CN114989416A - Polyaryletherketone heat-shrinkable material and preparation method thereof - Google Patents
Polyaryletherketone heat-shrinkable material and preparation method thereof Download PDFInfo
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- 229920006260 polyaryletherketone Polymers 0.000 title claims abstract description 89
- 239000002654 heat shrinkable material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 59
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 59
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 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 abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000002585 base Substances 0.000 claims description 32
- 238000001125 extrusion Methods 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 238000007493 shaping process Methods 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 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 14
- 239000012286 potassium permanganate Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical group C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 6
- 150000008041 alkali metal carbonates Chemical group 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims description 5
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- BATCUENAARTUKW-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-diphenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BATCUENAARTUKW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 37
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 229920006125 amorphous polymer Polymers 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 abstract 3
- 238000005260 corrosion Methods 0.000 description 22
- 230000007797 corrosion Effects 0.000 description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 238000005453 pelletization Methods 0.000 description 18
- 239000004033 plastic Substances 0.000 description 18
- 229920003023 plastic Polymers 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000012043 crude product Substances 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 238000010907 mechanical stirring Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000012467 final product Substances 0.000 description 8
- 238000010926 purge Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229920000412 polyarylene Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229920006257 Heat-shrinkable film Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000012704 multi-component copolymerization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G65/4018—(I) or (II) containing halogens other than as leaving group (X)
- C08G65/4025—(I) or (II) containing fluorine other than as leaving group (X)
-
- 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
- C08G65/4043—(I) or (II) containing oxygen other than as phenol or carbonyl group
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- 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
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Abstract
本发明提供了一种聚芳醚酮热收缩材料的制备方法，包括如下步骤：A)在惰性气体的存在下，4,4'‑二氟二苯甲酮、对苯二酚、与溶剂和催化剂混合，反应，再加入含柔性基团的二酚单体，继续反应，得到改性聚醚醚酮树脂；B)将改性聚醚醚酮树脂挤出，得到聚芳醚酮热收缩材料。本发明创造性的通过共聚改性改变PEEK对称的紧密结构，破坏大分子链的规整性，从而降低大分子间的作用力，使PEEK分子结构变得比较柔顺。同时，由于柔性基团的引入，共聚物由部分结晶向非结晶聚合物过渡，由于这种改性使PEEK的结晶能力下降，无定形区变大，故可用于制备高收缩材料，最高热收缩率可高达2:1。The invention provides a preparation method of a polyaryletherketone heat shrinkable material, comprising the following steps: A) in the presence of an inert gas, 4,4'-difluorobenzophenone, hydroquinone, and a solvent and The catalyst is mixed and reacted, and then the diphenol monomer containing a flexible group is added, and the reaction is continued to obtain a modified polyetheretherketone resin; B) Extruding the modified polyetheretherketone resin to obtain a polyaryletherketone heat shrinkable material . The invention creatively changes the symmetrical tight structure of PEEK through copolymerization modification, destroys the regularity of the macromolecular chain, thereby reducing the force between macromolecules and making the PEEK molecular structure more flexible. At the same time, due to the introduction of flexible groups, the copolymer transitions from partially crystalline to amorphous polymers. Since this modification reduces the crystallization ability of PEEK and enlarges the amorphous region, it can be used to prepare high shrinkage materials with the highest thermal shrinkage. The ratio can be as high as 2:1.
Description
技术领域technical field
本发明涉及热收缩材料技术领域，尤其是涉及一种聚芳醚酮热收缩材料及其制备方法。The invention relates to the technical field of heat shrinkable materials, in particular to a polyaryletherketone heat shrinkable material and a preparation method thereof.
背景技术Background technique
热收缩高分子材料主要特性是加热收缩包覆在物体外表面，能够起到绝缘、防潮、密封、保护和接续等作用，热收缩材料广泛应用于电子元件绝缘隔热保护，通讯电缆、电力电缆的接头绝缘保护，电气部件屏蔽连接、绝缘密封，化工、石油管道的密封防腐等领域。The main feature of heat-shrinkable polymer materials is that they are coated on the outer surface of the object by heating and shrinking, which can play the role of insulation, moisture-proof, sealing, protection and connection. Insulation protection of joints, shielding connection of electrical components, insulation sealing, sealing and anti-corrosion of chemical and petroleum pipelines, etc.
传统热收缩高分子材料，如聚氯乙烯、聚乙烯、聚丙烯和聚酯等使用温度较低，往往超过150℃收缩效果开始变差，无法满足日益提升的耐高温环境需求。另一方面，这些树脂阻燃、耐辐照、抗溶剂和耐摩擦性能也较差，在航空航天、精密电子、石油化工等领域的使用也受到限制。Traditional heat-shrinkable polymer materials, such as polyvinyl chloride, polyethylene, polypropylene and polyester, are used at relatively low temperatures, and their shrinkage effects often begin to deteriorate when the temperature exceeds 150 °C, which cannot meet the increasing demand for high-temperature resistant environments. On the other hand, these resins have poor flame retardancy, radiation resistance, solvent resistance, and friction resistance, and their use in aerospace, precision electronics, petrochemicals, and other fields is also limited.
聚醚醚酮(PEEK)是一种半结晶型的芳香族高分子材料，自问世起就被作为一种重要的战略性军工材料。PEEK也是一种具有优异性能的特种工程塑料，能在较宽的温度范围内和比较苛刻的化学物理环境中使用。具有优异的机械性能、电性能、耐辐射性、耐化学腐蚀性、耐剥离性、耐热性、耐磨性、自润滑性、尺寸稳定性、阻燃性等优点。利用PEEK制备热收缩材料不仅能够有效拓宽聚合物热收缩材料的应用环境。Polyetheretherketone (PEEK) is a semi-crystalline aromatic polymer material, which has been used as an important strategic military material since its inception. PEEK is also a special engineering plastic with excellent properties, which can be used in a wide temperature range and harsh chemical and physical environments. It has excellent mechanical properties, electrical properties, radiation resistance, chemical corrosion resistance, peel resistance, heat resistance, wear resistance, self-lubrication, dimensional stability, flame retardancy and other advantages. Using PEEK to prepare heat shrinkable materials can not only effectively broaden the application environment of polymer heat shrinkable materials.
但是目前普通PEEK经过特殊工艺处理只能得到1.4:1以下的热收缩率，无法满足热收缩材料的使用要求。提高PEEK基热收缩材料的收缩比对于拓展PEEK的应用领域是十分必要的。However, at present, ordinary PEEK can only obtain a heat shrinkage rate below 1.4:1 after special processing, which cannot meet the requirements of heat shrinkable materials. It is necessary to improve the shrinkage ratio of PEEK-based heat shrinkable materials to expand the application field of PEEK.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明要解决的技术问题在于提供一种聚芳醚酮热收缩材料及其制备方法，本发明提供的聚芳醚酮热收缩材料收缩率高。In view of this, the technical problem to be solved by the present invention is to provide a polyaryletherketone heat-shrinkable material and a preparation method thereof. The polyaryletherketone heat-shrinkable material provided by the present invention has a high shrinkage rate.
本发明提供了一种聚芳醚酮热收缩材料的制备方法，包括如下步骤：The invention provides a preparation method of a polyaryletherketone heat shrinkable material, comprising the following steps:
A)在惰性气体的存在下，4,4'-二氟二苯甲酮、对苯二酚、与溶剂和催化剂混合，反应，再加入含柔性基团的二酚单体，继续反应，得到改性聚醚醚酮树脂；A) In the presence of inert gas, 4,4'-difluorobenzophenone and hydroquinone are mixed with a solvent and a catalyst to react, and then a diphenol monomer containing a flexible group is added to continue the reaction to obtain Modified polyetheretherketone resin;
B)将改性聚醚醚酮树脂挤出，得到聚芳醚酮热收缩材料。B) Extruding the modified polyetheretherketone resin to obtain a polyaryletherketone heat shrinkable material.
优选的，所述含柔性基团的二酚单体选自4,4'-(α-甲基苯亚甲基)双酚、2,2-二(4-羟基苯基)丙烷、4,4'-二羟基四苯甲烷、4,4二羟基二苯基甲烷、2,2-双-(4-羟苯基)六氟丙烷或4,4'-二羟基二苯醚中的一种或几种；Preferably, the flexible group-containing diphenol monomer is selected from 4,4'-(α-methylbenzylidene)bisphenol, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-(α-methylbenzylidene)bisphenol, 2,2-bis(4-hydroxyphenyl)propane, One of 4'-dihydroxytetraphenylmethane, 4,4 dihydroxydiphenylmethane, 2,2-bis-(4-hydroxyphenyl)hexafluoropropane or 4,4'-dihydroxydiphenyl ether or several;
所述催化剂为碱金属碳酸盐；所述碱金属碳酸盐为碳酸钠和/或碳酸钾；Described catalyst is alkali metal carbonate; Described alkali metal carbonate is sodium carbonate and/or potassium carbonate;
所述溶剂为环丁砜和/或二甲基亚砜；The solvent is sulfolane and/or dimethyl sulfoxide;
所述惰性气体为氮气、氦气或氩气。The inert gas is nitrogen, helium or argon.
优选的，所述对苯二酚和含柔性基团的二酚单体摩尔比优选为(0.8～0.9)：(0.1～0.2)；Preferably, the molar ratio of the hydroquinone to the flexible group-containing diphenol monomer is preferably (0.8-0.9): (0.1-0.2);
所述对苯二酚和含柔性基团的二酚单体的总和与4,4'-二氟二苯甲酮的摩尔比为1:(0.99～1.01)；The molar ratio of the sum of the hydroquinone and the diphenol monomers containing flexible groups to 4,4'-difluorobenzophenone is 1:(0.99-1.01);
所述对苯二酚、含柔性基团的二酚单体和4,4'-二氟二苯甲酮的总和与溶剂的质量比为1:(10～15)；The mass ratio of the sum of the hydroquinone, the diphenol monomer containing the flexible group and the 4,4'-difluorobenzophenone to the solvent is 1:(10-15);
所述对苯二酚和含柔性基团的二酚单体的总和与催化剂的摩尔比为(2.2～2.5)：1。The molar ratio of the sum of the hydroquinone and the diphenol monomer containing the flexible group to the catalyst is (2.2-2.5):1.
优选的，步骤A)所述反应具体为：在170℃～190℃成盐反应0.5～1h，而后程序升温反应；所述程序升温反应具体为：210～230℃反应1h，升温至240～260℃反应1h，升温至280～300℃反应1h。Preferably, the reaction in step A) is specifically: a salt-forming reaction at 170°C to 190°C for 0.5-1 h, and then a temperature-programmed reaction; the temperature-programmed reaction is specifically: a reaction at 210-230°C for 1 hour, and the temperature is raised to 240-260°C ℃ for 1 hour, and the temperature was raised to 280-300 ℃ for 1 hour.
优选的，步骤A)所述继续反应具体为：280～300℃反应1～2hr后，升高温度至280～320℃反应3～6hr；Preferably, the continued reaction in step A) is specifically: after the reaction at 280-300 °C for 1-2 hr, the temperature is raised to 280-320 °C and the reaction is performed for 3-6 hr;
所述继续反应后还包括洗涤、干燥；所述干燥具体为：120～150℃干燥10～20h。The continued reaction also includes washing and drying; the drying is specifically: drying at 120-150° C. for 10-20 hours.
优选的，步骤B)所述改性聚醚醚酮树脂还包括加入耐高温润滑剂、高锰酸钾混合；所述混合速度为35～50r/min，混合时间35～50min；Preferably, the modified polyetheretherketone resin in step B) further comprises adding a high temperature resistant lubricant and potassium permanganate to mix; the mixing speed is 35-50r/min, and the mixing time is 35-50min;
所述改性聚醚醚酮树脂、耐高温润滑剂、高锰酸钾的质量比为100：(0～1)：(0～0.00004)。The mass ratio of the modified polyether ether ketone resin, high temperature resistant lubricant and potassium permanganate is 100:(0-1):(0-0.00004).
优选的，步骤B)所述挤出参数具体为：Preferably, the extrusion parameters described in step B) are specifically:
挤出机温度为340℃～380℃，挤出速度为80～120r/min，主喂料速度为8～10r/min。The extruder temperature is 340℃～380℃, the extrusion speed is 80～120r/min, and the main feeding speed is 8～10r/min.
本发明提供了一种聚芳醚酮热收缩材料，由上述技术方案任一项所述的制备方法制备得到。The present invention provides a polyaryletherketone heat shrinkable material, which is prepared by the preparation method described in any one of the above technical solutions.
本发明提供了一种聚芳醚酮热收缩制品，由上述技术方案所述的聚芳醚酮热收缩材料制备得到。The present invention provides a polyaryletherketone heat-shrinkable product, which is prepared from the polyaryletherketone heat-shrinkable material described in the above technical solution.
本发明提供了一种聚芳醚酮热收缩基管的制备方法，包括：The invention provides a preparation method of a polyaryletherketone heat-shrinkable base tube, comprising:
将上述技术方案所述的聚芳醚酮热收缩材料挤出，经过口模、芯棒、冷却定型得到；所述挤出参数为：The polyaryl ether ketone heat shrinkable material described in the above technical solution is extruded, and obtained through a die, a mandrel, and cooling and shaping; the extrusion parameters are:
挤出机温度为340℃～380℃，挤出速度为30～60r/min，主喂料速度为4～8r/min。The extruder temperature is 340℃～380℃, the extrusion speed is 30～60r/min, and the main feeding speed is 4～8r/min.
与现有技术相比，本发明提供了一种聚芳醚酮热收缩材料的制备方法，包括如下步骤：A)在惰性气体的存在下，4,4'-二氟二苯甲酮、对苯二酚、与溶剂和催化剂混合，反应，再加入含柔性基团的二酚单体，继续反应，得到改性聚醚醚酮树脂；B)将改性聚醚醚酮树脂挤出，得到聚芳醚酮热收缩材料。本发明创造性的通过共聚改性改变PEEK对称的紧密结构，破坏大分子链的规整性，从而降低大分子间的作用力，使PEEK分子结构变得比较柔顺。同时，由于柔性基团的引入，共聚物由部分结晶向非结晶聚合物过渡，由于这种改性使PEEK的结晶能力下降，无定形区变大，故可用于制备高收缩材料，最高热收缩率可高达2:1。Compared with the prior art, the present invention provides a method for preparing a polyaryletherketone heat-shrinkable material, comprising the following steps: A) in the presence of an inert gas, 4,4'-difluorobenzophenone, paraffin diphenol, mixed with a solvent and a catalyst, reacted, and then added a diphenol monomer containing a flexible group, and continued the reaction to obtain a modified polyether ether ketone resin; B) extruding the modified polyether ether ketone resin to obtain Polyaryletherketone heat shrinkable material. The invention creatively changes the symmetrical tight structure of PEEK through copolymerization modification, destroys the regularity of the macromolecular chain, thereby reducing the force between macromolecules and making the PEEK molecular structure more flexible. At the same time, due to the introduction of flexible groups, the copolymer transitions from partially crystalline to amorphous polymers. Since this modification reduces the crystallization ability of PEEK and enlarges the amorphous region, it can be used to prepare high shrinkage materials with the highest thermal shrinkage. The ratio can be as high as 2:1.
由于共聚物依然保有一定的结晶度，利用结晶分子的支撑作用，使材料能够保持良好的收缩性能。PEEK基热收缩材料具有良好的耐腐蚀、耐辐照、耐摩擦性能，可以方便、灵活的设计制备成热收缩管、膜等，在电子电气元件高温绝缘、核工业辐射屏蔽、石油化工高温防腐等领域具有广泛的应用前景。Since the copolymer still retains a certain degree of crystallinity, the material can maintain good shrinkage performance by using the support of crystalline molecules. PEEK-based heat shrinkable materials have good corrosion resistance, radiation resistance and friction resistance, and can be conveniently and flexibly designed and prepared into heat shrinkable tubes, films, etc. It has broad application prospects in other fields.
具体实施方式Detailed ways
本发明提供了一种聚芳醚酮热收缩材料及其制备方法，本领域技术人员可以借鉴本文内容，适当改进工艺参数实现。特别需要指出的是，所有类似的替换和改动对本领域技术人员来说是显而易见的，它们都属于本发明保护的范围。本发明的方法及应用已经通过较佳实施例进行了描述，相关人员明显能在不脱离本发明内容、精神和范围内对本文的方法和应用进行改动或适当变更与组合，来实现和应用本发明技术。The present invention provides a polyarylene ether ketone heat shrinkable material and a preparation method thereof, which can be achieved by those skilled in the art by appropriately improving the process parameters for reference. It should be particularly pointed out that all similar replacements and modifications are obvious to those skilled in the art, and they all belong to the protection scope of the present invention. The method and application of the present invention have been described through the preferred embodiments, and it is obvious that relevant persons can make changes or appropriate changes and combinations of the methods and applications herein without departing from the content, spirit and scope of the present invention, so as to realize and apply the present invention. Invention technology.
本发明提供了一种聚芳醚酮热收缩材料的制备方法，包括如下步骤：The invention provides a preparation method of a polyaryletherketone heat shrinkable material, comprising the following steps:
A)在惰性气体的存在下，4,4'-二氟二苯甲酮、对苯二酚、与溶剂和催化剂混合，反应，再加入含柔性基团的二酚单体，继续反应，得到改性聚醚醚酮树脂；A) In the presence of inert gas, 4,4'-difluorobenzophenone and hydroquinone are mixed with a solvent and a catalyst to react, and then a diphenol monomer containing a flexible group is added to continue the reaction to obtain Modified polyetheretherketone resin;
B)将改性聚醚醚酮树脂挤出，得到聚芳醚酮热收缩材料。B) Extruding the modified polyetheretherketone resin to obtain a polyaryletherketone heat shrinkable material.
本发明提供的含柔性基团的聚芳醚酮基热收缩材料，能够实现高收缩率，同时具有出色的耐高温、耐溶剂、阻燃、耐摩擦以及耐辐照。The flexible group-containing polyaryletherketone-based heat-shrinkable material provided by the present invention can achieve high shrinkage rate, and at the same time has excellent high temperature resistance, solvent resistance, flame retardancy, friction resistance and radiation resistance.
本发明提供了一种聚芳醚酮热收缩材料，通过4,4'-二氟二苯甲酮、对苯二酚与含柔性基团的二酚单体进行共聚，随后进行多组分共混、挤出成型和扩张定型等工序，制备了高收缩率聚芳醚酮热收缩材料。The invention provides a polyaryletherketone heat-shrinkable material, which is copolymerized by 4,4'-difluorobenzophenone, hydroquinone and a diphenol monomer containing a flexible group, followed by multi-component copolymerization. The heat-shrinkable material of polyaryletherketone with high shrinkage rate was prepared by mixing, extrusion molding and expansion and shaping.
本发明提供的一种聚芳醚酮热收缩材料的制备方法首先将在惰性气体的存在下，4,4'-二氟二苯甲酮、对苯二酚、与溶剂和催化剂混合，反应。The preparation method of a polyaryletherketone heat shrinkable material provided by the present invention firstly mixes 4,4'-difluorobenzophenone, hydroquinone, a solvent and a catalyst in the presence of an inert gas, and reacts.
优选具体为：Preferred are:
在装有机械搅拌、温度计和通惰性气体的三颈瓶中加入4,4'-二氟二苯甲酮和对苯二酚，随后加入溶剂和催化剂，混合，反应。Add 4,4'-difluorobenzophenone and hydroquinone to a three-necked flask equipped with mechanical stirring, thermometer and inert gas, then add solvent and catalyst, mix and react.
本发明所述催化剂为碱金属碳酸盐；所述碱金属碳酸盐为碳酸钠和/或碳酸钾；The catalyst of the present invention is an alkali metal carbonate; the alkali metal carbonate is sodium carbonate and/or potassium carbonate;
所述溶剂为环丁砜和/或二甲基亚砜；The solvent is sulfolane and/or dimethyl sulfoxide;
所述惰性气体包括但不限于氮气、氦气或氩气。The inert gas includes, but is not limited to, nitrogen, helium, or argon.
本发明所述反应具体为：在170℃～190℃成盐反应0.5～1h，而后程序升温反应；所述程序升温反应具体为：210～230℃反应1h，升温至240～260℃反应1h，升温至280～300℃反应1h。The reaction described in the present invention is specifically: a salt-forming reaction at 170-190°C for 0.5-1h, and then a temperature-programmed reaction; the temperature-programmed reaction is specifically: 210-230°C for 1h, and the temperature is raised to 240-260°C for 1h, The temperature was raised to 280-300 °C for 1 h.
上述反应后再加入含柔性基团的二酚单体，继续反应，得到改性聚醚醚酮树脂。After the above reaction, a diphenol monomer containing a flexible group is added, and the reaction is continued to obtain a modified polyether ether ketone resin.
本发明继续反应具体为：280～300℃反应1～2hr后，升高温度至280～320℃反应3～6hr；The continuation reaction of the present invention is specifically as follows: after 1-2 hours of reaction at 280-300° C., the temperature is raised to 280-320° C. for 3-6 hours of reaction;
本发明所述继续反应后还包括洗涤、干燥。The continuous reaction in the present invention also includes washing and drying.
优选具体为：冷水中出料。粗产品经粉碎机粉碎，分别用丙酮和蒸馏水洗涤8～10次，以除去无机盐和有机溶剂，最后产物干燥，得到白色聚合物粉末样品。本发明所述干燥具体为：120～150℃干燥10～20h。Preferably, it is specifically: discharging in cold water. The crude product is pulverized by a pulverizer, washed with acetone and distilled water for 8-10 times to remove inorganic salts and organic solvents, and finally the product is dried to obtain a white polymer powder sample. The drying in the present invention is specifically: drying at 120-150° C. for 10-20 hours.
按照本发明，所述含柔性基团的二酚单体选自4,4'-(α-甲基苯亚甲基)双酚、2,2-二(4-羟基苯基)丙烷、4,4'-二羟基四苯甲烷、4,4二羟基二苯基甲烷、2,2-双-(4-羟苯基)六氟丙烷或4,4'-二羟基二苯醚中的一种或几种。According to the present invention, the flexible group-containing diphenol monomer is selected from 4,4'-(α-methylbenzylidene)bisphenol, 2,2-bis(4-hydroxyphenyl)propane, 4,4'-(α-methylbenzylidene)bisphenol, 2,2-bis(4-hydroxyphenyl)propane, One of ,4'-dihydroxytetraphenylmethane, 4,4-dihydroxydiphenylmethane, 2,2-bis-(4-hydroxyphenyl)hexafluoropropane or 4,4'-dihydroxydiphenyl ether species or several.
具体的，所述对苯二酚和含柔性基团的二酚单体摩尔比优选为(0.8～0.9)：(0.1～0.2)；更优选为(0.82～0.88)：(0.12～0.18)；Specifically, the molar ratio of the hydroquinone to the flexible group-containing diphenol monomer is preferably (0.8-0.9):(0.1-0.2); more preferably (0.82-0.88):(0.12-0.18);
所述对苯二酚和含柔性基团的二酚单体的总和与4,4'-二氟二苯甲酮的摩尔比为1:(0.99～1.01)；可以为1:0.99、1：1或1:1.01。The molar ratio of the sum of the hydroquinone and the diphenol monomer containing a flexible group to 4,4'-difluorobenzophenone is 1:(0.99-1.01); it can be 1:0.99, 1: 1 or 1:1.01.
所述对苯二酚、含柔性基团的二酚单体和4,4'-二氟二苯甲酮的总和与溶剂的质量比优选为1:(10～15)；更优选为1:(11～14)。The mass ratio of the sum of the hydroquinone, the diphenol monomer containing a flexible group and 4,4'-difluorobenzophenone to the solvent is preferably 1: (10-15); more preferably 1: (11-14).
所述对苯二酚和含柔性基团的二酚单体的总和与催化剂的摩尔比优选为(2.2～2.5)：1；具体可以为2.2:1、2.3:1、2.4:1或2.5:1。The molar ratio of the sum of the hydroquinone and the diphenol monomer containing a flexible group to the catalyst is preferably (2.2-2.5):1; specifically, it may be 2.2:1, 2.3:1, 2.4:1 or 2.5: 1.
本发明其中一些实施例中，反应式如下：In some embodiments of the present invention, the reaction formula is as follows:
其中，R为如下结构:Among them, R is the following structure:
即为，含柔性基团的二酚单体为4,4'-(α-甲基苯亚甲基)双酚(290.36)，2,2-二(4-羟基苯基)丙烷(228.29)，4,4'-二羟基四苯甲烷(352.43)，4,4二羟基二苯基甲烷(200.24)，2,2-双-(4-羟苯基)六氟丙烷(336.23)，4,4'-二羟基二苯醚(202.21)。That is, the diphenol monomers containing flexible groups are 4,4'-(α-methylbenzylidene)bisphenol (290.36), 2,2-bis(4-hydroxyphenyl)propane (228.29) , 4,4'-dihydroxytetraphenylmethane (352.43), 4,4 dihydroxydiphenylmethane (200.24), 2,2-bis-(4-hydroxyphenyl)hexafluoropropane (336.23), 4, 4'-Dihydroxydiphenyl ether (202.21).
将改性聚醚醚酮树脂挤出，得到聚芳醚酮热收缩材料。The modified polyetheretherketone resin is extruded to obtain a polyaryletherketone heat shrinkable material.
在本发明其中一些优选实施方式中，上述步骤为：将改性聚醚醚酮树脂、耐高温润滑剂、高锰酸钾混合挤出，得到聚芳醚酮热收缩材料。In some of the preferred embodiments of the present invention, the above steps are: mixing and extruding the modified polyetheretherketone resin, a high temperature resistant lubricant, and potassium permanganate to obtain a polyaryletherketone heat shrinkable material.
本发明所述混合速度为35～50r/min，混合时间35～50min；The mixing speed of the present invention is 35-50 r/min, and the mixing time is 35-50 min;
按照本发明，所述改性聚醚醚酮树脂、耐高温润滑剂、高锰酸钾的质量比优选为100：(0～1)：(0～0.00004)；更优选为100：(0.1～1)：(0.00001～0.00004)。According to the present invention, the mass ratio of the modified polyetheretherketone resin, the high temperature resistant lubricant and the potassium permanganate is preferably 100:(0～1):(0～0.00004); more preferably 100:(0.1～ 1): (0.00001 to 0.00004).
本发明所述耐高温润滑剂为液晶聚芳醚酮、纳米二氧化硅。The high temperature resistant lubricant of the present invention is liquid crystal polyaryl ether ketone and nano-silica.
本发明所述挤出优选在挤出机中挤出，优选采用耐高温耐腐蚀塑料挤出机。The extrusion in the present invention is preferably extruded in an extruder, preferably a high-temperature and corrosion-resistant plastic extruder.
所述挤出参数具体为：The extrusion parameters are specifically:
挤出机温度优选为340℃～380℃，更优选为345℃～380℃，挤出速度优选为80～120r/min，更优选为85～110r/min，主喂料速度为8～10r/min；具体可以为8、9或10；或者上述任意二者之间的点值。The temperature of the extruder is preferably 340℃～380℃, more preferably 345℃～380℃, the extrusion speed is preferably 80～120r/min, more preferably 85～110r/min, and the main feeding speed is 8～10r/min min; specifically, it can be 8, 9 or 10; or a point value between any of the above.
挤出后，采用常规切粒工艺进行切粒干燥，最终得到高收缩率聚芳醚酮热收缩专用料。After extrusion, the conventional pelletizing process is used for pelletizing and drying, and finally a special material for heat shrinkage of polyaryletherketone with high shrinkage rate is obtained.
本发明提供了一种聚芳醚酮热收缩材料，由上述技术方案任一项所述的制备方法制备得到。The present invention provides a polyaryletherketone heat shrinkable material, which is prepared by the preparation method described in any one of the above technical solutions.
本发明提供了一种聚芳醚酮热收缩制品，由上述技术方案所述的聚芳醚酮热收缩材料制备得到。The present invention provides a polyaryletherketone heat-shrinkable product, which is prepared from the polyaryletherketone heat-shrinkable material described in the above technical solution.
本发明所述聚芳醚酮热收缩制品包括但不限于聚芳醚酮热收缩异形件、聚芳醚酮热收缩膜、聚芳醚酮热收缩管。The polyaryletherketone heat-shrinkable products of the present invention include, but are not limited to, polyaryletherketone heat-shrinkable shaped parts, polyaryletherketone heat-shrinkable films, and polyaryletherketone heat-shrinkable tubes.
本发明提供了一种聚芳醚酮热收缩管，由上述技术方案所述的聚芳醚酮热收缩材料制备得到。The present invention provides a polyaryletherketone heat-shrinkable tube, which is prepared from the polyaryletherketone heat-shrinkable material described in the above technical solution.
本发明提供了一种聚芳醚酮热收缩基管的制备方法，包括：The invention provides a preparation method of a polyaryletherketone heat-shrinkable base tube, comprising:
将上述技术方案所述的聚芳醚酮热收缩材料挤出，经过口模、芯棒、冷却定型得到；所述挤出参数为：The polyaryl ether ketone heat shrinkable material described in the above technical solution is extruded, and obtained through a die, a mandrel, and cooling and shaping; the extrusion parameters are:
挤出机温度为340℃～380℃，更优选为345℃～380℃，挤出速度为30～60r/min，更优选为35～55r/min，主喂料速度为4～8r/min。The extruder temperature is 340℃～380℃, more preferably 345℃～380℃, the extrusion speed is 30～60r/min, more preferably 35～55r/min, and the main feeding speed is 4～8r/min.
将上述获得的基管在280～310℃加热，并通过抽真空或通入压缩气体的方法使基管扩张，扩张倍率在1.6～2倍并冷却定型，得到所需高收缩率聚芳醚酮热收缩材料。The base tube obtained above is heated at 280-310°C, and the base tube is expanded by vacuuming or feeding compressed gas, the expansion ratio is 1.6-2 times, and cooling and shaping to obtain the desired high shrinkage rate polyaryletherketone Heat shrinkable material.
本发明提供了一种聚芳醚酮热收缩材料的制备方法，包括如下步骤：A)在惰性气体的存在下，4,4'-二氟二苯甲酮、对苯二酚、与溶剂和催化剂混合，反应，再加入含柔性基团的二酚单体，继续反应，得到改性聚醚醚酮树脂；B)将改性聚醚醚酮树脂挤出，得到聚芳醚酮热收缩材料。本发明创造性的通过共聚改性改变PEEK对称的紧密结构，破坏大分子链的规整性，从而降低大分子间的作用力，使PEEK分子结构变得比较柔顺。同时，由于柔性基团的引入，共聚物由部分结晶向非结晶聚合物过渡，由于这种改性使PEEK的结晶能力下降，无定形区变大，故可用于制备高收缩材料。同时利用高锰酸钾的高温氧化交联特性赋予聚芳醚酮热收缩材料的高回复率，本发明所制得的聚芳醚酮热收缩材料最高收缩比可高达2:1，并保持最高91.8％的回复率。The invention provides a preparation method of a polyaryletherketone heat-shrinkable material, comprising the following steps: A) in the presence of an inert gas, 4,4'-difluorobenzophenone, hydroquinone, and a solvent and The catalyst is mixed and reacted, and then the diphenol monomer containing a flexible group is added, and the reaction is continued to obtain a modified polyetheretherketone resin; B) Extruding the modified polyetheretherketone resin to obtain a polyaryletherketone heat shrinkable material . The invention creatively changes the symmetrical tight structure of PEEK through copolymerization modification, destroys the regularity of the macromolecular chain, thereby reducing the force between macromolecules and making the PEEK molecular structure more flexible. At the same time, due to the introduction of flexible groups, the copolymer transitions from partially crystalline to amorphous polymers. Since this modification reduces the crystallization ability of PEEK and enlarges the amorphous region, it can be used to prepare high shrinkage materials. At the same time, the high-temperature oxidative cross-linking properties of potassium permanganate are used to endow the polyaryletherketone heat-shrinkable material with a high recovery rate. 91.8% response rate.
由于共聚物依然保有一定的结晶度，利用结晶分子的支撑作用，使材料能够保持良好的收缩性能。PEEK基热收缩材料具有良好的耐腐蚀、耐辐照、耐摩擦性能，可以方便、灵活的设计制备成热收缩管、膜等，在元件高温绝缘、辐射防护、石油化工高温防腐等领域具有广泛的应用前景。Since the copolymer still retains a certain degree of crystallinity, the material can maintain good shrinkage performance by using the support of crystalline molecules. PEEK-based heat shrinkable materials have good corrosion resistance, radiation resistance and friction resistance, and can be conveniently and flexibly designed and prepared into heat shrinkable tubes, films, etc. application prospects.
为了进一步说明本发明，以下结合实施例对本发明提供的一种聚芳醚酮热收缩材料及其制备方法进行详细描述。In order to further illustrate the present invention, a polyaryl ether ketone heat shrinkable material provided by the present invention and its preparation method are described in detail below with reference to the examples.
实施例1Example 1
(1)改性聚醚醚酮树脂合成：(1) Synthesis of modified polyether ether ketone resin:
在装有机械搅拌、温度计和通氮气的三颈瓶中加入21.602g的4,4'-二氟二苯甲酮和9.910g对苯二酚，随后加入335.34g的环丁砜和23.318g的碳酸钠，搅拌升温，在170℃成盐0.5h，升温至210℃、240℃和280℃各反应1h后，加入2.022g的4,4'-二羟基二苯醚(202.21)，继续反应1h后，升高温度至280℃反应3h，冷水中出料。粗产品经粉碎机粉碎，分别用丙酮和蒸馏水洗涤8次，以除去无机盐和有机溶剂，最后产物在120℃干燥10h，得到白色聚合物粉末样品。21.602g of 4,4'-difluorobenzophenone and 9.910g of hydroquinone were added to a three-necked flask equipped with mechanical stirring, a thermometer and a nitrogen purge, followed by 335.34g of sulfolane and 23.318g of sodium carbonate , stir and heat up, form a salt at 170°C for 0.5h, heat up to 210°C, 240°C and 280°C for each reaction for 1h, add 2.022g of 4,4'-dihydroxydiphenyl ether (202.21), continue to react for 1h, The temperature was raised to 280°C for 3 hours, and the material was discharged in cold water. The crude product was pulverized by a pulverizer, washed with acetone and distilled water for 8 times to remove inorganic salts and organic solvents, and the final product was dried at 120 °C for 10 h to obtain a white polymer powder sample.
(2)高收缩率聚芳醚酮热收缩专用料制备：(2) Preparation of high shrinkage polyaryletherketone heat shrinkable special material:
将烘干的改性聚醚醚酮树脂100份、液晶聚芳醚酮1份、高锰酸钾0.00004份，在高混机中均匀混合。混合速度为35r/min，混合时间35min。将混合后的原料加入到耐高温耐腐蚀塑料挤出机的料筒中。挤出机温度范围在380℃，挤出速度控制在80r/min，主喂料速度控制在8r/min。采用常规切粒工艺进行切粒干燥，最终得到高收缩率聚芳醚酮热收缩专用料。100 parts of the dried modified polyetheretherketone resin, 1 part of liquid crystal polyaryletherketone, and 0.00004 part of potassium permanganate were uniformly mixed in a high mixer. The mixing speed is 35r/min, and the mixing time is 35min. The mixed raw materials are added to the barrel of the high temperature and corrosion resistant plastic extruder. The temperature range of the extruder is 380°C, the extrusion speed is controlled at 80r/min, and the main feeding speed is controlled at 8r/min. The conventional pelletizing process is used for pelletizing and drying, and finally a special material for heat shrinkage of polyaryletherketone with high shrinkage rate is obtained.
(3)高收缩率聚芳醚酮热收缩材料制备：(3) Preparation of high shrinkage polyaryletherketone heat shrinkable material:
把高收缩率聚芳醚酮热收缩专用料使用耐高温耐腐蚀塑料挤出机，挤出机温度范围在380℃，挤出速度控制在30r/min，主喂料速度控制在4r/min。经过特定口模、芯棒、冷却定型等辅机挤成基管待用。Use a high-temperature and corrosion-resistant plastic extruder for the high-shrinkage polyaryletherketone heat-shrinkable special material. The extruder temperature range is 380°C, the extrusion speed is controlled at 30r/min, and the main feeding speed is controlled at 4r/min. It is extruded into a base tube after a specific die, mandrel, cooling and shaping and other auxiliary machines for use.
将上述获得的基管在310℃加热，并通过抽真空或通入压缩气体的方法使基管扩张，扩张倍率在1.6倍并冷却定型，得到所需高收缩率聚芳醚酮热收缩材料。The base tube obtained above is heated at 310°C, and the base tube is expanded by vacuuming or passing in compressed gas, the expansion ratio is 1.6 times, and cooling is set to obtain the desired high shrinkage rate polyarylene ether ketone heat shrinkable material.
实施例2Example 2
(1)改性聚醚醚酮树脂合成：(1) Synthesis of modified polyether ether ketone resin:
在装有机械搅拌、温度计和通氮气的三颈瓶中加入22.038g的4,4'-二氟二苯甲酮和8.809g的对苯二酚，随后加入980.955g的二甲基亚砜和34.55g的碳酸钾，搅拌升温，在190℃成盐1h，升温至230℃、260℃和300℃各反应1h后，加入4.044g的4,4'-二羟基二苯醚(202.21)，继续反应2h后，升高温度至320℃反应6h，冷水中出料。粗产品经粉碎机粉碎，分别用丙酮和蒸馏水洗涤10次，以除去无机盐和有机溶剂，最后产物在150℃干燥20h，得到白色聚合物粉末样品。22.038g of 4,4'-difluorobenzophenone and 8.809g of hydroquinone were added to a three-necked flask equipped with mechanical stirring, a thermometer and a nitrogen purge, followed by 980.955g of dimethyl sulfoxide and 34.55g of potassium carbonate was stirred and heated up, formed into a salt at 190°C for 1h, heated to 230°C, 260°C and 300°C for each reaction for 1h, then added 4.044g of 4,4'-dihydroxydiphenyl ether (202.21), and continued After 2 hours of reaction, the temperature was raised to 320°C for 6 hours, and the material was discharged in cold water. The crude product was pulverized by a pulverizer, washed 10 times with acetone and distilled water, respectively, to remove inorganic salts and organic solvents, and the final product was dried at 150 °C for 20 h to obtain a white polymer powder sample.
(2)高收缩率聚芳醚酮热收缩专用料制备：(2) Preparation of high shrinkage polyaryletherketone heat shrinkable special material:
将烘干的改性聚醚醚酮树脂100份，在高混机中均匀混合。混合速度为50r/min，混合时间50min。将混合后的原料加入到耐高温耐腐蚀塑料挤出机的料筒中。挤出机温度范围在340℃℃，挤出速度控制在120r/min，主喂料速度控制在10r/min。采用常规切粒工艺进行切粒干燥，最终得到高收缩率聚芳醚酮热收缩专用料。Mix 100 parts of the dried modified polyether ether ketone resin uniformly in a high mixer. The mixing speed is 50r/min, and the mixing time is 50min. The mixed raw materials are added to the barrel of the high temperature and corrosion resistant plastic extruder. The extruder temperature range is 340°C, the extrusion speed is controlled at 120r/min, and the main feeding speed is controlled at 10r/min. The conventional pelletizing process is used for pelletizing and drying, and finally a special material for heat shrinkage of polyaryletherketone with high shrinkage rate is obtained.
(3)高收缩率聚芳醚酮热收缩材料制备：(3) Preparation of high shrinkage polyaryletherketone heat shrinkable material:
把高收缩率聚芳醚酮热收缩专用料使用耐高温耐腐蚀塑料挤出机，挤出机温度范围在340℃，挤出速度控制在60r/min，主喂料速度控制在8r/min。经过特定口模、芯棒、冷却定型等辅机挤成基管待用。Use a high-temperature and corrosion-resistant plastic extruder for the high-shrinkage polyaryletherketone heat-shrinkable special material. The temperature range of the extruder is 340°C, the extrusion speed is controlled at 60r/min, and the main feeding speed is controlled at 8r/min. It is extruded into a base tube after a specific die, mandrel, cooling and shaping and other auxiliary machines for use.
将上述获得的基管在280℃加热，并通过抽真空或通入压缩气体的方法使基管扩张，扩张倍率在2倍并冷却定型，得到所需高收缩率聚芳醚酮热收缩材料。The base tube obtained above is heated at 280°C, and the base tube is expanded by means of vacuuming or passing compressed gas, the expansion ratio is 2 times, and cooling is set to obtain the desired high shrinkage rate polyarylene ether ketone heat shrinkable material.
实施例3Example 3
(1)改性聚醚醚酮树脂合成：(1) Synthesis of modified polyether ether ketone resin:
在装有机械搅拌、温度计和通氮气的三颈瓶中加入21.602g的4,4'-二氟二苯甲酮和9.910g对苯二酚，随后加入335.34g的环丁砜和23.318g的碳酸钠，搅拌升温，在170℃成盐0.5h，升温至210℃、240℃和280℃各反应1h后，加入2.002g的4,4二羟基二苯基甲烷(200.24)，继续反应1h后，升高温度至280℃反应3-6h，冷水中出料。粗产品经粉碎机粉碎，分别用丙酮和蒸馏水洗涤8次，以除去无机盐和有机溶剂，最后产物在120℃干燥10h，得到白色聚合物粉末样品。21.602g of 4,4'-difluorobenzophenone and 9.910g of hydroquinone were added to a three-necked flask equipped with mechanical stirring, a thermometer and a nitrogen purge, followed by 335.34g of sulfolane and 23.318g of sodium carbonate , stir and heat up, form a salt at 170°C for 0.5h, heat up to 210°C, 240°C and 280°C for each reaction for 1h, add 2.002g of 4,4-dihydroxydiphenylmethane (200.24), continue to react for 1h, liter Reaction at high temperature to 280°C for 3-6h, and discharging in cold water. The crude product was pulverized by a pulverizer, washed with acetone and distilled water for 8 times to remove inorganic salts and organic solvents, and the final product was dried at 120 °C for 10 h to obtain a white polymer powder sample.
(2)高收缩率聚芳醚酮热收缩专用料制备：(2) Preparation of high shrinkage polyaryletherketone heat shrinkable special material:
将烘干的改性聚醚醚酮树脂100份、纳米二氧化硅1份、高锰酸钾0.00004份，在高混机中均匀混合。混合速度为35r/min，混合时间35min。将混合后的原料加入到耐高温耐腐蚀塑料挤出机的料筒中。挤出机温度范围在380℃，挤出速度控制在80r/min，主喂料速度控制在8r/min。采用常规切粒工艺进行切粒干燥，最终得到高收缩率聚芳醚酮热收缩专用料。Mix 100 parts of the dried modified polyether ether ketone resin, 1 part of nano-silica, and 0.00004 parts of potassium permanganate in a high-speed mixer. The mixing speed was 35r/min, and the mixing time was 35min. The mixed raw materials are added to the barrel of the high temperature and corrosion resistant plastic extruder. The temperature range of the extruder is 380°C, the extrusion speed is controlled at 80r/min, and the main feeding speed is controlled at 8r/min. The conventional pelletizing process is used for pelletizing and drying, and finally a special material for heat shrinkage of polyaryletherketone with high shrinkage rate is obtained.
(3)高收缩率聚芳醚酮热收缩材料制备：(3) Preparation of high shrinkage polyaryletherketone heat shrinkable material:
把高收缩率聚芳醚酮热收缩专用料使用耐高温耐腐蚀塑料挤出机，挤出机温度范围在380℃，挤出速度控制在30r/min，主喂料速度控制在4r/min。经过特定口模、芯棒、冷却定型等辅机挤成基管待用。Use a high-temperature and corrosion-resistant plastic extruder for the high-shrinkage polyaryletherketone heat-shrinkable special material. The extruder temperature range is 380°C, the extrusion speed is controlled at 30r/min, and the main feeding speed is controlled at 4r/min. It is extruded into a base tube after a specific die, mandrel, cooling and shaping and other auxiliary machines for use.
将上述获得的基管在310℃加热，并通过抽真空或通入压缩气体的方法使基管扩张，扩张倍率在1.8倍并冷却定型，得到所需高收缩率聚芳醚酮热收缩材料。The base tube obtained above was heated at 310°C, and the base tube was expanded by vacuuming or feeding compressed gas, the expansion ratio was 1.8 times, and cooling to shape, to obtain the desired high shrinkage polyaryletherketone heat shrinkable material.
(3)高收缩率聚芳醚酮热收缩材料制备：(3) Preparation of high shrinkage polyaryletherketone heat shrinkable material:
把高收缩率聚芳醚酮热收缩专用料使用耐高温耐腐蚀塑料挤出机，挤出机温度范围在340℃～380℃，挤出速度控制在30-60r/min，主喂料速度控制在4-8r/min。经过特定口模、芯棒、冷却定型等辅机挤成基管待用。Use high-temperature and corrosion-resistant plastic extruder for high-shrinkage polyaryletherketone heat-shrinkable special material. At 4-8r/min. It is extruded into a base tube after a specific die, mandrel, cooling and shaping and other auxiliary machines for use.
将上述获得的基管在280～310℃加热，并通过抽真空或通入压缩气体的方法使基管扩张，扩张倍率在1.6～2倍并冷却定型，得到所需高收缩率聚芳醚酮热收缩材料。The base tube obtained above is heated at 280-310°C, and the base tube is expanded by vacuuming or feeding compressed gas, the expansion ratio is 1.6-2 times, and cooling and shaping to obtain the desired high shrinkage rate polyaryletherketone Heat shrinkable material.
实施例4Example 4
(1)改性聚醚醚酮树脂合成：(1) Synthesis of modified polyether ether ketone resin:
在装有机械搅拌、温度计和通氮气的三颈瓶中加入21.602g的4,4'-二氟二苯甲酮和9.910g对苯二酚，随后加入335.34g的环丁砜和23.318g的碳酸钠，搅拌升温，在170℃成盐0.5h，升温至210℃、240℃和280℃各反应1h后，加入2.283g的2,2-二(4-羟基苯基)丙烷(228.29)，继续反应1h后，升高温度至280℃反应3h，冷水中出料。粗产品经粉碎机粉碎，分别用丙酮和蒸馏水洗涤8次，以除去无机盐和有机溶剂，最后产物在120℃干燥10h，得到白色聚合物粉末样品。21.602g of 4,4'-difluorobenzophenone and 9.910g of hydroquinone were added to a three-necked flask equipped with mechanical stirring, a thermometer and a nitrogen purge, followed by 335.34g of sulfolane and 23.318g of sodium carbonate , stirred and heated up, formed a salt at 170°C for 0.5h, heated to 210°C, 240°C and 280°C for each reaction for 1h, then added 2.283g of 2,2-bis(4-hydroxyphenyl)propane (228.29) to continue the reaction After 1 hour, the temperature was raised to 280°C for 3 hours, and the material was discharged in cold water. The crude product was pulverized by a pulverizer, washed with acetone and distilled water for 8 times to remove inorganic salts and organic solvents, and the final product was dried at 120 °C for 10 h to obtain a white polymer powder sample.
(2)高收缩率聚芳醚酮热收缩专用料制备：(2) Preparation of high shrinkage polyaryletherketone heat shrinkable special material:
将烘干的改性聚醚醚酮树脂100份、液晶聚芳醚酮1份、高锰酸钾0.00004份，在高混机中均匀混合。混合速度为35r/min，混合时间35min。将混合后的原料加入到耐高温耐腐蚀塑料挤出机的料筒中。挤出机温度范围在380℃，挤出速度控制在80r/min，主喂料速度控制在8r/min。采用常规切粒工艺进行切粒干燥，最终得到高收缩率聚芳醚酮热收缩专用料。100 parts of the dried modified polyetheretherketone resin, 1 part of liquid crystal polyaryletherketone, and 0.00004 part of potassium permanganate were uniformly mixed in a high mixer. The mixing speed was 35r/min, and the mixing time was 35min. The mixed raw materials are added to the barrel of the high temperature and corrosion resistant plastic extruder. The temperature range of the extruder is 380°C, the extrusion speed is controlled at 80r/min, and the main feeding speed is controlled at 8r/min. The conventional pelletizing process is used for pelletizing and drying, and finally a special material for heat shrinkage of polyaryletherketone with high shrinkage rate is obtained.
(3)高收缩率聚芳醚酮热收缩材料制备：(3) Preparation of high shrinkage polyaryletherketone heat shrinkable material:
把高收缩率聚芳醚酮热收缩专用料使用耐高温耐腐蚀塑料挤出机，挤出机温度范围在380℃，挤出速度控制在30r/min，主喂料速度控制在4r/min。经过特定口模、芯棒、冷却定型等辅机挤成基管待用。Use a high-temperature and corrosion-resistant plastic extruder for the high-shrinkage polyaryletherketone heat-shrinkable special material. The extruder temperature range is 380°C, the extrusion speed is controlled at 30r/min, and the main feeding speed is controlled at 4r/min. It is extruded into a base tube after a specific die, mandrel, cooling and shaping and other auxiliary machines for use.
将上述获得的基管在310℃加热，并通过抽真空或通入压缩气体的方法使基管扩张，扩张倍率在1.8倍并冷却定型，得到所需高收缩率聚芳醚酮热收缩材料。The base tube obtained above was heated at 310°C, and the base tube was expanded by vacuuming or feeding compressed gas, the expansion ratio was 1.8 times, and cooling to shape, to obtain the desired high shrinkage polyaryletherketone heat shrinkable material.
实施例5Example 5
(1)改性聚醚醚酮树脂合成：(1) Synthesis of modified polyether ether ketone resin:
在装有机械搅拌、温度计和通氮气的三颈瓶中加入21.602g的4,4'-二氟二苯甲酮和8.809g的对苯二酚，随后加入335.34g的环丁砜和23.318g的碳酸钠，搅拌升温，在170℃成盐0.5h，升温至210℃、240℃和280℃各反应1h后，加入6.725g的2,2-双-(4-羟苯基)六氟丙烷(336.23)，继续反应1h后，升高温度至280℃反应3h，冷水中出料。粗产品经粉碎机粉碎，分别用丙酮和蒸馏水洗涤8次，以除去无机盐和有机溶剂，最后产物在120℃干燥10h，得到白色聚合物粉末样品。21.602g of 4,4'-difluorobenzophenone and 8.809g of hydroquinone were added to a three-necked flask equipped with mechanical stirring, a thermometer and a nitrogen purge, followed by 335.34g of sulfolane and 23.318g of carbonic acid. Sodium, stirred and heated up, formed into a salt at 170°C for 0.5h, heated to 210°C, 240°C and 280°C for each reaction for 1h, then added 6.725g of 2,2-bis-(4-hydroxyphenyl)hexafluoropropane (336.23 g ), after continuing the reaction for 1 h, the temperature was raised to 280 °C for 3 h, and the material was discharged in cold water. The crude product was pulverized by a pulverizer, washed with acetone and distilled water for 8 times to remove inorganic salts and organic solvents, and the final product was dried at 120 °C for 10 h to obtain a white polymer powder sample.
(2)高收缩率聚芳醚酮热收缩专用料制备：(2) Preparation of high shrinkage polyaryletherketone heat shrinkable special material:
将烘干的改性聚醚醚酮树脂100份、纳米二氧化硅1份、高锰酸钾0.00004份，在高混机中均匀混合。混合速度为35r/min，混合时间35min。将混合后的原料加入到耐高温耐腐蚀塑料挤出机的料筒中。挤出机温度范围在380℃，挤出速度控制在80r/min，主喂料速度控制在8r/min。采用常规切粒工艺进行切粒干燥，最终得到高收缩率聚芳醚酮热收缩专用料。Mix 100 parts of the dried modified polyether ether ketone resin, 1 part of nano-silica, and 0.00004 parts of potassium permanganate in a high-speed mixer. The mixing speed was 35r/min, and the mixing time was 35min. The mixed raw materials are added to the barrel of the high temperature and corrosion resistant plastic extruder. The temperature range of the extruder is 380°C, the extrusion speed is controlled at 80r/min, and the main feeding speed is controlled at 8r/min. The conventional pelletizing process is used for pelletizing and drying, and finally a special material for heat shrinkage of polyaryletherketone with high shrinkage rate is obtained.
(3)高收缩率聚芳醚酮热收缩材料制备：(3) Preparation of high shrinkage polyaryletherketone heat shrinkable material:
把高收缩率聚芳醚酮热收缩专用料使用耐高温耐腐蚀塑料挤出机，挤出机温度范围在380℃，挤出速度控制在30r/min，主喂料速度控制在4r/min。经过特定口模、芯棒、冷却定型等辅机挤成基管待用。Use a high-temperature and corrosion-resistant plastic extruder for the high-shrinkage polyaryletherketone heat-shrinkable special material. The extruder temperature range is 380°C, the extrusion speed is controlled at 30r/min, and the main feeding speed is controlled at 4r/min. It is extruded into a base tube after a specific die, mandrel, cooling and shaping and other auxiliary machines for use.
将上述获得的基管在310℃加热，并通过抽真空或通入压缩气体的方法使基管扩张，扩张倍率在2倍并冷却定型，得到所需高收缩率聚芳醚酮热收缩材料。The base tube obtained above is heated at 310°C, and the base tube is expanded by means of vacuuming or passing compressed gas, the expansion ratio is 2 times, and cooling is set to obtain the desired high shrinkage rate polyaryletherketone heat shrinkable material.
实施例6Example 6
(1)改性聚醚醚酮树脂合成：(1) Synthesis of modified polyether ether ketone resin:
在装有机械搅拌、温度计和通氮气的三颈瓶中加入21.602g的4,4'-二氟二苯甲酮和8.809g的对苯二酚，随后加入335.34g的环丁砜和23.318g的碳酸钠，搅拌升温，在170℃成盐0.5h，升温至210℃、240℃和280℃各反应1h后，加入5.807g的4,4'-(α-甲基苯亚甲基)双酚(290.36)，继续反应1h后，升高温度至280℃反应3h，冷水中出料。粗产品经粉碎机粉碎，分别用丙酮和蒸馏水洗涤8次，以除去无机盐和有机溶剂，最后产物在120℃干燥10h，得到白色聚合物粉末样品。21.602g of 4,4'-difluorobenzophenone and 8.809g of hydroquinone were added to a three-necked flask equipped with mechanical stirring, a thermometer and a nitrogen purge, followed by 335.34g of sulfolane and 23.318g of carbonic acid. Sodium, stirred and heated up, formed into a salt at 170°C for 0.5h, heated to 210°C, 240°C and 280°C for each reaction for 1h, then added 5.807g of 4,4'-(α-methylbenzylidene)bisphenol ( 290.36), after continuing the reaction for 1 hour, the temperature was raised to 280°C for 3 hours, and the material was discharged in cold water. The crude product was pulverized by a pulverizer, washed with acetone and distilled water for 8 times to remove inorganic salts and organic solvents, and the final product was dried at 120 °C for 10 h to obtain a white polymer powder sample.
(2)高收缩率聚芳醚酮热收缩专用料制备：(2) Preparation of high shrinkage polyaryletherketone heat shrinkable special material:
将烘干的改性聚醚醚酮树脂100份、液晶聚芳醚酮1份、高锰酸钾0.00004份，在高混机中均匀混合。混合速度为35r/min，混合时间35min。将混合后的原料加入到耐高温耐腐蚀塑料挤出机的料筒中。挤出机温度范围在380℃，挤出速度控制在80r/min，主喂料速度控制在8r/min。采用常规切粒工艺进行切粒干燥，最终得到高收缩率聚芳醚酮热收缩专用料。100 parts of the dried modified polyetheretherketone resin, 1 part of liquid crystal polyaryletherketone, and 0.00004 part of potassium permanganate were uniformly mixed in a high mixer. The mixing speed was 35r/min, and the mixing time was 35min. The mixed raw materials are added to the barrel of the high temperature and corrosion resistant plastic extruder. The temperature range of the extruder is 380°C, the extrusion speed is controlled at 80r/min, and the main feeding speed is controlled at 8r/min. The conventional pelletizing process is used for pelletizing and drying, and finally a special material for heat shrinkage of polyaryletherketone with high shrinkage rate is obtained.
(3)高收缩率聚芳醚酮热收缩材料制备：(3) Preparation of high shrinkage polyaryletherketone heat shrinkable material:
把高收缩率聚芳醚酮热收缩专用料使用耐高温耐腐蚀塑料挤出机，挤出机温度范围在380℃，挤出速度控制在30r/min，主喂料速度控制在4r/min。经过特定口模、芯棒、冷却定型等辅机挤成基管待用。Use a high-temperature and corrosion-resistant plastic extruder for the high-shrinkage polyaryletherketone heat-shrinkable special material. The extruder temperature range is 380°C, the extrusion speed is controlled at 30r/min, and the main feeding speed is controlled at 4r/min. It is extruded into a base tube after a specific die, mandrel, cooling and shaping and other auxiliary machines for use.
将上述获得的基管在310℃加热，并通过抽真空或通入压缩气体的方法使基管扩张，扩张倍率在2倍并冷却定型，得到所需高收缩率聚芳醚酮热收缩材料。The base tube obtained above is heated at 310°C, and the base tube is expanded by means of vacuuming or passing compressed gas, the expansion ratio is 2 times, and cooling is set to obtain the desired high shrinkage rate polyaryletherketone heat shrinkable material.
实施例7Example 7
(1)改性聚醚醚酮树脂合成：(1) Synthesis of modified polyether ether ketone resin:
在装有机械搅拌、温度计和通氮气的三颈瓶中加入21.602g的4,4'-二氟二苯甲酮和8.809g的对苯二酚，随后加入335.34g的环丁砜和23.318g的碳酸钠，搅拌升温，在170℃成盐0.5h，升温至210℃、240℃和280℃各反应1h后，加入7.049g的4,4'-二羟基四苯甲烷(352.43)，继续反应1h后，升高温度至280℃反应6h，冷水中出料。粗产品经粉碎机粉碎，分别用丙酮和蒸馏水洗涤8次，以除去无机盐和有机溶剂，最后产物在120℃干燥10h，得到白色聚合物粉末样品。21.602g of 4,4'-difluorobenzophenone and 8.809g of hydroquinone were added to a three-necked flask equipped with mechanical stirring, a thermometer and a nitrogen purge, followed by 335.34g of sulfolane and 23.318g of carbonic acid. Sodium, stir and heat up, form salt at 170°C for 0.5h, heat up to 210°C, 240°C and 280°C for each reaction for 1h, add 7.049g of 4,4'-dihydroxytetraphenylmethane (352.43), continue to react for 1h , raise the temperature to 280 ℃ and react for 6h, and discharge in cold water. The crude product was pulverized by a pulverizer, washed with acetone and distilled water for 8 times to remove inorganic salts and organic solvents, and the final product was dried at 120 °C for 10 h to obtain a white polymer powder sample.
(2)高收缩率聚芳醚酮热收缩专用料制备：(2) Preparation of high shrinkage polyaryletherketone heat shrinkable special material:
将烘干的改性聚醚醚酮树脂100份、纳米二氧化硅1份、高锰酸钾0.00004份，在高混机中均匀混合。混合速度为35r/min，混合时间35min。将混合后的原料加入到耐高温耐腐蚀塑料挤出机的料筒中。挤出机温度范围在380℃，挤出速度控制在80r/min，主喂料速度控制在8r/min。采用常规切粒工艺进行切粒干燥，最终得到高收缩率聚芳醚酮热收缩专用料。Mix 100 parts of the dried modified polyether ether ketone resin, 1 part of nano-silica, and 0.00004 parts of potassium permanganate in a high-speed mixer. The mixing speed is 35r/min, and the mixing time is 35min. The mixed raw materials are added to the barrel of the high temperature and corrosion resistant plastic extruder. The temperature range of the extruder is 380°C, the extrusion speed is controlled at 80r/min, and the main feeding speed is controlled at 8r/min. The conventional pelletizing process is used for pelletizing and drying, and finally a special material for heat shrinkage of polyaryletherketone with high shrinkage rate is obtained.
(3)高收缩率聚芳醚酮热收缩材料制备：(3) Preparation of high shrinkage polyaryletherketone heat shrinkable material:
把高收缩率聚芳醚酮热收缩专用料使用耐高温耐腐蚀塑料挤出机，挤出机温度范围在380℃，挤出速度控制在30r/min，主喂料速度控制在4r/min。经过特定口模、芯棒、冷却定型等辅机挤成基管待用。Use a high-temperature and corrosion-resistant plastic extruder for the high-shrinkage polyaryletherketone heat-shrinkable special material. The extruder temperature range is 380°C, the extrusion speed is controlled at 30r/min, and the main feeding speed is controlled at 4r/min. It is extruded into a base tube after a specific die, mandrel, cooling and shaping and other auxiliary machines for use.
将上述获得的基管在310℃加热，并通过抽真空或通入压缩气体的方法使基管扩张，扩张倍率在2倍并冷却定型，得到所需高收缩率聚芳醚酮热收缩材料。The base tube obtained above is heated at 310°C, and the base tube is expanded by means of vacuuming or passing compressed gas, the expansion ratio is 2 times, and cooling is set to obtain the desired high shrinkage rate polyaryletherketone heat shrinkable material.
对比例1Comparative Example 1
(1)聚醚醚酮树脂合成：(1) Synthesis of polyether ether ketone resin:
在装有机械搅拌、温度计和通氮气的三颈瓶中加入21.602g的4,4'-二氟二苯甲酮和11.10g对苯二酚，随后加入335.34g的环丁砜和23.318g的碳酸钠，搅拌升温，在170℃成盐0.5h，升温至210℃、240℃各反应1h后，升高温度至280℃反应4h，冷水中出料。粗产品经粉碎机粉碎，分别用丙酮和蒸馏水洗涤8次，以除去无机盐和有机溶剂，最后产物在120℃干燥10h，得到白色聚合物粉末样品。21.602g of 4,4'-difluorobenzophenone and 11.10g of hydroquinone were added to a three-necked flask equipped with mechanical stirring, a thermometer and a nitrogen purge, followed by 335.34g of sulfolane and 23.318g of sodium carbonate , stir to heat up, form salt at 170°C for 0.5h, heat up to 210°C and 240°C for each reaction for 1h, raise the temperature to 280°C and react for 4h, and discharge in cold water. The crude product was pulverized by a pulverizer, washed with acetone and distilled water for 8 times to remove inorganic salts and organic solvents, and the final product was dried at 120 °C for 10 h to obtain a white polymer powder sample.
(2)聚醚醚酮热收缩专用料制备：(2) Preparation of polyetheretherketone heat shrinkable special material:
将烘干的聚醚醚酮树脂100份，在高混机中均匀混合。混合速度为35r/min，混合时间35min。将混合后的原料加入到耐高温耐腐蚀塑料挤出机的料筒中。挤出机温度范围在380℃，挤出速度控制在80r/min，主喂料速度控制在8r/min。采用常规切粒工艺进行切粒干燥，最终得到聚醚醚酮颗粒。Mix 100 parts of the dried polyether ether ketone resin uniformly in a high mixer. The mixing speed is 35r/min, and the mixing time is 35min. The mixed raw materials are added to the barrel of the high temperature and corrosion resistant plastic extruder. The extruder temperature range is 380°C, the extrusion speed is controlled at 80r/min, and the main feeding speed is controlled at 8r/min. The conventional pelletizing process is used for pelletizing and drying, and finally the polyether ether ketone pellets are obtained.
(3)聚醚醚酮热收缩材料制备：(3) Preparation of polyether ether ketone heat shrinkable material:
把聚醚醚酮热收缩专用料使用耐高温耐腐蚀塑料挤出机，挤出机温度范围在380℃，挤出速度控制在30r/min，主喂料速度控制在4r/min。经过特定口模、芯棒、冷却定型等辅机挤成基管待用。Use a high temperature and corrosion resistant plastic extruder for the heat shrinkable special material of polyether ether ketone. The temperature range of the extruder is 380°C, the extrusion speed is controlled at 30r/min, and the main feeding speed is controlled at 4r/min. It is extruded into a base tube after a specific die, mandrel, cooling and shaping and other auxiliary machines for use.
将上述获得的基管在310℃加热，并通过抽真空或通入压缩气体的方法使基管扩张，扩张倍率在1.4、1.6和2倍并冷却定型，得到对比聚醚醚酮热收缩材料。The base tube obtained above was heated at 310°C, and the base tube was expanded by vacuuming or passing compressed gas, and the expansion ratio was 1.4, 1.6, and 2 times, and cooled to form a comparative polyetheretherketone heat shrinkable material.
表1.高收缩率聚芳醚酮热收缩材料的耐溶剂性能Table 1. Solvent resistance properties of high shrinkage polyaryletherketone heat shrinkable materials
注：将耐400℃等级热收缩材料浸泡在溶剂中168h，观察材料的表面变化情况Note: Immerse the 400℃ heat shrinkable material in the solvent for 168h to observe the surface change of the material
表2.高收缩率聚芳醚酮热收缩材料的性能Table 2. Properties of high shrinkage polyaryletherketone heat shrinkable materials
表3table 3
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above are only the preferred embodiments of the present invention. It should be pointed out that for those skilled in the art, without departing from the principles of the present invention, several improvements and modifications can be made. It should be regarded as the protection scope of the present invention.
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