CN102634009B - Polyaryletherketone and preparation method thereof - Google Patents
Polyaryletherketone and preparation method thereof Download PDFInfo
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- CN102634009B CN102634009B CN201210086808.7A CN201210086808A CN102634009B CN 102634009 B CN102634009 B CN 102634009B CN 201210086808 A CN201210086808 A CN 201210086808A CN 102634009 B CN102634009 B CN 102634009B
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Abstract
The invention provides polyaryletherketone which has a structural formula (I). R is H or methyl. The m is larger than or equal to 1 and smaller than or equal to 4. The n refers to polymerization degree. The invention further provides a preparation method of the polyaryletherketone, which includes subjecting polyaryletherketone having a structural formula (II) and acrylate having a structural formula (III) to esterification in the presence of dehydrant and catalyst so as to obtain the polyaryletherketone having the structural formula (I), wherein the R is H or methyl, and the n stands for polymerization degree. The polyaryletherketone having the structural formula (I) has many crosslinking points and fine thermal insulation, and can be used as products such as high temperature resistant ultraviolet-light curing coating and the like. Tests show that glass transition temperature of the polyaryletherketone having the structural formula (I) is 140 DEG C to 265 DEG C, initial weightlessness temperature is 300 DEG C to 385 DEG C, and 5%-weightlessness temperature is 400 DEG C to 490 DEG C.
Description
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of polyaryletherketone and preparation method thereof.
Background technology
Polyaryletherketone is a kind of aromatic thermoplastic special engineering plastics, there is the performances such as good thermotolerance, chemical stability, antifatigue, radiation hardness, flame retardant resistance and dimensional stability, be widely used in the various fields such as electric, aerospace and automotive industry.Phenolphthalein polyaryletherketone (PEK-C) is a kind of polymkeric substance with undefined structure of the nineties research in last century development, is a kind of novel polyaryletherketone.Except having the feature of traditional polyaryletherketone, phenolphthalein polyaryletherketone also has advantages of that the good and processability of solubility property is well etc. outstanding, is also widely used in various fields.But, in the molecular structure due to phenolphthalein polyaryletherketone, lack polar group, make its coating adhesion poor, greatly limited the application of phenolphthalein polyaryletherketone in the fields such as coating.
And in general, in molecular structure due to acrylate, contain the reactive groups such as two keys, can there is crosslinking reaction and solidify in the resin that is grafted with propenyl ester group on molecular chain, thereby there is good characteristic, can be used as photo-cured coating and coated material etc., as polyacrylic ester, polyester acrylate and Granted publication number, be disclosed a kind of polyurethane acrylate resin of Chinese patent literature (PUA) of CN100575380C etc., all can be used as ultraviolet solidified aqueous coating and apply; At Yang Jianjun etc., deliver, name is called in the article of research > > of < < polymerization of acrylic modified polyurethane soap-free emulsion, adopt acrylate monomer to carry out grafting, copolymerization and modification to the aqueous polyurethane that contains carbon-carbon double bond, prepare acrylic acid modified polyurethane soap-free emulsion, the performances such as water resistance, solvent resistance and tensile strength that significantly improved urethane (PU) emulsion coating, are beneficial to application.
In sum, the applicant considers, propenyl ester group is introduced in the molecular structure of phenolphthalein polyaryletherketone, and both advantages are combined, and obtains the better materials of over-all properties such as the more and resistance toheat of cross-linking set is better, thereby expands its range of application.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of polyaryletherketone and preparation method thereof, and polyaryletherketone provided by the invention has more cross-linking set and good resistance toheat.
The invention provides a kind of polyaryletherketone with formula (I) structure:
Wherein, R is H or methyl; 1≤m≤4; N is the polymerization degree.
Preferably, 1≤n≤500.
The present invention also provides a kind of preparation method of polyaryletherketone, comprising:
Under the existence of dewatering agent and catalyzer, the acrylate that has the polyaryletherketone of formula (II) structure and have formula (III) structure is carried out to esterification in organic solvent, the polyaryletherketone of (I) structure that obtains thering is formula;
Wherein, R is H or methyl; 1≤m≤4; N is the polymerization degree.
Preferably, 1≤n≤500; The described acrylate with formula (III) structure is hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 410 or vinylformic acid-4-hydroxyl butyl ester.
The polyaryletherketone preferably, with formula (II) structure with described in there is the acrylate of formula (III) structure mol ratio be 1: 1～10: 1.
Preferably, described dewatering agent is N, N '-dicyclohexylcarbodiimide, N, and N '-DIC or 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, described catalyzer is DMAP.
Preferably, described dewatering agent with described in there is formula (III) structure the mol ratio of acrylate for (0.1～5): 1, the mol ratio of described catalyzer and described dewatering agent is (0.1～1): 1.
Preferably, described organic solvent is dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF).
Preferably, described in, there is the quality of polyaryletherketone of formula (II) structure and the ratio of the volume of described organic solvent is (0.1～1) g: 1mL.
Preferably, the temperature of described esterification is 10 ℃～40 ℃, and the time of described esterification is 12h～48h.
Compared with prior art, it is raw material that polyaryletherketone and the acrylate of (II) structure that has formula take in the present invention, take organic solvent as reaction medium, under the effect of dewatering agent and catalyzer, carry out esterification, the polyaryletherketone of (I) structure that obtains thering is formula, wherein, R is H or methyl; 1≤m≤4; N is the polymerization degree.The present invention is grafted to propenyl ester group on the side chain of phenolphthalein polyaryletherketone, the polyaryletherketone of (I) structure that obtains thering is formula, and it has more cross-linking set and good resistance toheat, can be used as the products such as high temperature resistant type ultraviolet-curing paint.Experimental result shows, polyaryletherketone provided by the invention is white, has formula (I) structure, its limiting viscosity >=0.05dL/g, second-order transition temperature is 140 ℃～265 ℃, and the temperature of initial weightlessness is 300 ℃～385 ℃, and weightless 5% temperature is 400 ℃～490 ℃.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the polyaryletherketone with formula (IV) structure that obtains of the embodiment of the present invention 2;
Fig. 2 is the infrared spectrogram of the polyaryletherketone with formula (IV) structure that obtains of the embodiment of the present invention 2.
Embodiment
The invention provides a kind of polyaryletherketone with formula (I) structure:
Wherein, R is H or methyl; 1≤m≤4; N is the polymerization degree.
Polyaryletherketone provided by the invention has formula (I) structure, and wherein, R is H or methyl, is preferably H; 1≤m≤4, m is preferably 2 or 3; N is the polymerization degree, preferably 1≤n≤500, more preferably 2≤n≤200, most preferably 3≤n≤100.
The present invention is grafted to propenyl ester group on the side chain of phenolphthalein polyaryletherketone, the polyaryletherketone of (I) structure that obtains thering is formula, and it has more cross-linking set and good resistance toheat, can be used as the products such as high temperature resistant type ultraviolet-curing paint.
The color in the present invention, with the polyaryletherketone of formula (I) structure is white;
Described limiting viscosity >=the 0.05dL/g with the polyaryletherketone of formula (I) structure;
The described second-order transition temperature with the polyaryletherketone of formula (I) structure is 140 ℃～265 ℃;
The temperature of the initial weightlessness of the described polyaryletherketone with formula (I) structure is 300 ℃～385 ℃, and weightless 5% temperature is 400 ℃～490 ℃.
The present invention also provides a kind of preparation method of polyaryletherketone, comprising:
Under the existence of dewatering agent and catalyzer, the acrylate that has the polyaryletherketone of formula (II) structure and have formula (III) structure is carried out to esterification in organic solvent, the polyaryletherketone of (I) structure that obtains thering is formula;
Wherein, R is H or methyl; 1≤m≤4; N is the polymerization degree.
The present invention preferably at rare gas element as under nitrogen protection; by thering is the polyaryletherketone of formula (II) structure, acrylate, dewatering agent, catalyzer and the organic solvent with formula (III) structure adds in reactor, the polyaryletherketone of (I) structure that obtains having formula after esterification.
It is raw material that the polyaryletherketone of (II) structure that has formula is take in the present invention, on the side chain of the described polyaryletherketone with formula (II) structure, contain carboxyl, overall molecular structure is similar to the molecular structure of phenolphthalein polyaryletherketone, can be referred to as PEK-L, the polyaryletherketone that the polyaryletherketone therefore, with formula (II) structure can be (I) structure that has formula provides the characteristic of phenolphthalein polyaryletherketone.
The present invention is not particularly limited the described polymerization degree (n) with the polyaryletherketone of formula (II) structure, preferably 1≤n≤500, more preferably 2≤n≤200, most preferably 3≤n≤100;
The present invention is not particularly limited the described source with the polyaryletherketone of formula (II) structure, preferably according to following preparation method, prepares:
Under basic cpd and existence with aqua, phenolphthalin and 4,4 '-Diflurodiphenyketone is reacted in organic solvent to the polyaryletherketone of (II) structure that obtains thering is formula.
The preparation method of the described polyaryletherketone with formula (II) structure preferably at rare gas element as under nitrogen protection; by phenolphthalin, 4; 4 '-Diflurodiphenyketone, basic cpd, band aqua and organic solvent add in reactor, the polyaryletherketone of (II) structure that obtains having formula after reaction.
In the preparation method of the described polyaryletherketone with formula (II) structure, described phenolphthalin is referred to as PPL; Described 4,4 '-Diflurodiphenyketone is preferably 4,4 '-difluoro benzophenone or 4,4 '-bis-chloro benzophenone, more preferably 4,4 '-difluoro benzophenone; The mol ratio of described phenolphthalin and described 4,4 '-Diflurodiphenyketone is preferably (1～3): 1, more preferably (1～2.5): 1, most preferably be 1: 1;
Described basic cpd can be to having reacted katalysis, and described basic cpd is preferably Anhydrous potassium carbonate (K
2cO
3) or anhydrous sodium carbonate (Na
2cO
3), Anhydrous potassium carbonate more preferably; The mol ratio of described basic cpd and described phenolphthalin is preferably (1～3): 1, more preferably (1.1～2.5): 1, most preferably be (1.15～2): 1;
Described organic solvent is the medium of reaction, and described organic solvent is preferably dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF), more preferably dimethyl sulfoxide (DMSO); The consumption of described organic solvent adopts and makes the consoluet consumption of above-mentioned raw materials;
The described water that reaction can be produced with aqua is separated from reaction system, thereby improves reaction efficiency, and described band aqua is preferably dimethylbenzene or toluene, more preferably toluene; Described organic solvent and described volume ratio with aqua are preferably 1: (1～3), more preferably 1: (1.5～2.5), most preferably are 1: (1.8～2).
The preparation method's of the described polyaryletherketone with formula (II) structure reaction formula is preferably suc as formula shown in (1):
The described preparation method with the polyaryletherketone of formula (II) structure is preferably specially:
Under basic cpd and the existence with aqua, phenolphthalin and 4,4 '-Diflurodiphenyketone is carried out to the first step reaction in organic solvent, obtain intermediate product;
Described intermediate product is carried out to second step reaction, the polyaryletherketone of (II) structure that obtains thering is formula.
Wherein, described the first step reaction be take nucleophilic substitution reaction as main, and the temperature of described the first step reaction is preferably 130 ℃～150 ℃, more preferably 135 ℃～145 ℃; The time of described the first step reaction is preferably 1h～3h, more preferably 1.5h～2.5h;
Describedly with aqua, take the water that reaction produces out of, preferably steam after whole described band aquas, obtain intermediate product, described intermediate product comprises the product of nucleophilic substitution reaction and a small amount of oligopolymer etc.;
Described second step reaction be take polycondensation as main, and the temperature of described second step reaction is preferably 170 ℃～180 ℃; The time of described second step reaction is preferably 3h～5h, more preferably 3.5h～4.5h.
When reaction obtains yellow thick polymer product, by dimethyl formamide (DMF) dilution static layering, then supernatant liquid static layering being obtained is slowly poured in the mixing sinking agent being made into by ethanol and hydrochloric acid, separate out a large amount of white masses, it is boiled to wash be repeatedly placed in vacuum drying oven dryly, obtain polyaryletherketone white, that there is formula (II) structure.
Limiting viscosity gained white, that have the polyaryletherketone of formula (II) structure is 0.29dL/g, and second-order transition temperature is 191 ℃, and the temperature of initial weightlessness is 391 ℃, and weightless 5% temperature is 403 ℃.
In the preparation method of the above-mentioned polyaryletherketone with formula (II) structure, one of phenolphthalin is raw material, and described phenolphthalin can be buied from the market, also can prepare according to following preparation method:
Take zinc powder as catalyzer, after being mixed, phenolphthalein (ph), sodium hydroxide, deionized water and ethanol reacts, preferably 11h～13h, more preferably pour in hydrochloric acid acidifying after 11.5h～12.5h into and filter, the crude product that filtration is obtained repeatedly boils after washing with deionized water and refilters, dry, obtain phenolphthalin, productive rate is more than 95%, and reaction formula is suc as formula shown in (2):
In the preparation method of the polyaryletherketone with formula (I) structure provided by the invention, another raw material is for having the acrylate of formula (III) structure, in the molecular structure of the described acrylate with formula (III) structure, contain the reactive groups such as two keys, it provides the cross-linking set that can carry out crosslinking reaction for having the polyaryletherketone of formula (I) structure.
The described acrylate with formula (III) structure is preferably hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 410 or vinylformic acid-4-hydroxyl butyl ester.In the present invention, change the polyaryletherketone with formula (II) structure with described in there is the mol ratio of the acrylate of formula (III) structure, can obtain the esterification products of a series of different percentage of grafting, the present invention to the described polyaryletherketone with formula (II) structure with described in there is the acrylate of formula (III) structure mol ratio be not particularly limited, be preferably 1: 1～10: 1, more preferably 2: 1～8: 1, most preferably be 4: 1～6: 1.
In the preparation method of the polyaryletherketone with formula (I) structure provided by the invention, described dewatering agent is beneficial to reaction to carry out, and can improve reaction efficiency; Described dewatering agent is preferably N, N '-dicyclohexylcarbodiimide (DCC), N, N '-DIC (DIC) or 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC), N more preferably, N '-dicyclohexylcarbodiimide; Described dewatering agent with described in there is the acrylate of formula (III) structure mol ratio be preferably (0.1～5): 1, more preferably (1～4): 1, most preferably be (1～1.5): 1.
Described catalyzer is the conventional catalyzer in this area, is preferably DMAP (DMAP), and it has efficient katalysis; The mol ratio of described catalyzer and described dewatering agent is preferably (0.1～1): 1, more preferably (0.8～1): 1.
Described organic solvent is the conventional organic solvent in this area, is preferably dimethyl sulfoxide (DMSO) (DMSO) or tetrahydrofuran (THF) (THF), more preferably dimethyl sulfoxide (DMSO); Described have the quality of polyaryletherketone of formula (II) structure and the ratio of the volume of described organic solvent is preferably (0.1～1) g: 1mL, more preferably (0.5～0.8) g: 1mL.
The present invention carries out esterification by the acrylate that has the polyaryletherketone (PEK-L) of formula (II) structure and have formula (III) structure under the effect of dewatering agent and catalyzer, obtain esterification products, the polyaryletherketone with formula (I) structure, reaction formula is preferably suc as formula shown in (3):
Wherein, the temperature of described esterification is preferably 10 ℃～40 ℃, more preferably 20 ℃～30 ℃; The time of described esterification is preferably 12h～48h, and more preferably 15h～40h, most preferably is 20h～30h.The preparation method of the polyaryletherketone with formula (I) structure provided by the invention is simple to operate, and reaction conditions is gentle, and productive rate is higher, is suitable for suitability for industrialized production.
After esterification finishes, obtain suspension liquid, after the present invention is filtered, pour in the mixing solutions being made into by ethanol and hydrochloric acid and precipitate, to remove the residual impurity such as dewatering agent, then precipitation gained material is repeatedly boiled and washed, then it is dry to be placed in vacuum drying oven, obtains white cotton-shaped product.
Obtain, after white cotton-shaped product, it being carried out to Infrared spectroscopy and nuclear magnetic resonance spectroscopy.Analytical results shows, the cotton-shaped product of described white is for having the polyaryletherketone of formula (I) structure.
By described in there is formula (I) structure polyaryletherketone at 25 ℃, be dissolved in DMF, measure its limiting viscosity.Measurement result shows, described in there is the limiting viscosity >=0.05dL/g of the polyaryletherketone of formula (I) structure.
Utilize METTLER TOLEDO DSC1 differential scanning calorimeter to there is the second-order transition temperature of the polyaryletherketone of formula (I) structure described in measuring; condition determination is as follows: under nitrogen protection; heat-up rate is 10 ℃/min, and the temperature range of mensuration is 0 ℃～300 ℃.Measurement result shows, described in there is the polyaryletherketone of formula (I) structure second-order transition temperature be 140 ℃～265 ℃.
Utilize METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer to there is the thermal decomposition performance of the polyaryletherketone of formula (I) structure described in measuring; condition determination is as follows: under nitrogen protection; heat-up rate is 10 ℃/min, and the temperature range of mensuration is 0 ℃～550 ℃.Measurement result shows, described in there is the polyaryletherketone of formula (I) structure the temperature of initial weightlessness be 300 ℃～385 ℃, weightless 5% temperature is 400 ℃～490 ℃.
Experimental result shows, the polyaryletherketone with formula (I) structure provided by the invention has the characteristic of propenyl ester group and phenolphthalein polyaryletherketone simultaneously, there is more cross-linking set and good resistance toheat, can be used as the products such as high temperature resistant type ultraviolet-curing paint.
In order to further illustrate the present invention, below in conjunction with embodiment, polyaryletherketone provided by the invention and preparation method thereof is described particularly.
In the there-necked flask of 100mL, add successively 12.81g (0.04mol) phenolphthalin, 8.73g (0.04mol) 4,4 '-difluoro benzophenone, 11.06g (0.08mol) K
2cO
3, 34mLDMSO and 38mL toluene, pass into nitrogen and stir, be warming up to 140 ℃ and react, after reaction 2h, dewater, steam whole toluene, be then slowly warming up to 175 ℃, after isothermal reaction 4h, after DMF dilution for the thick product of yellow that reaction is obtained, static layering, the supernatant liquid obtaining is slowly poured in the mixed solvent being made into by ethanol and hydrochloric acid, is separated out a large amount of white masses, by its repeatedly boil wash be placed in vacuum drying oven dry, obtain white product PEK-L, productive rate is 88%.
By the PEK-L of 0.53g (1mmol) embodiment 1 preparation, 0.11g (1mmol) Hydroxyethyl acrylate, 0.21g (1mmol) DCC, 0.01g (0.1mmol) DMAP and 10mLDMSO are placed in the there-necked flask of 100mL, logical nitrogen also stirs, at the temperature of 25 ℃, carry out esterification, after 24h, obtain flaxen suspension liquid, after being filtered, under vigorous stirring, slowly pour in the mixing solutions being made into by ethanol and hydrochloric acid and precipitate, to remove residual DCC and the dicyclohexylurea (DCU) in DCC (DCU), precipitation gained material is repeatedly boiled and washed, be placed in again vacuum drying oven dry, obtain white product, the polyaryletherketone (PEK-LH) with formula (IV) structure, productive rate is 79%.
Gained white product is carried out to nuclear magnetic resonance spectroscopy, and analytical results is referring to Fig. 1, and Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the polyaryletherketone with formula (IV) structure that obtains of the embodiment of the present invention 2.As shown in Figure 1, the absorption peak that is water impurity at the peak of 3.3081ppm chemical shift place, at the peak of 2.5008ppm chemical shift place, it is the absorption peak of solvent DMSO, it at the peak of 7.7337ppm chemical shift place, is the absorption peak of the hydrogen of 14 on benzophenone phenyl ring, it at the peak of 7.5099ppm chemical shift place, is the absorption peak of hydrogen of 7 in side-chain benzene ring, it at the peak of 7.3566ppm chemical shift place, is the absorption peak of hydrogen of 5 in side-chain benzene ring, it at the peak of 7.2019ppm chemical shift place, is the absorption peak of hydrogen of 6 in side-chain benzene ring, at the peak of 7.0738ppm chemical shift place, be on benzophenone phenyl ring 1, 2, 4, the absorption peak of the hydrogen of 13, it at the peak of 6.4310ppm chemical shift place, is the absorption peak of hydrogen of 3 on main chain, 6.2954 and the peak of 6.2524ppm chemical shift place be the absorption peak of hydrogen of 12 in pendant double bonds, it at the peak of 6.1193ppm chemical shift place, is the absorption peak of hydrogen of 10 in pendant double bonds, it at the peak of 5.8800ppm chemical shift place, is the absorption peak of hydrogen of 11 in pendant double bonds, at the peak of 4.3554ppm chemical shift place, it is side chain 8, the absorption peak of the hydrogen of 9.
Gained white product is carried out to Infrared spectroscopy, and analytical results is referring to Fig. 2, and Fig. 2 is the infrared spectrogram of the polyaryletherketone with formula (IV) structure that obtains of the embodiment of the present invention 2.As shown in Figure 2, at wave number 2942cm
-1place on phenyl ring=C-H stretching vibration characteristic peak, at wave number 1597cm
-1and wave number 1493cm
-1place is the C=C stretching vibration absorption peak of phenyl ring, at wave number 1239cm
-1with wave number 1162cm
-1place is respectively Ar-O-Ar key asymmetrical stretching vibration absorption peak and symmetrical stretching vibration absorption peak, at wave number 767cm
-1hydrocarbon formation vibration on the phenyl ring that place is ortho position replacement, illustrates and in polymer architecture, contains aromatic ring frame; At wave number 3076cm
-1place in alkene=the stretching vibration characteristic peak of C-H, at wave number 1660cm
-1place is for the stretching vibration characteristic peak of the two keys of C=C in alkene, at wave number 922cm
-1with wave number 858cm
-1place in alkene=formation vibration of C-H, illustrate and in polymer architecture, contains pair keys; At wave number 2852cm
-1place is the stretching vibration characteristic peak of alkyl C-H.
In sum, gained white product is for having the polyaryletherketone of formula (IV) structure:
According to method mentioned above, measure the limiting viscosity that gained has the polyaryletherketone of formula (IV) structure, result shows, its limiting viscosity is 0.29dL/g;
According to method mentioned above, measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (IV) structure respectively, result shows respectively, its second-order transition temperature is 170 ℃, and the temperature of initial weightlessness is 421 ℃, and weightless 5% temperature is 424 ℃.
By the PEK-L of 1.05g (2mmol) embodiment 1 preparation, 0.13g (1mmol) hydroxyethyl methylacrylate, 0.21g (1mmol) DCC, 0.01g (0.1mmol) DMAP and 10mLDMSO are placed in the there-necked flask of 100mL, logical nitrogen also stirs, at the temperature of 25 ℃, carry out esterification, after 24h, obtain flaxen suspension liquid, after being filtered, under vigorous stirring, slowly pour in the mixing solutions being made into by ethanol and hydrochloric acid and precipitate, to remove residual DCC and DCU, precipitation gained material is repeatedly boiled and washed, be placed in again vacuum drying oven dry, obtain white product, the polyaryletherketone with formula (I) structure, productive rate is 76%.
Obtain after white product, it is carried out to nuclear magnetic resonance spectroscopy and Infrared spectroscopy, analytical results shows, gained white product is for having the polyaryletherketone of formula (I) structure.
According to method mentioned above, measure the limiting viscosity that gained has the polyaryletherketone of formula (I) structure, result shows, its limiting viscosity is 0.29dL/g;
According to method mentioned above, measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure respectively, result shows respectively, its second-order transition temperature is 150 ℃, and the temperature of initial weightlessness is 336 ℃, and weightless 5% temperature is 419 ℃.
By the PEK-L of 1.58g (3mmol) embodiment 1 preparation, 0.13g (1mmol) Propylene glycol monoacrylate, 0.21g (1mmol) DCC, 0.01g (0.1mmol) DMAP and 10mLDMSO are placed in the there-necked flask of 100mL, logical nitrogen also stirs, at the temperature of 25 ℃, carry out esterification, after 24h, obtain flaxen suspension liquid, after being filtered, under vigorous stirring, slowly pour in the mixing solutions being made into by ethanol and hydrochloric acid and precipitate, to remove residual DCC and DCU, precipitation gained material is repeatedly boiled and washed, be placed in again vacuum drying oven dry, obtain white product, the polyaryletherketone with formula (I) structure, productive rate is 73%.
Obtain after white product, it is carried out to nuclear magnetic resonance spectroscopy and Infrared spectroscopy, analytical results shows, gained white product is for having the polyaryletherketone of formula (I) structure.
According to method mentioned above, measure the limiting viscosity that gained has the polyaryletherketone of formula (I) structure, result shows, its limiting viscosity is 0.29dL/g;
According to method mentioned above, measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure respectively, result shows respectively, its second-order transition temperature is 152 ℃, and the temperature of initial weightlessness is 340 ℃, and weightless 5% temperature is 410 ℃.
Embodiment 5
By the PEK-L of 1.58g (3mmol) embodiment 1 preparation, 0.14g (1mmol) Rocryl 410, 0.21g (1mmol) DCC, 0.01g (0.1mmol) DMAP and 10mLDMSO are placed in the there-necked flask of 100mL, logical nitrogen also stirs, at the temperature of 25 ℃, carry out esterification, after 24h, obtain flaxen suspension liquid, after being filtered, under vigorous stirring, slowly pour in the mixing solutions being made into by ethanol and hydrochloric acid and precipitate, to remove residual DCC and DCU, precipitation gained material is repeatedly boiled and washed, be placed in again vacuum drying oven dry, obtain white product, the polyaryletherketone with formula (I) structure, productive rate is 70%.
Obtain after white product, it is carried out to nuclear magnetic resonance spectroscopy and Infrared spectroscopy, analytical results shows, gained white product is for having the polyaryletherketone of formula (I) structure.
According to method mentioned above, measure the limiting viscosity that gained has the polyaryletherketone of formula (I) structure, result shows, its limiting viscosity is 0.29dL/g;
According to method mentioned above, measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure respectively, result shows respectively, its second-order transition temperature is 159 ℃, and the temperature of initial weightlessness is 312 ℃, and weightless 5% temperature is 410 ℃.
Embodiment 6
By the PEK-L of 2.63g (5mmol) embodiment 1 preparation, 0.28g (2mmol) vinylformic acid-4-hydroxyl butyl ester, 0.42g (2mmol) DCC, 0.02g (0.2mmol) DMAP and 10mLDMSO are placed in the there-necked flask of 100mL, logical nitrogen also stirs, at the temperature of 25 ℃, carry out esterification, after 24h, obtain flaxen suspension liquid, after being filtered, under vigorous stirring, slowly pour in the mixing solutions being made into by ethanol and hydrochloric acid and precipitate, to remove residual DCC and DCU, precipitation gained material is repeatedly boiled and washed, be placed in again vacuum drying oven dry, obtain white product, the polyaryletherketone with formula (I) structure, productive rate is 69%.
Obtain after white product, it is carried out to nuclear magnetic resonance spectroscopy and Infrared spectroscopy, analytical results shows, gained white product is for having the polyaryletherketone of formula (I) structure.
According to method mentioned above, measure the limiting viscosity that gained has the polyaryletherketone of formula (I) structure, result shows, its limiting viscosity is 0.29dL/g;
According to method mentioned above, measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure respectively, result shows respectively, its second-order transition temperature is 149 ℃, and the temperature of initial weightlessness is 323 ℃, and weightless 5% temperature is 420 ℃.
Embodiment 7
By the PEK-L of 4.20g (8mmo1) embodiment 1 preparation, 0.22g (2mmol) Hydroxyethyl acrylate, 0.42g (2mmol) DCC, 0.02g (0.2mmol) DMAP and 10mLDMSO are placed in the there-necked flask of 100mL, logical nitrogen also stirs, at the temperature of 25 ℃, carry out esterification, after 24h, obtain flaxen suspension liquid, after being filtered, under vigorous stirring, slowly pour in the mixing solutions being made into by ethanol and hydrochloric acid and precipitate, to remove residual DCC and DCU, precipitation gained material is repeatedly boiled and washed, be placed in again vacuum drying oven dry, obtain white product, the polyaryletherketone with formula (I) structure, productive rate is 66%.
Obtain after white product, it is carried out to nuclear magnetic resonance spectroscopy and Infrared spectroscopy, analytical results shows, gained white product is for having the polyaryletherketone of formula (I) structure.
According to method mentioned above, measure the limiting viscosity that gained has the polyaryletherketone of formula (I) structure, result shows, its limiting viscosity is 0.29dL/g;
According to method mentioned above, measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure respectively, result shows respectively, its second-order transition temperature is 147 ℃, and the temperature of initial weightlessness is 307 ℃, and weightless 5% temperature is 403 ℃.
By the PEK-L of 3.68g (7mmol) embodiment 1 preparation, 0.22g (2mmol) Hydroxyethyl acrylate, 0.42g (2mmol) DCC, 0.02g (0.2mmol) DMAP and 10mLTHF are placed in the there-necked flask of 100mL, logical nitrogen also stirs, at the temperature of 25 ℃, carry out esterification, after 24h, obtain flaxen suspension liquid, after being filtered, under vigorous stirring, slowly pour in the mixing solutions being made into by ethanol and hydrochloric acid and precipitate, to remove residual DCC and DCU, precipitation gained material is repeatedly boiled and washed, be placed in again vacuum drying oven dry, obtain white product, the polyaryletherketone with formula (I) structure, productive rate is 61%.
Obtain after white product, it is carried out to nuclear magnetic resonance spectroscopy and Infrared spectroscopy, analytical results shows, gained white product is for having the polyaryletherketone of formula (I) structure.
According to method mentioned above, measure the limiting viscosity that gained has the polyaryletherketone of formula (I) structure, result shows, its limiting viscosity is 0.29dL/g;
According to method mentioned above, measure second-order transition temperature and the thermal decomposition performance that gained has the polyaryletherketone of formula (I) structure respectively, result shows respectively, its second-order transition temperature is 153 ℃, and the temperature of initial weightlessness is 310 ℃, and weightless 5% temperature is 409 ℃.
As seen from the above embodiment, in the molecular structure of the polyaryletherketone with formula (I) structure provided by the invention, contain propenyl ester group, there is more cross-linking set and good resistance toheat, can be used as the products such as high temperature resistant type ultraviolet-curing paint.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. the polyaryletherketone with formula (I) structure:
Wherein, R is H or methyl; 1≤m≤4; N is the polymerization degree.
2. polyaryletherketone according to claim 1, is characterized in that, 1≤n≤500.
3. a preparation method for polyaryletherketone, comprising:
Under the existence of dewatering agent and catalyzer, the acrylate that has the polyaryletherketone of formula (II) structure and have formula (III) structure is carried out to esterification in organic solvent, the polyaryletherketone of (I) structure that obtains thering is formula;
Wherein, R is H or methyl; 1≤m≤4; N is the polymerization degree.
4. preparation method according to claim 3, is characterized in that, 1≤n≤500; The described acrylate with formula (III) structure is hydroxyethyl methylacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 410 or vinylformic acid-4-hydroxyl butyl ester.
5. preparation method according to claim 3, is characterized in that, described in there is formula (II) structure polyaryletherketone with described in there is the acrylate of formula (III) structure mol ratio be 1: 1～10: 1.
6. preparation method according to claim 3, it is characterized in that, described dewatering agent is N, N '-dicyclohexylcarbodiimide, N, N '-DIC or 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, described catalyzer is DMAP.
7. preparation method according to claim 3, it is characterized in that, described dewatering agent with described in there is formula (III) structure the mol ratio of acrylate for (0.1～5): 1, the mol ratio of described catalyzer and described dewatering agent is (0.1～1): 1.
8. preparation method according to claim 3, is characterized in that, described organic solvent is dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF).
9. preparation method according to claim 3, is characterized in that, described in there is the quality of polyaryletherketone of formula (II) structure and the ratio of the volume of described organic solvent is (0.1～1) g: 1mL.
10. preparation method according to claim 3, is characterized in that, the temperature of described esterification is 10 ℃～40 ℃, and the time of described esterification is 12h～48h.
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