CN1388146A - Ether-ketone copolymer containing 1,5-naphthalene ring polyether and its synthesis - Google Patents
Ether-ketone copolymer containing 1,5-naphthalene ring polyether and its synthesis Download PDFInfo
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- CN1388146A CN1388146A CN 02109463 CN02109463A CN1388146A CN 1388146 A CN1388146 A CN 1388146A CN 02109463 CN02109463 CN 02109463 CN 02109463 A CN02109463 A CN 02109463A CN 1388146 A CN1388146 A CN 1388146A
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Abstract
The present invention is polyether-ether-ketone copolymer containing 1,5-naphthalene ring and its synthesis. The polyether-ether-ketone copolymer is synthesized with 4,4'-difluoro diphenyl ketone, 1,5-hydroxynaphthalene, hydroquinone and/or 4,4'-dihydroxyl biphenyl as material; anhydrous potassium carbonate or anhydrous sodium carbonate as catalyst; and diphenyl sulfone as solvent, and through forming salt, prepolymerization and polymerization. The technological process includes mixing of 4,4'-difluoro diphenyl ketone and diphenyl sulfone, nitrogen protection, heating and catalysis, adding hydroquinone and/or 4'4-dihydroxyl biphenyl, heating to 240-260 deg.C for reaction for 0.2-0.5 hr, adding catalyst and 1,5-hydroxynaphthalene and reaction at 290-320 deg.c for 1-5 hr. The polymer polymer product has high stability, good heat and irradiation crosslinking property, excellent mechanical property and high corrosion resistance.
Description
Technical field
The invention belongs to and contain 1, the synthetic method of the polyether-ether-ketone analog copolymer of 5-naphthalene nucleus.
Background technology
This polyreaction is a Success in Experiment on the synthetic technology basis of polyether-ether-ketone, thereby the synthetic method of polyether-ether-ketone is the background technology the most close with the present invention.
The structural formula of polyetheretherketonepolymer polymer is:
The synthetic of polyether-ether-ketone is with 4, and 4 '-difluorodiphenyl base ketone and Resorcinol are raw material, and sulfobenzide is a solvent, and Anhydrous potassium carbonate and anhydrous sodium carbonate are as catalyzer, and experience salify, pre-polymerization, polymeric process obtain polyetheretherketonepolymer polymer.Said salify is that bis-phenol (dihydroxy-benzene) and Anhydrous potassium carbonate, anhydrous sodium carbonate react, and sloughs two hydrogen ions, becomes the process of organic salt form.
Concrete technology comprises: with 4; 4 '-difluorodiphenyl base ketone and sulfobenzide join in the there-necked flask that mechanical stirring, thermometer are housed; nitrogen protection; be heated to 160 ℃ and add catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate; the adding Resorcinol that continues to heat up was heated to (180～200) ℃ temperature control 1 hour; be warmed up to 250 ℃ of reactions (0.2～0.5) hour gradually, the bis-phenol salify is finished substantially during this period.290 ℃ of following pre-polymerizations 1 hour, temperature control was finished polymerization in 3 hours under last 320 ℃ of conditions, obtained polyetheretherketonepolymer polymer afterwards.
Summary of the invention
Along with progressively the increasing of synthesized polymer species, further the polymkeric substance of modification and synthesizing seriesization becomes present research focus on the basis of original polymkeric substance in recent years.Naphthalene nucleus is incorporated in the polymkeric substance, can utilize being beneficial to bridging property and influencing the thermostability of polyetheretherketonepolymer polymer, heat cross-linking, cross-linking radiation and mechanical property etc. of naphthalene nucleus, and synthetic polymer, and then very wide application prospect is arranged in high temperature, high irradiation field.The present invention has designed and synthesized and has contained 1, the polyether-ether-ketone analog copolymer of 5-naphthalenediol.That is, with 1,5-naphthalenediol monomer and second kind of monomer, the third monomer or the 4th kind of monomer carry out polycondensation, prepare a series of superpolymer with high thermal stability, heat cross-linking, cross-linking radiation, good mechanical performance and erosion resistance.
What the present invention designed contains 1, and the structural formula of the polyether-ether-ketone analog copolymer of 5-naphthalenediol is:
N+m=1 is of the present invention to contain 1, the synthetic method of the polyether-ether-ketone analog copolymer of 5-naphthalene nucleus is described below: with two fluorine monomers and biphenol monomer is raw material, said pair of fluorine monomer is 4,4 '-difluorodiphenyl base ketone, said biphenol monomer comprises 1,5-naphthalenediol, 4,4 '-dihydroxybiphenyl and/or Resorcinol.With Anhydrous potassium carbonate, anhydrous sodium carbonate is catalyzer, is solvent with the sulfobenzide.Experience salify, pre-polymerization, polymeric process obtain containing 1, the polyether-ether-ketone analog copolymer of 5-naphthalene nucleus.Specific embodiment comprises:
With 4; 4 '-difluorodiphenyl base ketone and sulfobenzide mix stirring; nitrogen protection; can join mechanical stirring is housed; in the there-necked flask of thermometer; carry out mechanical stirring and nitrogen protection; be heated to (150～170) and ℃ add catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate again; (3～8) ℃ adding Resorcinol and/or 4 again heats up; 4 '-dihydroxybiphenyl; continue to be heated to (180～200) ℃ temperature control (0.3～1.5) hour; be warmed up to (240～260) ℃ reactions (0.2～0.5) hour gradually, not obvious with the reactant bubbling during this period; added bis-phenol salify is finished substantially and is as the criterion.Add remaining Anhydrous potassium carbonate, anhydrous sodium carbonate and 1 again, the 5-naphthalenediol reacts under (250～270) ℃ afterwards to the bis-phenol salify and finishes substantially.Temperature control (1～5) hour under (290～320) ℃ condition is finished pre-polymerization and polymerization at last, obtains random copolymers.
In product impouring water, pulverize, filter with pulverizer, solid directly to be boiled, filters with ethanol or acetone boiling method, repetition (5～6) is inferior, boils, filters with distilled water again, and repetition (5～6) is inferior, dries in baking oven, obtains refining multipolymer.
1,5-naphthalenediol, 4, the molar ratio scope of 4 '-dihydroxybiphenyl and Resorcinol is (1～99): (0～99): (99～0), but the molar ratio that will guarantee bis-phenol adds and is 1.The molar ratio scope of two fluorine monomers and biphenol monomer is (1.000～0.985): (0.985～1.000), the molar ratio scope of Anhydrous potassium carbonate and anhydrous sodium carbonate is 1: (19～29), the reaction bis-phenol or the mole number of two fluorine (a few side is as the criterion with mole number) and the molar ratio of catalyzer are 1: 1.03.
Anhydrous potassium carbonate that substep adds and anhydrous sodium carbonate add by the required ratio of each step bis-phenol salify.
The add-on of solvent sulfobenzide is along with 1,5-naphthalenediol or 4, and the increase of 4 '-dihydroxybiphenyl ratio and increasing, solid content is by 30% to 10%.And sulfobenzide need be added step by step when above 20% when containing naphthalene amount or biphenyl content, addition is according to the molar ratio of each step bis-phenol.Said solid content is the per-cent that the bis-phenol that adds in the system and two fluorine reaction monomers last quality after reacting account for total mass.By containing the add-on that to calculate the solvent sulfobenzide admittedly.For example, add the 0.25mol reactant, 4,4 '-difluorodiphenyl base ketone 55.92g, Resorcinol 22.47g, Anhydrous potassium carbonate 1.76g and anhydrous sodium carbonate 26.46g salify are emitted HF 0.5mol, and solid content is decided to be 20%, and the add-on that can calculate the solvent sulfobenzide is: (55.92+22.47+1.76+26.46-10)/and 0.2-(55.92+22.47+1.76+26.46-10).
Embodiment
Embodiment 1:
With 4; 4 '-difluorodiphenyl base ketone 55.92g and sulfobenzide 307.36g (solid content 20%) join mechanical stirring are housed; in the there-necked flask of thermometer; nitrogen protection; be heated to 160 ℃ and add Anhydrous potassium carbonate 1.41g and anhydrous sodium carbonate 21.17g again; reheat to 165 ℃ adding Resorcinol 22.47g; continued to be heated to 180 ℃ of temperature controls 1 hour; be warmed up to 250 ℃ of reactions 15 minutes gradually; add remaining Anhydrous potassium carbonate 0.35g again; anhydrous sodium carbonate 5.29g and 1; 5-naphthalenediol 8.17g is afterwards 260 ℃ of down reactions 1 hour, to 290 ℃ of temperature controls 1 hour again; be heated to 320 ℃ of reactions 3 hours at last, obtain terpolymer.
Embodiment 2:
With 4; 4 '-difluorodiphenyl base ketone 55.92g and sulfobenzide 123.49g (solid content 12%) join mechanical stirring are housed; in the there-necked flask of thermometer; nitrogen protection; be heated to 160 ℃ and add Anhydrous potassium carbonate 0.25g and anhydrous sodium carbonate 5.37g again; reheat to 165 ℃ adding Resorcinol 5.63g; continued to be heated to 180 ℃ of temperature controls 1 hour; be warmed up to 250 ℃ of reactions 15 minutes gradually; add remaining Anhydrous potassium carbonate 1.01g again; anhydrous sodium carbonate 21.48g and sulfobenzide 493.97g and 1; 5-naphthalenediol 32.65g is afterwards 260 ℃ of down reactions 1 hour, to 290 ℃ of temperature controls 1 hour again; be heated to 320 ℃ of reactions 3 hours at last, obtain terpolymer.
Compare with embodiment 1, because solid content becomes 12%, the sulfobenzide solvent adds at twice,, adding 1, has added the sulfobenzide solvent during 5-naphthalenediol for the second time that is; The Resorcinol quantitative change of being added is few, but add 1,5-naphthalenediol amount increases, the synthetic product is constant substantially.
Embodiment 3:
With 4; 4 '-difluorodiphenyl base ketone 55.92g and sulfobenzide 378.51g (solid content 18%) join mechanical stirring are housed; in the there-necked flask of thermometer; nitrogen protection; be heated to 160 ℃ and add Anhydrous potassium carbonate 1.58g and anhydrous sodium carbonate 23.81g again; reheat to 165 ℃ adding 4; 4 '-dihydroxybiphenyl 42.32g; continued to be heated to 180 ℃ of temperature controls 1 hour; be warmed up to 250 ℃ of reactions 15 minutes gradually; add remaining Anhydrous potassium carbonate 0.18g again; anhydrous sodium carbonate 2.65g and sulfobenzide 42.05g and 1; 5-naphthalenediol 4.08g; reacted 1 hour down at 260 ℃ afterwards; to 290 ℃ of temperature controls 1 hour again, be heated to 320 ℃ of reactions 3 hours at last, obtain terpolymer.
Among the embodiment 3, biphenol monomer selects 4 for use, 4 '-dihydroxybiphenyl and 1, and the 5-naphthalenediol, and the biphenol monomer of embodiment 2 has been selected Resorcinol and 1 for use, and the 5-naphthalenediol, building-up process and synthesis condition are basic identical, and the synthetic product is also basic identical.
Embodiment 4:
With 4; 4 '-difluorodiphenyl base ketone 55.92g and sulfobenzide 129.04g (solid content 12%) join mechanical stirring are housed; in the there-necked flask of thermometer; nitrogen protection; be heated to 160 ℃ and add Anhydrous potassium carbonate 0.25g and anhydrous sodium carbonate 5.37g again; reheat to 165 ℃ adding 4; 4 '-dihydroxybiphenyl 9.41g; continued to be heated to 180 ℃ of temperature controls 1 hour; be warmed up to 250 ℃ of reactions 15 minutes gradually; add remaining Anhydrous potassium carbonate 1.01g again; anhydrous sodium carbonate 21.48g and sulfobenzide 516.15g and 1; 5-naphthalenediol 32.65g; reacted 1 hour down at 260 ℃ afterwards; to 290 ℃ of temperature controls 1 hour again, be heated to 320 ℃ of reactions 3 hours at last, obtain terpolymer.
With embodiment 3 relatively, 4 of part, 4 '-dihydroxybiphenyl is by 1, and the 5-naphthalenediol substitutes.
Embodiment 5:
With 4; 4 '-difluorodiphenyl base ketone 55.65g and sulfobenzide 308.68g (solid content 20%) join mechanical stirring are housed; in the there-necked flask of thermometer; nitrogen protection; be heated to 160 ℃ and add Anhydrous potassium carbonate 1.58g and anhydrous sodium carbonate 23.81g again; reheat to 165 ℃ adding Resorcinol 22.47g and 4; 4 '-dihydroxybiphenyl 4.70g; continued to be heated to 180 ℃ of temperature controls 1 hour; be warmed up to 250 ℃ of reactions 15 minutes gradually; add remaining Anhydrous potassium carbonate 0.18g again; anhydrous sodium carbonate 2.65g and 1; 5-naphthalenediol 4.08g; reacted 1 hour down at 260 ℃ afterwards; to 290 ℃ of temperature controls 1 hour again, be heated to 320 ℃ of reactions 3 hours at last gradually, obtain tetrapolymer.
The biphenol monomer of embodiment 5 has been selected Resorcinol, 4 for use, 4 '-dihydroxybiphenyl and 1,5-naphthalenediol.In the biphenol monomer of each embodiment 1, the 5-naphthalenediol is absolutely necessary.
Claims (3)
1, a kind ofly contain 1,5-naphthalene nucleus polyether-ether-ketone analog copolymer is characterized in that its structural formula is:
n+m＝1
2, a kind of claim 1 contain 1, the synthetic method of 5-naphthalene nucleus polyether-ether-ketone analog copolymer is a raw material with two fluorine monomers and biphenol monomer, said pair of fluorine monomer is 4,4 '-difluorodiphenyl base ketone, biphenol monomer comprises Resorcinol; With Anhydrous potassium carbonate, anhydrous sodium carbonate is catalyzer; With the sulfobenzide is solvent; Experience salify, pre-polymerization, polymeric process obtain product; It is characterized in that said biphenol monomer also comprises 1,5-naphthalenediol and/or 4,4 '-dihydroxybiphenyl; 1,5-naphthalenediol, 4, the molar ratio scope of 4 '-dihydroxybiphenyl and Resorcinol is (1～99): (0～99): (99～0), and the molar ratio that guarantees bis-phenol adds and be 1; The molar ratio scope of two fluorine monomers and biphenol monomer is (1.000～0.985): (0.985～1.000); Said salify, pre-polymerization, the polymeric process comprises: with 4,4 '-difluorodiphenyl base ketone and sulfobenzide mix stirring, nitrogen protection, be heated to (150～170) and ℃ add catalyzer Anhydrous potassium carbonate and anhydrous sodium carbonate again, (3～8) ℃ adding Resorcinol and/or 4 again heats up, 4 '-dihydroxybiphenyl, continue to be heated to (180～200) ℃ temperature control (0.3～1.5) hour, be warmed up to (240～260) ℃ reactions (0.2～0.5) hour gradually, add Anhydrous potassium carbonate again, anhydrous sodium carbonate and 1, the 5-naphthalenediol reacts to the bis-phenol salify under (250～270) ℃ afterwards; Temperature control (1～5) hour under (290～320) ℃ condition is finished pre-polymerization and polymerization at last.
3, contain 1 according to claim 2 is described, the synthetic method of 5-naphthalene nucleus polyether-ether-ketone analog copolymer is characterized in that the solvent sulfobenzide adds step by step, promptly adding 1, adds sulfobenzide during the 5-naphthalenediol again one time.
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| CNB021094632A CN1166719C (en) | 2002-04-09 | 2002-04-09 | Ether-ketone copolymer containing 1,5-naphthalene ring polyether and its synthesis |
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| CNB021094632A CN1166719C (en) | 2002-04-09 | 2002-04-09 | Ether-ketone copolymer containing 1,5-naphthalene ring polyether and its synthesis |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009089722A1 (en) * | 2008-01-11 | 2009-07-23 | Jilin Zhong Yan High Performance Engineering Plastics Co., Ltd | A process for preparing a polyether ether ketone |
| CN104024304A (en) * | 2011-10-14 | 2014-09-03 | 威格斯制造有限公司 | Polymeric materials |
| CN105175714A (en) * | 2015-09-23 | 2015-12-23 | 中橡集团炭黑工业研究设计院 | Process method for preparing cyano polyetherketoneketone resin |
| CN107312312A (en) * | 2017-08-01 | 2017-11-03 | 芜湖领航新材料科技有限公司 | A kind of corrosion-resistant high polymer material |
| CN110845837A (en) * | 2013-06-26 | 2020-02-28 | 威格斯制造有限公司 | Polymer material |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100402581C (en) * | 2004-12-10 | 2008-07-16 | 吉林大学 | Polyaryl-ether-ketone viscosity regulator synthesized based on A2+B3 type monomer reaction and method therefor |
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2002
- 2002-04-09 CN CNB021094632A patent/CN1166719C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009089722A1 (en) * | 2008-01-11 | 2009-07-23 | Jilin Zhong Yan High Performance Engineering Plastics Co., Ltd | A process for preparing a polyether ether ketone |
| EP2292673A1 (en) * | 2008-01-11 | 2011-03-09 | Jilin Zhong Yan High Performance Engineering Plastics Co., Ltd | A process for preparing a polyether ether ketone |
| EP2292673A4 (en) * | 2008-01-11 | 2012-01-18 | Jilin Jinzheng Macromolecule Materials R & D Co Ltd | A process for preparing a polyether ether ketone |
| US8236919B2 (en) | 2008-01-11 | 2012-08-07 | Jilin Jinzheng Macromolecule Materials R & D Co., Ltd. | Process for preparing a polyether ether ketone |
| CN104024304A (en) * | 2011-10-14 | 2014-09-03 | 威格斯制造有限公司 | Polymeric materials |
| CN110845837A (en) * | 2013-06-26 | 2020-02-28 | 威格斯制造有限公司 | Polymer material |
| CN110845837B (en) * | 2013-06-26 | 2022-08-30 | 威格斯制造有限公司 | Polymer material |
| CN105175714A (en) * | 2015-09-23 | 2015-12-23 | 中橡集团炭黑工业研究设计院 | Process method for preparing cyano polyetherketoneketone resin |
| CN105175714B (en) * | 2015-09-23 | 2017-06-30 | 中橡集团炭黑工业研究设计院 | A kind of process for preparing cyano group ketone-grouped resin |
| CN107312312A (en) * | 2017-08-01 | 2017-11-03 | 芜湖领航新材料科技有限公司 | A kind of corrosion-resistant high polymer material |
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| CN1166719C (en) | 2004-09-15 |
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