CN102585210A - Phenolphthalein polyaryletherketone and preparation method thereof - Google Patents
Phenolphthalein polyaryletherketone and preparation method thereof Download PDFInfo
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- CN102585210A CN102585210A CN2012100412981A CN201210041298A CN102585210A CN 102585210 A CN102585210 A CN 102585210A CN 2012100412981 A CN2012100412981 A CN 2012100412981A CN 201210041298 A CN201210041298 A CN 201210041298A CN 102585210 A CN102585210 A CN 102585210A
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Abstract
本发明提供了一种具有式(I)结构的酚酞聚芳醚酮，其中，n为聚合度；1≤m≤5。本发明提供了一种酚酞聚芳醚酮的制备方法，包括以下步骤：将具有式(II)结构的酚酞聚芳醚酮、催化剂、有机溶剂和具有式(III)结构的环氧卤代烷烃混合，反应后得到具有式(I)结构的酚酞聚芳醚酮；其中，n为聚合度；1≤m≤5；X为卤素。在本发明提供的具有式(I)结构的酚酞聚芳醚酮中，环氧基团位于聚合物分子链的侧链，通过调节具有式(II)结构的酚酞聚芳醚酮和具有式(III)结构的环氧卤代烷烃的投料比，能够调控引入的环氧基团的数量，更加拓宽了酚酞聚芳醚酮的应用范围。另外，所述制备方法的反应条件温和，成本较低，易于推广。 The present invention provides a phenolphthalein polyaryletherketone having a structure of formula (I), wherein, n is the degree of polymerization; 1≤m≤5. The invention provides a preparation method of phenolphthalein polyarylether ketone, comprising the following steps: mixing the phenolphthalein polyarylether ketone having the structure of formula (II), a catalyst, an organic solvent and an epoxy haloalkane having the structure of formula (III) , after the reaction, the phenolphthalein polyaryletherketone having the structure of formula (I) is obtained; wherein, n is the degree of polymerization; 1≤m≤5; X is a halogen. In the phenolphthalein polyarylether ketone with formula (I) structure provided by the present invention, epoxy group is positioned at the side chain of polymer molecular chain, by adjusting the phenolphthalein polyarylether ketone with formula (II) structure and having formula ( The feed ratio of epoxy haloalkane with structure III) can regulate the amount of epoxy groups introduced, further broadening the application range of phenolphthalein polyaryletherketone. In addition, the preparation method has mild reaction conditions, low cost and easy popularization. 
Description
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of phenolphthalein polyaryletherketone and preparation method thereof.
Background technology
Phenolphthalein polyaryletherketone (PEK-C) is a kind of polyaryletherketone with undefined structure of the nineties research in last century and development.Except having the characteristics of traditional polyaryletherketone, like high temperature resistant, radiation hardness, chemical-resistant resistance, good insulation preformance and mechanical property good outside, the phenolphthalein polyaryletherketone also has the good and processability of solvability and waits outstanding advantage well, is one type of high performance engineering plastics.And the resin that contains epoxide group is one type of important thermosetting resin, has that mechanical property is good, an advantage such as strong adhesion and good heat resistance, has been widely used as the materials such as matrix resin of structural adhesive and fibre composite.Because phenolphthalein polyaryletherketone and the characteristics that contain the resin of epoxide group; The phenolphthalein polyaryletherketone that contains epoxide group can combine both characteristics; Have good performance, can be used as materials such as high-temperature-resistant adhesive, high performance composite matrix resin and functional high molecule material.
At present, prior art discloses multiple phenolphthalein polyaryletherketone that contains epoxide group and preparation method thereof, such as deliver at Chen Tianlu etc., name is called in the article of " contain the synthetic of epoxy-terminated phenolphthalein polyaryletherketone E-PEK and characterize "; According to the method for synthetic phenolphthalein polyaryletherketone, at first with phenolphthalein and 4,4 '-two chloro benzophenones carry out nucleophilic condensation polymerization with different molar ratios; Generation contains-the polyetherketone low molecular weight prepolymer of OK end group, under 90 ℃～105 ℃ temperature, the polyetherketone low molecular weight prepolymer of said containing-OK end group and excessive epoxy chloropropane are reacted then; Behind reaction 4h～8h, obtain containing epoxy-terminated phenolphthalein polyaryletherketone (E-PEK) bullion, at last reaction product is disperseed deposition in ethanol-Virahol; Through filtering, water repeatedly washs, to remove the salt that generates in the dereaction; Reaction product vacuum-drying under 80 ℃～120 ℃ temperature after filtering is obtained flaxen powdery resin to constant weight, promptly pure contain epoxy-terminated phenolphthalein polyaryletherketone; Productive rate＞90% (Chen Tianlu etc.; Applied chemistry, 1993,10 (1): 39～42).
The molecular weight that contains epoxy-terminated phenolphthalein polyaryletherketone of above-mentioned preparing method's preparation is 1000～8000; Can be dissolved in general organic solvent, the second-order transition temperature after the curing (Tg) is 183 ℃～215 ℃, has better machining property and application performance; But the epoxide group of gained phenolphthalein polyaryletherketone is the end group of molecular chain-end; Fixed amount can not be regulated and control the quantity of epoxide group according to application demand, thereby makes the range of application of gained phenolphthalein polyaryletherketone less.
Summary of the invention
In view of this, the technical problem that the present invention will solve is to provide a kind of phenolphthalein polyaryletherketone and preparation method thereof, and the epoxide group of phenolphthalein polyaryletherketone provided by the invention is positioned at the side chain of polymer molecular chain, and its quantity can be regulated and control, and range of application is wider.
The invention provides a kind of phenolphthalein polyaryletherketone with formula (I) structure:
Wherein, n is the polymerization degree; 1≤m≤5.
Preferably, 1≤n≤500.
Preferably, m is 1 or 2.
The present invention also provides a kind of preparation method of phenolphthalein polyaryletherketone, may further comprise the steps:
The epoxy halogenated alkane mixing that will have phenolphthalein polyaryletherketone, catalyzer, the organic solvent of formula (II) structure and have formula (III) structure, the phenolphthalein polyaryletherketone that obtains having formula (I) structure after the reaction;
Wherein, n is the polymerization degree; 1≤m≤5; X is a halogen.
Preferably, 1≤n≤500; Said epoxy halogenated alkane with formula (III) structure is epoxy chloropropane or 1,2-epoxy chlorobutane.
Preferably, said phenolphthalein polyaryletherketone and said mol ratio with epoxy halogenated alkane of formula (III) structure with formula (II) structure is 1: 3～1: 0.1.
Preferably, said catalyzer is NaH, K
2CO
3, NaOH or KOH.
Preferably, said catalyzer and said mol ratio with phenolphthalein polyaryletherketone of formula (II) structure are (2～4): 1.
Preferably, said organic solvent is DMSO 99.8MIN., N or chloroform.
Preferably, the temperature of said reaction is 30 ℃～50 ℃, and the time of said reaction is 8h～12h.
Compared with prior art, the present invention is a raw material with phenolphthalein polyaryletherketone with formula (II) structure and the epoxy halogenated alkane with formula (III) structure, is medium with the organic solvent; Under the effect of catalyzer, react; The phenolphthalein polyaryletherketone of (I) structure that obtains having formula, wherein, n is the polymerization degree; 1≤m≤5.Phenolphthalein polyaryletherketone with formula (I) structure provided by the invention contains epoxide group, has the premium properties of phenolphthalein polyaryletherketone and epoxide group simultaneously, can be used as materials such as high-temperature-resistant adhesive, high performance composite matrix resin and functional high molecule material; In the phenolphthalein polyaryletherketone with formula (I) structure provided by the invention; Epoxide group is positioned at the side chain of polymer molecular chain; The phenolphthalein polyaryletherketone and feed ratio that have formula (II) structure through adjusting with epoxy halogenated alkane of formula (III) structure; Can regulate and control the quantity of the epoxide group of introducing on the phenolphthalein polyaryletherketone molecular chain, widen the range of application of phenolphthalein polyaryletherketone more.Experimental result shows that phenolphthalein polyaryletherketone provided by the invention is a white, has formula (I) structure, and its temperature of weightless 5% is about 400 ℃, and weightless 10% temperature is more than 450 ℃.
Description of drawings
The infrared spectrogram of the phenolphthalein polyaryletherketone that Fig. 1 obtains for the embodiment of the invention 2;
The hydrogen nuclear magnetic resonance spectrogram of the phenolphthalein polyaryletherketone that Fig. 2 obtains for the embodiment of the invention 2.
Embodiment
The invention provides a kind of phenolphthalein polyaryletherketone with formula (I) structure:
Wherein, n is the polymerization degree; 1≤m≤5.
In the present invention, infrared spectrogram and hydrogen nuclear magnetic resonance spectrogram prove that all phenolphthalein polyaryletherketone provided by the invention has formula (I) structure, and wherein, n is the polymerization degree, preferred 1≤n≤500, more preferably 2≤n≤200, most preferably 3≤n≤100; 1≤m≤5, m is preferably 1 or 2, and more preferably 1.
Phenolphthalein polyaryletherketone with formula (I) structure provided by the invention contains epoxide group; Belong to the epoxy phenolphthalein polyaryletherketone in the polyaryletherketone product; The premium properties that has phenolphthalein polyaryletherketone and epoxide group simultaneously can be used as materials such as high-temperature-resistant adhesive, high performance composite matrix resin and functional high molecule material; In the phenolphthalein polyaryletherketone with formula (I) structure provided by the invention; Epoxide group is positioned at the side chain of polymer molecular chain; Its quantity can be regulated and control, thereby can access the phenolphthalein polyaryletherketone of a series of different epoxy group content, has widened the range of application of phenolphthalein polyaryletherketone more.
In the present invention, said color with phenolphthalein polyaryletherketone of formula (I) structure is white; The temperature of said phenolphthalein polyaryletherketone with formula (I) structure weightless 5% is about 400 ℃, and weightless 10% temperature is more than 450 ℃.
The present invention also provides a kind of preparation method of phenolphthalein polyaryletherketone, may further comprise the steps:
The epoxy halogenated alkane mixing that will have phenolphthalein polyaryletherketone, catalyzer, the organic solvent of formula (II) structure and have formula (III) structure, the phenolphthalein polyaryletherketone that obtains having formula (I) structure after the reaction;
Wherein, n is the polymerization degree; 1≤m≤5; X is a halogen.
The present invention is preferably under nitrogen protection; Phenolphthalein polyaryletherketone, catalyzer and the organic solvent that will have formula (II) structure add in the reactor drum; Preferably 30 ℃～50 ℃, more preferably under 35 ℃～45 ℃ temperature, stir; Preferably at 20min～40min, more preferably add the epoxy halogenated alkane with formula (III) structure, the phenolphthalein polyaryletherketone that obtains having formula (I) structure after the reaction behind 25min～35min.
The present invention is a raw material with the phenolphthalein polyaryletherketone with formula (II) structure; Said phenolphthalein polyaryletherketone with formula (II) structure is an imino-phenolphthalein polyaryletherketone, abbreviates PEK-IH as, and it provides the characteristic of phenolphthalein polyaryletherketone for the phenolphthalein polyaryletherketone with formula (I) structure; The present invention does not have particular restriction to the said polymerization degree (n) with phenolphthalein polyaryletherketone of formula (II) structure; Preferred 1≤n≤500, more preferably 2≤n≤200, most preferably 3≤n≤100;
The present invention does not have particular restriction to said source with phenolphthalein polyaryletherketone of formula (II) structure, can buy from market, can make according to following preparation method yet:
With 3, two (4-hydroxy phenyl) phthalimidines and 4 of 3-, the 4-difluoro benzophenone reacts under the effect of salt of wormwood, the phenolphthalein polyaryletherketone of (II) structure that obtains having formula.
Preferably under nitrogen protection, with 3, two (4-hydroxy phenyl) phthalimidines, 4 of 3-in 4-difluoro benzophenone and the salt of wormwood adding reactor drum, preferably make it to react according to following method in the present invention:
At first under 110 ℃～130 ℃ temperature, react, preferably under stirring condition, react, more preferably 115 ℃～125 ℃ of the temperature of said reaction, the time of said reaction is preferably 3h～4h;
Preferably be warming up to 120 ℃～140 ℃ then and continue reaction, preferably under stirring condition, continue reaction, the time of said reaction is preferably 1h～1.5h;
Preferably be warming up to 140 ℃～150 ℃ again and continue reaction, no longer change until the viscosity of reaction system, preferably under stirring condition, continue reaction, the time of said reaction is preferably 3h～5h.
Can obtain having the phenolphthalein polyaryletherketone of formula (II) structure according to the method described above, yield is greater than 90%.
The present invention is another raw material with the epoxy halogenated alkane with formula (III) structure, and it provides epoxide group for the phenolphthalein polyaryletherketone with formula (I) structure, wherein, 1≤m≤5, m is preferably 1 or 2, and more preferably 1; X is a halogen, is preferably F or Cl, more preferably Cl; Said epoxy halogenated alkane with formula (III) structure is preferably epoxy chloropropane or 1,2-epoxy chlorobutane, more preferably epoxy chloropropane.
Under the effect of catalyzer, nucleophilic substitution reaction takes place in said epoxy halogenated alkane and said phenolphthalein polyaryletherketone with formula (II) structure with formula (III) structure in organic solvent, the phenolphthalein polyaryletherketone of (I) structure that obtains having formula.
In said phenolphthalein polyaryletherketone with formula (I) structure; Epoxide group is positioned at the side chain of polymer molecular chain; The phenolphthalein polyaryletherketone and feed ratio that have formula (II) structure through adjusting with epoxy halogenated alkane of formula (III) structure; Can regulate and control the quantity of the epoxide group of introducing on the phenolphthalein polyaryletherketone molecular chain, thereby can access the phenolphthalein polyaryletherketone of a series of different epoxy group content, widen the range of application of phenolphthalein polyaryletherketone more.
In the present invention, said phenolphthalein polyaryletherketone and said mol ratio with epoxy halogenated alkane of formula (III) structure with formula (II) structure be preferably 1: 3～and 1: 0.1, more preferably 1: 2～1: 0.5;
The present invention does not have particular restriction to said catalyzer, and said catalyzer is preferably NaH, K
2CO
3, NaOH or KOH, more preferably NaH; Said catalyzer and said mol ratio with phenolphthalein polyaryletherketone of formula (II) structure are preferably (2～4): 1, more preferably (2.5～3.5): 1;
The present invention does not have particular restriction to said organic solvent, and said organic solvent is preferably DMSO 99.8MIN. (DMSO), N or chloroform, more preferably DMSO 99.8MIN. (DMSO); The present invention does not have particular restriction to the consumption of said organic solvent, and employing can get final product the consoluet consumption of above-mentioned raw materials.
After reaction stops, obtaining containing the brown solution of phenolphthalein polyaryletherketone product, the present invention boils phenolphthalein polyaryletherketone product deposition, filtration back repeatedly with deionized water and washes with ethanol, obtains the phenolphthalein polyaryletherketone product of white after the drying.
In the present invention, the temperature of said reaction is preferably 30 ℃～50 ℃, more preferably 35 ℃～45 ℃; The time of said reaction is preferably 8h～12h, and more preferably 9h～11h most preferably is 9.5h～10h.
After obtaining the phenolphthalein polyaryletherketone product of white, it is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy.Gained infrared spectrogram and hydrogen nuclear magnetic resonance spectrogram prove that all gained phenolphthalein polyaryletherketone product has formula (I) structure.
Utilize METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer test gained to have the thermal decomposition performance of the phenolphthalein polyaryletherketone of formula (I) structure; Test condition is following: logical nitrogen is protected; Heat-up rate is 10 ℃/min, and the TR of test is 0 ℃～550 ℃.Test result shows, the temperature of said phenolphthalein polyaryletherketone weightless 5% with formula (I) structure is about 400 ℃, and weightless 10% temperature is more than 450 ℃.
Experiment shows; The present invention introduces epoxide group on phenolphthalein polyaryletherketone molecular side chain; Prepare epoxy phenolphthalein polyaryletherketone with novel texture; Increased the kind of epoxy phenolphthalein polyaryletherketone, it can be used as materials such as high-temperature-resistant adhesive, high performance composite matrix resin and functional high molecule material; In the phenolphthalein polyaryletherketone with formula (I) structure provided by the invention; Epoxide group is positioned at the side chain of polymer molecular chain; The phenolphthalein polyaryletherketone and feed ratio that have formula (II) structure through adjusting with epoxy halogenated alkane of formula (III) structure; Can regulate and control the quantity of the epoxide group of introducing on the phenolphthalein polyaryletherketone molecular chain, thereby can access the phenolphthalein polyaryletherketone of a series of different epoxy group content, widen the range of application of phenolphthalein polyaryletherketone more.
In addition, preparation method provided by the invention not only reaction conditions is gentle, implement easily, and the monomer cost is lower, has higher performance, is easy to apply, and has remarkable economic efficiency and social benefit.
In order to further specify the present invention, phenolphthalein polyaryletherketone provided by the invention and preparation method thereof is described in detail below in conjunction with embodiment.
Embodiment 1
In the flask that mechanical stirring, TM, logical nitrogen tube and prolong are housed, add 3.175g 3, two (4-hydroxy phenyl) phthalimidines of 3-, 2.185g 4,4-difluoro benzophenone and 1.604g salt of wormwood; Under 120 ℃ temperature, stir 4h; Be warming up to 130 ℃ then, constant temperature 1h continued is warming up to 145 ℃, under 145 ℃ temperature, stirs 3h; The phenolphthalein polyaryletherketone (PEK-IH) of (II) structure that obtains having formula, yield is greater than 90%.
Embodiment 2
The 0.486g PEK-IH of embodiment 1 preparation and 0.104g NaH placed have TM, be connected with nitrogen tube and churned mechanically there-necked flask; Add 18mL DMSO in 30 ℃ of stirring 30min, add the 0.25mL epoxy chloropropane again, behind the reaction 8h; Solution impouring with above-mentioned reaction under vigorous stirring fills in the 50mL alcoholic acid beaker; The filtration back is boiled repeatedly with deionized water and is washed, and obtains the phenolphthalein polyaryletherketone product of white after the drying, and productive rate is 93%.
The gained white product is carried out IR spectroscopy, and the result is referring to Fig. 1, the infrared spectrogram of the phenolphthalein polyaryletherketone that Fig. 1 obtains for the embodiment of the invention 2.Can know wave number 3436cm by Fig. 1
-1The place is terminal phenolphthalein hydroxyl vibration peak, wave number 3062cm
-1The place is C-H stretching vibration peak on the phenyl ring, wave number 1700cm
-1The place is the carbonylic stretching vibration peak on the phenolphthalein structure unit lactone, wave number 1656cm
-1The place is benzophenone carbonylic stretching vibration peak, wave number 1583cm
-1, wave number 1498cm
-1, wave number 1414cm
-1, wave number 1372cm
-1The place is phenyl ring skeleton stretching vibration peak, wave number 1241cm
-1The place is C-O-C stretching vibration peak on the aryl oxide, i.e. the characteristic peak of aryl oxide, wave number 1164cm
-1The place is C-O stretching vibration peak in the phenolphthalein lactone, wave number 1111cm
-1, wave number 1055cm
-1, wave number 1010cm
-1With wave number 955cm
-1The place is phenyl ring in-plane bending vibration peak, wave number 2982cm
-1, wave number 2906cm
-1With wave number 929cm
-1The place replaces characteristic peak for epoxide group.In sum, gained phenolphthalein polyaryletherketone has formula (IV) structure.
The gained white product is carried out nuclear magnetic resonance spectroscopy, and the result is referring to Fig. 2, the hydrogen nuclear magnetic resonance spectrogram of the phenolphthalein polyaryletherketone that Fig. 2 obtains for the embodiment of the invention 2.Can know by Fig. 2; 7.73ppm the peak of chemical shift place belongs to 2 ', 3 hydrogen, the peak of 7.60ppm chemical shift place belongs to 4 hydrogen, and the peak of 7.51ppm chemical shift place belongs to 5,6 hydrogen; 7.28ppm the peak of chemical shift place belongs to 2 hydrogen; 7.10ppm the peak of chemical shift place belongs to 1,1 ' hydrogen, the peak of 3.64ppm chemical shift place belongs to the hydrogen of A position, and the peak of 2.38ppm chemical shift place belongs to the hydrogen of B position; 2.21ppm the peak of chemical shift place belongs to the hydrogen of C position, the peak of 3.33ppm, 2.50ppm chemical shift place is respectively impurity H
2The fignal center of O and solvent DMSO.In sum, gained phenolphthalein polyaryletherketone has formula (IV) structure:
According to the thermal decomposition performance of method test gained phenolphthalein polyaryletherketone mentioned above, the result shows that its temperature of weightless 5% is 450 ℃, and weightless 10% temperature is 525 ℃.
The 0.486g PEK-IH of embodiment 1 preparation and 0.104g NaH placed have TM, be connected with nitrogen tube and churned mechanically there-necked flask; Add 18mL DMSO in 30 ℃ of stirring 30min, add the 0.056mL epoxy chloropropane again, behind the reaction 8h; Solution impouring with above-mentioned reaction under vigorous stirring fills in the 50mL alcoholic acid beaker; The filtration back is boiled repeatedly with deionized water and is washed, and obtains the phenolphthalein polyaryletherketone product of white after the drying, and productive rate is 91%.
The gained white product is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy respectively, and the result shows that it has formula (IV) structure.
According to the thermal decomposition performance of method test gained phenolphthalein polyaryletherketone mentioned above, the result shows that its temperature of weightless 5% is 410 ℃, and weightless 10% temperature is 500 ℃.
Embodiment 4
The 0.486g PEK-IH of embodiment 1 preparation placed with 0.104g NaH have TM, be connected with nitrogen tube and churned mechanically there-necked flask, add 18mL DMSO, add the 0.04mL epoxy chloropropane again in 30 ℃ of stirring 30min; Be warming up to 35 ℃; Behind the reaction 8h, obtain pale brown look viscous solution, stopped reaction; And under vigorous stirring, above-mentioned solution impouring is filled in the 50mL alcoholic acid beaker; The filtration back is boiled repeatedly with deionized water and is washed, and obtains the phenolphthalein polyaryletherketone product of white after the drying, and productive rate is 93%.
The gained white product is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy respectively, and the result shows that it has formula (IV) structure.
According to the thermal decomposition performance of method test gained phenolphthalein polyaryletherketone mentioned above, the result shows that its temperature of weightless 5% is 406 ℃, and weightless 10% temperature is 490 ℃.
Embodiment 5
The 0.486g PEK-IH of embodiment 1 preparation placed with 0.104g NaH have TM, be connected with nitrogen tube and churned mechanically there-necked flask, add 18mL DMSO, add the 0.024mL epoxy chloropropane again in 30 ℃ of stirring 30min; Be warming up to 35 ℃; Behind the reaction 9h, obtain brown solution, stopped reaction; And under vigorous stirring, above-mentioned solution impouring is filled in the 50mL alcoholic acid beaker; The filtration back is boiled repeatedly with deionized water and is washed, and obtains the phenolphthalein polyaryletherketone product of white after the drying, and productive rate is 89%.
The gained white product is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy respectively, and the result shows that it has formula (IV) structure.
According to the thermal decomposition performance of method test gained phenolphthalein polyaryletherketone mentioned above, the result shows that its temperature of weightless 5% is 396 ℃, and weightless 10% temperature is 481 ℃.
Embodiment 6
The 0.486g PEK-IH of embodiment 1 preparation placed with 0.104g NaH have TM, be connected with nitrogen tube and churned mechanically there-necked flask, add 20mL DMSO, add the 0.008mL epoxy chloropropane again in 30 ℃ of stirring 30min; Be warming up to 40 ℃; Behind the reaction 10h, obtain brown solution, stopped reaction; And under vigorous stirring, above-mentioned solution impouring is filled in the 50mL alcoholic acid beaker; The filtration back is boiled repeatedly with deionized water and is washed, and obtains the phenolphthalein polyaryletherketone product of white after the drying, and productive rate is 92%.
The gained white product is carried out IR spectroscopy and nuclear magnetic resonance spectroscopy respectively, and the result shows that it has formula (IV) structure.
According to the thermal decomposition performance of method test gained phenolphthalein polyaryletherketone mentioned above, the result shows that its temperature of weightless 5% is 386 ℃, and weightless 10% temperature is 479 ℃.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle 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 claim of the present invention.
Claims (10)
1. the phenolphthalein polyaryletherketone that has formula (I) structure:
Wherein, n is the polymerization degree; 1≤m≤5.
2. phenolphthalein polyaryletherketone according to claim 1 is characterized in that, 1≤n≤500.
3. phenolphthalein polyaryletherketone according to claim 1 is characterized in that, m is 1 or 2.
4. the preparation method of a phenolphthalein polyaryletherketone may further comprise the steps:
The epoxy halogenated alkane mixing that will have phenolphthalein polyaryletherketone, catalyzer, the organic solvent of formula (II) structure and have formula (III) structure, the phenolphthalein polyaryletherketone that obtains having formula (I) structure after the reaction;
Wherein, n is the polymerization degree; 1≤m≤5; X is a halogen.
5. preparation method according to claim 4 is characterized in that, 1≤n≤500; Said epoxy halogenated alkane with formula (III) structure is epoxy chloropropane or 1,2-epoxy chlorobutane.
6. preparation method according to claim 4 is characterized in that, said phenolphthalein polyaryletherketone and said mol ratio with epoxy halogenated alkane of formula (III) structure with formula (II) structure is 1: 3～1: 0.1.
7. preparation method according to claim 4 is characterized in that, said catalyzer is NaH, K
2CO
3, NaOH or KOH.
8. preparation method according to claim 4 is characterized in that, said catalyzer and said mol ratio with phenolphthalein polyaryletherketone of formula (II) structure are (2～4): 1.
9. preparation method according to claim 4 is characterized in that, said organic solvent is DMSO 99.8MIN., N or chloroform.
10. preparation method according to claim 4 is characterized in that, the temperature of said reaction is 30 ℃～50 ℃, and the time of said reaction is 8h～12h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850921A (en) * | 2012-10-10 | 2013-01-02 | 中国科学院长春应用化学研究所 | Paint composition |
| CN102875800A (en) * | 2012-10-10 | 2013-01-16 | 中国科学院长春应用化学研究所 | Phenolphthalein polyarylether ketone copolymer and preparation method thereof |
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| CN102850921A (en) * | 2012-10-10 | 2013-01-02 | 中国科学院长春应用化学研究所 | Paint composition |
| CN102875800A (en) * | 2012-10-10 | 2013-01-16 | 中国科学院长春应用化学研究所 | Phenolphthalein polyarylether ketone copolymer and preparation method thereof |
| CN102850921B (en) * | 2012-10-10 | 2015-09-16 | 中国科学院长春应用化学研究所 | A kind of coating composition |
| WO2018094763A1 (en) * | 2016-11-22 | 2018-05-31 | 常州天晟新材料股份有限公司 | Method for preparing foaming material of phenolphthalein-based polyaryletherketone structure |
| US11001689B2 (en) | 2016-11-22 | 2021-05-11 | Jiangsu Sinc-Tech Polymerization New Materials Industry Technology Research Institute | Method of preparation of cardo polyetherketone (PEK-C) structural foam material |
| CN111497227A (en) * | 2020-05-28 | 2020-08-07 | 中国科学院长春应用化学研究所 | Phenolphthalein polyaryletherketone/sulfone special material for 3D printing and preparation method thereof |
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