CN1166719C - Synthetic method of polyether ether ketone copolymer containing 1,5-naphthalene ring - Google Patents
Synthetic method of polyether ether ketone copolymer containing 1,5-naphthalene ring Download PDFInfo
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 17
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 17
- 238000010189 synthetic method Methods 0.000 title 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims abstract description 46
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 39
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 4,4'-difluorodiphenyl ketone Chemical class 0.000 claims abstract description 16
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 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 20
- 239000000178 monomer Substances 0.000 claims description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 18
- 229930185605 Bisphenol Natural products 0.000 claims description 16
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical group OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 9
- 238000001308 synthesis method Methods 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- MYTMXVHNEWBFAL-UHFFFAOYSA-L dipotassium;carbonate;hydrate Chemical compound O.[K+].[K+].[O-]C([O-])=O MYTMXVHNEWBFAL-UHFFFAOYSA-L 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920006029 tetra-polymer Polymers 0.000 description 1
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Abstract
本发明属于含1，5-萘环的聚醚醚酮类共聚物及其合成方法。以4，4′-二氟二苯基酮、1，5-萘二酚、对苯二酚和/或4，4′-二羟基联苯为原料，以无水碳酸钾、无水碳酸钠为催化剂，以二苯砜为溶剂；经历成盐、预聚、聚合的过程得产物。工艺过程包括：将4，4′-二氟二苯基酮和二苯砜混合搅拌、氮气保护、加热催化，再加入对苯二酚和/或4，4′-二羟基联苯，继续加热升温到(240～260)℃反应(0.2～0.5)小时，再加入催化剂以及1，5-萘二酚，最后在(290～320)℃条件下控温(1～5)小时。本发明设计并制备出一系列具有高热稳定性、热交联性、辐照交联性、良好的力学性能和耐腐蚀性的高聚物。The invention belongs to a polyether ether ketone copolymer containing 1,5-naphthalene ring and a synthesis method thereof. Using 4,4'-difluorodiphenyl ketone, 1,5-naphthalenediol, hydroquinone and/or 4,4'-dihydroxybiphenyl as raw materials, anhydrous potassium carbonate, anhydrous sodium carbonate As a catalyst, diphenyl sulfone is used as a solvent; the product is obtained through the process of salt formation, prepolymerization and polymerization. The process includes: mixing and stirring 4,4'-difluorodiphenyl ketone and diphenyl sulfone, nitrogen protection, heating and catalysis, adding hydroquinone and/or 4,4'-dihydroxybiphenyl, and continuing heating Raise the temperature to (240-260)°C and react for (0.2-0.5) hours, then add the catalyst and 1,5-naphthalenediol, and finally control the temperature at (290-320)°C for (1-5) hours. The invention designs and prepares a series of polymers with high thermal stability, thermal crosslinkability, radiation crosslinkability, good mechanical properties and corrosion resistance.
Description
技术领域technical field
本发明属于含1，5-萘环的聚醚醚酮类共聚物的合成方法。The invention belongs to a synthesis method of a polyetheretherketone copolymer containing 1,5-naphthalene ring.
背景技术Background technique
本聚合反应是在聚醚醚酮的合成技术基础上实验成功的，因而聚醚醚酮的合成方法是与本发明最相近的背景技术。The polymerization reaction is successfully experimentally based on the synthesis technology of polyetheretherketone, so the synthesis method of polyetheretherketone is the closest background technology to the present invention.
聚醚醚酮聚合物的结构式是：The structural formula of polyetheretherketone polymer is:
聚醚醚酮的合成是用4，4’-二氟二苯基酮和对苯二酚为原料，二苯砜为溶剂，无水碳酸钾和无水碳酸钠作为催化剂，经历成盐、预聚、聚合的过程，得到聚醚醚酮聚合物。所说的成盐是双酚(苯二酚)和无水碳酸钾、无水碳酸钠反应，脱去两个氢离子，变成有机盐形式的过程。The synthesis of polyether ether ketone is to use 4,4'-difluorodiphenyl ketone and hydroquinone as raw materials, diphenyl sulfone as solvent, anhydrous potassium carbonate and anhydrous sodium carbonate as catalysts, undergo salt formation, pretreatment Polymerization and polymerization process to obtain polyether ether ketone polymer. Said salification is a process in which bisphenol (diphenol) reacts with anhydrous potassium carbonate and anhydrous sodium carbonate to remove two hydrogen ions and become an organic salt.
具体工艺包括：将4，4’-二氟二苯基酮和二苯砜加入到装有机械搅拌、温度计的三口瓶中，氮气保护，加热到160℃加入催化剂无水碳酸钾和无水碳酸钠，继续升温加入对苯二酚加热到(180～200)℃控温1小时，逐渐升温到250℃反应(0.2～0.5)小时，在这段时间里双酚成盐基本完成。之后在290℃下预聚1小时，最后320℃条件下控温3小时完成聚合，得到聚醚醚酮聚合物。The specific process includes: adding 4,4'-difluorodiphenyl ketone and diphenyl sulfone into a three-necked flask equipped with mechanical stirring and a thermometer, under nitrogen protection, heating to 160°C, adding catalyst anhydrous potassium carbonate and anhydrous carbonic acid Sodium, continue to raise the temperature, add hydroquinone, heat to (180-200) ° C and control the temperature for 1 hour, gradually raise the temperature to 250 ° C and react for (0.2-0.5) hours, during this time, the bisphenol salt formation is basically completed. Thereafter, prepolymerization was carried out at 290° C. for 1 hour, and finally the polymerization was completed under temperature control at 320° C. for 3 hours to obtain a polyether ether ketone polymer.
发明内容Contents of the invention
近年来随着合成聚合物种类的逐步增多，进一步在原来聚合物的基础上改性和合成系列化的聚合物成为了现在的研究热点。将萘环引入到聚合物中，可以利用萘环的利于交联性来影响聚醚醚酮聚合物的热稳定性、热交联性、辐照交联性和力学性能等，而合成聚合物，进而在高温、高辐照领域有很广阔的应用前景。本发明设计并合成了含1，5-萘二酚的聚醚醚酮类共聚物。即，用1，5-萘二酚单体与第二种单体、第三种单体或第四种单体进行缩聚反应，制备出一系列具有高热稳定性、热交联性、辐照交联性、良好的力学性能和耐腐蚀性的高聚物。In recent years, with the gradual increase in the number of synthetic polymers, further modification and synthesis of serialized polymers on the basis of the original polymers have become a research hotspot. Introducing the naphthalene ring into the polymer can take advantage of the favorable crosslinking properties of the naphthalene ring to affect the thermal stability, thermal crosslinkability, radiation crosslinkability and mechanical properties of the polyether ether ketone polymer, and the synthetic polymer , and then has a broad application prospect in the field of high temperature and high radiation. The invention designs and synthesizes the polyether ether ketone copolymer containing 1,5-naphthalene diol. That is, use 1,5-naphthalenediol monomer to carry out polycondensation reaction with the second monomer, the third monomer or the fourth monomer to prepare a series of High polymer with cross-linking, good mechanical properties and corrosion resistance.
本发明设计的含1，5-萘二酚的聚醚醚酮类共聚物的结构式是：The structural formula of the polyether ether ketone copolymer containing 1,5-naphthalenediol designed by the present invention is:
n+m＝1n+m=1
本发明的含1，5-萘环的聚醚醚酮类共聚物的合成方法叙述如下：以双氟单体和双酚单体为原料，所说的双氟单体是4，4’-二氟二苯基酮，所说的双酚单体包括1，5-萘二酚、4，4’-二羟基联苯和/或对苯二酚。以无水碳酸钾、无水碳酸钠为催化剂，以二苯砜为溶剂。经历成盐、预聚、聚合的过程，得到含1，5-萘环的聚醚醚酮类共聚物。具体工艺过程包括：The synthesis method of the polyether ether ketone copolymer containing 1,5-naphthalene ring of the present invention is described as follows: with difluoromonomer and bisphenol monomer as raw materials, said difluoromonomer is 4,4'- Difluorodiphenyl ketone, said bisphenol monomer includes 1,5-naphthalenediol, 4,4'-dihydroxybiphenyl and/or hydroquinone. Anhydrous potassium carbonate and anhydrous sodium carbonate are used as catalysts, and diphenyl sulfone is used as solvent. Through the process of salt formation, prepolymerization and polymerization, the polyether ether ketone copolymer containing 1,5-naphthalene ring is obtained. The specific process includes:
将4，4’-二氟二苯基酮和二苯砜混合搅拌、氮气保护，可以加入到装有机械搅拌、温度计的三口瓶中，进行机械搅拌和氮气保护，加热到(150～170)℃再加入催化剂无水碳酸钾和无水碳酸钠，再升温(3～8)℃加入对苯二酚和/或4，4’-二羟基联苯，继续加热到(180～200)℃控温(0.3～1.5)小时，逐渐升温到(240～260)℃反应(0.2～0.5)小时，在这段时间里以反应物冒泡不明显、已加入的双酚成盐基本完成为准。再加入剩余的无水碳酸钾、无水碳酸钠以及1，5-萘二酚，之后在(250～270)℃下反应至双酚成盐基本完成。最后在(290～320)℃条件下控温(1～5)小时，完成预聚和聚合，得到无规共聚物。Mix and stir 4,4'-difluorodiphenyl ketone and diphenyl sulfone, nitrogen protection, can be added to a three-necked flask equipped with mechanical stirring and thermometer, carry out mechanical stirring and nitrogen protection, heat to (150 ~ 170) Then add the catalyst anhydrous potassium carbonate and anhydrous sodium carbonate, then add hydroquinone and/or 4,4'-dihydroxybiphenyl at a temperature of (3-8) °C, and continue heating to (180-200) °C Warm for (0.3-1.5) hours, then gradually raise the temperature to (240-260)°C for (0.2-0.5) hours, during this period, the reactant does not bubble obviously and the added bisphenol salt formation is basically completed. Then add the remaining anhydrous potassium carbonate, anhydrous sodium carbonate and 1,5-naphthalenediol, and then react at (250-270)°C until the bisphenol salt formation is basically completed. Finally, the temperature is controlled under the condition of (290-320)°C for (1-5) hours to complete the pre-polymerization and polymerization to obtain a random copolymer.
将产物倾入水中，用粉碎机粉碎、过滤，将固体直接用乙醇或丙酮煮沸法煮沸、过滤，重复(5～6)次，再用蒸馏水煮沸、过滤，重复(5～6)次，在烘箱中烘干，得到精制共聚物。Pour the product into water, pulverize and filter with a pulverizer, boil and filter the solid directly with ethanol or acetone boiling method, repeat (5-6) times, then boil and filter with distilled water, repeat (5-6) times, in Dry in an oven to obtain a refined copolymer.
1，5-萘二酚、4，4’-二羟基联苯和对苯二酚的摩尔比率范围为(1～99)∶(0～99)∶(99～0)，但要保证双酚的摩尔比率加和为1。双氟单体和双酚单体的摩尔比率范围为(1.000～0.985)∶(0.985～1.000)，无水碳酸钾和无水碳酸钠的摩尔比率范围为1∶(19～29)，反应双酚或双氟(以摩尔数少的一方为准)的摩尔数和催化剂的摩尔比率为1∶1.03。The molar ratio range of 1,5-naphthalenediol, 4,4'-dihydroxybiphenyl and hydroquinone is (1～99):(0～99):(99～0), but it is necessary to ensure that bisphenol The molar ratios add up to 1. The molar ratio range of difluoro monomer and bisphenol monomer is (1.000～0.985):(0.985～1.000), the molar ratio range of anhydrous potassium carbonate and anhydrous sodium carbonate is 1:(19～29), the reaction bis The molar ratio of the molar number of phenol or bisfluoro (according to the side with the smaller molar number) and the catalyst is 1:1.03.
分步添加的无水碳酸钾和无水碳酸钠按各步双酚成盐所需的比率添加。The anhydrous potassium carbonate and anhydrous sodium carbonate added step by step are added according to the required ratio of bisphenol salt formation in each step.
溶剂二苯砜的加入量随着1，5-萘二酚或4，4’-二羟基联苯比率的增加而增加，含固量由30％到10％。并且当含萘量或联苯含量在20％以上时需要将二苯砜分步添加，添加量按照各步双酚的摩尔比例。所说的含固量是体系中加入的双酚和双氟反应单体经反应后所剩的质量占总质量的百分比。通过含固可以计算溶剂二苯砜的加入量。例如，加入0.25mol反应物，4，4’-二氟二苯基酮55.92g，对苯二酚22.47g，无水碳酸钾1.76g和无水碳酸钠26.46g成盐放出HF 0.5mol，含固量定为20％，可以计算出溶剂二苯砜的加入量是：(55.92+22.47+1.76+26.46-10)/0.2-(55.92+22.47+1.76+26.46-10)。The addition amount of solvent diphenyl sulfone increases along with the increase of 1,5-naphthalenediol or 4,4'-dihydroxybiphenyl ratio, and the solid content is from 30% to 10%. And when the content of naphthalene or biphenyl is above 20%, diphenyl sulfone needs to be added step by step, and the addition amount is according to the molar ratio of bisphenol in each step. The said solid content is the percentage of the remaining mass after the reaction of the bisphenol and bisfluoro-reactive monomers added in the system to the total mass. The addition amount of solvent diphenyl sulfone can be calculated by the solid content. For example, add 0.25mol reactant, 4,4'-difluorodiphenyl ketone 55.92g, hydroquinone 22.47g, anhydrous potassium carbonate 1.76g and anhydrous sodium carbonate 26.46g salt and release HF 0.5mol, containing The fixed amount is set at 20%, and the addition amount of solvent diphenylsulfone can be calculated as: (55.92+22.47+1.76+26.46-10)/0.2-(55.92+22.47+1.76+26.46-10).
具体实施方式Detailed ways
实施例1：Example 1:
将4，4’-二氟二苯基酮55.92g和二苯砜307.36g(含固量20％)加入到装有机械搅拌、温度计的三口瓶中，氮气保护，加热到160℃再加入无水碳酸钾1.41g和无水碳酸钠21.17g，再加热到165℃加入对苯二酚22.47g，继续加热到180℃控温1小时，逐渐升温到250℃反应15分钟，再加入剩余的无水碳酸钾0.35g、无水碳酸钠5.29g和1，5-萘二酚8.17g，之后在260℃下反应1小时，到290℃再控温1小时，最后加热到320℃反应3小时，得到三元共聚物。Add 55.92 g of 4,4'-difluorodiphenyl ketone and 307.36 g of diphenyl sulfone (20% solid content) into a three-necked flask equipped with mechanical stirring and a thermometer, under nitrogen protection, heat to 160°C, and then add Water potassium carbonate 1.41g and anhydrous sodium carbonate 21.17g, then heated to 165°C, added hydroquinone 22.47g, continued heating to 180°C temperature control for 1 hour, gradually raised the temperature to 250°C for 15 minutes, then added the remaining 0.35g of potassium carbonate water, 5.29g of anhydrous sodium carbonate and 8.17g of 1,5-naphthalenediol, then react at 260°C for 1 hour, then control the temperature at 290°C for 1 hour, and finally heat to 320°C for 3 hours. A terpolymer is obtained.
实施例2：Example 2:
将4，4’-二氟二苯基酮55.92g和二苯砜123.49g(含固量12％)加入到装有机械搅拌、温度计的三口瓶中，氮气保护，加热到160℃再加入无水碳酸钾0.25g和无水碳酸钠5.37g，再加热到165℃加入对苯二酚5.63g，继续加热到180℃控温1小时，逐渐升温到250℃反应15分钟，再加入剩余的无水碳酸钾1.01g、无水碳酸钠21.48g和二苯砜493.97g以及1，5-萘二酚32.65g，之后在260℃下反应1小时，到290℃再控温1小时，最后加热到320℃反应3小时，得到三元共聚物。Add 55.92g of 4,4'-difluorodiphenyl ketone and 123.49g of diphenyl sulfone (12% solid content) into a three-necked flask equipped with a mechanical stirrer and a thermometer, under nitrogen protection, heat to 160°C, and then add no Water potassium carbonate 0.25g and anhydrous sodium carbonate 5.37g, then heated to 165°C, added hydroquinone 5.63g, continued heating to 180°C temperature control for 1 hour, gradually raised the temperature to 250°C for 15 minutes, then added the remaining Potassium carbonate 1.01g, anhydrous sodium carbonate 21.48g, diphenyl sulfone 493.97g and 1,5-naphthalene diol 32.65g, then react at 260°C for 1 hour, then control the temperature at 290°C for 1 hour, and finally heat to React at 320°C for 3 hours to obtain a terpolymer.
与实施例1比较，由于含固量变为12％，二苯砜溶剂分两次添加，即，在添加1，5-萘二酚时第二次加入了二苯砜溶剂；所添加的对苯二酚量变少，但添加的1，5-萘二酚量增加，合成的产物基本不变。Compared with Example 1, since the solid content becomes 12%, the diphenyl sulfone solvent is added twice, that is, the diphenyl sulfone solvent is added for the second time when adding 1,5-naphthalenediol; The amount of diphenol decreases, but the amount of 1,5-naphthalene diol added increases, and the synthesized product remains basically unchanged.
实施例3：Example 3:
将4，4’-二氟二苯基酮55.92g和二苯砜378.51g(含固量18％)加入到装有机械搅拌、温度计的三口瓶中，氮气保护，加热到160℃再加入无水碳酸钾1.58g和无水碳酸钠23.81g，再加热到165℃加入4，4’-二羟基联苯42.32g，继续加热到180℃控温1小时，逐渐升温到250℃反应15分钟，再加入剩余的无水碳酸钾0.18g、无水碳酸钠2.65g和二苯砜42.05g以及1，5-萘二酚4.08g，之后在260℃下反应1小时，到290℃再控温1小时，最后加热到320℃反应3小时，得到三元共聚物。Add 55.92g of 4,4'-difluorodiphenyl ketone and 378.51g of diphenyl sulfone (18% solid content) into a three-necked flask equipped with mechanical stirring and a thermometer, under nitrogen protection, heat to 160°C, and then add no Water potassium carbonate 1.58g and anhydrous sodium carbonate 23.81g, then heated to 165°C, added 42.32g of 4,4'-dihydroxybiphenyl, continued to heat to 180°C and controlled the temperature for 1 hour, then gradually raised the temperature to 250°C for 15 minutes, Then add the remaining 0.18g of anhydrous potassium carbonate, 2.65g of anhydrous sodium carbonate, 42.05g of diphenylsulfone and 4.08g of 1,5-naphthalenediol, then react at 260°C for 1 hour, and then control the temperature at 290°C for 1 hour Hours, and finally heated to 320 ° C for 3 hours to obtain a terpolymer.
实施例3中，双酚单体选用4，4’-二羟基联苯和1，5-萘二酚，而实施例2的双酚单体选用了对苯二酚和1，5-萘二酚，合成过程及合成条件基本相同，合成的产物也基本相同。In embodiment 3, bisphenol monomer selects 4,4'-dihydroxy biphenyl and 1,5-naphthalenediol, and the bisphenol monomer of embodiment 2 selects hydroquinone and 1,5-naphthalenediol For phenol, the synthesis process and conditions are basically the same, and the synthesized products are also basically the same.
实施例4：Example 4:
将4，4’-二氟二苯基酮55.92g和二苯砜129.04g(含固量12％)加入到装有机械搅拌、温度计的三口瓶中，氮气保护，加热到160℃再加入无水碳酸钾0.25g和无水碳酸钠5.37g，再加热到165℃加入4，4’-二羟基联苯9.41g，继续加热到180℃控温1小时，逐渐升温到250℃反应15分钟，再加入剩余的无水碳酸钾1.01g、无水碳酸钠21.48g和二苯砜516.15g以及1，5-萘二酚32.65g，之后在260℃下反应1小时，到290℃再控温1小时，最后加热到320℃反应3小时，得到三元共聚物。Add 55.92g of 4,4'-difluorodiphenyl ketone and 129.04g of diphenyl sulfone (12% solid content) into a three-necked flask equipped with mechanical stirring and a thermometer, under nitrogen protection, heat to 160°C, and then add no 0.25g of potassium carbonate water and 5.37g of anhydrous sodium carbonate, then heated to 165°C and added 9.41g of 4,4'-dihydroxybiphenyl, continued heating to 180°C and controlled the temperature for 1 hour, then gradually raised the temperature to 250°C for 15 minutes, Then add the remaining 1.01g of anhydrous potassium carbonate, 21.48g of anhydrous sodium carbonate, 516.15g of diphenyl sulfone and 32.65g of 1,5-naphthalenediol, then react at 260°C for 1 hour, and then control the temperature at 290°C for 1 hour Hours, and finally heated to 320 ° C for 3 hours to obtain a terpolymer.
跟实施例3比较，部分的4，4’-二羟基联苯被1，5-萘二酚替代。Compared with Example 3, part of 4,4'-dihydroxybiphenyl is replaced by 1,5-naphthalenediol.
实施例5：Example 5:
将4，4’-二氟二苯基酮55.65g和二苯砜308.68g(含固量20％)加入到装有机械搅拌、温度计的三口瓶中，氮气保护，加热到160℃再加入无水碳酸钾1.58g和无水碳酸钠23.81g，再加热到165℃加入对苯二酚22.47g和4，4’-二羟基联苯4.70g，继续加热到180℃控温1小时，逐渐升温到250℃反应15分钟，再加入剩余的无水碳酸钾0.18g、无水碳酸钠2.65g和1，5-萘二酚4.08g，之后在260℃下反应1小时，逐渐到290℃再控温1小时，最后加热到320℃反应3小时，得到四元共聚物。Add 55.65 g of 4,4'-difluorodiphenyl ketone and 308.68 g of diphenyl sulfone (20% solid content) into a three-necked flask equipped with mechanical stirring and a thermometer, under nitrogen protection, heat to 160 ° C, and then add no Water potassium carbonate 1.58g and anhydrous sodium carbonate 23.81g, then heated to 165°C, add hydroquinone 22.47g and 4,4'-dihydroxybiphenyl 4.70g, continue to heat to 180°C and control the temperature for 1 hour, then gradually increase the temperature React at 250°C for 15 minutes, then add the remaining anhydrous potassium carbonate 0.18g, anhydrous sodium carbonate 2.65g and 1,5-naphthalene diol 4.08g, then react at 260°C for 1 hour, gradually reach 290°C and then control Warm for 1 hour, and finally heated to 320°C for 3 hours to obtain a tetrapolymer.
实施例5的双酚单体选用了对苯二酚、4，4’-二羟基联苯和1，5-萘二酚。各实施例的双酚单体中1，5-萘二酚是必不可少的。The bisphenol monomer of embodiment 5 has selected hydroquinone, 4,4'-dihydroxybiphenyl and 1,5-naphthalenediol for use. 1,5-Naphthalenediol is essential in the bisphenol monomers of each example.
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