CN106565957A - A method of synthesizing polyethersulfone resin - Google Patents
A method of synthesizing polyethersulfone resin Download PDFInfo
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- CN106565957A CN106565957A CN201610891243.8A CN201610891243A CN106565957A CN 106565957 A CN106565957 A CN 106565957A CN 201610891243 A CN201610891243 A CN 201610891243A CN 106565957 A CN106565957 A CN 106565957A
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- bisphenol
- salt
- dimethylbenzene
- diphenyl sulfone
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- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
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- Polymers & Plastics (AREA)
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Abstract
The invention relates to a method of synthesizing polyethersulfone resin. Bisphenol S and 4,4'-dichlorodiphenyl sulfone are adopted as main raw materials. Firstly, the bisphenol S forms a bisphenol S salt under an alkaline condition, and then the bisphenol S salt and the 4,4'-dichlorodiphenyl sulfone are subjected to polymerization with the existence of a polyethylene glycol type catalyst to form the polyethersulfone resin. The method is low in cost and simple, after-treatment is easy, and performance indexes of a prepared product are good.
Description
Technical field
The present invention relates to a kind of synthetic method of engineering plastics, and in particular to a kind of synthetic method of polyethersulfone resin.
Background technology
Plastics belong to one of requisite material in life, in daily life, the clothing, food, lodging and transportion -- basic necessities of life of people all with plastics
It is closely bound up.Classify according to use requirement, plastics are divided into three kinds：General-purpose plastics, engineering plastics and special engineering plastics.Extraordinary work
Engineering plastics refer to the class engineering plastics that combination property is higher, Long-Time Service temperature is more than 150 DEG C, relative to ordinary skill modeling
For material, special engineering plastics have more preferable heat resistance, mechanical property etc..It is same the urgent need for meeting arms race
When, important effect is also functioned in the update of other field product, such as：Nuclear energy field, mechanical manufacturing field, oil
Work field, automobile industry, aviation field, electronic information field etc..In the world today, in order to meet the needs of every field, greatly
Many special engineering plastics have been carried out industrialized production, such as：Polysulfones (PSU), polyphenylene oxide (PPO), polytetrafluoroethylene (PTFE) (PTFE),
PAEK (PAEK), polyimides (PI) etc..
Polyethersulfone resin belongs to the resinoid one kind of aromatic polysulfones, and referring to has the one of sulfuryl and aromatic core to birds of the same feather flock together on macromolecular chain
Compound, it is transparent, amber, is interconnected by ether, phenyl and sulfuryl and is formed, and ether possesses flexibility, and phenyl ring has rigidity,
The big conjugated system that sulfuryl and total unit are formed, so, polyether sulfone molecule have simultaneously flexible and rigid structure and
Conjugated system, whole molecule seems quite stable.Therefore, it possesses good mechanical property, and higher temperature classification is excellent
Anti-flammability, in addition its acid-fast alkali-proof and hydrolytic resistance are all very good, just because of these superior performances so that polyethersulfone resin
It is widely used in electronics, space flight and aviation, communication and medicine equipment etc..With the development of science and technology, polyethersulfone resin is in the whole world
Special status is occupied in plastics, it is more urgent to the demand of this kind of polymeric material.
The polyether sulfone synthesis of China has the research experience of decades, but yield is but difficult to always the demand maintained market,
Cast aside yield not talk, the polyether sulfone of China's production lacks high and new technology added value, and the quality of product also lags behind always foreign countries
Product, many important production parts, still will meet demand by import.
At present, synthesizing polyether sulphone resin mainly has a three kinds of methods, the first dehydrohalogenation method, the method have the advantages that it is a lot,
Such as：Process is more steady, reacts the temperature for needing than relatively low, can be more as the reagent of solvent, reacts easily controllable, cost compared with
It is low, but, the method easily produces the branched phenomenon of strand, can produce impact to the linear structure of polyether sulfone strand, from
And the performance of PES resins is affected, the reduction of such as mechanical strength, heat resistance is deteriorated, and melt index is little, rear processing difficulties etc.；The
Two kinds of methods are melting desalination process, and the method advantage is can be readily attained linear macromolecular polyethersulfone resin, are had the disadvantage anti-
The field that should be operated is harsher, need 300 DEG C of high temperature and the condition of vacuum, and the product for obtaining is difficult to purify and takes off
Salt treatment；The third method is single phenol or bisphenol S desalination process, wherein, bisphenol S synthetic method be current China use it is most conventional
Method, the product that this kind of method is obtained is not in substantial amounts of side chain, but can generate in the first step salt-forming reaction water and
Shipwreck is to eliminate and higher to reaction temperature requirement, typically will be more than 200 DEG C, and the molecular weight of high polymer of synthesis is still
It is so less desirable, therefore, in the urgent need to one kind is with low cost, method is simple, convenient post-treatment, and polyethersulfone resin is polymerized
Spend higher method to meet the demand of social development.
The content of the invention
The technical problem to be solved in the present invention is that the side chain for occurring in the synthesis of current polyethersulfone resin is more, in reaction
Solvent be difficult to remove, the problems such as the product degree of polymerization for obtaining is not high, there is provided a kind of with low cost, method is simple, post processing side
And the higher method of the polyethersulfone resin degree of polymerization just,.
The technical solution adopted for the present invention to solve the technical problems is：
(1) salt-forming reaction
Bisphenol S and salt forming agent are added in the four-hole boiling flask equipped with condensation water knockout drum and the 250mL of thermometer, wherein into salt
Alkali and the mol ratio of bisphenol S are 1.1: 1.0 in agent, and with sulfolane solvent is made, and dimethylbenzene makees water entrainer, the wherein matter of dimethylbenzene
Measure as the 50% of sulfolane quality, 150 DEG C of condensing refluxes are heated to, until dimethylbenzene is all steamed with water；
(2) polymerisation
Second raw material 4,4 '-dichloro diphenyl sulfone and catalyst polyethylene glycol are added in above-mentioned flask, wherein 4,4 '-two
Chloro-diphenyl sulfone is 1.0: 1.0,4 with the mol ratio of bisphenol S, and 4 '-dichloro diphenyl sulfone is 1.0 with the mass ratio of catalyst polyethylene glycol
: 0.115, it is 210 DEG C to continue to heat up up to temperature, equilibrium temperature polymerisation 8-13h；(3) product post processing
Liquid obtained above is poured in 500mL beakers, adds 100mL hot distilled waters, beaker neutrality to be carved with white films
Shape thing is produced, and opens heating devices heat stirring until seething with excitement, persistently stirring boiling 1h, and liquid is outwelled after product cooling must be consolidated
Body product, 2-3 rear addition absolute ethyl alcohol of cyclic washing repeats operation above, and heating washing 2-3 time is cooled down, decompression suction filtration,
It is drying to obtain required product.
Used as limitation of the invention, the salt forming agent described in step (1) of the present invention is the K of mass fraction 30%2CO3Alkali
Solution.
Used as limitation of the invention further, step (2) catalyst polyethylene glycol of the present invention is polyethylene glycol
600。
After above-mentioned technical scheme, the beneficial effect that the present invention is obtained is：The synthetic method of the present invention is with low cost,
Method is simple, product convenient post-treatment, and the main performance index of the polyethersulfone resin synthesized using this method is better than the existing country
Product, the degree of polymerization is also superior to existing home products.
Specific embodiment
Now the present invention is further detailed explanation.
The present invention will be described further with regard to following examples, however, it should be noted that these embodiments are only to illustrate
It is used, and is not necessarily to be construed as the restriction of present invention enforcement.
Embodiment 1
(1) salt-forming reaction
10.0g bisphenol Ss and 20.3g 30% are added in the four-hole boiling flask equipped with condensation water knockout drum and the 250mL of thermometer
K2CO3The aqueous solution, with 50mL sulfolane solvent is made, and 40mL dimethylbenzene makees water entrainer, is heated to 150 DEG C of condensing refluxes, directly
All steamed with water to dimethylbenzene；
(2) polymerisation
11.48g4,4 '-dichloro diphenyl sulfone and 1.0g catalyst polyethylene glycols 600 are added in above-mentioned flask, continues to heat up
Until temperature is 210 DEG C, equilibrium temperature polymerisation 8h；
(3) product post processing
Liquid obtained above is poured in 500mL beakers, adds 100mL hot distilled waters, beaker neutrality to be carved with white films
Shape thing is produced, and opens heating devices heat stirring until seething with excitement, persistently stirring boiling 1h, and liquid is outwelled after product cooling must be consolidated
Body product, 2-3 rear addition absolute ethyl alcohol of cyclic washing repeats operation above, and heating washing 2-3 time is cooled down, decompression suction filtration,
It is drying to obtain required product.
Embodiment 2
(1) salt-forming reaction
20.0g bisphenol Ss and 40.60g are added in the four-hole boiling flask equipped with condensation water knockout drum and the 250mL of thermometer
30% K2CO3The aqueous solution, with 100mL sulfolane solvent is made, and 80mL dimethylbenzene makees water entrainer, is heated to 150 DEG C and is condensed back
Stream, until dimethylbenzene is all steamed with water；
(2) polymerisation
22.96g4,4 '-dichloro diphenyl sulfone and 2.0g catalyst polyethylene glycols 600 are added in above-mentioned flask, continues to heat up
Until temperature is 210 DEG C, equilibrium temperature polymerisation 12h；
(3) product post processing
Liquid obtained above is poured in 500mL beakers, adds 100mL hot distilled waters, beaker neutrality to be carved with white films
Shape thing is produced, and opens heating devices heat stirring until seething with excitement, persistently stirring boiling 1h, and liquid is outwelled after product cooling must be consolidated
Body product, 2-3 rear addition absolute ethyl alcohol of cyclic washing repeats operation above, and heating washing 2-3 time is cooled down, decompression suction filtration,
It is drying to obtain required product.
Embodiment 3
(1) salt-forming reaction
200.0g bisphenol Ss and 406g are added in the four-hole boiling flask equipped with condensation water knockout drum and the 3000mL of thermometer
30% K2CO3The aqueous solution, with 1000mL sulfolane solvent is made, and 800mL dimethylbenzene makees water entrainer, is heated to 150 DEG C of condensations
Backflow, until dimethylbenzene is all steamed with water；
(2) polymerisation
229.6g 4,4 '-dichloro diphenyl sulfone and 20.0g catalyst polyethylene glycols 600 are added in above-mentioned flask, continues to rise
Temperature is 210 DEG C up to temperature, equilibrium temperature polymerisation 12h；
(3) product post processing
Liquid obtained above is poured in plastic bucket, 2000mL hot distilled waters are added, it is membranaceous that bucket neutrality is carved with white
Thing is produced, and opens stirring heating water bath to 98 DEG C, persistently stirs 1h, liquid is outwelled after product cooling and obtains solid product, repeatedly
2-3 rear addition absolute ethyl alcohol of washing repeats operation above, and heating washing 2-3 time is cooled down, and decompression suction filtration is drying to obtain institute
Need product.
The test of properties of product：
(1) respectively according to GB1040, the standard of GB9341 is tested the physics characteristic of product, and with it is existing
Polyethersulfone resin test result is as shown in table 1：
The mechanical performance of the PES of table 1
| Embodiment | Tensile strength/MPa | Heat distortion temperature/DEG C | Fire resistance/level |
| Embodiment 1 | 85 | 212 | V-0 |
| Embodiment 2 | 87 | 212 | V-0 |
| Embodiment 3 | 87 | 212 | V-0 |
| Contrast factory products | 85 | 210 | V-0 |
As it can be seen from table 1 its tensile strength of the product obtained by the present invention and heat distortion temperature are better than existing home products.
(2) product and contrast product to obtaining carries out gel chromatography analysis, and sample is located as follows before analysis
Reason：
(A) 0.03g samples are weighed in the volumetric flask of 10mL with electronic analytical balance, addition DMF constant volumes obtain concentration and are
The solution of 3mg/mL, can not artificially apply external force and accelerate it to dissolve during solid dissolving, such as heating, solvent auxiliary,
Be stirred vigorously, sonic oscillation etc., can only stand dissolves it, and needs time enough, time of repose about 2h.
(B) after sample is completely dissolved, also solution is filtered.Filtration adopt specification for 10mL needleless injector with
0.45 μm of nylon organic phase formula filter, draws first before filtration the sample solution cleaning filter of 1mL or so, how to inhale afterwards
The solution cleaning reagent bottle of 1mL is taken, cleaning is extracted the sample solution of more than 2mL and is expelled in reagent bottle by filter after finishing,
Subsequently the good numbering of sealing mark sends to detection.
The result that gel chromatography is measured is as shown in the institute of table 2：
The sample of table 2 and the GPC testing results for optimizing product
| Embodiment | Mn | Mw | Mp | MZ | MZ+1 | PDI |
| Embodiment 1 | 44839 | 73003 | 68093 | 107491 | 146616 | 1.628 |
| Embodiment 2 | 48341 | 74056 | 72567 | 104049 | 136522 | 1.532 |
| Embodiment 3 | 57927 | 93278 | 79657 | 116387 | 152506 | 1.457 |
| Contrast product | 56962 | 93278 | 77026 | 143834 | 208966 | 1.638 |
Find out from polymer gel chromatogram analysis data, amplification test of the present invention is that the number of the product that embodiment 3 is obtained is equal
Molecular weight, weight average molecular weight, peak molecular weight and mean molecule quantity are above the corresponding numerical value of domestic contrast product.
With the above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff is complete
Entirely various change and modification can be carried out in the range of without departing from this invention technological thought.The technology of this invention
Property scope is not limited to the content on specification, it is necessary to its technical scope is determined according to right.
Claims (3)
1. a kind of method of synthesizing polyether sulphone resin, it is characterised in that the method is followed the steps below：
(1) salt-forming reaction
Bisphenol S and salt forming agent are added in the four-hole boiling flask equipped with condensation water knockout drum and thermometer, wherein in salt forming agent alkali with it is double
The mol ratio of phenol S is 1.1: 1.0, and with sulfolane solvent is made, and dimethylbenzene makees water entrainer, and the wherein quality of dimethylbenzene is sulfolane matter
The 50% of amount, is heated to 150 DEG C of condensing refluxes, until dimethylbenzene is all steamed with water；
(2) polymerisation
Second raw material 4,4 '-dichloro diphenyl sulfone and catalyst polyethylene glycol are added in above-mentioned four-hole boiling flask, wherein 4,4 '-two
Chloro-diphenyl sulfone is 1.0: 1.0,4 with the mol ratio of bisphenol S, and 4 '-dichloro diphenyl sulfone is 1.0 with the mass ratio of catalyst polyethylene glycol
: 0.115,210 DEG C are continuously heating to, stable polymerisation 8-13h at this temperature；
(3) product post processing
Liquid obtained above is poured in 500mL beakers, adds 100mL hot distilled waters, beaker neutrality to be carved with white membranoid substance
Produce, open heating devices heat stirring until boiling, persistently stirring boiling 1h, liquid is outwelled after product cooling and obtains solid product
Product, 2-3 rear addition absolute ethyl alcohol of cyclic washing repeats operation above, and heating washing 2-3 time is cooled down, and decompression suction filtration is dried
Obtain final product required product.
2. the method for a kind of synthesizing polyether sulphone resin according to claim 1, it is characterised in that described in step (1) into
Salt agent is K that mass fraction is 30%2CO3Aqueous alkali.
3. the method for a kind of synthesizing polyether sulphone resin according to claim 1, it is characterised in that step (2) catalyst is poly-
Ethylene glycol 600.
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| CN201610891243.8A CN106565957A (en) | 2016-10-13 | 2016-10-13 | A method of synthesizing polyethersulfone resin |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019219866A1 (en) | 2018-05-17 | 2019-11-21 | Solvay Specialty Polymers Usa, Llc | Method of making a three-dimensional object using a poly(aryl ether sulfone) (paes) polymer of low polydispersity |
| CN111788252A (en) * | 2018-02-07 | 2020-10-16 | 江门市优巨新材料有限公司 | Polyether sulphone-etherimide copolymer and preparation method thereof |
| CN117069652A (en) * | 2023-10-16 | 2023-11-17 | 富海(东营)新材料科技有限公司 | Double-onium salt catalyst and application thereof in polyether sulfone synthesis |
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| CN104387587A (en) * | 2014-11-07 | 2015-03-04 | 四川大学 | High-fluidity polyether sulfone/amide copolymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104387587A (en) * | 2014-11-07 | 2015-03-04 | 四川大学 | High-fluidity polyether sulfone/amide copolymer and preparation method thereof |
Non-Patent Citations (1)
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| 卜小蒙: "聚醚砜合成工艺的再研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111788252A (en) * | 2018-02-07 | 2020-10-16 | 江门市优巨新材料有限公司 | Polyether sulphone-etherimide copolymer and preparation method thereof |
| CN111788252B (en) * | 2018-02-07 | 2023-04-28 | 广东优巨先进新材料股份有限公司 | Polyether sulfone-ether imide copolymer and preparation method thereof |
| WO2019219866A1 (en) | 2018-05-17 | 2019-11-21 | Solvay Specialty Polymers Usa, Llc | Method of making a three-dimensional object using a poly(aryl ether sulfone) (paes) polymer of low polydispersity |
| CN112119110A (en) * | 2018-05-17 | 2020-12-22 | 索尔维特殊聚合物美国有限责任公司 | Method for making three-dimensional objects using low polydispersity poly (aryl ether sulfone) (PAES) polymers |
| CN117069652A (en) * | 2023-10-16 | 2023-11-17 | 富海(东营)新材料科技有限公司 | Double-onium salt catalyst and application thereof in polyether sulfone synthesis |
| CN117069652B (en) * | 2023-10-16 | 2024-01-12 | 富海(东营)新材料科技有限公司 | Double-onium salt catalyst and application thereof in polyether sulfone synthesis |
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