result of the high-rigidity high-toughness polypropylene composite material is as follows: flexural modulus 2716MPa and notched impact strength 20.6KJ/m2The elongation at break was 116%.
Comparative example 2
Mixing 100 parts of pulvis Talci (brand)
3CA, France IMERYS company) and 1.5 parts of silane coupling agent (KH-570, Kyoho chemical Co., Ltd.) are placed in a high-speed mixer with a heating function (the temperature is set at 80 ℃) to be mixed for 3min at a medium and low speed, mixed for 5min at a high speed, and transferred to 29 parts of a side feeding port of a double-screw extruder after being mixed uniformly;
26 parts of homopolypropylene (PPH, L5E89, MI (3.0 g/10min, 2.16kg, 230 ℃), 30 parts of propylene random copolymer (PPR, C4220, MI (0.5 g/10min, 2.16kg, 230 ℃), 14 parts of ethylene-octene copolymer (POE, 8150, MI (0.5 g/10min, 2.16kg, 190 ℃), 1 part of other additives (0.5 part of lubricant calcium stearate, Shijia Yongfeng chemical engineering plastics additive factory, 0.5 part of antioxidant B225, BASF company) and the like are put into a high-speed mixer to be dry-mixed for 3min, and the mixture is uniformly mixed and then transferred to 71 parts of main feeding port;
and (3) after the materials are metered and added through a main feed and a side feed of a double-screw extruder (the processing temperature is 160-.
The performance test result of the high-rigidity high-toughness polypropylene composite material is as follows: flexural modulus 1990MPa, notched impact strength 48.7KJ/m2Elongation at break was 319%.
Comparative example 3
Mixing 100 parts of pulvis Talci (brand)
3CA, France IMERYS company) and 1.5 parts of MAH-PP powder (100 meshes, the grafting ratio is 1.0 percent) are placed in a high-speed mixer with a heating function (the temperature is set at 80 ℃) to be mixed for 3min at a low speed, the mixture is mixed for 5min at a high speed, and 29 parts of the mixture is transferred to a side feeding port of a double-screw extruder after being mixed uniformly;
26 parts of homopolypropylene (PPH, L5E89, MI (3.0 g/10min, 2.16kg, 230 ℃), 30 parts of propylene random copolymer (PPR, C4220, MI (0.5 g/10min, 2.16kg, 230 ℃), 14 parts of ethylene-octene copolymer (POE, 8150, MI (0.5 g/10min, 2.16kg, 190 ℃), 1 part of other additives (0.5 part of lubricant calcium stearate, Shijia Yongfeng chemical engineering plastics additive factory, 0.5 part of antioxidant B225, BASF company) and the like are put into a high-speed mixer to be dry-mixed for 3min, and the mixture is uniformly mixed and then transferred to 71 parts of main feeding port;
and (3) after the materials are metered and added through a main feed and a side feed of a double-screw extruder (the processing temperature is 160-.
The performance test result of the high-rigidity high-toughness polypropylene composite material is as follows: flexural modulus 2069MPa, notched impact strength 44.1KJ/m2The elongation at break was 208%.
Comparative example 4
Mixing 100 parts of pulvis Talci (brand)
3CA, IMERYS, France) and 1.2 parts of beta nucleating agent (WBG-II, Guangdong bright Linna functional material havingLimit company), placing in a high-speed mixer with heating function (the temperature is set at 80 ℃) to mix for 3min at medium and low speed, mixing for 5min at high speed, transferring 29 parts to a side feeding port of a double-screw extruder after mixing uniformly;
26 parts of homopolypropylene (PPH, L5E89, MI (3.0 g/10min, 2.16kg, 230 ℃), 30 parts of propylene random copolymer (PPR, C4220, MI (0.5 g/10min, 2.16kg, 230 ℃), 14 parts of ethylene-octene copolymer (POE, 8150, MI (0.5 g/10min, 2.16kg, 190 ℃), 1 part of other additives (0.5 part of lubricant calcium stearate, Shijia Yongfeng chemical engineering plastics additive factory, 0.5 part of antioxidant B225, BASF company) and the like are put into a high-speed mixer to be dry-mixed for 3min, and the mixture is uniformly mixed and then transferred to 71 parts of main feeding port;
and (3) after the materials are metered and added through a main feed and a side feed of a double-screw extruder (the processing temperature is 160-.
The performance test result of the high-rigidity high-toughness polypropylene composite material is as follows: 1860MPa flexural modulus, 63.3KJ/m notched impact strength2The elongation at break was 432%.
Comparative example 5
Mixing 29 parts of talcum powder (brand)
3CA, IMERYS, france) was placed at the side feed port of the twin screw extruder;
26 parts of homopolypropylene (PPH, L5E89, MI 3.0g/10min, 2.16kg, 230 ℃), 30 parts of propylene random copolymer (PPR, C4220, MI 0.5g/10min, 2.16kg, 230 ℃), 14 parts of ethylene-octene copolymer (POE, 8150, MI 0.5g/10min, 2.16kg, 190 ℃), 0.5 part of MAH-PP powder (100 mesh, graft ratio 1.0%), 0.4 part of β nucleating agent (WBG-II, guangdong-wulinna functional material limited), 0.5 part of silane coupling agent (KH-570, santong-shaxing chemical limited), 1 part of other additives (0.5 part of lubricant calcium stearate, shijia-yongfeng chemical plastics additive plant, 0.5 part of antioxidant B225, BASF company) and the like are put into a high-speed mixer for 3min, mixed uniformly and transferred to a main feed port 71 min;
and (3) after the materials are metered and added through a main feed and a side feed of a double-screw extruder (the processing temperature is 160-.
The performance test result of the high-rigidity high-toughness polypropylene composite material is as follows: the flexural modulus is 1967MPa, and the notched impact strength is 52.1KJ/m2Elongation at break was 287%.
Table 2 formulation of raw materials in each proportion and results of performance test
As can be seen from the results in tables 1 and 2, the toughness of the polypropylene composite material is improved by the pre-blending treatment process and the melt extrusion process of the talcum powder on the basis of high filler content, the problem that the rigidity and the toughness of the polypropylene composite material are simultaneously improved is successfully solved, the high-rigidity high-toughness polypropylene composite material is prepared, and the requirements of the flexural modulus of more than or equal to 2000MPa and the notch impact strength of more than or equal to 50KJ/m are simultaneously met2The elongation at break is more than or equal to 200 percent. Further broadens the application field of the high-rigidity high-toughness polypropylene composition.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (22)
1. A method for preparing a polypropylene composite, the polypropylene composite comprising, by weight: 60-80 parts of a first component and 20-60 parts of a second component;
the first component comprises: by weight, (A) 40-70 parts of polypropylene, (B) 5-20 parts of polyolefin elastomer, (D) 0.5-6 parts of optional compatibilizer, (E) 0.3-3 parts of optional coupling agent, and (F) 0.2-5 parts of auxiliary agent;
wherein the second component comprises: (C) a modified inorganic filler;
the preparation method of the modified inorganic filler comprises the following steps: uniformly mixing inorganic filler, an interfacial compatibilizer and a beta nucleating agent, wherein the mixing step comprises the following steps: sequentially carrying out first mixing and second mixing, wherein the rotating speed of the second mixing is higher than that of the first mixing, the temperature of the first mixing and the temperature of the second mixing are respectively 60-120 ℃, the inorganic filler is talc, the weight ratio of the beta nucleating agent to the interfacial compatibilizer is 0.04-2:1, the interfacial compatibilizer is a mixture of a polar monomer graft polymer and a silane coupling agent, the weight ratio of the silane coupling agent to the polar monomer graft polymer is 0.1-10:1, and the total amount of the interfacial compatibilizer and the beta nucleating agent is 3-15 parts relative to 100 parts of the amount of the inorganic filler,
the beta nucleating agent is one or more selected from rare earth organic complexes and aromatic amide compounds;
the silane coupling agent is one or more of an aminosilane coupling agent and an epoxy silane coupling agent;
the preparation method of the polypropylene composite material comprises the following steps: (1) putting (A) polypropylene, (B) polyolefin elastomer, (D) optional compatibilizer, (E) optional coupling agent and (F) auxiliary agent into a high-speed mixer for dry mixing for 3-5min, and putting the mixture into a main feeding bin of a double-screw extruder for standby after uniform mixing; adding the modified inorganic filler (C) into a side feeding port of a double-screw extruder;
(2) and melting, extruding, air-drying and granulating the main feeding bin material and the side feeding port material through a double-screw extruder.
2. The production method according to claim 1, wherein, in the production method of the modified inorganic filler, the weight ratio of the β nucleating agent to the interfacial compatibilizer is 0.2 to 0.5: 1.
3. The production method according to claim 1, wherein, in the production method of the modified inorganic filler, the β nucleating agent is a rare earth organic complex.
4. The production method according to claim 1, wherein, in the production method of the modified inorganic filler, the weight ratio of the silane coupling agent to the polar monomer graft polymer is 0.3 to 4: 1.
5. The production method according to claim 1, wherein, in the production method of the modified inorganic filler, the polar monomer is selected from one or more of carboxylic acid, carboxylic acid derivative, amine-based compound, hydroxyl compound, epoxy compound, and ionic compound.
6. The production method according to claim 1, wherein, in the production method of the modified inorganic filler, the polar monomer is selected from one or more of acid anhydride, carboxylic acid, amine-based compound, hydroxyl compound, epoxy compound, and ionic compound.
7. The preparation method as claimed in claim 1, wherein, in the preparation method of the modified inorganic filler, the inorganic filler is talcum powder, the length-diameter ratio of the talcum powder is not less than 15, and the mesh number is 2000-8000 mesh.
8. The preparation method as claimed in claim 7, wherein, in the preparation method of the modified inorganic filler, the talc has an aspect ratio of not less than 30 and a mesh number of 3000-5000 mesh.
9. The production method as claimed in claim 1, wherein, in the production method of the modified inorganic filler, the rotation speed of the first mixing is 10 to 100rpm, and the rotation speed of the second mixing is 100-1000 rpm.
10. The production method according to claim 1 or 9, wherein, in the production method of the modified inorganic filler, the time of the first mixing and the time of the second mixing are each 3 to 5 min.
11. The production method according to claim 1, wherein in the production method of the modified inorganic filler, the total amount of the interfacial compatibilizer and the β nucleating agent is used in an amount of 6 to 10 parts relative to 100 parts of the amount of the inorganic filler.
12. The preparation method according to claim 1, wherein the first component comprises by weight: (A) 45-60 parts of polypropylene; (B) 10-15 parts of polyolefin elastomer; (D) 1-5 parts of optional compatibilizer; (E) optional coupling agent 0.5-1.5 weight portions; (F) auxiliary agent: 0.3 to 1.5 portions.
13. The process according to claim 1, wherein 3 or more of component (A)/component (B) or less is 6 or less on a weight basis.
14. The production method according to claim 1 or 12, wherein,
the melt flow rate of the polypropylene of the component (A) is less than or equal to 5g/10 min;
the polyolefin elastomer of the component (B) is selected from one or more of ethylene-based elastomer and propylene-based elastomer;
the compatibilizer of the component (D) is maleic anhydride grafted polypropylene, and the grafting rate of the maleic anhydride is 0.8-2%;
the coupling agent of the component (E) is one or more selected from titanate coupling agent and silane coupling agent;
the auxiliary agent of the component (F) comprises one or more of lubricant, antioxidant, light stabilizer, nucleating agent and pigment.
15. The production method according to claim 14, wherein the polypropylene of component (A) has a melt flow rate of 3g/10min or less.
16. The production method according to claim 14, wherein the polypropylene of component (a) is selected from one or more of homo-polypropylene, block co-polypropylene and random co-polypropylene.
17. The production process according to claim 14, wherein the melt flow rate of the maleic anhydride-grafted polypropylene of the component (D) is 10 to 400g/10min, and the grafting ratio of maleic anhydride is 1 to 1.5%.
18. The production method according to claim 17, wherein the melt flow rate of the maleic anhydride-grafted polypropylene of the component (D) is 50 to 200g/10 min.
19. The production method according to claim 14, wherein the maleic anhydride-grafted polypropylene of the component (D) is in the form of powder having a mesh size of 10 to 200 mesh.
20. The production method according to claim 19, wherein the maleic anhydride-grafted polypropylene of the component (D) is in the form of powder having a mesh size of 30 to 100 mesh.
21. The method of claim 14, wherein the lubricant is calcium stearate.
22. The production method according to claim 1, wherein the conditions of the melt extrusion include: the temperature is 180 ℃ and 280 ℃, the rotating speed is 50-500rpm, and the material retention time is 1-10 min.
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| CN110218394A (en) * | 2019-05-24 | 2019-09-10 | 骆驼集团塑胶制品有限公司 | A kind of electrolyte resistance polypropylene modified material of low temperature ultra-toughness and preparation method thereof |
| CN112538215B (en) * | 2019-09-20 | 2023-07-25 | 茂名骐锋新材料有限公司 | Impact-resistant low-temperature-resistant high-transparency polypropylene composition |
| CN112552594B (en) * | 2020-12-09 | 2023-03-14 | 重庆澳彩新材料股份有限公司 | Polypropylene-based composite material, preparation method thereof and high-tensile MPP pipeline |
| CN114410013A (en) * | 2022-01-17 | 2022-04-29 | 上海金发科技发展有限公司 | Talcum powder filled polypropylene composite material and preparation method and application thereof |
| CN114507399B (en) * | 2022-03-24 | 2023-08-08 | 成都金发科技新材料有限公司 | Polypropylene material and preparation method and application thereof |
| CN115612206A (en) * | 2022-10-13 | 2023-01-17 | 常州市升越模塑股份有限公司 | High-melt-strength polypropylene material and preparation process thereof |
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