CN116891607A - A method to improve the impact resistance of random copolymerized polypropylene - Google Patents
A method to improve the impact resistance of random copolymerized polypropylene Download PDFInfo
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- -1 polypropylene Polymers 0.000 title claims abstract description 101
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 99
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000001746 injection moulding Methods 0.000 claims abstract description 18
- 229920005604 random copolymer Polymers 0.000 claims abstract description 11
- 239000000155 melt Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 10
- 239000000806 elastomer Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000005452 bending Methods 0.000 abstract 1
- 229920001400 block copolymer Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005243 fluidization Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
Description
技术领域Technical field
本发明涉及高分子复合材料技术领域，公开一种提升无规共聚聚丙烯抗冲击性能的方法。The invention relates to the technical field of polymer composite materials and discloses a method for improving the impact resistance of random copolymerized polypropylene.
背景技术Background technique
无规共聚聚丙烯产品具有优异的透明性能，主要用于生产整理箱、保鲜盒、收纳盒等家居用品。但无规共聚聚丙烯因自身特性，其冲击性能较差，在制品运输过程中易出现破损，增加了制品企业成本。同时，应用在冰激凌盒、冷冻食品包装盒、低温储藏盒等低温领域也受到了限制。Random copolymerized polypropylene products have excellent transparency properties and are mainly used in the production of household items such as organizing boxes, crisper boxes, and storage boxes. However, due to its own characteristics, random copolymer polypropylene has poor impact performance and is prone to breakage during product transportation, which increases the cost of product companies. At the same time, applications in low-temperature fields such as ice cream boxes, frozen food packaging boxes, and low-temperature storage boxes are also limited.
现阶段，厂家主要采用将普通透明料与弹性体POE等进行掺混，一定程度上能提高产品的抗冲击性能。但按上述加工方式，不但增加了生产成本，同时添加弹性体POE后，制品的刚性降低显著,产品的安全性能也会受到影响。因此，一种提升无规共聚聚丙烯抗冲击性能的方法可以在在保证产品弯曲模量、拉伸强度、透明性等性能不变的基础上，提升无规共聚聚丙烯的抗冲击性能。At this stage, manufacturers mainly blend ordinary transparent materials with elastomer POE, etc., which can improve the impact resistance of the product to a certain extent. However, the above processing method not only increases the production cost, but also adds elastomer POE, the rigidity of the product is significantly reduced, and the safety performance of the product will also be affected. Therefore, a method to improve the impact resistance of random copolymerized polypropylene can improve the impact resistance of random copolymerized polypropylene while ensuring that the product's flexural modulus, tensile strength, transparency and other properties remain unchanged.
发明内容Contents of the invention
本发明的构思在于：通过高抗冲透明聚丙烯替代无规共聚聚丙烯产品添加弹性体进行改性，改善无规共聚聚丙烯产品的冲击性能，同时不改变产品的弯曲模量、拉伸强度、透明性等性能。The idea of the invention is to replace random copolymerized polypropylene products with high-impact transparent polypropylene and add elastomers for modification, thereby improving the impact properties of random copolymerized polypropylene products without changing the flexural modulus and tensile strength of the products. , transparency and other properties.
本发明提供一种提升无规共聚聚丙烯抗冲击性能的方法，具体包括如下步骤：将无规共聚聚丙烯与高抗冲透明聚丙烯产品按如下比例进行混合后，进行注塑制备；The invention provides a method for improving the impact resistance of random copolymerized polypropylene, which specifically includes the following steps: mixing random copolymerized polypropylene and high-impact transparent polypropylene products in the following proportions, and then performing injection molding preparation;
无规共聚聚丙烯50-100份；50-100 parts of random copolymerized polypropylene;
高抗冲透明聚丙烯50-400份；High impact transparent polypropylene 50-400 parts;
所述无规共聚聚丙烯材料的常温悬臂梁冲击强度为3～10kJ/m2，弯曲模量为800～1100MPa；The normal temperature Izod impact strength of the random copolymer polypropylene material is 3-10kJ/m 2 and the flexural modulus is 800-1100MPa;
所述高抗冲透明聚丙烯材料为无规共聚聚丙烯、嵌段共聚聚丙烯、均聚聚丙烯中的任意一种或两种以上混合物；所述高抗冲透明聚丙烯材料的常温悬臂梁冲击强度为8-35kJ/m2，弯曲模量为800-1200MPa，熔融指数为15-30g/10min。The high-impact transparent polypropylene material is any one or a mixture of two or more of random copolymerized polypropylene, block copolymerized polypropylene, and homopolymerized polypropylene; the normal-temperature cantilever beam of the high-impact transparent polypropylene material The impact strength is 8-35kJ/m 2 , the flexural modulus is 800-1200MPa, and the melt index is 15-30g/10min.
优选地，所述无规共聚聚丙烯材料的雾度8-17％。Preferably, the haze of the random copolymerized polypropylene material is 8-17%.
进一步地，所述无规共聚聚丙烯材料的拉伸屈服应力为20～30MPa。Further, the tensile yield stress of the random copolymerized polypropylene material is 20 to 30 MPa.
优选地，所述高抗冲透明聚丙烯材料的拉伸屈服应力为20-30MPa。Preferably, the tensile yield stress of the high-impact transparent polypropylene material is 20-30 MPa.
进一步地，所述高抗冲透明聚丙烯材料的雾度为8-15％。Further, the haze of the high-impact transparent polypropylene material is 8-15%.
进一步地，所述注塑制备采用注塑机进行制备，所述注塑机包括四段温区，各温度控制为：一段190-210℃，二段195-215℃，三段195-215℃，四段190-210℃。Further, the injection molding preparation is carried out by an injection molding machine. The injection molding machine includes four temperature zones, and each temperature is controlled as follows: one section 190-210°C, two sections 195-215°C, three sections 195-215°C, and four sections 190-210℃.
进一步地，所述高抗冲透明聚丙烯材料采用Spheripol二代环管工艺制备，所述Spheripol二代环管工艺设备包括第一环管反应器、第二环管反应器和立式气相流化床反应器。Further, the high-impact transparent polypropylene material is prepared using the Spheripol second-generation loop process. The Spheripol second-generation loop process equipment includes a first loop reactor, a second loop reactor and a vertical gas phase fluidization bed reactor.
进一步地，所述Spheripol二代环管工艺采用齐格勒-纳塔催化剂为主催化体系，三乙基铝为助催化剂。Furthermore, the Spheripol second-generation loop process uses Ziegler-Natta catalyst as the main catalytic system and triethylaluminum as the cocatalyst.
进一步地，所述Spheripol二代环管工艺中，在第一环管反应器和第二环管反应器内制备初始聚丙烯粉料；第一环管反应器和第二环管反应器温度为60～80℃，反应压力为3～5MPa，氢气浓度为1500～3500mg/kg，乙烯加入量为1％～10％，环管浆液密度450～550kg/m3。Further, in the Spheripol second-generation loop process, the initial polypropylene powder is prepared in the first loop reactor and the second loop reactor; the temperature of the first loop reactor and the second loop reactor is 60～80℃, reaction pressure is 3～5MPa, hydrogen concentration is 1500～3500mg/kg, ethylene addition amount is 1%～10%, loop slurry density is 450～550kg/m 3 .
进一步地，所述Spheripol二代环管工艺中，所述初始聚丙烯粉料在立式气相流化床反应器丙烯、乙烯、氢气反应，得到高抗冲透明聚丙烯材料；立式气相流化床气相组成乙烯/乙烯+丙烯摩尔体积比为0.1～0.5，氢气/乙烯摩尔体积比为0.4～0.7，乙烯加入量为5％～10％。Further, in the Spheripol second-generation loop process, the initial polypropylene powder reacts with propylene, ethylene, and hydrogen in a vertical gas-phase fluidized bed reactor to obtain a high-impact transparent polypropylene material; vertical gas-phase fluidization The bed gas phase composition has a molar volume ratio of ethylene/ethylene+propylene of 0.1 to 0.5, a hydrogen/ethylene molar volume ratio of 0.4 to 0.7, and an ethylene addition amount of 5% to 10%.
本发明取得的有益效果：Beneficial effects achieved by the present invention:
本发明提供的一种提升无规共聚聚丙烯抗冲击性能的方法，通过将无规共聚聚丙烯与高抗冲透明聚丙烯产品按一定比例混合后制样，来达到提升无规共聚聚丙烯产品的抗冲击性能的目的，可替代无规共聚聚丙烯添加弹性体POE改性来提升无规聚丙烯产品的抗冲击性能，降低生产成本，同时使聚丙烯材料的成分更加安全，具有更加广泛的应用范围。The invention provides a method for improving the impact resistance of random copolymerized polypropylene. By mixing random copolymerized polypropylene and high-impact transparent polypropylene products in a certain proportion and then preparing samples, the random copolymerized polypropylene product can be improved. For the purpose of improving impact resistance, it can replace random copolymerized polypropylene and add elastomer POE modification to improve the impact resistance of random polypropylene products, reduce production costs, and at the same time make the composition of polypropylene materials safer and have a wider range of applications. Application scope.
具体实施方式Detailed ways
为了使本发明的目的、技术方案和优点更加清楚明确，结合以下实施例，对本发明进行进一步的详细说明。In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention will be further described in detail with reference to the following examples.
应当说明的是，本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径而得。It should be noted that the present invention is not limited to the following examples. The methods described are conventional methods unless otherwise stated. The raw materials can be obtained from public commercial sources unless otherwise stated.
除非另有定义，本文中使用的技术和科学术语与本发明所属领域普通技术人员的通常理解具有相同的含义。Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
各实施例中的性能测试标准如下：The performance test standards in each embodiment are as follows:
(1)拉伸屈服应力：GB/T 1040.1-2018(1) Tensile yield stress: GB/T 1040.1-2018
(2)弯曲模量：GB/T 9341-2008(2) Flexural modulus: GB/T 9341-2008
(3)悬臂梁冲击强度：GB/T 1843-2008(3) Izod impact strength: GB/T 1843-2008
(4)雾度：GB T 2410-2008(4) Haze: GB T 2410-2008
本发明实施例及对比例中所用无规共聚聚丙烯、高抗冲透明聚丙烯和弹性体POE为同一批材料。所述无规共聚聚丙烯材料的常温悬臂梁冲击强度为3～10kJ/m2，弯曲模量为800～1100MPa，拉伸屈服应力为20～30MPa；所述高抗冲透明聚丙烯为嵌段共聚聚丙烯，其悬臂梁冲击强度为20～30kJ/m2，弯曲模量为950～1200MPa，拉伸屈服应力25～30MPa；所述弹性体POE为陶氏8999。The random copolymerized polypropylene, high-impact transparent polypropylene and elastomer POE used in the examples and comparative examples of the present invention are from the same batch of materials. The normal temperature Izod impact strength of the random copolymer polypropylene material is 3-10kJ/m 2 , the flexural modulus is 800-1100MPa, and the tensile yield stress is 20-30MPa; the high-impact transparent polypropylene is a block The copolymerized polypropylene has an Izod impact strength of 20-30kJ/m 2 , a flexural modulus of 950-1200MPa, and a tensile yield stress of 25-30MPa; the elastomer POE is Dow 8999.
实施例1Example 1
按质量份分别称取100份无规共聚聚丙烯和100份高抗冲透明聚丙烯，混合均匀后制样。注塑机各温区温度控制为：一段190-210℃，二段195-215℃，三段195-215℃，四段190-210℃。Weigh 100 parts of random copolymerized polypropylene and 100 parts of high-impact transparent polypropylene respectively according to mass parts, mix them evenly and prepare samples. The temperature control of each temperature zone of the injection molding machine is: 190-210℃ in the first stage, 195-215℃ in the second stage, 195-215℃ in the third stage, and 190-210℃ in the fourth stage.
实施例2Example 2
按质量份分别称取100份无规共聚聚丙烯和150份高抗冲透明聚丙烯，混合均匀后制样。注塑机各温区温度控制为：一段190-210℃，二段195-215℃，三段195-215℃，四段190-210℃。Weigh 100 parts of random copolymerized polypropylene and 150 parts of high-impact transparent polypropylene in parts by mass, mix them evenly and prepare samples. The temperature control of each temperature zone of the injection molding machine is: 190-210℃ in the first stage, 195-215℃ in the second stage, 195-215℃ in the third stage, and 190-210℃ in the fourth stage.
实施例3Example 3
按质量份分别称取100份无规共聚聚丙烯和200份高抗冲透明聚丙烯，混合均匀后制样。注塑机各温区温度控制为：一段190-210℃，二段195-215℃，三段195-215℃，四段190-210℃。Weigh 100 parts of random copolymerized polypropylene and 200 parts of high-impact transparent polypropylene according to mass parts, mix them evenly and prepare samples. The temperature control of each temperature zone of the injection molding machine is: 190-210℃ in the first stage, 195-215℃ in the second stage, 195-215℃ in the third stage, and 190-210℃ in the fourth stage.
实施例4Example 4
按质量份分别称取100份无规共聚聚丙烯和300份高抗冲透明聚丙烯，混合均匀后制样。注塑机各温区温度控制为：一段190-210℃，二段195-215℃，三段195-215℃，四段190-210℃。Weigh 100 parts of random copolymerized polypropylene and 300 parts of high-impact transparent polypropylene in parts by mass, mix them evenly and prepare samples. The temperature control of each temperature zone of the injection molding machine is: 190-210℃ in the first stage, 195-215℃ in the second stage, 195-215℃ in the third stage, and 190-210℃ in the fourth stage.
实施例5Example 5
按质量份分别称取200份无规共聚聚丙烯和100份高抗冲透明聚丙烯，混合均匀后制样。注塑机各温区温度控制为：一段190-210℃，二段195-215℃，三段195-215℃，四段190-210℃。Weigh 200 parts of random copolymerized polypropylene and 100 parts of high-impact transparent polypropylene in parts by mass, mix them evenly and prepare samples. The temperature control of each temperature zone of the injection molding machine is: 190-210℃ in the first stage, 195-215℃ in the second stage, 195-215℃ in the third stage, and 190-210℃ in the fourth stage.
对比例1Comparative example 1
称取100份无规共聚聚丙烯，注塑机各温区温度控制为：一段190-210℃，二段195-215℃，三段195-215℃，四段190-210℃。Weigh 100 parts of random copolymerized polypropylene, and control the temperature of each temperature zone of the injection molding machine as follows: one section 190-210°C, two sections 195-215°C, three sections 195-215°C, and four sections 190-210°C.
对比例2Comparative example 2
按质量份分别称取100份无规共聚聚丙烯和0.05份弹性体POE，混合均匀后制样。注塑机各温区温度控制为：一段190-210℃，二段195-215℃，三段195-215℃，四段190-210℃。Weigh 100 parts of random copolymerized polypropylene and 0.05 parts of elastomer POE in parts by mass, mix them evenly and prepare a sample. The temperature control of each temperature zone of the injection molding machine is: 190-210℃ in the first stage, 195-215℃ in the second stage, 195-215℃ in the third stage, and 190-210℃ in the fourth stage.
对比例3Comparative example 3
按质量份分别称取100份无规共聚聚丙烯和0.1份弹性体POE，混合均匀后制样。注塑机各温区温度控制为：一段190-210℃，二段195-215℃，三段195-215℃，四段190-210℃。Weigh 100 parts of random copolymer polypropylene and 0.1 part of elastomer POE in parts by mass, mix them evenly and prepare samples. The temperature control of each temperature zone of the injection molding machine is: 190-210℃ in the first stage, 195-215℃ in the second stage, 195-215℃ in the third stage, and 190-210℃ in the fourth stage.
对比例4Comparative example 4
按质量份分别称取100份无规共聚聚丙烯和0.15份弹性体POE，混合均匀后制样。注塑机各温区温度控制为：一段190-210℃，二段195-215℃，三段195-215℃，四段190-210℃。Weigh 100 parts of random copolymerized polypropylene and 0.15 parts of elastomer POE in parts by mass, mix them evenly and prepare samples. The temperature control of each temperature zone of the injection molding machine is: 190-210℃ in the first stage, 195-215℃ in the second stage, 195-215℃ in the third stage, and 190-210℃ in the fourth stage.
测试效果Test effect
所得实施例1-5及对比例1-4的聚丙烯材料产品，经性能测试，其结果如下表1所示：The obtained polypropylene material products of Examples 1-5 and Comparative Examples 1-4 were tested for performance, and the results are as shown in Table 1 below:
表1对比例1-4及实施例1-5性能测试结果Table 1 Comparative Examples 1-4 and Examples 1-5 Performance Test Results
以上对本发明的一种提升无规共聚聚丙烯抗冲击性能的方法进行了详细介绍，以上仅为示例性实施例，并不能以此限制本发明的保护范围，依照本发明申请范围所做的均等变化与改进，仍然归属本发明专利范围。The above is a detailed introduction to a method of improving the impact resistance of random copolymerized polypropylene according to the present invention. The above are only exemplary embodiments and cannot be used to limit the scope of protection of the present invention. The equalization made in accordance with the application scope of the present invention is Changes and improvements still fall within the patent scope of the present invention.
Claims (10)
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| CN202310623082.4A CN116891607A (en) | 2023-05-30 | 2023-05-30 | A method to improve the impact resistance of random copolymerized polypropylene |
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