CN1195002C - Polyaryl thioether sulfone and its preparation method - Google Patents
Polyaryl thioether sulfone and its preparation method Download PDFInfo
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- CN1195002C CN1195002C CNB021138036A CN02113803A CN1195002C CN 1195002 C CN1195002 C CN 1195002C CN B021138036 A CNB021138036 A CN B021138036A CN 02113803 A CN02113803 A CN 02113803A CN 1195002 C CN1195002 C CN 1195002C
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- polyaryl thioether
- thioether sulfone
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Abstract
The present invention relates to polyaryl thioether sulfone and a preparing method thereof, which is characterized in that a third monomer halogenating aryl compound which is at least one of trichlorobene, dichloro nitrobenzene, dichloro aniline, dichlorobenzene, dichloro benzonitrile, dichloro benzophenone, dichloro diphenylsilane and/or dichloro phenyl ether is lead into a reaction system of water containing sodium sulfide Na2S*xH2O and dichloro diphenyl sulfone. Multicomponent composite catalysts and auxiliary agents are used; products of polyaryl thioether sulfone with the external appearance in white color or light color and different granularity can be produced by changing solvents and regulating and controlling technical conditions. Solution limiting viscosity number eta is from 0.15 to 0.54; glass transition temperature Tg is at least 210 DEG C; heat distortion temperature T is at least 180 DEG C; thermal decomposition temperature Td is at least 480 DEG C. The present invention can be widely used for the fields, such as spaceflight aviation, machinery, electron electricity and chemical industry, and the present invention has obvious economic and social benefits.
Description
One, technical field
The present invention relates to a kind of polyaryl thioether sulfone and preparation method thereof, belong to the synthetic field of polymer.
Two, background technology
Poly arylidene thio-ester comprises a big class sulfur-bearing aryl polymer, as polyphenylene sulfide, and PPSS, polyphenylene sulfide ketone and polyphenylene sulfide acid amides etc., polyphenylene sulfide is industrialization on a large scale now.The Edmonds of Phillips Petroleum Co in 1967, J.T and Hill, H.W is a raw material with sodium sulphite and santochlor, has started the road of synthetic poly arylidene thio-ester in polar organic solvent, U.S 3354129.After this, a large amount of research report is arranged successively, the adjustment that mainly concentrates on selection by catalyzer and auxiliary agent and processing condition is to obtain the high-molecular weight resin, thereby further improve, improve the toughness of the performance of resin, particularly resin, JP87190228,61207439,61306330; EP320142,355499,409105; CN95111495.6 etc., but the polyarylene sulfide resin kind of above research all concentrates on polyphenylene sulfide.The Campbell of PhillipsPetroleum Co in 1977, R.W is a raw material with sodium sulphite and dichloro-sulfobenzide, LioAc is a catalyzer, in N-Methyl pyrrolidone, synthesized PPSS, afterwards, Phillips Petroleum Co has synthesized a series of PPSS, patent applied for U.S 4102875 arranged, U.S 4301274 etc., except that there being indivedual patents that monomer sodium sulphite is made into the Sodium sulfhydrate, other patents have all continued this primitive reaction system, have made the PPSS of different viscosity.But these reaction system starting material are more single, and product structure and performance variation are few, and reaction system protection is ineffective, and poor stability, product color are relatively poor.
Three, summary of the invention
The objective of the invention is provides a kind of polyaryl thioether sulfone and preparation method thereof at the deficiencies in the prior art.Be characterized in the PPSS reaction system, introducing the 3rd monomer, auxiliary agent and composite catalyst, synthesized the different novel polyaryl thioether sulfone of structure, obtained new performance and new purposes.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
Polyaryl thioether sulfone starting raw material recipe ingredient is:
Na
2SxH
2O Na
260% 100 parts of S content ≈
90～305 parts of dichloro-sulfobenzides
0.1～50 part of halogenated aromatic compound
5～200 parts of catalyzer
5～150 parts of auxiliary agents
230～2300 parts of solvents
Wherein halogenated aromatic compound is at least a in trichloro-benzene, dichloro-oil of mirbane, dichloro-aniline, dichloro-benzonitrile, dichlorobenzene, dichloro-benzophenone, dichloro-diphenyl silane and/or the dichloro-phenyl ether.
Catalyzer is at least a in lithium chloride, tertiary sodium phosphate, sodium-acetate, hydroxy acid sodium, epsilon-amino caproic acid, hexanolactam, paratoluenesulfonic acid sodium salt and/or the Sodium Benzoate.
Auxiliary agent is Paraformaldehyde 96, phenyl aldehyde, sodium formiate, NaBH
4And/or it is at least a in the sodium hydroxide.
Solvent is at least a in N-Methyl pyrrolidone, N-methyl caprolactam, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), HMPA and/or the sulfobenzide.
The preparation method of polyaryl thioether sulfone
1, Na
2SxH
2The O dehydration
With solvent 230-2300 part, 5～150 parts of auxiliary agents and 5～200 parts of addings of catalyzer have in the reactor of agitator, thermometer and water trap, and the back that stirs adds Na
2SxH
2O Na
260%100 parts of S content ≈ are at N
2Protection in 100～210 ℃ of temperature, was dewatered 0.2～2 hour down.
2, oligopolymer generates
After the reaction system dehydration, add 90～305 parts of dichloro-sulfobenzides, in 100～210 ℃ of reactions of temperature 0.5～6 hour.
3, the preparation of polyaryl thioether sulfone
In aforementioned oligopolymer, add 0.1～50 part of surplus catalyzer and halogenated aromatic compound and continue to be warming up to 210～260 ℃, kept thermotonus 0.5～6 hour, after cooling, decompression, filtering, deionized water wash with heat is clean, again with light saccharoid in 120 ℃ of dryings of temperature 12 hours, obtain polyaryl thioether sulfone.
Polyaryl thioether sulfone is the product of the white or the different-grain diameter of light outward appearance, and productive rate is 88～98%, solution properties viscosity number η=0.15～0.58, second-order transition temperature Tg 〉=210 ℃, heat-drawn wire T 〉=180 ℃, heat decomposition temperature T
d〉=480 ℃.Can be widely used in the resin base of special engineering plastics, special fibre, film and high performance composite thereof, to satisfy the demand of space flight and aviation, machinery, automobile, electric and chemical industry.
The present invention has following advantage
1, introduce the 3rd monomer halogenated aromatic compound in reaction system, by the conversion of solvent, suitably the adjusting process condition can realize the preparation of the polyaryl thioether sulfone of multiple novel texture.
2, adopt polycomponent composite catalyst and auxiliary agent, the protection of reinforcement system is carried out reaction stage by stage, and it is more stable to have technology, easy to control, the advantage that the reaction times is short.
3, the polyaryl thioether sulfone molecular weight height of Huo Deing, solution properties viscosities il=0.15～0.58, second-order transition temperature Tg 〉=210 ℃ have excellent thermal characteristics, electrical property, corrosion-resistant and physical and mechanical property.
Four, embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment
1, with N-Methyl pyrrolidone 250 grams, sodium hydroxide 4 grams, sodium formiate 5 grams and lithium chloride 5 grams add and have agitator, in the reactor of thermometer and water trap, after stirring, add Na again
2SxH
2O Containing Sulfur sodium ≈ 60%52 grams are at N
2Under the gas shiled, heat temperature raising to 190 ℃ divides water outlet 14 grams, adds dichloro-sulfobenzide 128 grams then, in 170 ℃～180 ℃ reactions of temperature 2.5 hours, adds sodium-acetate 8 grams, and dichlorobenzene 4 grams are warming up to 210～220 ℃, keep this temperature to react 3 hours again.After cooling, decompression, filtering, clean with the deionized water wash of heat, again with product in 120 ℃ of dryings of temperature 12 hours, obtain polyaryl thioether sulfone, productive rate is 95%.
2, with sulfobenzide 280 gram, sodium hydroxide 2 grams, sodium formiate 2 grams and sodium-acetate 6 grams in the identical equipment of adding embodiment 1, after stirring, add Na again
2SxH
2O 52 grams are at N
2Protection is warming up to 200 ℃ down, divides water outlet 16 grams, adds dichloro-sulfobenzide 128 grams then, in 170～180 ℃ of reactions of temperature 3 hours, adds ε-Ji Neixianan 5 grams, and dichloro-oil of mirbane 2 grams are warming up to 220～230 ℃, keep this temperature to react 2.5 hours again.After cooling, decompression, filtering, clean with the deionized water wash of heat, again with product in 120 ℃ of dryings of temperature 12 hours, obtain polyaryl thioether sulfone, productive rate is 93%.
3, with N,N-DIMETHYLACETAMIDE 260 gram, sodium hydroxide 6 grams, Paraformaldehyde 96 6 grams and Sodium Benzoate 6 grams in the identical equipment of adding embodiment 1, after stirring, add Na again
2SxH
2O 52 grams are at N
2Under the gas shiled, be warming up to 150 ℃, divide water outlet 13 grams, add dichloro-sulfobenzide 126 grams then, in 160～170 ℃ of reactions of temperature 3 hours, add epsilon-amino acetate 9 grams, dichloro-benzophenone 8 grams are warming up to 200～210 ℃, keep this temperature to react 3 hours again.After cooling, decompression, filtering, clean with the deionized water wash of heat, again with product in 120 ℃ of dryings of temperature 12 hours, obtain the pure white polyaryl thioether sulfone, productive rate is 93%.
4, with dimethyl sulfoxide (DMSO) 270 gram, sodium hydroxide 3 grams, phenyl aldehyde 5 grams and hydroxy acid sodium 4 grams in the identical equipment of adding embodiment 1, after stirring, add Na again
2SxH
2O 52 grams are at N
2Under the gas shiled, be warming up to 160 ℃, divide water outlet 11 grams, add dichloro-sulfobenzide 128 grams then, in 160 ℃～170 ℃ reactions of temperature 2.5 hours, add tertiary sodium phosphate 8 grams, dichloro-benzonitrile 2 grams are warming up to 210 ℃, keep this temperature to react 3 hours again.After cooling, decompression, filtering, clean with the deionized water wash of heat, again with product in 120 ℃ of dryings of temperature 12 hours, obtain polyaryl thioether sulfone, productive rate is 92%.
5, with HMPA 250 gram, sodium hydroxide 4 grams, sodium formiate 8 grams, paratoluenesulfonic acid sodium salt 5 grams add in the identical equipment of embodiment 1, after stirring, add Na again
2SxH
2O 52 grams are at N
2Protection is warming up to 210 ℃ down, divides water outlet 19 grams, adds dichloro-sulfobenzide 125 grams then, in 170 ℃～180 ℃ of temperature, reacts 2.6 hours, adds lithium chloride 8 grams, and dichloro-diphenyl ether 6 grams are warming up to 220～240 ℃, react 2.5 hours.After cooling, decompression, filtering, clean with the deionized water wash of heat, again with product in 120 ℃ of dryings of temperature 12 hours, obtain polyaryl thioether sulfone, productive rate 96%.
Claims (5)
1, polyaryl thioether sulfone starting raw material recipe ingredient is by weight:
Na
2SxH
2O Na
260% 100 parts of S content ≈
90～305 parts of dichloro-sulfobenzides
0.1～50 part of halogenated aromatic compound
5～200 parts of catalyzer
5～150 parts of auxiliary agents
230～2300 parts of solvents
Wherein halogenated aromatic compound is at least a in trichloro-benzene, dichloro-oil of mirbane, dichloro-aniline, dichloro-benzonitrile, dichlorobenzene, dichloro-benzophenone, dichloro-diphenyl silane and/or the dichloro-phenyl ether.
2,, it is characterized in that catalyzer is at least a in lithium chloride, tertiary sodium phosphate, sodium-acetate, hydroxy acid sodium, epsilon-amino caproic acid, hexanolactam, p-methyl benzenesulfonic acid sodium and/or the Sodium Benzoate according to the described polyaryl thioether sulfone of claim 1.
3,, it is characterized in that auxiliary agent is Paraformaldehyde 96, phenyl aldehyde, sodium formiate, NaBH according to the described polyaryl thioether sulfone of claim 1
4And/or it is at least a in the sodium hydroxide.
4,, it is characterized in that solvent is at least a in N-Methyl pyrrolidone, N-methyl caprolactam, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), HMPA and/or the sulfobenzide according to the described polyaryl thioether sulfone of claim 1.
5, according to the manufacture method of the described polyaryl thioether sulfone of claim 1～4, it is characterized in that:
(1) Na
2SxH
2The O dehydration
With 230～2300 parts of solvents, 5～150 parts of auxiliary agents and 5～200 parts of addings of catalyzer have agitator, in the reactor of thermometer and water trap, after stirring, add Na
2SxH
2O Na
260%100 parts of S content ≈ are at N
2Under the gas shiled,, dewatered 0.2～2 hour in 100～210 ℃ of temperature,
(2) oligopolymer generates
After the reaction system dehydration, add 90～305 parts of dichloro-sulfobenzides, in 100～210 ℃ of reactions of temperature 0.5～6 hour,
(3) preparation of polyaryl thioether sulfone
In oligopolymer, add 0.1～50 part of surplus catalyzer and halogenated aromatic compound and continue to be warming up to 210～260 ℃, keep this temperature to react again 0.5～6 hour, with product cooling, decompression, filtration, and with heat the deionization washes clean, again with reactant in 120 ℃ of dryings of temperature 12 hours, obtain polyaryl thioether sulfone.
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|---|---|---|---|
| CNB021138036A CN1195002C (en) | 2002-05-31 | 2002-05-31 | Polyaryl thioether sulfone and its preparation method |
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| CN1195002C true CN1195002C (en) | 2005-03-30 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974688B (en) * | 2006-12-12 | 2010-10-13 | 中国乐凯胶片集团公司 | Water-base pigment ink |
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| US8240252B2 (en) * | 2005-03-07 | 2012-08-14 | Nikica Maljkovic | Ammunition casing |
| US8445629B2 (en) * | 2006-08-17 | 2013-05-21 | Dic Corporation | Method for producing polyarylene sulfide |
| CN102976983B (en) * | 2012-10-25 | 2015-10-21 | 华中科技大学 | A kind of sulfuryl fluorinated diamine compound and polyimide film material and method for making thereof |
| CN102942696A (en) * | 2012-11-14 | 2013-02-27 | 四川大学 | Atmospheric pressure high-glass temperature polyarylene sulfide sulfone and preparation method thereof |
| CN103087317B (en) * | 2013-02-04 | 2015-04-01 | 四川华通特种工程塑料研究中心有限公司 | Manufacturing method of high-molecular-weight polyphenylene sulfide sulfone |
| CN104292463A (en) * | 2014-09-19 | 2015-01-21 | 中山市鸿程科研技术服务有限公司 | Polyarylene sulfide sulfone and preparation method thereof |
| CN107955159B (en) * | 2016-10-14 | 2020-11-20 | 徐州工程学院 | Silicon-containing main chain arylethernitrile copolymer and preparation method thereof |
| CN107955158A (en) * | 2016-10-14 | 2018-04-24 | 徐州工程学院 | A kind of siliceous main chain aryl oxide ketone copolymers and preparation method thereof |
| CN106750302B (en) * | 2017-01-13 | 2019-01-08 | 四川中科兴业高新材料有限公司 | A kind of preparation method of heat-resisting, corrosion resistant high molecular weight poly arylidene thio-ester sulfone |
| CN108384008A (en) * | 2018-02-26 | 2018-08-10 | 四川理工学院 | A kind of cyano-containing polyphenylene sulfide sulphone resin and preparation method thereof |
| CN110256674A (en) * | 2019-07-16 | 2019-09-20 | 中国石油化工股份有限公司 | A kind of synthetic method of high molecular weight poly arylidene thio-ester sulfone |
| CN110527092B (en) * | 2019-09-06 | 2021-12-17 | 珠海长先新材料科技股份有限公司 | Method for preparing high molecular weight poly (arylene sulfide sulfone) |
| CN114213659B (en) * | 2021-12-27 | 2024-03-26 | 中鼎凯瑞科技成都有限公司 | Heat-resistant silicon-containing polyarylene sulfide and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1974688B (en) * | 2006-12-12 | 2010-10-13 | 中国乐凯胶片集团公司 | Water-base pigment ink |
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