CN116041855B - High-melt-strength micro-foaming polypropylene composite material and preparation method thereof - Google Patents
High-melt-strength micro-foaming polypropylene composite material and preparation method thereof Download PDFInfo
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- CN116041855B CN116041855B CN202310002013.1A CN202310002013A CN116041855B CN 116041855 B CN116041855 B CN 116041855B CN 202310002013 A CN202310002013 A CN 202310002013A CN 116041855 B CN116041855 B CN 116041855B
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- -1 polypropylene Polymers 0.000 title claims abstract description 97
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 94
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 94
- 238000005187 foaming Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000004088 foaming agent Substances 0.000 claims abstract description 15
- 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 abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 6
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 6
- 229920000098 polyolefin Polymers 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 12
- 239000000155 melt Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J9/10—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 nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
-
- 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
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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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)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
The invention discloses a high-melt-strength micro-foaming polypropylene composite material, which comprises the following components in parts by weight: 70-90 parts of polypropylene, 10-30 parts of modified polypropylene, 0-30 parts of talcum powder, 0-3 parts of antioxidant, 1-3 parts of chemical foaming agent and 3-5 parts of maleic anhydride grafted modified polypropylene. The invention adopts hydrogenated polybutadiene (not completely hydrogenated) to graft on the polypropylene main chain to prepare polypropylene with long branched chains, so that the polypropylene has higher melt strength and is convenient for foaming control.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a high melt strength micro-foaming polypropylene composite material and a preparation method thereof.
Background
The micro-foaming polypropylene material is widely used in light-weight products of automobiles due to the unique sandwich structure of the foaming surface layer crust of the core layer. The material has good melt strength, good processability and appearance, and is mainly used for automobile door panels, instrument frameworks, center consoles and the like. Two difficulties exist in the foaming process, namely, the foaming is difficult to control, and the foam is easy to merge or break mainly due to low melt strength of polypropylene, so that the foaming process is difficult to control; secondly, the foam uniformity is difficult to control, which is mainly caused by the difficulty in dispersing the foaming agent uniformly and the non-uniform internal structure of polypropylene which is a semi-crystalline polymer.
The invention adopts acrylate grafted polypropylene to form a long-chain branched structure, on one hand, the method introduces ester groups, has low thermal stability, and on the other hand, the branched chain is limited in length and cannot be branched by an ultra-long branched chain. A micro-foaming polypropylene composite material, a preparation method and application thereof are also reported, and the melt strength of polypropylene is improved by using a method of using polyethylene and ethylene octene copolymer, but the addition of the polyethylene and the ethylene octene copolymer can reduce the heat resistance of the polypropylene composite material.
Therefore, the prior art is directed to the problem that the foaming is difficult to control, and the method for improving the melt strength of the polypropylene mainly comprises the following steps: (1) The high melt strength polypropylene is obtained by controlling the structure of the polypropylene from the synthesis end mainly through adjusting the catalyst, and the process cost is high. (2) The melt strength is improved by using other high melt strength polyolefin in combination, such as polyethylene, ethylene-octene copolymer, etc., but the addition of these polyolefin decreases the heat resistance, mechanical properties, etc. of the material. (3) The melt strength is improved through the polypropylene crosslinking reaction, and the crosslinking process has a plurality of side reactions and is difficult to control.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high melt strength micro-foaming polypropylene composite material and a preparation method thereof by grafting a polypropylene with a saturated polyolefin long-chain polymer.
In order to achieve the above purpose, the present invention provides the following technical solutions:
The high-melt-strength micro-foaming polypropylene composite material comprises the following components in parts by weight: 70-90 parts of polypropylene, 10-30 parts of modified polypropylene, 0-30 parts of talcum powder, 0-3 parts of antioxidant, 1-3 parts of chemical foaming agent and 3-5 parts of maleic anhydride grafted modified polypropylene;
The modified polypropylene comprises the following components: 90-100 parts of polypropylene with a melt index of 30-50 parts, 5-10 parts of hydrogenated polyolefin, 0-3 parts of antioxidant and 0-2 parts of initiator.
Preferably, the hydrogenated polyolefin is hydrogenated polybutadiene with a hydrogenation rate of 90% to 95%.
Preferably, the number of talcum powder is 1000-3000 mesh.
Preferably, the foaming agent is azo foaming agent.
Preferably, the grafting rate of the maleic anhydride grafted modified polypropylene is 0.5-1.5%.
Preferably, the initiator comprises at least one of dicumyl peroxide, di-tert-butyl hydroperoxide and bi-di-penta.
In addition, the application also provides a method for preparing the high melt strength micro-foaming polypropylene composite material, which comprises the following steps:
(1) Placing the modified polypropylene in a main bin of an extruder, uniformly mixing talcum powder, an antioxidant and maleic anhydride grafted modified polypropylene in a high-speed mixer, adding the mixture into an auxiliary bin of the extruder, and performing extrusion granulation in a double-screw extruder to obtain a polypropylene composite material with high melt strength;
(2) And (3) uniformly mixing the prepared polypropylene composite material with high melt strength with a foaming agent in a high-speed mixer, adding the mixture into an injection molding machine, and foaming the mixture in the injection molding machine to prepare the high melt strength micro-foaming polypropylene composite material.
Preferably, the modified polypropylene is a grafting modified product prepared by mixing polypropylene with hydrogenated polyolefin, an antioxidant and an initiator and extruding the mixture through a double screw.
The beneficial effects of the invention are as follows:
(1) The invention adopts hydrogenated polybutadiene (not completely hydrogenated) to graft on the polypropylene main chain to prepare polypropylene with long branched chains, so that the polypropylene has higher melt strength and is convenient for foaming control. Compared with the method of regulating the synthesis end of the catalyst, the method for preparing the long-chain branched polypropylene has the advantages of simple operation, low cost and continuous production.
(2) Hydrogenated polybutadiene is selected as a long-chain branch, and has structural properties similar to those of polypropylene and excellent compatibility. The chain structure is also a saturated chain, so that the stability is better in the processing and storage processes, and the defects of excessive crosslinking and instability caused by excessive double bonds are avoided.
(3) The molecular weight of the selected hydrogenated polybutadiene is 500-3000, the length of the branched chain can be selected and freely combined, and the long-chain branched polypropylene with proper chain length can be prepared.
(4) The high melt strength micro-foaming polypropylene composite material prepared by the process can be continuously produced, and has low cost and excellent performance.
Detailed Description
In order to make the technical solution of the present application better understood, the following description of the technical solution of the present application will be made in a clear and complete manner, and other similar embodiments obtained by those skilled in the art without making any inventive effort on the basis of the embodiments of the present application shall fall within the scope of protection of the present application.
Example 1:
the high-melt-strength micro-foaming polypropylene composite material comprises the following components in parts by weight: 70 parts of polypropylene, 10 parts of modified polypropylene, 1 part of talcum powder, 1 part of antioxidant, 1 part of chemical foaming agent and 3 parts of maleic anhydride grafted modified polypropylene (grafting ratio is 0.5 percent);
The modified polypropylene comprises the following components: 90 parts of polypropylene with a melt index of 30-50, 5 parts of hydrogenated polyolefin, 0.5 part of antioxidant and 0.5 part of initiator dicumyl oxide.
In addition, the application also provides a method for preparing the high melt strength micro-foaming polypropylene composite material, which comprises the following steps:
(1) Placing the modified polypropylene in a main bin of an extruder, uniformly mixing talcum powder, an antioxidant and maleic anhydride grafted modified polypropylene in a high-speed mixer, adding the mixture into an auxiliary bin of the extruder, and performing extrusion granulation in a double-screw extruder to obtain a polypropylene composite material with high melt strength;
(2) And (3) uniformly mixing the prepared polypropylene composite material with high melt strength with a foaming agent in a high-speed mixer, adding the mixture into an injection molding machine, and foaming the mixture in the injection molding machine to prepare the high melt strength micro-foaming polypropylene composite material.
The modified polypropylene is a grafting modified product prepared by mixing polypropylene with hydrogenated polyolefin, an antioxidant and an initiator and extruding through double screws.
Example 2:
The high-melt-strength micro-foaming polypropylene composite material comprises the following components in parts by weight: 90 parts of polypropylene, 30 parts of modified polypropylene, 30 parts of talcum powder, 3 parts of antioxidant, 3 parts of chemical foaming agent and 5 parts of maleic anhydride grafted modified polypropylene (the grafting ratio is 1.5 percent);
the modified polypropylene comprises the following components: 100 parts of polypropylene with a melt index of 30-50, 10 parts of hydrogenated polyolefin, 3 parts of antioxidant and 2 parts of initiator di-tert-butyl hydroperoxide.
The preparation method is the same as in example 1.
Example 3:
The high-melt-strength micro-foaming polypropylene composite material comprises the following components in parts by weight: 80 parts of polypropylene, 20 parts of modified polypropylene, 20 parts of talcum powder, 2 parts of antioxidant, 2 parts of chemical foaming agent and 4 parts of maleic anhydride grafted modified polypropylene (grafting ratio is 1 percent);
The modified polypropylene comprises the following components: 95 parts of polypropylene with a melt index of 30-50, 8 parts of hydrogenated polyolefin, 2 parts of antioxidant and 1 part of initiator.
The preparation method is the same as in example 1.
Example 4:
the high-melt-strength micro-foaming polypropylene composite material comprises the following components in parts by weight: 80 parts of polypropylene, 25 parts of modified polypropylene, 10 parts of talcum powder, 2 parts of antioxidant, 2 parts of chemical foaming agent and 4 parts of maleic anhydride grafted modified polypropylene (grafting ratio is 1 percent);
The modified polypropylene comprises the following components: 95 parts of polypropylene with a melt index of 30-50, 7 parts of hydrogenated polyolefin, 2 parts of antioxidant, 1 part of initiator dicumyl oxide and 1 part of initiator biwurtzite.
The preparation method is the same as in example 1.
Comparative example:
The high-melt-strength micro-foaming polypropylene composite material comprises the following components in parts by weight: 80 parts of polypropylene, 25 parts of POE, 10 parts of talcum powder, 2 parts of antioxidant, 2 parts of chemical foaming agent and 4 parts of maleic anhydride grafted modified polypropylene.
The cell densities of examples 1-4 and comparative examples were measured and the results are shown in the following table:
As can be seen from the data in the table, the cell densities of examples 1 to 4 prepared after the addition of the modified polypropylene are significantly increased and the foaming effect is better than that of the comparative example.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (5)
1. The high-melt-strength micro-foaming polypropylene composite material is characterized by comprising the following components in parts by weight: 70-90 parts of polypropylene, 10-30 parts of modified polypropylene, 0-30 parts of talcum powder, 0-3 parts of antioxidant, 1-3 parts of chemical foaming agent and 3-5 parts of maleic anhydride grafted modified polypropylene;
the modified polypropylene comprises the following components: 90-100 parts of polypropylene with a melt index of 30-50 parts, 5-10 parts of hydrogenated polyolefin, 0-3 parts of antioxidant and 0.5-2 parts of initiator;
the modified polypropylene is a grafting modified substance prepared by mixing polypropylene with hydrogenated polyolefin, an antioxidant and an initiator and extruding through double screws;
The hydrogenated polyolefin is hydrogenated polybutadiene, and the hydrogenation rate is 90-95%.
2. The high melt strength micro-expanded polypropylene composite according to claim 1, wherein the talc powder has a mesh size of 1000 to 3000 mesh.
3. The high melt strength micro-expanded polypropylene composite according to claim 1, wherein the foaming agent is an azo-type foaming agent.
4. The high melt strength micro-expanded polypropylene composite according to claim 1, wherein the grafting ratio of the maleic anhydride grafted modified polypropylene is 0.5% to 1.5%.
5. The high melt strength micro-blown polypropylene composite of claim 1 wherein the initiator comprises at least one of dicumyl peroxide, di-t-butyl hydroperoxide, bi-di-penta.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310002013.1A CN116041855B (en) | 2023-01-03 | 2023-01-03 | High-melt-strength micro-foaming polypropylene composite material and preparation method thereof |
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| CN202310002013.1A CN116041855B (en) | 2023-01-03 | 2023-01-03 | High-melt-strength micro-foaming polypropylene composite material and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1340066C (en) * | 1988-03-29 | 1998-09-29 | William James Work | Graft copolymers and blends thereof with polyolefins |
| CN101724161A (en) * | 2008-10-24 | 2010-06-09 | 中国石油化工股份有限公司 | Method for improving melt strength of polypropylene |
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| JP2013539812A (en) * | 2010-10-14 | 2013-10-28 | リライアンス、インダストリーズ、リミテッド | Preparation process of high melt strength propylene polymer |
| CN103665534B (en) * | 2012-09-18 | 2016-01-20 | 中国石油化工股份有限公司 | High melt strength, propylene prepared by a kind of pre-irradiation technology and preparation method thereof |
| CN103044773B (en) * | 2012-12-24 | 2015-08-12 | 上海普利特复合材料股份有限公司 | A kind of enhancing melt strength polypropylene material and preparation method thereof |
| CN103497423A (en) * | 2013-09-22 | 2014-01-08 | 山东中宏塑业有限公司 | High melt strength polypropylene (PP) composition and preparation method thereof |
| CN108285574B (en) * | 2017-01-10 | 2021-02-02 | 神华集团有限责任公司 | Foamable polypropylene composition, foamed polypropylene and preparation method thereof |
| CN112759826B (en) * | 2019-10-21 | 2021-10-22 | 国家能源投资集团有限责任公司 | Expandable polypropylene composition, expanded polypropylene and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1340066C (en) * | 1988-03-29 | 1998-09-29 | William James Work | Graft copolymers and blends thereof with polyolefins |
| CN101724161A (en) * | 2008-10-24 | 2010-06-09 | 中国石油化工股份有限公司 | Method for improving melt strength of polypropylene |
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