CN110563905A - Novel crystallizable and dissolvable polyether-ether-ketone resin containing phthalazinone structure and preparation method thereof - Google Patents
Novel crystallizable and dissolvable polyether-ether-ketone resin containing phthalazinone structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a novel crystallizable and dissolvable polyetheretherketone resin containing phthalazinone biphenyl structure and a preparation method thereof, belonging to the technical field of high polymer materials. Under the protection of nitrogen, mixed bisphenol and double-halogen monomer in equal molar ratio are used as synthetic monomers. Toluene or xylene is used as a water-carrying agent, potassium carbonate and/or sodium carbonate is used as a catalyst, and sulfolane or dimethyl sulfoxide is used as a solvent for reaction; synthesizing for 4.5-10 hours at 175-240 ℃. The resin is crystalline resin, and the relative molecular weight of the resin is more than 3.5 ten thousand; the resin has a thermal tensile deformation rate of 0-1200% at 300 ℃, and can be dissolved in 1,1 ', 2, 2' -tetrachloroethane and/or o-chlorophenol. The novel crystallizable and dissolvable polyetheretherketone resin containing phthalazinone biphenyl structure has the characteristics of higher molecular weight, better stretching capacity, stronger molecular orientation capacity, excellent dissolving performance and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a novel crystallizable and dissolvable polyether ether ketone resin containing a phthalazinone biphenyl structure and a preparation method thereof.
Background
the polyether ketone resin containing the phthalazinone biphenyl structure has the characteristics of high tensile strength, high heat resistance level, good wear resistance, good solubility and the like. The polyether ketone resin containing the phthalazinone biphenyl structure can be used for manufacturing various structural members and products by injection, extrusion and other thermoforming methods, can be used as a membrane material, a sheet material, a plate material and other structural materials, and is widely applied to the fields of aerospace, vehicles, nuclear energy, petrochemical industry, environmental engineering and the like. The high-temperature resistant special insulating paint, coating and the like can also be prepared by dissolution processing. Due to the characteristics of chemical structure, the material can also be used as an ideal material for membrane separation.
In the field of fibers, polyarylether resins can be prepared into fiber membranes for use by electrostatic spinning according to the existing patents, and can also be prepared into fibers for reinforcement by dry spinning according to the existing invention. However, the prior polyarylether resins containing phthalein side groups prepared into corresponding fibers for reinforcement have corresponding problems and defects.
In patent CN 85108751A, a classical polyaryletherketone resin containing phthalein side groups is prepared by using phenolphthalein and dichlorobenzophenone as monomers, sodium carbonate and/or potassium carbonate as a catalyst, an aprotic polar solvent such as N-methylpyrrolidone (NMP), sulfolane or diphenylsulfone as a reaction solvent, and toluene or xylene or no water-carrying agent at a reaction temperature of 170-320 ℃. The polymers all contain symbolic phthalein side groups. On one hand, the existence of larger phthalein side groups can pull the molecular chain spacing of the resin apart, weaken the acting force among molecular chains and ensure that the polyaryletherketone resin has excellent solubility. Meanwhile, the existence of larger phthalein side groups can aggravate the entanglement among molecular chains of the polyarylether resin, so that the slippage change among the molecular chains of corresponding polymers is more difficult, and the high temperature resistance of the resin is improved. On the other hand, the existence of larger phthalein side groups enables the molecular chain spacing of the resin to be pulled apart, weakens the acting force among the molecular chains, and enables the resins to be amorphous resins. Even if the soluble crystallizable resin containing phthalein side groups can be obtained by introducing the crystalline unit, the molecular weight of the corresponding resin can not meet the requirements of engineering use. Meanwhile, the existence of larger phthalein side groups can also aggravate the entanglement among molecular chains of the polyarylether resin, and the slippage change among the molecular chains is more difficult, so that the corresponding resin is difficult to be stretched at high temperature by high times. Secondly, the entanglement among molecular chains of the polyarylether resin can cause that resin molecules can not be oriented to a large degree in the stretching process, and further the self-reinforcement of the resin is carried out. Therefore, the corresponding classical polyarylether resins containing phthalein side groups are not suitable for the preparation of reinforcing fibers.
In patent CN1098097A, bisphenol monomer containing phthalazinone biphenyl structure and 4, 4' -dihalobenzophenone monomer are used as raw materials, and polymerization reaction is performed at high temperature, azeotropic dehydration is performed during the reaction, and after the reaction is finished, precipitant is added. The polymer was precipitated with stirring and separated by filtration to give a polymer. On one hand, the existence of the phthalazinone biphenyl structure weakens the acting force among molecular chains, so that the resins are amorphous resins. Even if the soluble crystallizable resin containing the phthalazinone structure can be obtained by introducing the crystallization element, the molecular weight of the corresponding resin cannot meet the requirements of engineering use. Meanwhile, the existence of the phthalazinone biphenyl structure with an intramolecular bond angle can also aggravate the entanglement among molecular chains of the polyarylether resin, and the slippage change among the molecular chains is more difficult, so that the corresponding resin is difficult to be stretched at high tensile deformation rate at high temperature. Secondly, entanglement between molecular chains of the polyarylether resin may cause failure of the resin molecules to undergo a large degree of orientation during stretching. Naturally, self-reinforcement of the resin by molecular orientation crystallization cannot be performed. Therefore, the corresponding classical polyarylether resins containing phthalazinone structures are not suitable for the preparation of reinforcing fibers.
A series of crystalline polyarylether resins of classical structure and their preparation route are reported in British patent BP1414421, US4320224, US4638044 and US 4774314. The main chains of the molecules of these resins obtained in the above-mentioned patents are all rigid chains and can be regularly arranged, so that the resins obtained are all crystalline resins. Meanwhile, the resin has a rigid main chain and can be regularly arranged, so that the solubility of the corresponding resin is extremely poor, and the resin can only be dissolved in concentrated sulfuric acid at present. Therefore, the conventional polyarylether materials can only be used for preparing reinforcing fibers by melt extrusion, and the corresponding application is greatly limited by the higher melt viscosity.
In addition, in the published patent CN109096485A, a series of polyetheretherketone materials with crystallinity, high number average relative molecular weight, high thermal tensile deformation rate, strong molecular orientation ability and good solubility have been obtained by ternary copolycondensation. But there is room for further improvement in the tensile properties of the corresponding materials.
In summary, the various polyaromatic ether materials reported in the existing patents at home and abroad have more or less various problems. The patent aims to develop a brand new soluble polyarylether resin with crystallizability, and combines various excellent performances of the two classic polyarylether materials containing phenolphthalein side groups and an amorphous polyarylether material containing phthalazinone biphenyl structures. Compared with the polyetheretherketon material disclosed in the patent CN109096485A, the polyetheretherketon resin developed by the patent has the advantages of crystallization capacity, higher number-average relative molecular mass, higher thermal stretching capacity, stronger molecular orientation capacity and good solubility (so that the influence of higher melt viscosity in the melt processing process can be avoided). So that the corresponding resin is suitable for preparing the fiber material for reinforcement.
disclosure of Invention
The invention provides a novel crystallizable and dissolvable polyetheretherketone resin containing phthalazinone biphenyl structure and a preparation method thereof.
The technical scheme of the invention is as follows:
The novel crystallizable and soluble polyether ether ketone resin containing phthalazinone biphenyl structure has the following structural formula:
In the structural formula, the ratio of n/(n + m) is 0.1-0.9.
The preparation method of the novel crystallizable and dissolvable polyetheretherketone ketone resin containing phthalazinone structure comprises the following preparation route:
The method comprises the following specific steps: under the protection of nitrogen, bisphenol monomers and double-halogen monomers in equal molar ratio are used as monomers; wherein the bisphenol monomer is a mixture of 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one (DHPZ) and 4, 4' -dihydroxybiphenyl in a molar ratio of 1: 9-9: 1; the ratio of n/(n + m) is 0.1-0.9; the double-halogen monomer is 1, 3-di (4' -fluorobenzoyl) benzene; toluene is used as a water-carrying agent to carry water for 1-3 hours at 110-130 ℃, or xylene is used as a water-carrying agent to carry water for 1-3 hours at 140-170 ℃; potassium carbonate and/or sodium carbonate which is 1-1.4 times of the total molar weight of bisphenol monomers is used as a catalyst, and sulfolane or dimethyl sulfoxide is used as a solvent; continuously heating to react for 4.5-10 hours at the temperature of 175-240 ℃; after post-treatment, the novel soluble crystallized polyetheretherketone ketone resin containing phthalazinone biphenyl structure is obtained. The resin is crystalline resin, and the number-average relative molecular weight is more than 3.5 ten thousand; the resin has a thermal tensile deformation rate of 0-1200% at 300 ℃, and can be dissolved in 1,1 ', 2, 2' -tetrachloroethane and/or o-chlorophenol.
The invention has the beneficial effect of preparing the novel soluble polyetheretherketone ketone resin containing phthalazinone biphenyl structure. The resin has the characteristics of good solubility, high heat resistance level, high mechanical strength, good dielectric property, radiation resistance, various processing modes and the like, as well as the traditional polyarylether resin containing a phthalein side group or phthalazinone biphenyl structure. However, the new type of poly (ether-ketone) -resin containing bisphenol fluorene structure has higher number average molecular weight, better stretching ability at 300 ℃ and stronger molecular orientation ability, which is suitable for engineering, compared with the poly (ether-ketone) -material disclosed in the patent CN 109096485A.
The characteristics enable the novel crystallization soluble polyether-ether-ketone resin containing the bisphenol fluorene structure to be competent in the field which can be competent by the traditional polyarylether resin, and the fiber for reinforcement can be prepared by means of a dry spinning process in the future, so that the novel crystallization soluble polyether-ether-ketone resin can be possibly applied to the field of composite materials.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative only and not to limit the scope of the invention. Specific properties of examples and comparative examples are shown in table 1.
example 1
Under the protection of nitrogen, 0.01mol of mixed bisphenol with the molar ratio of 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one (DHPZ) to 4,4 '-dihydroxybiphenyl being 9:1 is added into a three-necked bottle with a stirrer, a nitrogen inlet and a condenser, the ratio of n/(n + m) in the structural formula is 0.9, 0.01mol of 1, 3-bis (4' -fluorobenzoyl) benzene is taken as a double-halogen monomer, potassium carbonate with the molar weight being 1 time of the total molar weight of the mixed bisphenol monomers is taken as a catalyst, a proper amount of toluene is taken as a water-carrying agent, and a proper amount of sulfolane is taken as a solvent. Keeping the temperature at 110 ℃ for 1 hour, evaporating toluene, and heating to 175 ℃ for reaction for 4.5 hours. After final post-treatment, the novel soluble crystallized polyetheretherketone ketone resin containing phthalazinone biphenyl structure is obtained. The corresponding resin is crystalline resin, and the number average relative molecular weight is 3.5 ten thousand. The thermal tensile deformation rate of the corresponding resin at 300 ℃ is 300%. And the corresponding resin can be dissolved in 1,1 ', 2, 2' -tetrachloroethane.
example 2
According to the same operation procedure as in example 1, 0.01mol of a mixed bisphenol having a molar ratio of 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one (DHPZ) to 4,4 '-dihydroxybiphenyl of 5:5 in a structure wherein the ratio of n/(n + m) is 0.5, 0.01mol of a dihalogeno monomer 1, 3-bis (4' -fluorobenzoyl) benzene, potassium carbonate in an amount 1.2 times the total molar amount of the mixed bisphenol monomers as a catalyst, an appropriate amount of toluene as a water-carrying agent, and an appropriate amount of sulfolane as a solvent were charged in a three-necked flask equipped with a stirrer, a nitrogen inlet, and a condenser under a nitrogen protection condition. Keeping the temperature at 120 ℃ for 2 hours, evaporating toluene, and heating to 200 ℃ for reaction for 6 hours. After post-treatment, the novel soluble crystallized polyetheretherketone ketone resin containing phthalazinone biphenyl structure is obtained. The corresponding resin is crystalline resin, and the number average relative molecular weight is 4 ten thousand. The thermal tensile deformation at 300 ℃ of the corresponding resin was 750%. And the corresponding resin can be dissolved in a mixed solvent in which o-chlorophenol and 1,1,2,2, -tetrachloroethane are mixed in equal volumes.
Example 3
According to the same operation procedure as in example 1, 0.01mol of a mixed bisphenol having a molar ratio of 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one (DHPZ) to 4,4 '-dihydroxybiphenyl of 1:9, wherein the ratio of n/(n + m) is 0.1, 0.01mol of a 1, 3-bis (4' -fluorobenzoyl) benzene as a dihalogeno monomer, 0.4 mol of potassium carbonate which is the total molar amount of the mixed bisphenol monomers 1.4 times as a catalyst, an appropriate amount of toluene as a water-carrying agent, and an appropriate amount of sulfolane as a solvent were charged into a three-necked flask equipped with a stirrer, a nitrogen inlet, and a condenser under a nitrogen protection condition. Keeping the temperature at 130 ℃ for 3 hours, evaporating toluene, and heating to 240 ℃ for reaction for 10 hours. After final post-treatment, the novel soluble crystallized polyetheretherketone ketone resin containing phthalazinone biphenyl structure is obtained. The corresponding resin is crystalline resin, and the number average relative molecular weight is 6 ten thousand. The thermal tensile deformation at 300 ℃ of the corresponding resin was 1200%. And the corresponding resin can be dissolved in o-chlorophenol.
Example 4
Under the protection of nitrogen, 0.01mol of mixed bisphenol with the molar ratio of 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one (DHPZ) to 4,4 '-dihydroxybiphenyl being 9:1 is added into a three-necked bottle with a stirrer, a nitrogen inlet and a condenser, the ratio of n/(n + m) in the structural formula is 0.9, 0.01mol of 1, 3-bis (4' -fluorobenzoyl) benzene is taken as a double-halogen monomer, potassium carbonate and sodium carbonate which are mixed in an equal molar ratio and are 1 time of the total molar amount of the mixed bisphenol monomer are taken as catalysts, a proper amount of dimethylbenzene is taken as a water-carrying agent, and a proper amount of dimethyl sulfoxide is taken as a solvent. The temperature is kept at 140 ℃ for 1 hour, then toluene is evaporated, and the temperature is raised to 175 ℃ for reaction for 4.5 hours. After final post-treatment, the novel soluble crystallized polyetheretherketone ketone resin containing phthalazinone biphenyl structure is obtained. The corresponding resin is crystalline resin, and the number average relative molecular weight is 3.5 ten thousand. The thermal tensile deformation rate of the corresponding resin at 300 ℃ is 300%. And the corresponding resin can be dissolved in 1,1 ', 2, 2' -tetrachloroethane.
Example 5
According to the same operation procedure as in example 1, 0.01mol of a mixed bisphenol having a molar ratio of 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one (DHPZ) to 4,4 '-dihydroxybiphenyl of 5:5 in a structure wherein the ratio of n/(n + m) is 0.5, 0.01mol of a dihalogeno monomer 1, 3-bis (4' -fluorobenzoyl) benzene, 1.2 times the total molar amount of the mixed bisphenol monomers of sodium carbonate as a catalyst, an appropriate amount of xylene as a water-carrying agent, and an appropriate amount of dimethyl sulfoxide as a solvent were charged into a three-necked flask equipped with a stirrer, a nitrogen inlet, and a condenser under a nitrogen protection condition. Keeping the temperature at 150 ℃ for 2 hours, evaporating xylene, and heating to 200 ℃ for reaction for 6 hours. After final post-treatment, the novel soluble crystallized polyetheretherketone ketone resin containing phthalazinone biphenyl structure is obtained. The corresponding resin is crystalline resin, and the number average relative molecular weight is 4 ten thousand. The thermal tensile deformation at 300 ℃ of the corresponding resin was 750%. And the corresponding resin can be dissolved in a mixed solvent in which o-chlorophenol and 1,1,2,2, -tetrachloroethane are mixed in equal volumes.
Example 6
According to the same operation procedure as in example 1, 0.01mol of a mixed bisphenol having a molar ratio of 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one (DHPZ) to 4,4 '-dihydroxybiphenyl of 1:9, wherein the ratio of n/(n + m) is 0.1, 0.01mol of a 1, 3-bis (4' -fluorobenzoyl) benzene as a dihalogeno monomer, was charged into a three-necked flask equipped with a stirrer, a nitrogen inlet and a condenser under nitrogen protection, sodium carbonate in an amount 1.4 times the total molar amount of the mixed bisphenol monomers was used as a catalyst, an appropriate amount of xylene was used as a water-carrying agent, and an appropriate amount of dimethyl sulfoxide was used as a solvent. Keeping the temperature at 170 ℃ for 3 hours, evaporating xylene, and heating to 240 ℃ for reaction for 10 hours. After final post-treatment, the novel soluble crystallized polyetheretherketone ketone resin containing phthalazinone biphenyl structure is obtained. The corresponding resin is crystalline resin, and the number average relative molecular weight is 6 ten thousand. The thermal tensile deformation at 300 ℃ of the corresponding resin was 1200%. And the corresponding resin can be dissolved in o-chlorophenol.
Comparative example
0.1mol of 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one (DHPZ), 0.1mol of a dihalogeno monomer 4, 4' -difluorobenzophenone, 1.1 mol of potassium carbonate, which is 1.1 times the total molar amount of mixed bisphenol monomers, was charged into a three-necked flask equipped with a stirrer, a nitrogen inlet and a condenser under a nitrogen protection condition, 50ml of xylene was used as a water-carrying agent, and 88g of sulfolane was used as a solvent. Keeping the temperature at 160 ℃ for 1 hour, gradually evaporating xylene, and heating to 220 ℃ for reaction for 8 hours. Cooling the reaction mixture, adding sulfolane solvent for dilution, introducing methyl chloride gas at about 100 ℃ to seal the end group, cooling, filtering to remove the basin, precipitating in ethanol, and washing with water for three times. And finally carrying out post-treatment to obtain the classical polyether ketone resin containing the phthalazinone structure. The corresponding resin had a crystallinity of 0% and a number average relative molecular weight of 2 ten thousand. The corresponding resin had a thermal tensile set at 300 ℃ of 200%.
TABLE 1 comparison of Properties of polyaryletherketones containing phthalazinone structures
Through a brand new monomer combination, a novel soluble crystallization polyether ether ketone resin containing a phthalazinone biphenyl structure is obtained. The novel crystallizable and dissolvable polyetheretherketone ketone resin containing the phthalazinone structure has stronger crystallization capacity, higher number-average relative molecular mass suitable for engineering, higher tensile capacity at high temperature and stronger molecular orientation capacity.
The characteristics enable the novel crystallization soluble polyether-ether-ketone resin containing the bisphenol fluorene structure to be capable of not only being capable of.
Claims (4)
1. The novel crystallizable and dissolvable polyetheretherketone resin containing a phthalazinone structure is characterized in that the structural formula of the crystallizable and dissolvable polyetheretherketone resin containing a phthalazinone structure is as follows:
In the structural formula, the ratio of n/(n + m) is 0.1-0.9.
2. A preparation method of a novel crystallizable and dissolvable polyetheretherketone resin containing phthalazinone structure is characterized in that the preparation route is as follows:
The method comprises the following specific steps: under the protection of nitrogen, bisphenol monomers and double-halogen monomers in equal molar ratio are used as monomers; the ratio of n/(n + m) is 0.1-0.9; toluene is used as a water-carrying agent to carry water for 1-3 hours at 110-130 ℃, or xylene is used as a water-carrying agent to carry water for 1-3 hours at 140-170 ℃; potassium carbonate and/or sodium carbonate which is 1-1.4 times of the total molar weight of bisphenol monomers is used as a catalyst, and sulfolane or dimethyl sulfoxide is used as a solvent; continuously heating to react for 4.5-10 hours at the temperature of 175-240 ℃; after post-treatment, the novel soluble crystallized polyetheretherketone ketone resin containing phthalazinone biphenyl structure is obtained.
3. The preparation method according to claim 2, wherein the bisphenol monomer is a mixture of 4- (4-hydroxyphenyl) -2, 3-naphthyridin-1-one (DHPZ) and 4, 4' -dihydroxybiphenyl in a molar ratio of 1:9 to 9: 1.
4. The method according to claim 2 or 3, wherein the dihalogen monomer is 1, 3-bis (4' -fluorobenzoyl) benzene.
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| CN109456452A (en) * | 2018-10-09 | 2019-03-12 | 刘鹏 | A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion and preparation method thereof |
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| CN109456452A (en) * | 2018-10-09 | 2019-03-12 | 刘鹏 | A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion and preparation method thereof |
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| Title |
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| 尹春春: "《杂萘联苯结构聚芳醚共混改性研究》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Application publication date: 20191213 |