CN117024873A - Preparation method of modified polypropylene plastic - Google Patents
Preparation method of modified polypropylene plastic Download PDFInfo
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- CN117024873A CN117024873A CN202310707059.3A CN202310707059A CN117024873A CN 117024873 A CN117024873 A CN 117024873A CN 202310707059 A CN202310707059 A CN 202310707059A CN 117024873 A CN117024873 A CN 117024873A
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- -1 polypropylene Polymers 0.000 title claims abstract description 65
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 61
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 61
- 239000004033 plastic Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 25
- 229920001643 poly(ether ketone) Polymers 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 54
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims description 5
- 229930185605 Bisphenol Natural products 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- HKCNCNXZAZPKDZ-UHFFFAOYSA-N (4,4-difluorocyclohexa-1,5-dien-1-yl)-phenylmethanone Chemical compound C1=CC(F)(F)CC=C1C(=O)C1=CC=CC=C1 HKCNCNXZAZPKDZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000007599 discharging Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920006150 hyperbranched polyester Polymers 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明提供了改性聚丙烯塑料的制备方法,通过聚丙烯和改性聚醚酮共混制备而成,其中,所述改性聚醚酮通过碳纳米管改性,以原位聚合方式制备得到。以此提高碳纳米管在聚丙烯基体树脂中的分散性,从而提高所制备材料的综合性能。The invention provides a method for preparing modified polypropylene plastic, which is prepared by blending polypropylene and modified polyetherketone, wherein the modified polyetherketone is modified by carbon nanotubes and prepared by in-situ polymerization. get. In this way, the dispersion of carbon nanotubes in the polypropylene matrix resin is improved, thereby improving the overall performance of the prepared material.
Description
技术领域Technical field
本发明涉及一种改性聚丙烯塑料的制备方法,特别是通过纳米碳材料改性聚丙烯塑料的制备方法。The invention relates to a method for preparing modified polypropylene plastic, in particular to a method for preparing modified polypropylene plastic through nanocarbon materials.
背景技术Background technique
聚丙烯作为一种常用的工业塑料,具有优良的性能,比如高强度、高硬度、抗冲击性好、耐腐蚀性强以及成型性好等特点,因而被广泛应用于各个领域。As a commonly used industrial plastic, polypropylene has excellent properties, such as high strength, high hardness, good impact resistance, strong corrosion resistance and good formability, so it is widely used in various fields.
碳纳米管具有优异的力学性能和导电性,可添加到聚丙烯中,改善聚丙烯的性能。碳纳米管直接改性聚丙烯可以提高聚丙烯的机械强度、导电性、热稳定性和阻燃性,从而扩展聚丙烯的应用领域。然而,由于碳纳米管本身难以均匀分散在聚丙烯基体中,直接改性对聚丙烯的性能提高有限。Carbon nanotubes have excellent mechanical properties and electrical conductivity and can be added to polypropylene to improve its properties. Direct modification of polypropylene with carbon nanotubes can improve the mechanical strength, electrical conductivity, thermal stability and flame retardancy of polypropylene, thus expanding the application fields of polypropylene. However, since carbon nanotubes themselves are difficult to disperse uniformly in the polypropylene matrix, direct modification has limited improvement in the performance of polypropylene.
专利CN115850869A公开了一种聚丙烯改性热塑性屏蔽料及其制备方法,该专利以聚丙烯、聚烯烃弹性体和改性树脂为基体,通过添加导电填料、抗氧剂、润滑剂、加工助剂进行共混改性,其中添加的碳纳米管并未做进一步改性,而是直接添加到基体树脂中进行改性,从而提高材料的各项性能。Patent CN115850869A discloses a polypropylene modified thermoplastic shielding material and its preparation method. The patent uses polypropylene, polyolefin elastomer and modified resin as the matrix, and adds conductive fillers, antioxidants, lubricants, and processing aids. In blending modification, the added carbon nanotubes are not further modified, but are directly added to the matrix resin for modification, thereby improving the various properties of the material.
专利CN114539667A公开了一种持久抗菌的聚丙烯组合物及其制备方法和应用,该专利通过将碳纳米管接枝于超支化聚酯上,以此促进碳纳米管更好分散在聚丙烯基体中,提高聚丙烯的性能。Patent CN114539667A discloses a durable antibacterial polypropylene composition and its preparation method and application. This patent promotes better dispersion of carbon nanotubes in the polypropylene matrix by grafting carbon nanotubes onto hyperbranched polyester. , improve the performance of polypropylene.
现有技术通过不同的方法将碳纳米管添加到聚丙烯树脂中,但是起到的技术效果不尽相同。本发明试图提供一种与现有技术不同的碳纳米管改性聚丙烯材料,且具有良好的综合性能。The existing technology adds carbon nanotubes to polypropylene resin through different methods, but the technical effects are not the same. The present invention attempts to provide a carbon nanotube-modified polypropylene material that is different from the existing technology and has good comprehensive properties.
发明内容Contents of the invention
本发明提供了改性聚丙烯塑料的制备方法,通过聚丙烯和改性聚醚酮共混制备而成,其中,所述改性聚醚酮通过碳纳米管改性,以原位聚合方式制备得到。以此提高碳纳米管在聚丙烯基体树脂中的分散性,从而提高所制备材料的综合性能。The invention provides a method for preparing modified polypropylene plastic, which is prepared by blending polypropylene and modified polyetherketone, wherein the modified polyetherketone is modified by carbon nanotubes and prepared by in-situ polymerization. get. In this way, the dispersion of carbon nanotubes in the polypropylene matrix resin is improved, thereby improving the overall performance of the prepared material.
本发明提供的技术方案具体如下:The technical solutions provided by the present invention are as follows:
一种改性聚丙烯塑料的制备方法,通过聚丙烯和改性聚醚酮共混制备而成,其中,所述改性聚醚酮通过碳纳米管改性,以原位聚合方式制备得到。A method for preparing modified polypropylene plastic, which is prepared by blending polypropylene and modified polyetherketone, wherein the modified polyetherketone is modified by carbon nanotubes and prepared by in-situ polymerization.
本发明选择碳纳米管对聚丙烯进行改性,但是如果将碳纳米管直接加入聚丙烯中,由于其分散性不好,会使得制备出来的改性聚丙烯塑料性能不佳。发明人经过大量研究发现,将碳纳米管通过原位聚合的方式加入聚醚酮,使碳纳米管先在聚醚酮中进行预分散;然后将制备得到的改性聚醚酮再与聚丙烯进行共混,得到的改性聚丙烯塑料性能要优于碳纳米管直接对聚丙烯改性的样品。In the present invention, carbon nanotubes are selected to modify polypropylene. However, if carbon nanotubes are directly added to polypropylene, due to poor dispersion, the prepared modified polypropylene plastic will have poor performance. After extensive research, the inventor found that carbon nanotubes were added to polyetherketone through in-situ polymerization, so that the carbon nanotubes were first pre-dispersed in polyetherketone; then the prepared modified polyetherketone was mixed with polypropylene After blending, the properties of the modified polypropylene plastic obtained are better than those of samples in which carbon nanotubes directly modify polypropylene.
需要说明的是,碳纳米管通过原位聚合的方式改性聚醚酮是现有技术已经公开的技术,例如专利CN110183647A公开的一种碳纳米管/聚醚酮复合材料及其制备方法和应用,但是如本发明所述的将碳纳米管改性聚醚酮与聚丙烯材料共混改性,并非现有技术公开的内容。It should be noted that the modification of polyetherketone by carbon nanotubes through in-situ polymerization is a technology that has been disclosed in the prior art. For example, patent CN110183647A discloses a carbon nanotube/polyetherketone composite material and its preparation method and application. , but the blending and modification of carbon nanotube-modified polyetherketone and polypropylene materials as described in the present invention is not disclosed in the prior art.
所述改性聚醚酮的制备原料包含4,4-二氟二苯甲酮、4,4-二羟基二苯甲酮、碳纳米管。The raw materials for preparing the modified polyetherketone include 4,4-difluorobenzophenone, 4,4-dihydroxybenzophenone and carbon nanotubes.
所述改性聚醚酮的制备方法为:The preparation method of the modified polyetherketone is:
步骤一,将碳纳米管和有机溶剂加入反应器中分散均匀,得到碳纳米管分散液备用;Step 1: Add carbon nanotubes and organic solvent into the reactor and disperse them evenly to obtain a carbon nanotube dispersion liquid for later use;
步骤二,惰性气体气氛下,在反应器中加入溶剂、4,4’-二羟基二苯甲酮、4,4’-二氟二苯甲酮、成盐剂和所述碳纳米管分散液,开启搅拌,控制反应器温度在170~310℃进行反应2~6小时,出料,经冷却、洗涤、烘干,得到所述改性聚醚酮。Step 2: Add solvent, 4,4'-dihydroxybenzophenone, 4,4'-difluorobenzophenone, salt-forming agent and the carbon nanotube dispersion into the reactor under an inert gas atmosphere , start stirring, control the reactor temperature at 170-310°C, carry out the reaction for 2-6 hours, discharge the material, and obtain the modified polyetherketone after cooling, washing and drying.
在本发明的一个优选实例中,所述所述改性聚醚酮的制备方法步骤二中,反应原料加入反应器之后,反应体系依次在140~180℃下反应1~2小时,在210~230℃下反应2~3小时,在240~280℃下反应2~3小时,在300~310℃下反应0.5~1小时。In a preferred example of the present invention, in the second step of the preparation method of the modified polyetherketone, after the reaction raw materials are added to the reactor, the reaction system is sequentially reacted at 140-180°C for 1-2 hours, and at 210-210°C React at 230°C for 2 to 3 hours, at 240 to 280°C for 2 to 3 hours, and at 300 to 310°C for 0.5 to 1 hour.
所述惰性气体可以选择本领域常用的惰性气体,例如氮气、氩气等,这类气体可以单独或组合使用。The inert gas can be an inert gas commonly used in this field, such as nitrogen, argon, etc., and these gases can be used alone or in combination.
所述成盐剂可以选择本领域常用的用于制备聚醚酮的成盐剂,例如碳酸钾、碳酸钠、碳酸钙、碳酸镁、碳酸锂等,这类成盐剂可以单独或组合使用。在本发明的一个优选实例中,所述成盐剂为碳酸钾和碳酸钠,其中碳酸钾和碳酸钠的摩尔比为1:10。The salt-forming agent can be a salt-forming agent commonly used in the art for preparing polyetherketone, such as potassium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, lithium carbonate, etc. Such salt-forming agents can be used alone or in combination. In a preferred example of the present invention, the salt-forming agent is potassium carbonate and sodium carbonate, wherein the molar ratio of potassium carbonate and sodium carbonate is 1:10.
所述改性聚醚酮的制备方法中未作进一步限定的内容,还可以根据本领域常用的技术方案对工艺步骤、原料种类和用量等进行调整。例如所述步骤一中的有机溶剂可以选择甲苯、二甲苯、丙酮、丁酮、乙醚、三氯甲烷、二乙烯基苯等;所述步骤二中的溶剂可以采用二苯砜、联苯、蒽醌、邻苯二甲酸二丁酯、硅油等。The content of the preparation method of the modified polyetherketone is not further limited, and the process steps, raw material types and dosages can also be adjusted according to the technical solutions commonly used in the field. For example, the organic solvent in step one can be toluene, xylene, acetone, butanone, diethyl ether, chloroform, divinylbenzene, etc.; the solvent in step two can be diphenyl sulfone, biphenyl, anthracene, etc. Quinone, dibutyl phthalate, silicone oil, etc.
所述改性聚醚酮的制备方法中,所述步骤一为:将碳纳米管、4,4'-二苯亚甲基双酚、有机溶剂加入反应器中分散均匀,得到碳纳米管分散液备用。In the preparation method of the modified polyetherketone, the step one is: adding carbon nanotubes, 4,4'-diphenyldimethylbisphenol, and organic solvent into the reactor to disperse them evenly to obtain dispersed carbon nanotubes. Liquid for later use.
在所述改性聚醚酮的制备方法中,可以选择引入少量反应性化合物来调控聚醚酮的性能,并与碳纳米管通过堆积效应促进其分散。这类反应性化合物优选带有羟基基团和苯环结构的化合物,尤其是带有双羟基基团和苯环结构的化合物,例如双酚芴等。这类反应性化合物在单纯应用于聚醚酮的制备时,仅需要考虑其化学结构是否适用于聚醚酮的合成,但是在应用于本发明的技术方案时,即碳纳米管改性聚丙烯时,除了需要考虑对聚醚酮的影响,还需要考虑聚醚酮与聚丙烯共混后材料性能的情况。本发明优选采用4,4'-二苯亚甲基双酚作为反应性化合物对聚醚酮进行改性,一方面其能够促进碳纳米管在聚醚酮合成过程中的分散性,能够提高聚醚酮本身的性能,另一方面采用这种方法制备的改性聚醚酮在与聚丙烯共混时,相容性更好,所得到的改性聚丙烯具有更优异的性能。In the preparation method of the modified polyetherketone, a small amount of reactive compounds can be introduced to regulate the properties of the polyetherketone and promote their dispersion through a stacking effect with carbon nanotubes. Such reactive compounds are preferably compounds with a hydroxyl group and a benzene ring structure, especially compounds with a dihydroxyl group and a benzene ring structure, such as bisphenolfluorene and the like. When this type of reactive compound is simply used in the preparation of polyetherketone, it is only necessary to consider whether its chemical structure is suitable for the synthesis of polyetherketone. However, when applied to the technical solution of the present invention, that is, carbon nanotube modified polypropylene In addition to the impact on polyetherketone, it is also necessary to consider the material properties after blending polyetherketone and polypropylene. The present invention preferably uses 4,4'-diphenylmethylbisphenol as a reactive compound to modify polyetherketone. On the one hand, it can promote the dispersion of carbon nanotubes in the synthesis process of polyetherketone and improve the polyetherketone synthesis process. The properties of ether ketone itself, on the other hand, the modified polyether ketone prepared by this method has better compatibility when blended with polypropylene, and the obtained modified polypropylene has better properties.
所述改性聚醚酮的制备方法中,所述4,4'-二苯亚甲基双酚、4,4’-二羟基二苯甲酮、4,4’-二氟二苯甲酮的摩尔比为0.01~0.1:0.9~0.99:1~1.2;优选为0.1:0.9:1.05。In the preparation method of the modified polyetherketone, the 4,4'-diphenylmethylene bisphenol, 4,4'-dihydroxybenzophenone, and 4,4'-difluorobenzophenone The molar ratio is 0.01~0.1:0.9~0.99:1~1.2; preferably 0.1:0.9:1.05.
所述碳纳米管和4,4'-二苯亚甲基双酚的质量比为0.1~1:1,优选0.5~0.8:1。The mass ratio of the carbon nanotubes and 4,4'-diphenylmethylbisphenol is 0.1-1:1, preferably 0.5-0.8:1.
在本发明的一个优选实例中,制备得到的所述改性聚醚酮需要经过粉碎,以小颗粒或粉末状的形态与聚丙烯进行共混。优选将所述改性聚醚酮破碎成为粉末。聚醚酮在与聚丙烯熔融共混的过程中,聚丙烯是基体树脂,加工温度更宜设置在聚丙烯适用的范围之内,但聚醚酮的熔体流动温度较高,因此聚醚酮的粒径越小,其与聚丙烯之间的相容性越好。In a preferred example of the present invention, the prepared modified polyetherketone needs to be pulverized and blended with polypropylene in the form of small particles or powder. The modified polyetherketone is preferably crushed into powder. During the melt blending process of polyetherketone and polypropylene, polypropylene is the matrix resin, and the processing temperature should be set within the applicable range of polypropylene. However, the melt flow temperature of polyetherketone is relatively high, so polyetherketone The smaller the particle size, the better the compatibility with polypropylene.
所述碳纳米管可以选择本领域常用的碳纳米管,优选非功能化的碳纳米管,即多壁碳纳米管和/或单壁碳纳米管。功能化的碳纳米管,即碳纳米管经过改性,其结构带有活性基团,如羟基、羧基等基团,这类碳纳米管的结构通过改性受到一定程度破坏,其本身强度下降,进而可能会导致最终材料的性能下降。The carbon nanotubes can be selected from carbon nanotubes commonly used in the field, preferably non-functionalized carbon nanotubes, that is, multi-walled carbon nanotubes and/or single-walled carbon nanotubes. Functionalized carbon nanotubes, that is, carbon nanotubes that have been modified, have active groups in their structure, such as hydroxyl, carboxyl and other groups. The structure of this type of carbon nanotubes has been damaged to a certain extent through modification, and its strength has decreased. , which may lead to a decrease in the performance of the final material.
所述聚丙烯和改性聚醚酮的质量比为10:1~3。The mass ratio of polypropylene and modified polyetherketone is 10:1-3.
所述聚丙烯可以选择本领域常用的聚丙烯,例如均聚聚丙烯、共聚聚丙烯等。The polypropylene can be selected from polypropylene commonly used in this field, such as homopolymerized polypropylene, copolymerized polypropylene, etc.
所述聚丙烯和改性聚醚酮共混的方法可以采用本领域常用的技术方案。在本发明的一个优选实例中,所述聚丙烯和改性聚醚酮通过高速搅拌机进行预混合,再通过双螺杆挤出机共混制备,双螺杆挤出机的转速为200~900rpm,螺杆温度为180~230℃。The method of blending polypropylene and modified polyetherketone can adopt technical solutions commonly used in this field. In a preferred example of the present invention, the polypropylene and modified polyetherketone are premixed by a high-speed mixer, and then blended and prepared by a twin-screw extruder. The rotating speed of the twin-screw extruder is 200 to 900 rpm, and the screw The temperature is 180~230℃.
具体实施方式Detailed ways
以下结合具体实施例来进一步说明本发明。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。The present invention will be further described below in conjunction with specific examples. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in this technical field.
本发明实施例和对比例采用的原料如下:The raw materials used in the examples and comparative examples of the present invention are as follows:
聚丙烯,H309F,SK化学;Polypropylene, H309F, SK Chemical;
碳纳米管,XFM04,多壁碳纳米管,江苏先丰纳米材料科技有限公司。Carbon nanotubes, XFM04, multi-walled carbon nanotubes, Jiangsu Xianfeng Nanomaterials Technology Co., Ltd.
碳纳米管分散液1的制备方法:将17.62质量份的碳纳米管、35.24质量份的4,4'-二苯亚甲基双酚、300质量份的二甲苯加入反应器,进行磁力搅拌和超声2小时,出料备用。Preparation method of carbon nanotube dispersion 1: add 17.62 parts by mass of carbon nanotubes, 35.24 parts by mass of 4,4'-diphenylmethylenebisphenol, and 300 parts by mass of xylene into the reactor, perform magnetic stirring and Ultrasonic for 2 hours, then discharge and set aside.
碳纳米管分散液2的制备方法:将28.19质量份的碳纳米管、35.24质量份的4,4'-二苯亚甲基双酚、300质量份的二甲苯加入反应器,进行磁力搅拌和超声2小时,出料备用。Preparation method of carbon nanotube dispersion 2: add 28.19 parts by mass of carbon nanotubes, 35.24 parts by mass of 4,4'-diphenylmethylenebisphenol, and 300 parts by mass of xylene into the reactor, perform magnetic stirring and Ultrasonic for 2 hours, then discharge and set aside.
碳纳米管分散液3的制备方法:将28.03质量份的碳纳米管、35.04质量份的双酚芴、300质量份的二甲苯加入反应器,进行磁力搅拌和超声2小时,出料备用。Preparation method of carbon nanotube dispersion 3: Add 28.03 parts by mass of carbon nanotubes, 35.04 parts by mass of bisphenol fluorene, and 300 parts by mass of xylene into the reactor, perform magnetic stirring and ultrasonic for 2 hours, and discharge the materials for later use.
碳纳米管分散液4的制备方法:将28.19质量份的碳纳米管、300质量份的二甲苯加入反应器,进行磁力搅拌和超声2小时,出料备用。Preparation method of carbon nanotube dispersion 4: add 28.19 parts by mass of carbon nanotubes and 300 parts by mass of xylene into the reactor, perform magnetic stirring and ultrasonic for 2 hours, and discharge the materials for later use.
成盐剂1采用碳酸钾和碳酸钠质量为1:10的复合成盐剂。The salt-forming agent 1 uses a composite salt-forming agent with a mass of potassium carbonate and sodium carbonate of 1:10.
成盐剂2采用碳酸钾和碳酸钠质量为1:100的复合成盐剂。The salt-forming agent 2 uses a composite salt-forming agent with a mass of potassium carbonate and sodium carbonate of 1:100.
改性聚醚酮的制备方法为:氩气气氛下,将二苯砜、成盐剂、4,4-二轻基二苯甲酮、4,4’-二氟二苯甲酮、碳纳米管分散液(如有)加入反应器,控制反应器温度在180℃,开启搅拌和冷凝回流,反应2小时,在230℃下反应2小时,排除二甲苯,在280℃下反应2小时,在310℃下反应0.5小时,出料,经粉碎、洗涤、干燥,得到改性聚醚酮。The preparation method of modified polyetherketone is: under an argon atmosphere, combine diphenyl sulfone, salt-forming agent, 4,4-dihydroxybenzophenone, 4,4'-difluorobenzophenone, and carbon nanoparticles. Pipe dispersion (if any) is added to the reactor, control the reactor temperature at 180°C, start stirring and condensation reflux, react for 2 hours, react at 230°C for 2 hours, exclude xylene, react at 280°C for 2 hours, and React at 310°C for 0.5 hours, discharge, and obtain modified polyetherketone after crushing, washing, and drying.
实施例和对比例所用改性聚醚酮各原料种类和用量列于表1,以各组分之间的相对质量份计。The types and amounts of raw materials used in the modified polyetherketone used in the examples and comparative examples are listed in Table 1, based on the relative mass parts between each component.
表1改性聚醚酮各原料种类和用量(质量份)Table 1 Types and amounts of raw materials (parts by mass) of modified polyetherketone
实施例和对比例1改性聚丙烯塑料样品的制备方法为:将聚丙烯、改性聚醚酮、抗氧剂1010预先通过高速混合机混合均匀,加入双螺杆挤出机挤出造粒,挤出条件为螺杆转速为300rpm,螺杆温度从进料口到机头分段设置为190℃、190℃、200℃、200℃、210℃、220℃、230℃、220℃、190℃、185℃、180℃。其中,聚丙烯为粒料,改性聚醚酮预先破碎为粉末。Examples and Comparative Example 1 The preparation method of modified polypropylene plastic samples is as follows: mix polypropylene, modified polyetherketone, and antioxidant 1010 in advance through a high-speed mixer, then add them to a twin-screw extruder for extrusion and granulation. The extrusion conditions are that the screw speed is 300 rpm, and the screw temperature is set to 190°C, 190°C, 200°C, 200°C, 210°C, 220°C, 230°C, 220°C, 190°C, 185°C in sections from the feed port to the machine head. ℃, 180℃. Among them, polypropylene is in the form of pellets, and modified polyetherketone is crushed into powder in advance.
对比例2改性聚丙烯塑料样品的制备方法为:将聚丙烯、碳纳米管(碳纳米管的加入量为聚丙烯质量的0.6%)、抗氧剂1010预先通过高速混合机混合均匀,加入双螺杆挤出机挤出造粒,挤出条件为螺杆转速为300rpm,螺杆温度从进料口到机头分段设置为190℃、190℃、200℃、200℃、210℃、220℃、230℃、220℃、190℃、185℃、180℃。The preparation method of the modified polypropylene plastic sample of Comparative Example 2 is as follows: mix polypropylene, carbon nanotubes (the amount of carbon nanotubes added is 0.6% of the mass of polypropylene), and antioxidant 1010 in advance through a high-speed mixer, and then add The twin-screw extruder is used for extrusion and granulation. The extrusion conditions are as follows: the screw speed is 300 rpm, and the screw temperature is set from the feed port to the machine head to 190°C, 190°C, 200°C, 200°C, 210°C, 220°C, 230℃, 220℃, 190℃, 185℃, 180℃.
实施例和对比例1中聚丙烯和改性聚醚酮的用量列于表2,以各组分之间的相对质量份计。The amounts of polypropylene and modified polyetherketone used in Examples and Comparative Example 1 are listed in Table 2, based on the relative mass parts between each component.
表2实施例和对比例原料用量(质量份)Table 2 Examples and Comparative Examples Raw Material Amount (mass parts)
需要说明的是,对比例2并未添加改性聚醚酮,但所用的聚丙烯粒料经历相同加工步骤,用于性能对比。It should be noted that Comparative Example 2 did not add modified polyetherketone, but the polypropylene pellets used underwent the same processing steps for performance comparison.
对实施例和对比例样品进行性能测试,拉伸强度测试标准为ISO 527,样条尺寸为130mm*10mm*0.8mm,拉伸速率50mm/min;冲击强度测试标准为ISO 179测试,悬臂梁,样条尺寸80mm*10mm*4mm,A型缺口。Perform performance tests on the samples of the examples and comparative examples. The tensile strength test standard is ISO 527, the spline size is 130mm*10mm*0.8mm, and the tensile rate is 50mm/min; the impact strength test standard is ISO 179 test, cantilever beam, Spline size 80mm*10mm*4mm, A-shaped notch.
表3实施例和对比例性能测试结果Table 3 Examples and Comparative Examples Performance Test Results
需要说明的是,本发明实施例和对比例中未做说明的原料种类和用量、工艺步骤等,均采用的本领域常用原料和工艺,且这些未做说明的内容在实施例和对比例中均保持一致,不影响实施例和对比例进行横向对比,不影响本发明的技术效果。It should be noted that the types and amounts of raw materials, process steps, etc. that are not explained in the examples and comparative examples of the present invention are all commonly used raw materials and processes in this field, and these unexplained contents are in the examples and comparative examples. All remain consistent, and do not affect the horizontal comparison between the examples and comparative examples, nor the technical effects of the present invention.
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Application publication date: 20231110 |