CN107892746A - A kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin - Google Patents
A kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin Download PDFInfo
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- CN107892746A CN107892746A CN201711188865.5A CN201711188865A CN107892746A CN 107892746 A CN107892746 A CN 107892746A CN 201711188865 A CN201711188865 A CN 201711188865A CN 107892746 A CN107892746 A CN 107892746A
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- polyaryl ether
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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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/06—Polysulfones; Polyethersulfones
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Abstract
The invention discloses a kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin, including step：With 4; 4 ' dichloro diphenyl sulfones and bisphenol S or 4; 4 ' '-biphenyl diphenols or bisphenol-A are reaction monomers, using sulfolane as solvent, using sodium carbonate as salt forming agent; in the reactor of nitrogen charging gas shielded; reaction monomers are added sequentially, after monomer all dissolving, salt forming agent is added into system; continue stirring and be warming up to 170 DEG C~180 DEG C, salt-forming reaction 1~2 hour；It is warming up to 210 DEG C~250 DEG C after the completion of salt-forming reaction again, 6~8 hours of constant temperature polymerisation, then aromatic dicarboxylic phenol is added into system, continue to react 40min, to setting viscosity, obtain polymerization mucus；Then a certain proportion of deionized water and the mixture dilution polymerization mucus of sulfolane are added, crushes, purify, drying, obtaining pure coating level polyaryl ether sulphone resin superfines.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of work of coating level superfine powder polyaryl ether sulphone resin
Industry is combined to method.
Background technology
Poly (ether ketone ketone) material has the properties such as ageing-resistant, dimensional stability is high, corrosion-resistant, high temperature resistant, creep resistance,
It is good with the metal adhesion such as iron, aluminium that it has, and coating surface hardness is high and polyether sulphone superfine powder has non-stick cooker coating, low rubbed
The features such as wiping, so being widely used in kitchen, the powder spray and liquid coating of furniture.
Industrial important polyether sulphone includes polyether sulfone (PES), biphenyl polyether sulfone (PPSU) and polysulfones (PSU).It is existing
Polyether sulphone, which has, uses production technology of the diphenyl sulphone (DPS) for solvent, such as European patent document EP2008067700 and United States Patent (USP) text
US20100310804A1 is offered, and uses sulfolane to see Chinese patent literature CN85105138A for the production technology of solvent,
CN1765953A, CN1844196A, CN101704951A, CN101735459A.
Polyether sulphone is produced using diphenyl sulphone (DPS) dicyandiamide solution, corresponding monomer using alkali carbonate as salt forming agent, 250~
320 DEG C or so polymerize 2~3 hours, then add a certain amount of end-capping reagent and anti-degradation agent continues reaction and glued to demand for 1-2 hour
Degree, then obtain polyether sulphone pure resin with purification section by crushing；Sulfolane is used to produce polyether sulphone for dicyandiamide solution
Technique, with alkali metal hydroxide (KOH or NaOH) or alkali carbonate (Na2CO3、K2CO3Or the mixture of both)
For salt forming agent, dimethylbenzene for divide aqua, into after the completion of salt, after 230~250 DEG C of reactions arrive demand viscosity in 3~5 hours, crush,
Water process purifying process obtains pure polyaryl ether sulphone resin.Polyether sulphone prepared by both the above technique is straight after polymerization cools
Connect crushing, the sodium chloride concentration wrapped up in polymerization process in polymer is higher, directly crushes and may result in polymer crushing
More difficult, particle is larger after crushing.
The content of the invention
The defects of it is an object of the invention to overcome above-mentioned prior art, there is provided a kind of coating level superfine powder polyether sulphone
Industrialized synthesis method.The present invention is using sulfolane as solvent, with 4,4 '-dichloro diphenyl sulfone and bisphenol S or 4,4 '-'-biphenyl diphenol or
Bisphenol-A is reaction monomers, using aromatic series diphenol as end-capping reagent, and adds deionized water and the reduction of sulfolane mixed liquor by the later stage
The concentration of the side product chlorinated sodium wrapped up in polymer, to prepare the ultra-fine polyether sulphone powder of coating level, solves conventional synthesis work
The polyether sulphone coating particle diameter of skill synthesis is bigger than normal, caused by levelability is bad the problem of coating functional defect.
A kind of Industrialized synthesis method of coating level superfine powder polyether sulphone of the present invention, comprises the following steps：
(1) polymerisation
In the reactor of nitrogen filled protection, add sulfolane, be added sequentially reaction monomers, the solid content of system for 20%~
45%, after monomer all dissolving, then salt forming agent is added into system, carry out salt-forming reaction；Virtue is added after the completion of salt-forming reaction
Fragrant race's dihydric phenol carries out polymerisation, obtains polymerization mucus；After polymerisation terminates, deionized water and ring fourth are added into anti-system
The mixed solution of sulfone continues stirring reaction；
(2) post-process
But powder is ground into afterwards by the polymerization mucus diluted is water cooled, is removed again with deionized water boiling washing after filtering
Solvent and by-product salt, polyaryl ether sulphone resin powder is produced after re-dry.
The reaction equation of the present invention is as follows：
Preferably, the aromatic dicarboxylic phenol general structure is as follows：
Wherein R1For the alkyl of 1~28 carbon atom, the alcyl of 5~26 carbon atoms, 1~28 carbon atom alcoxyl
Base, the aryl of 6~26 carbon atoms, the alicyclic ring epoxide of the aryloxy group of 6~26 carbon atoms or 5~26 carbon atoms；R2、R3For
Hydrogen, the alkyl of 1~28 carbon atom, the alcyl of 5~25 carbon atoms, alkoxy, 6~25 carbon of 1~28 carbon atom
The alicyclic ring epoxide of the aryl of atom or 6~26 carbon atoms.
Preferably, the reaction monomers are bisphenol S, 4, in 4 '-'-biphenyl diphenol and bisphenol-A one or more mixtures with
The mixture of 4,4 '-dichloro diphenyl sulfone.
It is further preferred that the bisphenol S, 4, middle one or more mixture in 4 '-'-biphenyl diphenol and bisphenol-A
Mole summation is identical with 4,4 '-dichloro diphenyl sulfone mole.
Preferably, the weight ratio of the in the mixed solvent deionized water and sulfolane is 1-3:1-3.
Preferably, the salt forming agent is sodium carbonate.The dosage of the salt forming agent is bisphenol S, 4,4 '-'-biphenyl diphenol and bis-phenol
1.05~1.2 times of the mole summation of one or more mixtures in A.
Preferably, the mole of the aromatic dicarboxylic phenol is 4, the 1%~3% of 4 '-dichloro diphenyl sulfone mole.
Preferably, the quality of in the mixed solvent deionized water is 5~20% of gross mass in reaction system.
Preferably, in salt-forming reaction elementary reaction temperature between 170 DEG C~180 DEG C, the reaction time is 1~2 hour.
Preferably, 210 DEG C~250 DEG C are warming up to again in step (1), after the completion of salt-forming reaction, start with 50~70 turns/
Min mixing speed stirring, constant temperature add aromatic series into system after 1~2 hour, then with 70~90 turns/min of low whipping speed
Dihydric phenol, continue to react 40-50 minutes, obtain polymerization mucus；After polymerisation terminates, deionized water and ring are added into anti-system
The mixed solution of fourth sulfone continues 30~60min of stirring, and mixed solution temperature control is between 100~170 DEG C.
Beneficial effects of the present invention：
The present invention compared with prior art, has：
1) present invention is using sulfolane as solvent, using aromatic dicarboxylic phenol as end-capping reagent, the coating level polyether sulphone tool of preparation
There is good hydrophily, can be as excellent hydrophilic coating.
2) the technology of the present invention production polyaryl ether sulphone resin powder diameter is respectively less than 100 mesh, good dispersion, good leveling property, is
A kind of excellent coating selection.
3) production technology of the invention is simplified, system is simple, and reaction end is easily controllable.
Embodiment
The present invention is further illustrated below by embodiment, following examples are the specific embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments.
Embodiment 1
In the logical nitrogen tube of dress and 200 liters of stainless steel cauldrons of condensation water knockout drum and high-efficiency stirrer, first add
Start stirring after 100.00KG sulfolane and be warming up to 60 DEG C, be added sequentially 23.5KG 4,4 '-dichloro diphenyl sulfone, 15.00KG bis-phenols
S, 9.50KG sodium carbonate is added after monomer all dissolving, continue to be warming up to 170 DEG C under stirring, salt-forming reaction starts, condenser pipe
In begin with cooling water and drip, the salt-forming reaction time is 1.5 hours；250 DEG C are warming up to after the completion of salt-forming reaction again, constant temperature 4 is small
When；Add 0.396KG aromatic series diphenol and continue polymerisation 0.5~2 hour, obtain polymerization mucus；
After polymerisation terminates, 150 DEG C of deionized water is added into anti-system and the mixed solution of sulfolane continues to stir
Mix 30~60min, deionized water and each 10KG of sulfolane.
The polymerization mucus water cooling after dilution finally is ground into powder to be boiled 8 times with deionized water, until chlorion in water
Content is dried under vacuum to moisture weight content less than 0.5% untill below 50ppm, by the polymer after filtering, obtains coating level
Superfine powder polyphenylene ether sulfone (PPSU) pure resin.
Aromatic series diphenol structural formula is as follows：
Gained coating level superfine powder PPSU resin melting index Ms I=40.0g/10min (365.0 DEG C, 5KG).
Embodiment 2
With embodiment 1, except bisphenol S substitutes 4,4 '-'-biphenyl diphenol and addition are that other conditions are identical outside 20KG.
Gained coating level superfine powder PES resin melting index Ms I=38.0g/10min (380.0 DEG C, 2.16KG).
Embodiment 3
With embodiment 1, except bisphenol-A substitutes 4,4 '-'-biphenyl diphenol and addition are that other conditions are identical outside 18KG.
Gained coating level superfine powder PSU resin melting index Ms I=15.0g/10min (343.0 DEG C, 2.16KG).
Claims (10)
1. a kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin, it is characterised in that comprise the following steps：
(1) polymerisation
In the reactor of nitrogen filled protection, add sulfolane, be added sequentially reaction monomers, the solid content of system for 20%~
45%, after monomer all dissolving, then salt forming agent is added into system, carry out salt-forming reaction；Virtue is added after the completion of salt-forming reaction
Fragrant race's dihydric phenol carries out polymerisation, obtains polymerization mucus；After polymerisation terminates, deionized water and ring fourth are added into anti-system
The mixed solution of sulfone continues stirring reaction；
(2) post-process
But powder is ground into afterwards by the polymerization mucus diluted is water cooled, and solvent is removed with deionized water boiling washing again after filtering
And by-product salt, polyaryl ether sulphone resin powder is produced after re-dry.
2. a kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin according to claim 1, its feature
It is, the aromatic dicarboxylic phenol general structure is as follows：
Wherein R1For the alkyl of 1~28 carbon atom, the alcyl of 5~26 carbon atoms, the alkoxy of 1~28 carbon atom, 6
The alicyclic ring epoxide of the aryl of~26 carbon atoms, the aryloxy group of 6~26 carbon atoms or 5~26 carbon atoms；R2、R3For hydrogen, 1
The alkyl of~28 carbon atoms, the alcyl of 5~25 carbon atoms, alkoxy, 6~25 carbon atoms of 1~28 carbon atom
Aryl or 6~26 carbon atoms alicyclic ring epoxide.
3. a kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin according to claim 1, its feature
It is, the reaction monomers are bisphenol S, 4, one or more mixtures and 4,4 '-dichloro in 4 '-'-biphenyl diphenol and bisphenol-A
The mixture of diphenyl sulphone (DPS).
4. a kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin according to claim 3, its feature
It is, the bisphenol S, 4, the mole summation and 4 of middle one or more mixture in 4 '-'-biphenyl diphenol and bisphenol-A,
4 '-dichloro diphenyl sulfone mole is identical.
5. a kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin according to claim 1, its feature
It is, the weight ratio of the in the mixed solvent deionized water and sulfolane is 1-3:1-3.
6. a kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin according to claim 1, its feature
It is, the salt forming agent is sodium carbonate；The dosage of the salt forming agent is one kind in bisphenol S, 4,4 '-'-biphenyl diphenol and bisphenol-A
Or 1.05~1.2 times of the mole summation of a variety of mixtures.
7. a kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin according to claim 1, its feature
It is, the mole of the aromatic dicarboxylic phenol is 4, the 1%~3% of 4 '-dichloro diphenyl sulfone mole.
8. a kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin according to claim 1, its feature
It is, the quality of in the mixed solvent deionized water is 5~20% of gross mass in reaction system.
9. a kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin according to claim 1, its feature
It is, in salt-forming reaction elementary reaction temperature between 170 DEG C~180 DEG C, the reaction time is 1~2 hour.
10. a kind of Industrialized synthesis method of coating level superfine powder polyaryl ether sulphone resin according to claim 1, its feature
It is, is warming up to 210 DEG C~250 DEG C again in step (1), after the completion of salt-forming reaction, starts with 50~70 turns/min stirring
Speed stirs, and constant temperature adds aromatic dicarboxylic phenol into system after 1~2 hour, then with 70~90 turns/min of low whipping speed, after
Continuous reaction 40-50 minutes, obtain polymerization mucus；After polymerisation terminates, the mixed of deionized water and sulfolane is added into anti-system
Close solution and continue 30~60min of stirring, mixed solution temperature control is between 100~170 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285667A (en) * | 2023-04-10 | 2023-06-23 | 安迪森(苏州)硬质合金有限公司 | High-wear-resistance composite coating, preparation method and production equipment thereof |
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| US20110166317A1 (en) * | 2007-09-26 | 2011-07-07 | Ht Materials Corporation | High Temperature Poly(aryl ether)s Containing a Phthalazinone Moiety |
| CN104592515A (en) * | 2014-12-17 | 2015-05-06 | 江门市优巨新材料有限公司 | Industrialized synthesis method of polyether sulfone resin |
| CN105330838A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | Industrialized synthesis method of high-transparent polyaromatic ether sulfone resin |
| CN106832286A (en) * | 2017-03-01 | 2017-06-13 | 山东浩然特塑股份有限公司 | A kind of sulfone birds of the same feather flock together compound industrialization blowing dispersing technology |
-
2017
- 2017-11-24 CN CN201711188865.5A patent/CN107892746A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110166317A1 (en) * | 2007-09-26 | 2011-07-07 | Ht Materials Corporation | High Temperature Poly(aryl ether)s Containing a Phthalazinone Moiety |
| CN104592515A (en) * | 2014-12-17 | 2015-05-06 | 江门市优巨新材料有限公司 | Industrialized synthesis method of polyether sulfone resin |
| CN105330838A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | Industrialized synthesis method of high-transparent polyaromatic ether sulfone resin |
| CN106832286A (en) * | 2017-03-01 | 2017-06-13 | 山东浩然特塑股份有限公司 | A kind of sulfone birds of the same feather flock together compound industrialization blowing dispersing technology |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285667A (en) * | 2023-04-10 | 2023-06-23 | 安迪森(苏州)硬质合金有限公司 | High-wear-resistance composite coating, preparation method and production equipment thereof |
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Application publication date: 20180410 |