CN102558544A - Soluble and ultraviolet crosslinking polyaryl ether nitrile and preparation method thereof - Google Patents
Soluble and ultraviolet crosslinking polyaryl ether nitrile and preparation method thereof Download PDFInfo
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- 0 C*c(cccc1C(C)(C)C(C)(C)Oc2ccc(C=CC(c(cc3)ccc3Oc(cccc3C)c3C#N)=*)cc2)c1C#N Chemical compound C*c(cccc1C(C)(C)C(C)(C)Oc2ccc(C=CC(c(cc3)ccc3Oc(cccc3C)c3C#N)=*)cc2)c1C#N 0.000 description 5
- ACLVEZCDKFXULE-UHFFFAOYSA-N COc1ccc(C(c2ccccc22)(c(cc3)ccc3OC)OC2=O)cc1 Chemical compound COc1ccc(C(c2ccccc22)(c(cc3)ccc3OC)OC2=O)cc1 ACLVEZCDKFXULE-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to soluble and ultraviolet crosslinking polyaryl ether nitrile and a preparation method thereof, and belongs to the field of high molecular materials. The preparation method comprises the following steps of: selecting 4,4'-dyhydroxyl chalcone, 2,2'-diallyl bisphenol A and 2'-allyl phenyl-2,6-difluoro benzoic acid which contain allyl and vinyl structure bisphenol and difluoro monomer compounds as crosslinking points, wherein the content of the crosslinking points is controlled to be 5 to 40 percent; performing temperature control reaction at the temperature of between 145 and 165 DEG C and between 180 and 210 DEG C for 2 to 4 hours and 3 to 6 hours respectively by taking sulfolane or N-methyl pyrrolidone or dimethyl sulfoxide or N,N-dimethylacetylamide as a solvent, potassium carbonate or sodium carbonate as a catalyst and methylbenzene or dimethylbenzene as a dehydrating agent, crushing, washing for 6 to 8 times by using ethanol and water to remove organic small molecules, the organic solvent and inorganic salt, wherein the using amount of the dehydrating agent is 20 to 30 percent that of the solvent; and drying at the temperature of between 100 and 120 DEG C for 10 to 12 hours. The invention has the advantages that the high molecular materials are irradiated without damage, high efficiency and energy conservation are realized, residual toxicity and wastes are avoided, and a control method is convenient, so the soluble and ultraviolet crosslinking polyaryl ether nitrile is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to technical field of polymer materials.
Background technology
Poly (arylene ether nitrile) is one type of linear aromatic ring polymkeric substance with special molecular structure, and its macromolecular main chain is made up of rigidity, stable on heating phenylene and flexibility, stable on heating oxygen-ether linkage and strong polar itrile group side group is formed.Oxygen-ether linkage is given good flexibility of poly (arylene ether nitrile) molecular chain and workability; The existence of itrile group side group not only helps improving the solubility property of polymkeric substance; And the reactive force of polymer molecule interchain is strengthened; Cause polymer segment motion institute energy requirement to increase, improve the thermotolerance of polymkeric substance, itrile group can improve the flame retardancy of polymkeric substance.In addition, can also utilize the reaction of the active functional group of itrile group to carry out modification and prepare novel poly (arylene ether nitrile) functional high molecule material.Poly (arylene ether nitrile) is a kind of have excellent thermostability, oxidation-resistance, thermo-oxidative stability, the mechanical property of excellence and high performance engineering plastics of electric property and excellent machinability.Poly (arylene ether nitrile) be fit to make high heat-resisting, HS, low creep properties, dimensional stability, can be at the goods of-100～200 ℃ of life-time service, can be used as mould material, insulating material, matrix material, sticker and be widely used in fields such as aerospace, automobile, electronics, electric, machinery.But the solvent resistance and the anti-stress cracking of poly (arylene ether nitrile) are relatively poor, adopt the method that makes polarity itrile group heat cross-linking to obtain the higher network structure of thermotolerance usually and solve this shortcoming.Seek other etc. more effective approach further improve the use temperature of poly (arylene ether nitrile), improve solvent resistance and anti-stress cracking is significant.
Summary of the invention
The objective of the invention is: provide a kind of solvable can UV-crosslinked poly (arylene ether nitrile) and preparation method thereof; It is in the poly (arylene ether nitrile) segment, introduce the side group structure with the solubility property that improves material, widen the materials processed window; Simultaneously but three kinds of ultraviolet light cross-linking structures are incorporated in the poly (arylene ether nitrile) backbone structure; Further improve temperature classification, solvent resistance and the mechanical property of material through the uv irradiation crosslinking curing technology of convenient, efficient, environmental protection, provide the solvable of brand new can UV-crosslinked poly (arylene ether nitrile) high performance material and technology of preparing thereof.
Technical scheme of the present invention is:
Polymer architecture formula of the present invention is:
Preparing method of the present invention is:
Select 4; 4 '-dihydroxyl cinnamophenone, 2; 2 '-diallyl bisphenol, 2 '-allyl phenyl-2; Three kinds of 6-difluoro TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M.s contain allyl group and the vinyl structure bis-phenol is a cross-linking set with two fluorine monomer compounds, are incorporated in the poly (arylene ether nitrile) backbone structure with the mode of block, and cross-linking set content is controlled at 5～40%.Select hexafluoro bisphenol-a, dihydroxyphenyl propane, the synthetic poly (arylene ether nitrile) of phenolphthalein, improve the solubility property of poly (arylene ether nitrile).With tetramethylene sulfone or N-Methyl pyrrolidone or DMSO 99.8MIN. or N; The N-N,N-DIMETHYLACETAMIDE is a solvent; Solvent adding amount is advisable with solid content 20～35%; Salt of wormwood or yellow soda ash are catalyzer, and consumption is 1.05～1.15 times of biphenol monomer total mole number, and dewatering agent toluene or YLENE consumption are 20～30% of solvent for use amount.At 145～165 ℃; 180～210 ℃ of temperature ranges are carried out temperature control reaction 2～4h and 3～6h respectively; (18～25 ℃) are dispersed in the water under the reaction product room temperature condition; Remove organic molecule, organic solvent and inorganic salt 6～8 times with ethanol and water washing respectively after the pulverizing, at last in 100～120 ℃ of drying 10～12h.
The invention has the beneficial effects as follows: utilizing the ultraviolet light irradiation processing technology is under normal temperature, normal pressure, macromolecular material to be shone; To the material not damaged; Energy-efficient, light can be deep into the polymkeric substance internal action, and does not bring any residual hazard and refuse; Control method is easy, is suitable for industrialization and large-scale production.
The present invention be preparation novel solvable can UV-crosslinked poly (arylene ether nitrile) series high-performance material; Can improve the side group structure of polymer dissolution performance and allyl group or vinyl structure (cross-linking set) that can be UV-crosslinked through in polymer segment, introducing simultaneously; Polymkeric substance can carry out solution processing; UV-crosslinked curing under the room temperature condition then, obtain having high heat resistance more can and the crosslinked poly (arylene ether nitrile) material of use temperature.Utilize the ultraviolet light irradiation cross-linking technology of clean and effective further to improve the use temperature of the poly (arylene ether nitrile) material with excellent solution processing performance, improving materials processed performance and thermal property simultaneously is main innovate point of the present invention and major technique characteristics to satisfy different use temperatures and use range to the requirement of material.
Embodiment
The present invention adopts three kinds to contain allyl group and vinyl biphenol monomer compound and two fluorine monomer compounds, through nucleophilic substitution reaction, prepare a series of solution processable, can UV-crosslinked poly (arylene ether nitrile) high performance material.In the preparation process; Can select toluene or YLENE as dewatering agent; Select tetramethylene sulfone, N-Methyl pyrrolidone, DMSO 99.8MIN. or N; The N-N,N-DIMETHYLACETAMIDE is a solvent, and cross-linking set content is controlled at 5～40%, and cross-linking set is evenly distributed in the main polymer chain structure with the mode of block.It is solvable can UV-crosslinked poly (arylene ether nitrile) polymer architecture formula following that the present invention obtains:
(I) embodiment 1 to embodiment 3 polymer architecture formula
(II) embodiment 4 to embodiment 6 polymer architecture formulas
(III) embodiment 7 to embodiment 9 polymer architecture formulas
Solvablely can UV-crosslinked poly (arylene ether nitrile) polymerization process be: be that 1～1.02: 1 ratio joins in the there-necked flask that has mechanical stirring and water trap with two fluorine monomers and biphenol monomer according to mol ratio under the room temperature; Tetramethylene sulfone is as solvent; Solid content in the reaction system is 20～35%; With YLENE is dewatering agent, adds the Anhydrous potassium carbonate or the sodium carbonate catalyst of 1.05～1.15 times of bis-phenol mole numbers.Stirring is warming up to 145～160 ℃ of reaction 2～4h, and constantly emits the water that reaction generates, and then temperature of reaction is elevated to 180～210 ℃ and continues reaction 3～6h, steams and removes remaining YLENE in the reaction system.With being dispersed in the water under the polymer product room temperature condition, thick product through pulverizing, ethanol and zero(ppm) water repeatedly wash, drying obtain solvable can UV-crosslinked poly (arylene ether nitrile) polymkeric substance, productive rate is 96～98%.
Embodiment 1:
With 14.04g (0.101mol) 2, the 6-difluorobenzonilyile, hexafluoro bisphenol-a 31.93g (0.095mol), (with the tetramethylene sulfone is solvent to the 173ml tetramethylene sulfone; Solvent adding amount is advisable with solid content 20～35%, and present embodiment tetramethylene sulfone consumption calculates according to solid content 20%), 14.49g (0.105mol) Anhydrous potassium carbonate, 40ml YLENE join in the 500ml there-necked flask that mechanical stirring, TM and nitrogen protection are housed; Stirring is warming up to 140～160 ℃, and YLENE band water back flow reaction 2h is warming up to 180～210 ℃ of reaction 2～3h; System is cooled to below 100 ℃, adds 1.20g (0.005mol) 4,4 '-dihydroxyl cinnamophenone [4; 4 '-dihydroxyl cinnamophenone is as cross-linking set, and cross-linking set content is 5%, and promptly 4; The mol ratio of 4 '-dihydroxyl cinnamophenone/(4,4 '-dihydroxyl cinnamophenone+hexafluoro bisphenol-a) is 5%], be warming up to 140～160 ℃; YLENE band water back flow reaction 2h removes the YLENE in the reaction system gradually, is warming up to 180～210 ℃ of reaction 2～5h; Polymers soln is dispersed in the water, after the thick product of strip is pulverized, respectively with ethanol and zero(ppm) water boiling washing 6～8 times to remove organic solvent tetramethylene sulfone, a spot of organic molecule and inorganic salt; Product obtains white poly (arylene ether nitrile) powdered sample, productive rate 97% at 120 ℃ of dry 12h.
Embodiment 2:
Method such as embodiment 1 replace with dihydroxyphenyl propane, phenolphthalein with hexafluoro bisphenol-a respectively successively, and dihydroxyphenyl propane unit or phenolphthalein replace the hexafluoro bisphenol-a unit in the polymer architecture formula.[promptly 4, the mol ratio of 4 '-dihydroxyl cinnamophenone/(4,4 '-dihydroxyl cinnamophenone+dihydroxyphenyl propane) is 5% to obtain cross-linking set (4,4 '-dihydroxyl cinnamophenone) content at last respectively and be 5% white poly (arylene ether nitrile) powdered sample; 4, the mol ratio of 4 '-dihydroxyl cinnamophenone/(4,4 '-dihydroxyl cinnamophenone+phenolphthalein) is 5%], productive rate is 96～98%.
Embodiment 3:
Method such as embodiment 1 and embodiment 2 change 4 successively, and the molar content of 4 '-dihydroxyl cinnamophenone is 10%, 15%, 20%, 25%, 30%, 35%, 40%; [4,4 '-dihydroxyl cinnamophenone/(4,4 '-dihydroxyl cinnamophenone+hexafluoro bisphenol-a), 4; 4 '-dihydroxyl cinnamophenone/(4; 4 '-dihydroxyl cinnamophenone+dihydroxyphenyl propane), 4, the mol ratio of 4 '-dihydroxyl cinnamophenone/(4,4 '-dihydroxyl cinnamophenone+phenolphthalein) is respectively 10%, 15%, 20%, 25%, 30%, 35%, 40%]; Prepare a series of soluble poly aromatic ether nitrile polymers with different cross-linking set content, productive rate is 96～98%.Embodiment 1 to embodiment 3 polymer architecture is referring to polymer architecture (I).
Embodiment 4:
Method such as embodiment 1, with 4,4 '-dihydroxyl cinnamophenone replaces with 2; 2 '-diallyl bisphenol obtains 2, and 2 '-diallyl bisphenol is a cross-linking set; Cross-linking set content is 5% [2; 2 '-diallyl bisphenol/(2,2 '-diallyl bisphenol+hexafluoro bisphenol-a) mol ratio is 5%] solvable can UV-crosslinked poly (arylene ether nitrile) polymkeric substance, productive rate 98%.
Embodiment 5:
Method such as embodiment 4 replace with dihydroxyphenyl propane, phenolphthalein with hexafluoro bisphenol-a respectively successively, and dihydroxyphenyl propane unit or phenolphthalein replace the hexafluoro bisphenol-a unit in the polymer architecture formula.Obtain 2 respectively, 2 '-diallyl bisphenol cross-linking set content is 5%, contain two kinds of polymkeric substance of dihydroxyphenyl propane and phenolphthalein structure [2,2 '-diallyl bisphenol/(2,2 '-diallyl bisphenol+dihydroxyphenyl propane); 2,2 '-diallyl bisphenol/(2,2 '-diallyl bisphenol+phenolphthalein) mol ratio is 5%].Productive rate 96～98%.
Embodiment 6:
Method such as embodiment 4 and embodiment 5; Change 2 successively; The molar content of 2 '-diallyl bisphenol is 10%, 15%, 20%, 25%, 30%, 35%, 40%; Prepare a series ofly 2,2 '-diallyl bisphenol is that the different solubility of cross-linking set, cross-linking set content can UV-crosslinked poly (arylene ether nitrile) polymkeric substance.Embodiment 4 to embodiment 6 polymer architectures are referring to polymer architecture (II).
Embodiment 7:
With 33.94g (0.101mol) hexafluoro bisphenol-a, 13.21g (0.095mol) 2,6-difluorobenzonilyile; 173ml tetramethylene sulfone (solid content calculates according to 20%), 14.49g (0.105mol) Anhydrous potassium carbonate, 40ml YLENE join in the 500ml there-necked flask that mechanical stirring, TM and nitrogen protection are housed, and stir and are warming up to 140～160 ℃; YLENE band water back flow reaction 2h is warming up to 180～210 ℃ of reaction 2～3h, and system is cooled to below 100 ℃; Add 1.37g (0.005mol) 2 '-allyl phenyl-2, and 6-difluoro TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. [2 '-allyl phenyl-2,6-difluoro TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. is as cross-linking set; Cross-linking set content is 5%, i.e. 2 '-allyl phenyl-2,6-difluoro TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M./(2 '-allyl phenyl-2; 6-difluoro TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M.+2,6-difluorobenzonilyile) mol ratio is 5%], be warming up to 140～160 ℃; YLENE band water back flow reaction 2h removes the YLENE in the reaction system gradually, is warming up to 180～210 ℃ of reaction 2～5h; Polymers soln is dispersed in the water, after the thick product of strip is pulverized, respectively with ethanol and zero(ppm) water boiling washing 6～8 times to remove organic solvent tetramethylene sulfone, a spot of organic molecule and inorganic salt; Product obtains white poly (arylene ether nitrile) powdered sample, productive rate 97% at 120 ℃ of dry 12h.
Embodiment 8:
Method such as embodiment 7 use the hexafluoro bisphenol-a among dihydroxyphenyl propane and phenolphthalein replacement method such as the embodiment 7 successively, prepare two kinds of 2 '-allyl phenyls-2, and 6-difluoro TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. is a cross-linking set, and content is 5% poly (arylene ether nitrile) polymkeric substance, and productive rate is 96～98%.
Embodiment 9:
Method such as embodiment 7 and embodiment 8; Change 2 '-allyl phenyl-2 successively; The molar content of 6-difluoro TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. is 10%, 15%, 20%, 25%, 30%, 35%, 40%; Prepare a series ofly 2,2 '-diallyl bisphenol is the different soluble poly aromatic ether nitrile polymer of cross-linking set, cross-linking set content, and productive rate is 96～98%.Embodiment 7 to embodiment 9 polymer architectures are referring to polymer architecture (III).
Embodiment 10:
Method such as embodiment 1 to embodiment 9 replace with N-Methyl pyrrolidone or DMSO 99.8MIN. or DMAC N,N successively with sulfolane solvent, and solvent adding amount is to be advisable between the solid content 20～35%.
Claims (2)
- One kind solvable can UV-crosslinked polyarylether nitrile high-performance polymer, its structural formula is:
- 2. solvable preparation method that can UV-crosslinked polyarylether nitrile high-performance polymer; Its method is: select 4; 4 '-dihydroxyl cinnamophenone, 2,2 '-diallyl bisphenol, 2 '-allyl phenyl-2, it is cross-linking set that 6-difluoro TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. contains allyl group and vinyl structure bis-phenol and two fluorine monomer compounds for three kinds; Mode with block is incorporated in the poly (arylene ether nitrile) backbone structure, and cross-linking set content is controlled at 5～40%; Select hexafluoro bisphenol-a, dihydroxyphenyl propane, the synthetic poly (arylene ether nitrile) of phenolphthalein, improve the solubility property of poly (arylene ether nitrile); With tetramethylene sulfone or N-Methyl pyrrolidone or DMSO 99.8MIN. or N; The N-N,N-DIMETHYLACETAMIDE is a solvent; Solvent adding amount is a solid content 20～35%; Salt of wormwood or yellow soda ash are catalyzer, and consumption is 1.05～1.15 times of biphenol monomer total mole number, and dewatering agent toluene or YLENE consumption are 20～30% of solvent for use amount; At 145～165 ℃; 180～210 ℃ of temperature ranges are carried out temperature control reaction 2～4h and 3～6h respectively; Reaction product is disperseed in 18～25 ℃ of cold water; Remove organic molecule, organic solvent and inorganic salt 6～8 times with ethanol and water washing respectively after the pulverizing, at last in 100～120 ℃ of drying 10～12h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109236A (en) * | 2014-07-21 | 2014-10-22 | 四川大学 | Fatty cyclosemi aromatic polyarylether amide and preparation method thereof |
| CN105461918A (en) * | 2015-12-25 | 2016-04-06 | 吉林省聚科高新材料有限公司 | Soluble and ultraviolet-crosslinked polyaryl ether nitrile and preparation method thereof |
| CN105482097A (en) * | 2015-12-25 | 2016-04-13 | 吉林省聚科高新材料有限公司 | Soluble and ultraviolet crosslinking polyetherketoneketone and preparation method thereof |
| CN105585732A (en) * | 2015-12-30 | 2016-05-18 | 吉林省聚科高新材料有限公司 | Ultraviolet crosslinking polyaryletherketone porous membrane, preparation method and application of ultraviolet crosslinking polyaryletherketone porous membrane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381455A (en) * | 2008-10-08 | 2009-03-11 | 吉林大学 | Polyarylether material bearing a sulfonic acid group on a pendant group, and preparation method and application thereof |
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2011
- 2011-12-28 CN CN2011104463013A patent/CN102558544A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381455A (en) * | 2008-10-08 | 2009-03-11 | 吉林大学 | Polyarylether material bearing a sulfonic acid group on a pendant group, and preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109236A (en) * | 2014-07-21 | 2014-10-22 | 四川大学 | Fatty cyclosemi aromatic polyarylether amide and preparation method thereof |
| CN104109236B (en) * | 2014-07-21 | 2016-04-06 | 四川大学 | Fatty ring half aromatics polyarylether amide and preparation method thereof |
| CN105461918A (en) * | 2015-12-25 | 2016-04-06 | 吉林省聚科高新材料有限公司 | Soluble and ultraviolet-crosslinked polyaryl ether nitrile and preparation method thereof |
| CN105482097A (en) * | 2015-12-25 | 2016-04-13 | 吉林省聚科高新材料有限公司 | Soluble and ultraviolet crosslinking polyetherketoneketone and preparation method thereof |
| CN105585732A (en) * | 2015-12-30 | 2016-05-18 | 吉林省聚科高新材料有限公司 | Ultraviolet crosslinking polyaryletherketone porous membrane, preparation method and application of ultraviolet crosslinking polyaryletherketone porous membrane |
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Application publication date: 20120711 |