WO2022127859A1 - Reinforced polypropylene material, and preparation method therefor and application thereof - Google Patents
Reinforced polypropylene material, and preparation method therefor and application thereof Download PDFInfo
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- WO2022127859A1 WO2022127859A1 PCT/CN2021/138776 CN2021138776W WO2022127859A1 WO 2022127859 A1 WO2022127859 A1 WO 2022127859A1 CN 2021138776 W CN2021138776 W CN 2021138776W WO 2022127859 A1 WO2022127859 A1 WO 2022127859A1
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- polypropylene material
- reinforced polypropylene
- reinforcing fibers
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- -1 polypropylene Polymers 0.000 title claims abstract description 65
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 60
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 43
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 15
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 238000000071 blow moulding Methods 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims description 13
- 239000003365 glass fiber Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims description 4
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 229920001774 Perfluoroether Polymers 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 229920001780 ECTFE Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000007667 floating Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 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
- C08L23/12—Polypropene
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
-
- 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
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
Definitions
- the invention relates to the technical field of engineering plastics, in particular to a reinforced polypropylene material and a preparation method and application thereof.
- Polypropylene material is currently the most widely used polymer material. It has the advantages of excellent processing performance and mechanical properties, and is widely used in daily life and industrial production fields, such as: agricultural film, wire and cable, communication, housing construction and aviation manufacturing. Wait.
- the polyolefin materials suitable for blow molding and blister molding are basically HDPE or PP pure resins. These resins can be molded well, but they still need to be improved in terms of heat resistance and strength.
- the industry usually uses the high strength and high rigidity of glass fiber to improve product strength and heat resistance, but conventional glass fiber reinforced polypropylene materials have low melt strength, low melt elongation, and surface floating fibers and poor toughness. And other issues.
- the purpose of the present invention is to provide a reinforced polypropylene material with high surface gloss, good toughness and high melt strength, which is beneficial to blow molding, blister molding and other occasions.
- Another object of the present invention is to provide a method for preparing the above-mentioned reinforced polypropylene material.
- a reinforced polypropylene material, by weight, comprising the following components:
- the reinforcing fiber includes component I, component II and component III, wherein:
- Component I It is composed of reinforcing fibers with a length of less than 0.1 mm, and the percentage of the reinforcing fibers is 10-20%, preferably 14-18%;
- Component II It is composed of reinforcing fibers with a length of 0.1 mm-0.3 mm, and the percentage of the reinforcing fibers is 50-75%, preferably 60-70%;
- Component III It is composed of reinforcing fibers with a length of 0.4mm-0.8mm, and the percentage of the reinforcing fibers is 5-40%, preferably 15-25%.
- the melt index MI of the linear polypropylene is 0.01-10 g/10min, and the test conditions are 230° C., 2.16Kg load; preferably 0.1-3 g/10min.
- the melt index MI of the long-chain branched polypropylene is 0.01-10 g/10min, and the test conditions are 230° C., 2.16Kg load; preferably 0.1-3 g/10min.
- the reinforcing fibers are selected from one or a mixture of glass fibers, quartz fibers and basalt fibers; the average diameter of the reinforcing fibers is 5-20 microns.
- the present invention finds that the length of the reinforcing fiber is controlled to be less than 0.1mm, 0.1mm-0.3mm, 0.4mm-0.8mm, and by adjusting the content of each length distribution, the surface gloss of the reinforced polypropylene material can be improved, and the material can be improved. It has good toughness and can improve the melt strength of the material, which is beneficial to blow molding and blister molding.
- the compatibilizer is a graft polymer of a polar monomer and polypropylene, wherein the polar monomer is selected from one or a mixture of maleic anhydride, acrylic acid, and acrylate derivatives.
- the fluorine compound is ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy resin (PFA), polychlorinated One or more mixtures of trifluoroethylene (PCTFE), ethylene-monochlorotrifluoroethylene copolymer (ECTFE) or polyvinylidene fluoride (PVDF).
- ETFE ethylene-tetrafluoroethylene copolymer
- PTFE polytetrafluoroethylene
- FEP fluorinated ethylene propylene copolymer
- PFA perfluoroalkoxy resin
- PCTFE polychlorinated One or more mixtures of trifluoroethylene
- ECTFE ethylene-monochlorotrifluoroethylene copolymer
- PVDF polyvinylidene fluoride
- high molecular weight fluorine compounds are preferred, which do not melt during the molding process, and will be stretched into fibers under the action of the melt, so that the polypropylene molecular chain and the fluorine compound fibers will form an interpenetrating network, thereby further improving the The melt strength of the entire material. If the molecular weight is too low, the improvement of the melt strength is not obvious, and if the molecular weight is too high, the processing performance is affected. Therefore, preferably, the weight average molecular weight of the fluorine compound is 10-10 million, preferably 5-8 million.
- the present invention also provides a preparation method of the above-mentioned reinforced polypropylene material, comprising the following steps:
- the reinforced polypropylene material is prepared by melt blending and extrusion granulation through a twin-screw extruder.
- the position of the twin-screw extruder side feeding system can be adjusted, and the reinforcing fibers can be fed into the screw in the first to tenth zones, and added after the extruder die, and then directly combined with the polypropylene melt.
- the reinforcing fibers of the present invention enter the screw through different regions, so that the residence time of the reinforcing fibers in the extruder can be adjusted, and the shearing degree of the reinforcing fibers can be controlled, thereby controlling the retention length of the reinforcing fibers.
- the temperature of the first to second zones of the twin-screw extruder is 120°C-160°C
- the temperature of the third to fifth zone is 180°C-300°C
- the temperature of the fifth to tenth zone is 180°C-300°C
- the screw speed is 300rpm-600rpm.
- the present invention also provides the application of the above-mentioned reinforced polypropylene material in blow molding and suction molding occasions.
- the present invention has the following beneficial effects:
- the present invention provides a reinforced polypropylene material, including straight-chain polypropylene, long-chain branched polypropylene, a compatibilizer, reinforcing fibers and fluorine compounds, wherein the long molecular chain of the straight-chain polypropylene is used to increase the distance between the molecular chains.
- the entanglement between them is beneficial to improve the stability of the melt during extrusion and blistering; the addition of long-chain branched polypropylene can greatly improve the melt strength by using its branched structure; high molecular weight fluorine compounds are used in the molding process. It does not melt, and will be stretched into fibers under the action of the melt, so that the polypropylene molecular chain and the fluorine compound fibers will form an interpenetrating network, thereby further improving the melt strength of the entire material.
- the present invention Compared with glass fiber materials with conventional length (0.4-0.6mm), the present invention has high surface gloss, less floating fibers, high elongation at break, toughness, by controlling the length and content distribution of reinforcing fibers in the reinforcing polypropylene material. Good, it is conducive to testing such as falling balls, and has good melt elongation.
- the polypropylene material prepared by the invention has high surface gloss, good toughness and high melt strength, and is mainly suitable for blow molding and suction molding and other occasions.
- the raw materials used in the examples of the present invention and the comparative examples are all from commercially available;
- MI is 1g/10min (230°C, 2.16Kg load);
- Linear polypropylene 2 MI is 10g/10min (230°C, 2.16Kg load);
- Linear polypropylene 3 MI is 22g/10min (230°C, 2.16Kg load);
- MI is 2g/10min (230°C, 2.16Kg load);
- MI 10g/10min (230°C, 2.16Kg load);
- MI is 20g/10min (230°C, 2.16Kg load);
- Fluorine compound 1 weight average molecular weight 40W polytetrafluoroethylene
- Fluorine compound 2 weight average molecular weight 600W polytetrafluoroethylene
- Fluorine compound 3 weight average molecular weight 5W polytetrafluoroethylene.
- Maleic anhydride grafted polypropylene PP-g-MAH manufacturer Polyram; model: 1001CN;
- Glass fiber 1 It is a glass fiber raw material with an average diameter of 8 microns;
- Glass fiber 2 It is the glass fiber in the modified polypropylene material product, with an average diameter of 8 microns and a length of 0.4-0.6 mm.
- the reinforced polypropylene material is prepared by melt blending and extrusion granulation through a twin-screw extruder.
- the position of the extruder side feeding system can be adjusted, and the reinforcing fibers can enter the extruder screw in the first to tenth zones, and be added after the extruder die, and then directly combined with the polypropylene melt. Reinforcing fibers with different lengths and content distributions can be obtained by adjusting the position where the reinforcing fibers enter the extruder screw.
- the temperature of the first to second zone of the extruder is 120°C-160°C
- the temperature of the third to fifth zone is 180°C-300°C
- the temperature of the fifth to tenth zone is 180°C-300°C
- the screw speed is 300rpm-600rpm.
- Test method for the length and distribution of reinforcing fibers After injection molding, the splines are first separated from the matrix by a high-temperature sintering scheme, and then the length of the reinforcing fibers is measured by automatic imaging analysis technology.
- the polypropylene material of the present invention comprising straight-chain polypropylene, long-chain branched polypropylene, fluorine compounds and reinforcing fibers has significantly improved melt strength and melt fracture speed, and is suitable for blow molding and suction. plastic and other occasions.
- Comparative Example 1 without adding long-chain branched polypropylene, its melt strength and melt fracture velocity were poor; in Comparative Example 2, without adding fluorine compounds, its melt strength and melt fracture velocity were also poor.
Abstract
Disclosed in the present invention are a reinforced polypropylene material, and a preparation method therefor and an application thereof. The reinforced polypropylene material comprises: 30-70 parts of straight-chain polypropylene; 2-50 parts of long-chain branched polypropylene; 1-20 parts of a compatibilizer; 5-60 parts of a reinforcing fiber; and 0.1-20 parts of a fluorine compound. The polypropylene material prepared in the present invention has high surface gloss, good toughness, and high melt strength, and is mainly suitable for occasions such as blow molding and vacuum molding.
Description
本发明涉及工程塑料技术领域，特别涉及一种增强聚丙烯材料及其制备方法和应用。The invention relates to the technical field of engineering plastics, in particular to a reinforced polypropylene material and a preparation method and application thereof.
聚丙烯材料是目前用量最大的高分子材料，具有优异的加工性能和力学性能等优点，被广泛应用于日常生活和工业生产领域，如：农用薄膜、电线电缆、通讯、房屋建筑和航空制造业等。Polypropylene material is currently the most widely used polymer material. It has the advantages of excellent processing performance and mechanical properties, and is widely used in daily life and industrial production fields, such as: agricultural film, wire and cable, communication, housing construction and aviation manufacturing. Wait.
目前适用于吹塑和吸塑用的聚烯烃材料，基本都是HDPE或者PP纯树脂，这些树脂能较好地成型，但是在耐热和强度方面还需要改善。行业内通常是利用玻璃纤维的高强度和高刚性来提高产品强度和耐热，但常规的玻璃纤维增强聚丙烯材料具有熔体强度低，熔体延伸率低，还有表面浮纤和韧性差等问题。At present, the polyolefin materials suitable for blow molding and blister molding are basically HDPE or PP pure resins. These resins can be molded well, but they still need to be improved in terms of heat resistance and strength. The industry usually uses the high strength and high rigidity of glass fiber to improve product strength and heat resistance, but conventional glass fiber reinforced polypropylene materials have low melt strength, low melt elongation, and surface floating fibers and poor toughness. And other issues.
因此，有必要研究一种适用于吹塑和吸塑用的增强聚丙烯材料。Therefore, it is necessary to study a reinforced polypropylene material suitable for blow molding and blister molding.
发明内容SUMMARY OF THE INVENTION
为了克服现有技术的缺点与不足，本发明的目的在于提供一种表面光泽度高，韧性好且熔体强度高的利于吹塑和吸塑等场合的增强聚丙烯材料。In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a reinforced polypropylene material with high surface gloss, good toughness and high melt strength, which is beneficial to blow molding, blister molding and other occasions.
本发明的另一目的是提供上述增强聚丙烯材料的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned reinforced polypropylene material.
本发明是通过以下技术方案实现的：The present invention is achieved through the following technical solutions:
一种增强聚丙烯材料，按重量份计，包括以下组分：A reinforced polypropylene material, by weight, comprising the following components:
所述增强纤维包括组分I、组分II和组分Ⅲ，其中：The reinforcing fiber includes component I, component II and component III, wherein:
组分I：由长度为小于0.1mm的增强纤维组成，其占增强纤维的根数百分比为10-20％，优选为14-18％；Component I: It is composed of reinforcing fibers with a length of less than 0.1 mm, and the percentage of the reinforcing fibers is 10-20%, preferably 14-18%;
组分II：由长度为0.1mm-0.3mm的增强纤维组成，其占增强纤维的根数百分比为50-75％，优选为60-70％；Component II: It is composed of reinforcing fibers with a length of 0.1 mm-0.3 mm, and the percentage of the reinforcing fibers is 50-75%, preferably 60-70%;
组分Ⅲ：由长度为0.4mm-0.8mm的增强纤维组成，其占增强纤维的根数百分比为5-40％， 优选为15-25％。Component III: It is composed of reinforcing fibers with a length of 0.4mm-0.8mm, and the percentage of the reinforcing fibers is 5-40%, preferably 15-25%.
优选的，所述直链聚丙烯的熔融指数MI为0.01-10g/10min，测试条件为230℃，2.16Kg负荷；优选为0.1-3g/10min。Preferably, the melt index MI of the linear polypropylene is 0.01-10 g/10min, and the test conditions are 230° C., 2.16Kg load; preferably 0.1-3 g/10min.
优选的，所述长支链聚丙烯的熔融指数MI为0.01-10g/10min，测试条件为230℃，2.16Kg负荷；优选为0.1-3g/10min。Preferably, the melt index MI of the long-chain branched polypropylene is 0.01-10 g/10min, and the test conditions are 230° C., 2.16Kg load; preferably 0.1-3 g/10min.
优选的，所述增强纤维选自玻璃纤维、石英纤维、玄武岩纤维中的一种或几种的混合；所述增强纤维的平均直径为5-20微米。Preferably, the reinforcing fibers are selected from one or a mixture of glass fibers, quartz fibers and basalt fibers; the average diameter of the reinforcing fibers is 5-20 microns.
本发明通过研究发现，将增强纤维的长度控制为小于0.1mm、0.1mm-0.3mm、0.4mm-0.8mm，并通过调节各长度分布含量，能改善增强聚丙烯材料的表面光泽度，提高材料的韧性，且能提高材料的熔体强度，利于吹塑和吸塑等场合。Through research, the present invention finds that the length of the reinforcing fiber is controlled to be less than 0.1mm, 0.1mm-0.3mm, 0.4mm-0.8mm, and by adjusting the content of each length distribution, the surface gloss of the reinforced polypropylene material can be improved, and the material can be improved. It has good toughness and can improve the melt strength of the material, which is beneficial to blow molding and blister molding.
优选的，所述相容剂为极性单体与聚丙烯的接枝聚合物，其中极性单体选自马来酸酐、丙烯酸、丙烯酸酯类衍生物中的一种或几种的混合物。Preferably, the compatibilizer is a graft polymer of a polar monomer and polypropylene, wherein the polar monomer is selected from one or a mixture of maleic anhydride, acrylic acid, and acrylate derivatives.
优选的，所述氟类化合物为乙烯-四氟乙烯共聚物(ETFE)、聚四氟乙烯(PTFE)、氟化乙丙共聚物(FEP)、全氟烷氧基树脂(PFA)、聚氯三氟乙烯(PCTFE)、乙烯-一氯三氟乙烯共聚合物(ECTFE)或聚偏氟乙烯(PVDF)中一种或几种的混合物。Preferably, the fluorine compound is ethylene-tetrafluoroethylene copolymer (ETFE), polytetrafluoroethylene (PTFE), fluorinated ethylene propylene copolymer (FEP), perfluoroalkoxy resin (PFA), polychlorinated One or more mixtures of trifluoroethylene (PCTFE), ethylene-monochlorotrifluoroethylene copolymer (ECTFE) or polyvinylidene fluoride (PVDF).
本发明优选高分子量的氟类化合物，其在成型过程中不熔，在熔体的作用下会给拉伸为纤维，这样聚丙烯分子链和氟类化合物纤维会形成互穿网络，从而进一步提高整个材料的熔体强度。分子量过低，对熔体强度的改善不明显，分子量过高，影响其加工性能，因此，优选的，所述氟类化合物的重均分子量为10-1000万，优选为500-800万。In the present invention, high molecular weight fluorine compounds are preferred, which do not melt during the molding process, and will be stretched into fibers under the action of the melt, so that the polypropylene molecular chain and the fluorine compound fibers will form an interpenetrating network, thereby further improving the The melt strength of the entire material. If the molecular weight is too low, the improvement of the melt strength is not obvious, and if the molecular weight is too high, the processing performance is affected. Therefore, preferably, the weight average molecular weight of the fluorine compound is 10-10 million, preferably 5-8 million.
本发明还提供上述增强聚丙烯材料的制备方法，包括如下步骤：The present invention also provides a preparation method of the above-mentioned reinforced polypropylene material, comprising the following steps:
按照配方含量称量各组分，并将除增强纤维外的各组分混合均匀，随后将混合物加入双螺杆挤出机的主喂料***；同时将增强纤维加入双螺杆挤出机的侧喂料***，然后通过双螺杆挤出机熔融共混、挤出造粒制备得到增强聚丙烯材料。Weigh each component according to the formula content, and mix all components except the reinforcing fiber uniformly, then add the mixture to the main feeding system of the twin-screw extruder; at the same time, add the reinforcing fiber to the side feeding system of the twin-screw extruder The reinforced polypropylene material is prepared by melt blending and extrusion granulation through a twin-screw extruder.
双螺杆挤出机侧喂***可以调节位置，增强纤维可以在第一至第十区进入螺杆，以及在挤出机模头后再加入，然后和聚丙烯熔体直接结合。本发明增强纤维通过不同区域进入螺杆，可以调节增强纤维在挤出机的停留时间，控制增强纤维受剪切的程度，从而控制增强纤维的保留长度。The position of the twin-screw extruder side feeding system can be adjusted, and the reinforcing fibers can be fed into the screw in the first to tenth zones, and added after the extruder die, and then directly combined with the polypropylene melt. The reinforcing fibers of the present invention enter the screw through different regions, so that the residence time of the reinforcing fibers in the extruder can be adjusted, and the shearing degree of the reinforcing fibers can be controlled, thereby controlling the retention length of the reinforcing fibers.
优选的，双螺杆挤出机一至二区温度为120℃-160℃，三至五区温度为180℃-300℃，五至十区温度为180℃-300℃，螺杆转速为300rpm-600rpm。Preferably, the temperature of the first to second zones of the twin-screw extruder is 120°C-160°C, the temperature of the third to fifth zone is 180°C-300°C, the temperature of the fifth to tenth zone is 180°C-300°C, and the screw speed is 300rpm-600rpm.
本发明还提供了上述增强聚丙烯材料在吹塑和吸塑场合中的应用。The present invention also provides the application of the above-mentioned reinforced polypropylene material in blow molding and suction molding occasions.
本发明与现有技术相比，具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供了一种增强聚丙烯材料，包括直链聚丙烯、长支链聚丙烯、相容剂、增强纤维和氟类化合物，其中，利用直链聚丙烯的长分子链，增加分子链之间的缠结，利于提高挤出和吸塑时熔体的稳定；长支链聚丙烯的加入，利用其支链结构，可以极大提高熔体强度；高分子量的氟类化合物在成型过程中不熔，在熔体的作用下会被拉伸为纤维，这样聚丙烯分子链和氟类化合物纤维会形成互穿网络，从而进一步提高整个材料的熔体强度。The present invention provides a reinforced polypropylene material, including straight-chain polypropylene, long-chain branched polypropylene, a compatibilizer, reinforcing fibers and fluorine compounds, wherein the long molecular chain of the straight-chain polypropylene is used to increase the distance between the molecular chains. The entanglement between them is beneficial to improve the stability of the melt during extrusion and blistering; the addition of long-chain branched polypropylene can greatly improve the melt strength by using its branched structure; high molecular weight fluorine compounds are used in the molding process. It does not melt, and will be stretched into fibers under the action of the melt, so that the polypropylene molecular chain and the fluorine compound fibers will form an interpenetrating network, thereby further improving the melt strength of the entire material.
本发明通过控制增强聚丙烯材料中增强纤维的长度及含量分布，与常规长度(0.4-0.6mm)的玻纤材料相比，其表面光泽度高，浮纤少；断裂伸长率大，韧性好，利于落球等测试，且具有较好的熔体延伸性。Compared with glass fiber materials with conventional length (0.4-0.6mm), the present invention has high surface gloss, less floating fibers, high elongation at break, toughness, by controlling the length and content distribution of reinforcing fibers in the reinforcing polypropylene material. Good, it is conducive to testing such as falling balls, and has good melt elongation.
本发明制备得到的聚丙烯材料表面光泽度高，韧性好且熔体强度高，主要适用于吹塑和吸塑等场合。The polypropylene material prepared by the invention has high surface gloss, good toughness and high melt strength, and is mainly suitable for blow molding and suction molding and other occasions.
下面通过具体实施方式来进一步说明本发明，以下实施例为本发明较佳的实施方式，但本发明的实施方式并不受下述实施例的限制。The present invention will be further described below through specific embodiments. The following examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the following examples.
本发明实施例和对比例所采用的原料均来源于市购；The raw materials used in the examples of the present invention and the comparative examples are all from commercially available;
直链聚丙烯1：MI为1g/10min(230℃，2.16Kg负荷)；Linear polypropylene 1: MI is 1g/10min (230℃, 2.16Kg load);
直链聚丙烯2：MI为10g/10min(230℃，2.16Kg负荷)；Linear polypropylene 2: MI is 10g/10min (230℃, 2.16Kg load);
直链聚丙烯3：MI为22g/10min(230℃，2.16Kg负荷)；Linear polypropylene 3: MI is 22g/10min (230℃, 2.16Kg load);
长支链聚丙烯1：MI为2g/10min(230℃，2.16Kg负荷)；Long-chain branched polypropylene 1: MI is 2g/10min (230℃, 2.16Kg load);
长支链聚丙烯2：MI为10g/10min(230℃，2.16Kg负荷)；Long-chain branched polypropylene 2: MI is 10g/10min (230℃, 2.16Kg load);
长支链聚丙烯3：MI为20g/10min(230℃，2.16Kg负荷)；Long-chain branched polypropylene 3: MI is 20g/10min (230℃, 2.16Kg load);
氟类化合物1：重均分子量40W聚四氟乙烯；Fluorine compound 1: weight average molecular weight 40W polytetrafluoroethylene;
氟类化合物2：重均分子量600W聚四氟乙烯；Fluorine compound 2: weight average molecular weight 600W polytetrafluoroethylene;
氟类化合物3：重均分子量5W聚四氟乙烯。Fluorine compound 3: weight average molecular weight 5W polytetrafluoroethylene.
相容剂：Compatibilizer:
马来酸酐接枝聚丙烯PP-g-MAH：厂家Polyram；型号：1001CN；Maleic anhydride grafted polypropylene PP-g-MAH: manufacturer Polyram; model: 1001CN;
增强纤维：Reinforcing fibers:
玻璃纤维1：为玻璃纤维原料，平均直径为8微米；Glass fiber 1: It is a glass fiber raw material with an average diameter of 8 microns;
玻璃纤维2：为改性聚丙烯材料产品中的玻璃纤维，平均直径为8微米，长度为0.4-0.6mm。Glass fiber 2: It is the glass fiber in the modified polypropylene material product, with an average diameter of 8 microns and a length of 0.4-0.6 mm.
实施例1-11及对比例1-6：增强聚丙烯材料的制备Examples 1-11 and Comparative Examples 1-6: Preparation of Reinforced Polypropylene Materials
按照配方含量称量各组分，并将除增强纤维外的各组分混合均匀，随后将混合物加入双螺杆挤出机的主喂料***；同时将增强纤维加入双螺杆挤出机的侧喂料***，然后通过双螺杆挤出机熔融共混、挤出造粒制备得到增强聚丙烯材料。Weigh each component according to the formula content, and mix all components except the reinforcing fiber uniformly, then add the mixture to the main feeding system of the twin-screw extruder; at the same time, add the reinforcing fiber to the side feeding system of the twin-screw extruder The reinforced polypropylene material is prepared by melt blending and extrusion granulation through a twin-screw extruder.
其中挤出机侧喂***可以调节位置，增强纤维可以在第一至第十区进入挤出机螺杆，以及在挤出机模头后再加入，然后和聚丙烯熔体直接结合。通过调节增强纤维进入挤出机螺杆的位置，得到不同长度和含量分布的增强纤维。The position of the extruder side feeding system can be adjusted, and the reinforcing fibers can enter the extruder screw in the first to tenth zones, and be added after the extruder die, and then directly combined with the polypropylene melt. Reinforcing fibers with different lengths and content distributions can be obtained by adjusting the position where the reinforcing fibers enter the extruder screw.
其中挤出机一至二区温度为120℃-160℃，三至五区温度为180℃-300℃，五至十区温度为180℃-300℃，螺杆转速为300rpm-600rpm。The temperature of the first to second zone of the extruder is 120℃-160℃, the temperature of the third to fifth zone is 180℃-300℃, the temperature of the fifth to tenth zone is 180℃-300℃, and the screw speed is 300rpm-600rpm.
各性能的测试标准或方法：Test standards or methods for each performance:
增强纤维的长度以及分布的测试方法：注塑后的样条首先采用高温灼烧的方案将增强纤维在基体中分离出，再使用自动成像分析技术对增强纤维长度进行测量。Test method for the length and distribution of reinforcing fibers: After injection molding, the splines are first separated from the matrix by a high-temperature sintering scheme, and then the length of the reinforcing fibers is measured by automatic imaging analysis technology.
光泽度：ISO 2813-2014；60度角；Gloss: ISO 2813-2014; 60 degree angle;
断裂伸长率：ISO 527-1-2019：测试条件：23℃；Elongation at break: ISO 527-1-2019: Test condition: 23℃;
熔体强度、熔体断裂速度：熔体拉伸流变仪测试，测试条件：180℃；Melt strength, melt fracture speed: melt tensile rheometer test, test condition: 180 ℃;
表1各实施例与对比例中各组分的具体配比(重量份)及各性能测试结果The specific proportions (parts by weight) of each component in each embodiment and comparative example of table 1 and the test results of each performance
续表1Continued from Table 1
由上表可以看出，本发明包含直链聚丙烯、长支链聚丙烯、氟类化合物和增强纤维的聚丙烯材料，其熔体强度和熔体断裂速度明显提高，适用于吹塑和吸塑等场合。对比例1未加入长支链聚丙烯，其熔体强度和熔体断裂速度均较差；对比例2中未加入氟类化合物，其熔体强度和熔体断裂速度也较差。As can be seen from the above table, the polypropylene material of the present invention comprising straight-chain polypropylene, long-chain branched polypropylene, fluorine compounds and reinforcing fibers has significantly improved melt strength and melt fracture speed, and is suitable for blow molding and suction. plastic and other occasions. In Comparative Example 1 without adding long-chain branched polypropylene, its melt strength and melt fracture velocity were poor; in Comparative Example 2, without adding fluorine compounds, its melt strength and melt fracture velocity were also poor.
由上表实施例1-2和对比例3-5可以看出，增强纤维的长度及含量分布影响材料的光泽度和韧性，且对材料熔体延伸性也有影响，本发明通过控制改性聚丙烯中的增强纤维的长度及含量分布，制备得到的改性聚丙烯材料具有较好的光泽度和韧性，且熔体延伸性好，主要适用于吹塑和吸塑等场合。It can be seen from Examples 1-2 and Comparative Examples 3-5 in the above table that the length and content distribution of the reinforcing fibers affect the gloss and toughness of the material, and also have an impact on the melt extensibility of the material. The length and content distribution of reinforcing fibers in propylene, the prepared modified polypropylene material has good gloss and toughness, and good melt extensibility, which is mainly suitable for blow molding and blister molding and other occasions.
由实施例1-2和对比例6对比可以看出，本发明通过控制增强聚丙烯材料中增强纤维的长度及含量分布，与常规长度(0.4-0.6mm)的玻纤材料相比，其表面光泽度高；断裂伸长率大，韧性好，且具有较好的熔体延伸性。From the comparison of Examples 1-2 and Comparative Example 6, it can be seen that the present invention controls the length and content distribution of the reinforcing fibers in the reinforced polypropylene material. Compared with the glass fiber material of conventional length (0.4-0.6 mm), its surface is High gloss; high elongation at break, good toughness, and good melt elongation.
Claims (10)
- 一种增强聚丙烯材料，其特征在于，按重量份计，包括以下组分：A reinforced polypropylene material, characterized in that, in parts by weight, it comprises the following components:
所述增强纤维包括组分I、组分II和组分Ⅲ，其中：The reinforcing fiber includes component I, component II and component III, wherein:组分I：由长度为小于0.1mm的增强纤维组成，其占增强纤维的根数百分比为10-20％，优选为14-18％；Component I: It is composed of reinforcing fibers with a length of less than 0.1 mm, and the percentage of the reinforcing fibers is 10-20%, preferably 14-18%;组分II：由长度为0.1mm-0.3mm的增强纤维组成，其占增强纤维的根数百分比为50-75％，优选为60-70％；Component II: It is composed of reinforcing fibers with a length of 0.1 mm-0.3 mm, and the percentage of the reinforcing fibers is 50-75%, preferably 60-70%;组分Ⅲ：由长度为0.4mm-0.8mm的增强纤维组成，其占增强纤维的根数百分比为5-40％，优选为15-25％。Component III: It is composed of reinforcing fibers with a length of 0.4 mm-0.8 mm, and the percentage of the reinforcing fibers is 5-40%, preferably 15-25%. - 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述直链聚丙烯的熔融指数MI为0.01-10g/10min，测试条件为230℃，2.16Kg负荷；优选为0.1-3g/10min。The reinforced polypropylene material according to claim 1, wherein the melt index MI of the linear polypropylene is 0.01-10g/10min, and the test conditions are 230°C, 2.16Kg load; preferably 0.1-3g/10min .
- 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述长支链聚丙烯的熔融指数MI为0.01-10g/10min，测试条件为230℃，2.16Kg负荷；优选为0.1-3g/10min。The reinforced polypropylene material according to claim 1, wherein the melt index MI of the long-chain branched polypropylene is 0.01-10g/10min, and the test conditions are 230°C, 2.16Kg load; preferably 0.1-3g/ 10min.
- 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述增强纤维选自玻璃纤维、石英纤维、玄武岩纤维中的一种或几种的混合；所述增强纤维的平均直径为5-20微米。The reinforced polypropylene material according to claim 1, wherein the reinforcing fibers are selected from one or a mixture of glass fibers, quartz fibers, and basalt fibers; the average diameter of the reinforcing fibers is 5- 20 microns.
- 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述相容剂为极性单体与聚丙烯的接枝聚合物，其中极性单体选自马来酸酐、丙烯酸、丙烯酸酯类衍生物中的一种或几种的混合物。The reinforced polypropylene material according to claim 1, wherein the compatibilizer is a graft polymer of a polar monomer and polypropylene, wherein the polar monomer is selected from maleic anhydride, acrylic acid, acrylate One or more of the derivatives.
- 根据权利要求1所述的增强聚丙烯材料，其特征在于，所述氟类化合物为乙烯-四氟乙烯共聚物ETFE、聚四氟乙烯PTFE、氟化乙丙共聚物FEP、全氟烷氧基树脂PFA、聚氯三氟乙烯PCTFE、乙烯-一氯三氟乙烯共聚合物ECTFE或聚偏氟乙烯PVDF中的一种或几种的混合物。The reinforced polypropylene material according to claim 1, wherein the fluorine compound is ethylene-tetrafluoroethylene copolymer ETFE, polytetrafluoroethylene PTFE, fluorinated ethylene propylene copolymer FEP, perfluoroalkoxy One or more mixtures of resin PFA, polychlorotrifluoroethylene PCTFE, ethylene-monochlorotrifluoroethylene copolymer ECTFE or polyvinylidene fluoride PVDF.
- 根据权利要求6所述的增强聚丙烯材料，其特征在于，所述氟类化合物的重均分子量为10-1000万，优选为500-800万。The reinforced polypropylene material according to claim 6, wherein the weight average molecular weight of the fluorine compound is 10-10 million, preferably 5-8 million.
- 根据权利要求1-7任一项所述的增强聚丙烯材料的制备方法，其特征在于，包括如下步骤：按照配方含量称量各组分，并将除增强纤维外的各组分混合均匀，随后将混合物加入双螺杆 挤出机的主喂料***；同时将增强纤维加入双螺杆挤出机的侧喂料***，然后通过双螺杆挤出机熔融共混、挤出造粒制备得到增强聚丙烯材料。The preparation method of reinforced polypropylene material according to any one of claims 1-7, characterized in that it comprises the steps of: weighing each component according to the formula content, and mixing each component except the reinforcing fiber uniformly, Then, the mixture was added to the main feeding system of the twin-screw extruder; at the same time, the reinforcing fibers were added to the side-feeding system of the twin-screw extruder, and then the reinforced polymer was prepared by melt-blending and extrusion granulation through the twin-screw extruder. Acrylic material.
- 根据权利要求8所述的增强聚丙烯材料的制备方法，其特征在于，所述双螺杆挤出机一至二区温度为120℃-160℃，三至五区温度为180℃-300℃，五至十区温度为180℃-300℃，螺杆转速为300rpm-600rpm。The preparation method of reinforced polypropylene material according to claim 8, wherein the temperature of the first to second zones of the twin-screw extruder is 120°C-160°C, the temperature of the third to fifth zones is 180°C-300°C, and the temperature of the fifth zone is 180°C-300°C. The temperature of the tenth zone is 180℃-300℃, and the screw speed is 300rpm-600rpm.
- 根据权利要求1-7任一项所述的增强聚丙烯材料在吹塑或吸塑场合中的应用。Application of the reinforced polypropylene material according to any one of claims 1 to 7 in blow molding or blister molding.
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| CN101074276A (en) * | 2006-05-18 | 2007-11-21 | 中国石油天然气股份有限公司 | Long-chain branching polypropylene and its production |
| JP2011057811A (en) * | 2009-09-09 | 2011-03-24 | Daicel Polymer Ltd | Propylene based resin composition |
| CN102558675A (en) * | 2011-12-21 | 2012-07-11 | 上海普利特复合材料股份有限公司 | Polypropylene material with high melt strength and preparation method thereof |
| CN111500009A (en) * | 2020-04-13 | 2020-08-07 | 金发科技股份有限公司 | Reinforced polypropylene material and preparation method thereof |
| CN111534037A (en) * | 2020-04-20 | 2020-08-14 | 金发科技股份有限公司 | Reinforced polypropylene material and preparation method thereof |
| CN112708196A (en) * | 2020-12-18 | 2021-04-27 | 金发科技股份有限公司 | Reinforced polypropylene material and preparation method and application thereof |
| CN112724510A (en) * | 2020-12-18 | 2021-04-30 | 金发科技股份有限公司 | Reinforced polypropylene material and preparation method and application thereof |
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| CN112708196B (en) | 2022-08-09 |
| CN112708196A (en) | 2021-04-27 |
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