CN107955158A - A kind of siliceous main chain aryl oxide ketone copolymers and preparation method thereof - Google Patents
A kind of siliceous main chain aryl oxide ketone copolymers and preparation method thereof Download PDFInfo
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- CN107955158A CN107955158A CN201610899621.7A CN201610899621A CN107955158A CN 107955158 A CN107955158 A CN 107955158A CN 201610899621 A CN201610899621 A CN 201610899621A CN 107955158 A CN107955158 A CN 107955158A
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4018—(I) or (II) containing halogens other than as leaving group (X)
- C08G65/4025—(I) or (II) containing fluorine other than as leaving group (X)
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
- C08G65/4068—(I) or (II) containing elements not covered by groups C08G65/4018 - C08G65/4056
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
Abstract
A kind of siliceous main chain aryl oxide ketone copolymers of the present invention and preparation method thereof belong to the technical field of high molecular material.Siliceous main chain aryl ether ketone 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 double fluorobenzene ketone monomers etc., prepares a kind of siliceous main chain aryl oxide ketone copolymers.Such polymer improves melting, the dissolving processing performance of ketone-grouped resin, has preferable heat endurance and film forming, have potential application value in functional paint and seperation film field due to introducing silane backbone structure.
Description
Technical field
A kind of siliceous main chain aryl oxide ketone copolymers of the present invention and preparation belong to high molecular material and its technology neck of synthesis
Domain.
Background technology
Poly(aryl ether ketone) is the aromatic polymer that molecule main chain is made of ether, ketone group and phenyl, because its is excellent
The features such as heat-resisting, corrosion-resistant, antifriction scrape along good biocompatibility, in defence and military, weaponry, aerospace, electronics, vapour
The high-tech such as car, machinery, petroleum industry, nuclear energy and physical therapy health, which are possessed, to be widely applied.Under normal circumstances strand by ether,
When ketone, benzene ternary ordered structure are formed, polymer is semi-crystalline, and molecule chain rigidity is higher, causes the close of strand
Pile up, dissolubility is poor, and melting temperature is higher.Siliceous aromatic polymer is one that flexible silane structure is introduced to main polymer chain
Class aromatic polymer, what is be such as reported has siliceous Nomex, siliceous polyarylate, a Silicone Containing Polyimides, Han Gui polyoxadiazoles,
Siliceous polybenzimidazoles etc..Flexible silane structure can substantially increase glass transition temperature and the heat decomposition temperature section of polymer
Scope, thus this kind of material has more preferable thermoforming working ability；The solvability of polymer can also be effectively improved, is made
Be soluble in polar aprotic solvent such as DMF, DMA, NMP, DMSO, it might even be possible to be dissolved in weaker polar solvent chloroform with
In pyridine.
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 poly(aryl ether ketone) and characterization, Chemical Journal of Chinese Universities .2005,26 (8):1579-1581.]
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.
Double (4- hydroxy phenyls) alkyl silanes of 2,2'- of the present invention and other biphenol monomers are primary raw material and double fluorobenzene ketones
Monomer etc. carries out copolymerization, prepares the aryl oxide ketone copolymers of the siliceous alkyl structure of main chain.Such polymer is due to introducing silane
Backbone structure, improves melting, the dissolving processing performance of ketone-grouped resin, has preferable heat endurance and film forming, in work(
Energy coating and seperation film etc. field has potential application value.
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 is copolymerized with double fluorobenzene one monomers, so that silane backbone structure is introduced into aryl oxide ketone copolymers macromolecular, is prepared with excellent
Different melting, dissolving processing performance copolymer resins, such as poly(aryl ether ketone), Ether Ketone Ketone.
Technical scheme is as follows：
A kind of siliceous main chain aryl oxide ketone copolymers of the present invention, its structural formula are as follows:
Wherein X is:
Y is:
R1、R2For methyl, phenyl or vinyl etc..
P+q=1,0 ＜ p≤0.5,0.5≤q ＜ 1
It is solution polycondensation that the present invention, which prepares a kind of method of siliceous main chain aryl oxide ketone copolymers,.
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 is reacted with biphenol monomer and double fluorobenzene one monomers.This stage takes 12-24h, has part low molecular weight pre-polymerization
Thing produces, and system viscosity change is smaller.The stage, higher temperature can cause appearance 2, double (4- hydroxy phenyls) alkyl silanes of 2'-
The side reaction of intramolecular rearrangement.
(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 1-10 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 ketone 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。
Double (4- hydroxy phenyls) alkyl silanes of 2,2'- and another biphenol monomer A1Molal quantity and with double fluorobenzene one monomers A2
Mole ratio be p:q:1, p+q=1,0 ＜ p≤0.5,0.5≤q ＜ 1.
Wherein:A1It is not limited to comprising cutting:
Wherein:A2It is not limited to comprising cutting:
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 double fluorine
The molar ratio of monomer is 1.05~1.1.
The effect and benefit of the present invention：The present invention provides one kind to have synthesized siliceous main chain poly aryl ether ketone polymer and preparation
Method.Flexible silane structure introduce main polymer chain after, glass transition temperature and melt processing temperature substantially reduce, more added with
Beneficial to thermoplastic shaping；Solvability in a solvent is obviously improved, and is more conducive in fields such as coating, adhesive and seperation films
Application.
Brief description of the drawings
Fig. 1 is the FTIR spectrograms of the poly(aryl ether ketone) prepared by the embodiment of the present invention 1.In 1642cm-1It is benzophenone at wave number
The stretching vibration characteristic absorption peak of carbonyl, 1245cm-1It is diphenyl ether ehter bond stretching vibration peak at wave number, 1264cm-1It is at wave number
The characteristic absorption peak of silicon methyl, 1455cm-1For Si-Ph stretching vibration peaks, it was demonstrated that synthesize subject polymer.
Fig. 2 is the H-NMR spectrum of the poly(aryl ether ketone) prepared by the embodiment of the present invention 1.It is silicon methyl hydrogen at 0.57ppm
Chemical shift, it was demonstrated that synthesize subject polymer.
Fig. 3 is the DSC spectrograms of the poly(aryl ether ketone) prepared by the embodiment of the present invention 1.The polymer is amorphous polymer, glass
Glass transition temperature is 153.3 DEG C.
Fig. 4 is the TGA spectrograms of the poly(aryl ether ketone) prepared by the embodiment of the present invention 1.5% thermal weight loss under polymer condition of nitrogen gas
Temperature is 503 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 (10.90g) 4,4'- difluoros
Benzophenone, 0.055mo1 (7.6g) Anhydrous potassium carbonate, solvent are dimethyl sulfoxide (DMSO) (DMSO) 60mL.Under nitrogen protection, 80 DEG C
Lower reaction 24h.Then 160 DEG C are progressively warming up to, the reaction was continued.React 5 it is small when after, system becomes viscous, and it is molten to add appropriate DMSO
Agent, reaction was completed.Polymer solution is fallen in the water of stirring, white product separates out.Deionized water boiling washing product is several
It is secondary, when 80 DEG C of forced air dryings 12 are small, the siliceous main chain aryl ether ketone copolymer powder 20.96g of white, yield 97.7% must be refined.
The molecular weight of polymerFor 4.57 × 104g·mol-1, molecular weight distributing index 3.63.
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.Double fluorobenzene one monomers use (4- fluoro benzoyls) benzene of 1,4- bis- and 1,3- bis- (4- fluoro benzoyls)
Benzene, also 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 1.96-6.33 × 104g·mol-1Between siliceous main chain poly(aryl ether ketone) co-polymer powder, gained sample yield is between 91%-98%.Table 1 show 2,2'-
The performance parameter of copolymer obtained by double (4- hydroxy phenyls) dimethylsilane different contents.
Table 1:Performance of copolymer parameter
Embodiment 3
Double (4- hydroxy phenyls) the dimethylsilane 0.01mol (2.44g) of 2,2'- and 4,4'- difluoros are added in three-necked flask
Benzophenone 0.05mo1 (10.90g) and 0.011mo1 (1.52g) Anhydrous potassium carbonate, solvent are dimethyl sulfoxide (DMSO) (DMSO)
60mL, under nitrogen protection, reacts 6h 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 ketone copolymer powder, yield 96.9%, the molecular weight of polymerFor 4.71 × 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 ketone co-polymer powder, yield 90.4%, the molecular weight of polymer can also be obtainedFor 1.77 ×
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 2.23-3.67 × 104g·mol-1
Between siliceous main chain aryl ether ketone copolymer powder, yield is between 91%-97%.
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 ketone copolymer powder, yield 90%, the molecular weight of polymerFor 1.92
×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 ketone copolymers, its structural formula are as follows:
Wherein X is:
Y 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 ketone co-polymer of claim 1, with double (4- hydroxy phenyls) alkyl silanes of 2,2'-,
Other biphenol monomers and double fluorobenzene one monomers are raw material, using the salt of alkali or alkaline earth metal as catalyst.Double (the 4- of 2,2'-
Hydroxy phenyl) alkyl silane and another biphenol monomer molal quantity and be p with the mole ratios of double fluorobenzene one monomers:q:1, p+q
The molar ratio of=1,0 ＜ p≤0.5,0.5≤q ＜ 1, catalyst and double fluorobenzene one monomers is 1.05~1.1:1, initial solvent
Quality is 2-4 times of reactant quality.Reactant, solvent and catalyzer temperature-elevating are added in the container of inert gas shielding extremely
60-100 DEG C, after reacting 12-24h, when 150-200 DEG C of reaction 1-10 is small；Product is poured into cold water, through crushing, obtains powder
Shape sample, inorganic salts and solvent are removed with distilled water boiling washing, are drying to obtain the siliceous main chain aryl ether ketone copolymerization of white powder
Resin.
3. the preparation method of siliceous main chain poly (aryl ether ketone) copolymer as claimed in claim 2, it is characterised in that described is another
Biphenol monomer, includes but not limited to hydroquinone, '-biphenyl diphenol, 2,6- naphthalenediols, 4,4'- dihydroxy diphenyl ethers, 4,4'- dihydroxies
Base diphenyl sulfide, 4,4' dihydroxydiphenyl sulfone.Double fluorobenzene one monomers, including but not limited to 4,4'- difluoro benzophenones,
(4- fluoro benzoyls) benzene of 1,4- bis- and 1,3- bis- (4- fluoro benzoyls) benzene.
4. the preparation method of the siliceous poly aryl ether ketone polymer of main chain as claimed in claim 2, it is characterised in that described is molten
Agent, includes 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 |
|---|---|---|---|---|
| CN111925518A (en) * | 2020-08-12 | 2020-11-13 | 大连九信精细化工有限公司 | Polyaryletherketone polymer containing straight-chain siloxane structure, preparation method and application |
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Application publication date: 20180424 |