CN107955168A - A kind of siliceous main chain aryl oxide sulfone copolymer and preparation method thereof - Google Patents
A kind of siliceous main chain aryl oxide sulfone copolymer and preparation method thereof Download PDFInfo
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- CN107955168A CN107955168A CN201610898647.XA CN201610898647A CN107955168A CN 107955168 A CN107955168 A CN 107955168A CN 201610898647 A CN201610898647 A CN 201610898647A CN 107955168 A CN107955168 A CN 107955168A
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- 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
Abstract
A kind of siliceous main chain aryl oxide sulfone copolymer of the present invention and preparation method thereof belongs to the technical field of high molecular material.Siliceous main chain aryl ether sulfone copolymer structure formula is as follows:The present invention carries out copolymerization with double (4 hydroxy phenyl) alkyl silanes of 2,2' and other biphenol monomers for primary raw material and 4,4' dichloro diphenyl sulfone, prepares a kind of siliceous main chain aryl oxide sulfone copolymer.The analog copolymer improves melting, the dissolving processing performance of polyaryl ether sulphone resin, has preferable heat endurance and film forming, have potential application value in the field such as functional paint and seperation film due to introducing silane backbone structure.
Description
Technical field
A kind of siliceous main chain aryl oxide sulfone copolymer of the present invention and preparation belong to high molecular material and its technology neck of synthesis
Domain.
Background technology
Polyether sulfone is the thermoplastic macromolecule material containing sulfuryl, ether and phenyl on molecule main chain, due to sulfuryl
For the highest oxidation state of sulphur atom, most stable state is shown, enhance the resonance degree in contraposition, thus its imparting polymer is excellent
Good resistance to oxidation and heat endurance.Ether can rotate freely adjacent segment, and polymer chain link has in molten condition
There is good mobility, in appropriate temperature melt-processable, polyether sulfone is possessed certain toughness, the benzene on polymer chain
Base assigns high intensity and modulus.Therefore compared with common thermoplastic resin, polyether sulfone has excellent heat resistance, creep resistant
The features such as performance, impact resistance, chemical proofing, anti-flammability, transparent insulation stability and product, in defence and military, weapon
The high-tech such as equipment, aerospace, electronics, automobile, machinery, petroleum industry, nuclear energy and physical therapy health, which are possessed, to be widely applied.To the greatest extent
Pipe polyaryl ether sulphone resin has excellent physical and mechanical properties, but its processed and applied problem under some specific environments is still
An important factor for hindering its development.Siliceous aromatic polymer is that one kind fragrance that flexible silane structure is introduced to main polymer chain gathers
Compound, such as siliceous Nomex, siliceous polyarylate, Silicone Containing Polyimides, Han Gui polyoxadiazoles, siliceous polybenzimidazoles etc..It is soft
Property silane structure can substantially increase the glass transition temperature of polymer and heat decomposition temperature interval range, thus this kind of material has
There is more preferable thermoforming working ability；The solvability of polymer can also be effectively improved, is allowed to be soluble in aprotic, polar
Property solvent such as DMF, DMA, NMP, DMSO, it might even be possible to be dissolved in weaker polar solvent chloroform with pyridine.
102850547 A of patent CN disclose polyaryl ether sulphone resin and its preparation that a kind of main chain contains Si-O-Si structures
Method, 1 that Si-O-Si structures are contained with main chain, 1,3,3- tetramethyl disiloxane -1,3-, bis- (3- methoxyl group -4- propylbenzenes
Phenol) (2Si-PH) be raw material, with '-biphenyl diphenol and dichloro diphenyl sulfone copolycondensation, prepare the poly- virtue that main chain contains Si-O-Si structures
Ether sulfone resin.Resin has excellent heat resistance, dissolubility and an oxidation stability, but main chain contain Si-O-Si structures its in acid
Susceptible to hydrolysis and chain rupture under the conditions of alkali.
Song is just raw et al. with dimethyl dibenzyl base silane and 4, and 4 '-two phenoxy group benzene and m-phthaloyl chloride are monomer, are adopted
Synthesized ternary random backbone silicon hybridization polyaryletheretherketone ketone copolymers with the route of parental materials, compliance is good, and with compared with
High fracture toughness, its dissolubility are also greatly improved, but since silicon and phenyl ring are spaced methylene, destroy sigma-pi conjugated
Structure, heat endurance decrease.[leaf Shang Hui, Wen Hongli, Song Caisheng etc., the synthesis of main chain silicon hybridization polyaryletheretherketone ketone with
Characterization, Jiangxi Normal University's journal (natural science edition) .2005,29 (6):505-508.]
Zhou Qifeng et al. then uses the ethers such as 4,4 '-diacid chloride base phenyl-dimethyl silane and bis- phenoxy group benzene cyanogen of 2,5-
Monomer carries out cryogenic fluid electrophilic substitution reaction, and silane structure is incorporated into poly (arylene ether nitrile) system.The polymer prepared can
Be dissolved in polar organic solvent and there is good heat endurance, no matter in inert atmosphere or under air conditions, 350 DEG C with
Under do not decompose, but due to using parental materials route, backbone structure controllability is weaker.[Gao Zihong, the model Milky Way, Chen Xiaofang, Zhou Qi
Phoenix, the synthesis of novel siliceous polyether sulfone and characterization, Chemical Journal of Chinese Universities .2005,26 (8):1579-1581.]
Double (4- hydroxy phenyls) alkyl silanes of 2,2'- of the present invention and other biphenol monomers are primary raw material and 4,4 '-dichloro
Diphenyl sulphone (DPS) class monomer etc. carries out copolymerization, prepares the aryl ether sulfone co-polymer of siliceous backbone structure.Such polymer due to
Silane backbone structure is introduced, improves melting, the dissolving processing performance of polyaryl ether sulphone resin, there is preferable heat endurance and film forming
Property, there is potential application value in the field such as functional paint and seperation film.
The content of the invention
The technical problem to be solved in the present invention is be equipped with other bis-phenol lists with double (4- hydroxy phenyls) alkyl silanes of 2,2'-
Body and 4,4 '-dichloro diphenyl sulfone monomer copolymerization, so that silane backbone structure is introduced into aryl oxide sulfone copolymer macromolecular, is prepared
With excellent melt, dissolving processing performance copolymer resin.
Technical scheme is as follows：
A kind of siliceous main chain aryl oxide sulfone copolymer of the present invention, its structural formula are as follows:
Wherein X is:
P+q=1,0 ＜ p≤0.5,0.5≤q ＜ 1；R1、R2For methyl, phenyl or vinyl etc..
It is solution polycondensation that the present invention, which prepares a kind of method of siliceous main chain aryl oxide sulfone copolymer,.
Specific polymerization process can be divided into the following three stage：
(1) the low-temp reaction stage：Controlling reaction temperature first is protected in 60-100 DEG C in inert gas, such as nitrogen or argon gas
Under shield, catalyst, co-catalyst and biphenol monomer and 4,4 '-dichloro diphenyl sulfone monomer reaction.This stage takes 12-24h, has
Part low molecular weight prepolymer produces, and system viscosity change is smaller.The stage, higher temperature can cause appearance 2, double (the 4- hydroxyls of 2'-
Base phenyl) alkyl silane intramolecular rearrangement side reaction.
(2) heat up the condensation stage：It is warming up to 150-200 DEG C, further condensation reaction generation high polymer between oligomer, body
It is that viscosity progressively becomes larger.After viscosity is without significant change, stops heating, cool.When this stage takes that about 3-12 is small, if viscous
Solvent can suitably be added by spending height.
(3) discharge post-processing stages：Under agitation with water by polymer agglomerates, be precipitated out；Then separate, by water repeatedly
Wash to remove solvent and inorganic salts remaining in product；Finally drying can obtain siliceous main chain aryl ether sulfone copolymer resin.
The feature monomer that the present invention uses is double (4- hydroxy phenyls) alkyl silanes of 2,2'-, its synthetic method is referring to document
Journal of Organometallic Chemistry,1972,36(2):283-291。
The molal quantity of double (4- hydroxy phenyls) alkyl silanes of 2,2'- and another biphenol monomer X and with 4,4 '-dichloro diphenyl sulfone
The mole ratio of monomer is p:q:1, p+q=1,0 ＜ p≤0.5,0.5≤q ＜ 1.
Wherein X is included to cut and is not limited to:
The polymerization solvent that the present invention uses includes but not limited to, 1-methyl-2-pyrrolidinone (NMP), N, N- dimethyl methyls
The non-protonic polars such as acid amides (DMF), DMAC N,N' dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO) or sulfolane (TMS)
For organic solvent as polymerization solvent, the quality of initial solvent is 2-6 times of reactant quality.
The catalyst that the present invention uses is K2CO3Or Na2CO3Etc. the salt of alkali or alkaline earth metal, its dosage and 4,
The molar ratio of 4 '-dichloro diphenyl sulfone is 1.05~1.1, and co-catalyst is potassium fluoride, its dosage and 4,4 '-dichloro diphenyl sulfone rubs
You are than being 1.5~3:1.
The effect and benefit of the present invention：The present invention provides one kind to have synthesized siliceous main chain aryl oxide sulfone copolymer and preparation side
Method.After flexible silane structure introduces main polymer chain, glass transition temperature and melt processing temperature substantially reduce, advantageously
In thermoplastic shaping；Solvability in a solvent is obviously improved, and is more conducive in fields such as coating, adhesive and seperation films
Using.
Brief description of the drawings
Fig. 1 is the FTIR spectrograms of the polyether sulphone prepared by the embodiment of the present invention 1.In 1148cm-1It is diphenyl sulphone (DPS) at wave number
The stretching vibration characteristic absorption peak of base,；1264cm-1It is the characteristic absorption peak of silicon methyl, 1455cm at wave number-1Stretch for Si-Ph
Vibration peak, it was demonstrated that synthesize subject polymer.
Fig. 2 is the H-NMR spectrum of the polyether sulphone prepared by the embodiment of the present invention 1.It is silicon methyl hydrogen at 0.83ppm
Chemical shift, it was demonstrated that synthesize subject polymer.
Fig. 3 is the DSC spectrograms of the polyether sulphone prepared by the embodiment of the present invention 1.The polymer is amorphous polymer, glass
Glass transition temperature is 168.4 DEG C.
Fig. 4 is the TGA spectrograms of the polyether sulphone prepared by the embodiment of the present invention 1.5% thermal weight loss under polymer condition of nitrogen gas
Temperature is 515 DEG C, it was demonstrated that the material has preferable heat endurance.
Embodiment
The present invention is described in further details with reference to embodiment.
Embodiment 1
In the drying three-necked flask with mechanical agitation, reflux condensing tube and gas-guide tube, double (the 4- hydroxyls of 2,2'- are added
Phenyl) dimethylsilane 0.01mol (2.44g), the bisphenol-A of 0.04mo1 (9.12g), 0.05mo1 (14.35g) 4,4 '-dichloro
Diphenyl sulphone (DPS), 0.055mo1 (7.6g) Anhydrous potassium carbonate, 0.1mo1 (5.8g) anhydrous potassium fluoride, solvent are dimethyl sulfoxide (DMSO) (DMSO)
60mL.Under nitrogen protection, 24h is reacted at 80 DEG C.Then 180 DEG C are progressively warming up to, the reaction was continued.React 8 it is small when after, system
Become viscous, add appropriate DMSO solvents, reaction was completed.Polymer solution is fallen in the water of stirring, white product separates out.Go
Ionized water boiling washing product several times, when 80 DEG C of forced air dryings 12 are small, must refine the siliceous main chain polyethersulfone copolymer powder of white
23.19g, yield 96.3%.The molecular weight of polymerFor 3.25 × 104g·mol-1, molecular weight distributing index is
1.93。
Wherein siliceous biphenol monomer is using double (4- hydroxy phenyls) aminomethyl phenyl silanes of 2,2'-, double (the 4- hydroxy benzenes of 2,2'-
Base) diphenyl silane, double (4- hydroxy phenyls) the ethylene methacrylic base silanes of 2,2'-, other copolymerization biphenol monomers using hydroquinone,
'-biphenyl diphenol, 2,6- naphthalenediols, 4,4'- dihydroxy diphenyl ethers, 4,4'- dihydroxy diphenyl sulfide, 4,4'- dihydroxydiphenylsulisomers,
It can obtain analog result.4,4 '-dichloro diphenyl sulfone monomer uses (4- fluoro benzoyls) benzene of 1,4- bis- and (the 4- fluorobenzene first of 1,3- bis-
Acyl group) benzene, it can obtain analog result.
Embodiment 2
It is identical with the method for embodiment 1, change successively in embodiment 1 double (4- hydroxy phenyls) dimethylsilanes of 2,2'- with
The ingredient proportion p/q of bisphenol-A, after processing same as Example 1, respectively obtains molecular weight in 2.47-4.38 × 104g·mol-1Between siliceous main chain aryl ether sulfone copolymer powder, gained sample yield is between 90%-97%.Table 1 show the double (4- of 2,2'-
Hydroxy phenyl) performance parameter of copolymer obtained by dimethylsilane different content.
Table 1:Polymer performance parameter
Embodiment 3
Double (4- hydroxy phenyls) the dimethylsilane 0.01mol (2.44g) of 2,2'- and 4,4'- dichloros are added in three-necked flask
Diphenyl sulphone (DPS) 0.05mo1 (14.35g) and 0.011mo1 (1.52g) Anhydrous potassium carbonate, solvent are dimethyl sulfoxide (DMSO) (DMSO)
60mL, under nitrogen protection, reacts 12h at 80 DEG C.Then bisphenol-A 0.04mo1 (9.12g) and Anhydrous potassium carbonate are added
0.044mo1 (6.08g) is warming up to 180 DEG C, when reaction 6 is small.After system becomes viscous, appropriate solvent is added, reaction was completed, can obtain
To siliceous main chain aryl ether sulfone copolymer powder, yield 94.2%, the molecular weight of polymerFor 3.81 × 104g·mol-1。
Embodiment 4
Identical with the method for embodiment 1, initial polymerization temperature is changed to 100 DEG C, and the reaction time is changed to 12h, remaining complete phase
Together, siliceous main chain aryl ether sulfone copolymer powder, yield 87.6%, the molecular weight of polymer can also be obtainedFor 1.97 ×
104g·mol-1。
Embodiment 5
Identical with the method for embodiment 1, reactant quality is constant, and it is 50ml to change first set reaction solvent dosage successively,
100ml or 150ml, remaining is identical, can also obtain the molecular weight of polymerFor 2.08-3.51 × 104g·mol-1
Between siliceous main chain aryl ether sulfone copolymer powder, yield is between 91%-95%.
Embodiment 6
It is identical with the method for embodiment 1, only change 0.055mo1 Anhydrous potassium carbonates into 0.055mo1 natrium carbonicum calcinatums, remaining
It is identical, it can also obtain siliceous main chain aryl ether sulfone copolymer powder, yield 87%, the molecular weight of polymerFor 1.63
×104g·mol-1。
Embodiment 7
Solvent in embodiment 1 to 6 is changed to 1-methyl-2-pyrrolidinone (NMP), obtains same or like result.
Claims (4)
1. siliceous main chain aryl oxide sulfone copolymer, its structural formula are as follows:
Wherein X is:
P+q=1,0 ＜ p≤0.5,0.5≤q ＜ 1；R1、R2For methyl, phenyl or vinyl etc..
2. a kind of preparation method of the aryl ether sulfone co-polymer of claim 1, with double (4- hydroxy phenyls) alkyl silanes of 2,2'-,
Other biphenol monomers and 4,4 '-dichloro diphenyl sulfone monomer is raw material, using the salt of alkali or alkaline earth metal as catalyst, fluorination
Potassium is co-catalyst.The molal quantity of double (4- hydroxy phenyls) alkyl silanes of 2,2'- and another biphenol monomer and with 4,4 '-dichloro two
The mole ratio of benzene sulfone monomer is p:q:1, p+q=1,0 ＜ p≤0.5,0.5≤q ＜ 1, catalyst and 4,4 '-dichloro diphenyl sulfone
The molar ratio of monomer is 1.05~1.1:1, co-catalyst and 4, the molar ratio of 4 '-dichloro diphenyl sulfone is 1.5~3:1, it is initial molten
The quality of agent is 2-4 times of reactant quality.Reactant, solvent and catalyzer temperature-elevating are added in the container of inert gas shielding
To 60-100 DEG C, after reacting 12-24h, when 150-200 DEG C of reaction 3-12 is small；Product is poured into cold water, through crushing, obtains powder
Last shape sample, removes inorganic salts and solvent with distilled water boiling washing, is drying to obtain the siliceous main chain aryl ether sulfone of white powder and is total to
Copolymer resin.
3. the preparation method of siliceous main chain aryl oxide sulfone copolymer as claimed in claim 2, it is characterised in that described is another double
Phenol monomer, includes but not limited to hydroquinone, '-biphenyl diphenol, 2,6- naphthalenediols, 4,4'- dihydroxy diphenyl ethers, 4,4'- dihydroxy
Diphenyl sulfide, 4,4' dihydroxydiphenyl sulfone.
4. the preparation method of siliceous main chain aryl oxide sulfone copolymer as claimed in claim 2, it is characterised in that the solvent,
Including but not limited to, 1-methyl-2-pyrrolidinone (NMP), n,N-Dimethylformamide (DMF), n,N-dimethylacetamide
(DMAc), dimethyl sulfoxide (DMSO) (DMSO) or sulfolane (TMS).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073740A (en) * | 2022-07-19 | 2022-09-20 | 宁夏清研高分子新材料有限公司 | Polysulfone polymer and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850547A (en) * | 2012-10-15 | 2013-01-02 | 吉林大学 | Polyarylether sulphone resin with Si-O-Si structure in main chain and preparation method of resin |
| KR20140109619A (en) * | 2013-03-06 | 2014-09-16 | 동우 화인켐 주식회사 | Poly(ethersulfone) resin |
-
2016
- 2016-10-14 CN CN201610898647.XA patent/CN107955168A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850547A (en) * | 2012-10-15 | 2013-01-02 | 吉林大学 | Polyarylether sulphone resin with Si-O-Si structure in main chain and preparation method of resin |
| KR20140109619A (en) * | 2013-03-06 | 2014-09-16 | 동우 화인켐 주식회사 | Poly(ethersulfone) resin |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073740A (en) * | 2022-07-19 | 2022-09-20 | 宁夏清研高分子新材料有限公司 | Polysulfone polymer and preparation method thereof |
| CN115073740B (en) * | 2022-07-19 | 2023-08-29 | 宁夏清研高分子新材料有限公司 | Polysulfone polymer and preparation method thereof |
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