CN102558518B - Aromatic copolyester and preparation method thereof - Google Patents
Aromatic copolyester and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of material synthesis and preparation, and discloses novel aromatic copolyester and a preparation method thereof. The aromatic copolyester provided by the invention has repeating structural units shown in the description, wherein n=50 to 500, and m=0 to 10. The aromatic copolyester provided by the invention has excellent fire retardance, excellent ultraviolet shielding property, relatively high molecular weight, good mechanical properties, and the like, such that diverse requirements of different areas on the performance of the desired polymer products are satisfied.
Description
Technical field
The invention belongs to the synthetic preparation field of material, be specifically related to aromatic copolyester of a kind of novelty and preparation method thereof.
Background technology
Utilize terephthalic acid and ethylene glycol successfully to obtain polyethylene terephthalate (PET) beginning since nineteen forty-one, polyester just progresses in people's routine work and life as a kind of engineering plastics, and is bringing into play the effect becoming more and more important.Through development and the progress of a century and a half science and technology, its kind also a kind ofly increases to present tens kinds by initial.According to the difference of diacid groups in these polyester molecule chains, they can be divided into aromatic polyester, aliphatic polyester, present cycloaliphatic polyesters and comprise two kinds or the prepared all kinds of copolyesters of two or more diprotic acid simultaneously.Wherein, being most widely used at present, is also that the polyester kind of studying is the earliest aromatic polyester.
Aromatic polyester, as its name suggests, on polymer molecular chain, to contain aromatic series unit, as the polyester of phenyl ring, naphthalene nucleus, can obtain half/Wholly aromatic polyester through polycondensation by the derivative of aromatic acid, ester, acid anhydrides or acyl chlorides and fat or alicyclic dibasic alcohol or aromatic series phenols, also can pass through polycondensation by the derivative of aliphatic dibasic acid, ester, acid anhydrides or acyl chlorides and aromatic series phenols and prepare semi-aromatic polyester.This kind polyester has good weathering resistance, electrical insulating property, chemical proofing, wear resistance, and lower water-absorbent and stable size, is widely used in the industrial circles such as light industry, machinery, electronics, food product pack.
Polyarylester, as a kind of aromatic polyester of full fragrant, obtains by derivative, acid anhydrides or acyl chlorides and the polycondensation of aromatic series phenols of aromatic acid, ester.Different from semi-aromatic polyesters such as polyethylene terephthalate above-mentioned (PET), polybutylene terephthalate (PBT), Poly(Trimethylene Terephthalate) (PTT) is, although this kind polyester is started late, but due to aromatic series unit content higher in its molecular chain, double-spiral structure and hard stick characteristics, there is excellent resistance toheat and mechanical property, all obtained developing widely and applying in military project hi-tech and civil area in recent years.1973, first Japanese You Niqika company succeeded in developing polyphenyl dioctyl phthalate bisphenol A-type polyarylester, and commodity are called U polymkeric substance.(Song Caisheng, synthetic and sign, Jiangxi Normal University's journal, 2009,1 of 1,3-bis-(4-formyl chloride benzoyl) benzene) 1979, Beyer Co., Ltd of West Germany succeeds in developing the polyarylester of commodity APE by name.Other is also engaged in identical or similar polyarylester development as General Electric Corporation, Hooke company and Tan Jin (Teijin) company.But the strong characteristic of its molecular chain is in providing better resistance toheat, also reduced to a great extent processing characteristics, higher processing temperature is had higher requirement to production unit, has increased virtually cost, has hindered further developing of it.
The semi-aromatic polyester of preparing for the derivative by aliphatic dibasic acid, ester, acid anhydrides or acyl chlorides and the polycondensation of aromatic series phenols, the lower requirement that is difficult to reach actual use of polymericular weight that utilizes traditional method to prepare, or adopt active higher monomer can prepare the product of higher molecular weight, but compare with traditional semi-aromatic polyester (as PET, PBT), both are more or less the same at performance, the former price is but very high, becomes the Main Bottleneck that limits its extensive industrialization.
The main method of preparing at present polyarylester has high-temperature fusion polycondensation, solution polycondensation and interfacial polycondensation.Melt phase polycondensation is the most simple and effective polycondensation method of one.Reaction mass only has monomer and proper catalyst, thereby product is pure, need not separate, and the production efficiency of reactor is also higher.But its temperature of reaction is higher, need reach 300～330 DEG C, energy consumption is large, need blanketing with inert gas to prevent high temperature oxidation, and molten mass viscosity is very high simultaneously, stirs difficulty, and acetic acid or dihydroxyphenyl propane are not easy to remove, therefore the polymerization degree is not high.
Solution polycondensation is because being subject to the restriction of solvent boiling point, and polymeric reaction temperature is relatively low, so monomer should have higher reactive behavior, otherwise can only adopt the solution polymerization of high boiling solvent.When solution polycondensation carries out at relatively low temperature, side reaction is less, and the relative molecular weight of product is lower.In addition, the Separation and Recovery of solvent is difficulty rather, and the production efficiency of reactor is relatively high compared with production cost low and polymkeric substance.
Interfacial polycondensation requires to have at least one to belong to high reactivity monomer in monomer, and guarantee reaction is carried out fast.But do not require the high purity of two kinds of monomers and the proportioning of the molar mass such as strict, just can ensure to obtain the polymkeric substance that molecular weight is relatively high.(Pan Zuren compiles for polymer chemistry, the third edition, 195) this polymerization process temperature of reaction is low in addition, therefore side reaction is less, is more novel a kind of polymerization process, and polycarbonate as widely used in the current whole world has 90% to be all to synthesize by interfacial polycondensation.(superpolymer synthesis technique is learned, the second edition, Zhao Deren etc., 315)
Summary of the invention
The object of this invention is to provide a kind of aromatic copolyester of novelty, this aromatic copolyester has excellent flame retardant resistance, ultraviolet-shielding type, higher molecular weight and mechanical property etc. preferably.
Another object of the present invention is to provide a kind of preparation method of above-mentioned aromatic copolyester, and the method speed of response is fast, and production cost is low.
Technical scheme of the present invention is as follows:
The invention provides a kind of aromatic copolyester of novelty, this aromatic copolyester has following repeated structural unit:
Wherein:
n＝50～500，m＝0～10。
The present invention also provides a kind of preparation method of above-mentioned aromatic copolyester, and the method comprises the following steps:
(1) bisphenol cpd, alkali and phase transition interfacial polycondensation catalyzer organic quaternary ammonium salt are joined in distilled water, form the water white transparency aqueous solution of bisphenol cpd;
(2), by one or more the mixture in aromatic dimethyl chloride or aliphatics diacid chloride, join and in halogenated hydrocarbon solvent, dissolve the transparent organic solution that forms acyl chlorides; (3) under the condition that is 600～1200rpm at rotating speed, stir, the organic solution that above-mentioned steps (2) is configured is added drop-wise in the aqueous solution of step (1), after 10～30 DEG C of reaction 0.5～3h, and stopped reaction; Reaction soln is poured fast into precipitating in the precipitation agent of vigorous stirring, precipitating product cleans with alkaline aqueous solution, acidic aqueous solution and distilled water respectively, Büchner funnel vacuumizing filtration, and 50～100 DEG C of dry 8～16h of vacuum drying oven, obtain aromatic copolyester product.
Described bisphenol cpd and the mol ratio of alkali are 1: 2～1: 4, preferably 1: 2.5～1: 3.5.
The mol ratio of described bisphenol cpd and phase transition interfacial polycondensation catalyzer organic quaternary ammonium salt is 1: 0.001～1: 0.1, preferably 1: 0.001～1: 0.05.
The mol ratio of described aromatic dimethyl chloride and aliphatics diacid chloride is 1: 9～1: 0.1, preferably 1: 4～1: 0.25.
The mol ratio of described bisphenol cpd and acyl chlorides (total amount of substance of the mixture of one or more in aromatic dimethyl chloride or the aliphatics diacid chloride adding according to reality is determined) is 1: 1～1: 1.5, preferably 1: 1.05～1: 1.3.Described precipitation agent and the volume ratio of halohydrocarbon are 1: 1～1: 10, preferably 1: 1.5～1: 5.
Described bisphenol cpd is selected from 4,4-dihydroxy phenyl thioether, 2, the mixture of one or more in 2-bis-(4-hydroxy phenyl) propane or 2,2-bis-(4-hydroxy phenyl) HFC-236fa.
Described alkali is selected from one or both mixture of sodium hydroxide or potassium hydroxide.
Described phase transition interfacial polycondensation catalyzer organic quaternary ammonium salt is selected from one or more the mixture in cetyl trimethylammonium bromide, benzyl trimethyl ammonium chloride, phenyl trimethyl ammonium chloride or Tetrabutyl amonium bromide.
Described aromatic dimethyl chloride is selected from one or both the mixture in p-phthaloyl chloride or m-phthaloyl chloride.
Described aliphatics diacid chloride is selected from one or more the mixture in oxalyl chloride, malonyl chloride, succinic chloride, glutaryl chlorine, Adipoyl Chloride, pimeloyl chloride, suberoyl chlorine, azelaoyl chloride, sebacoyl chloride, undecane diacid chloride, dodecane diacid chloride or tridecane diacid chloride.
Described halohydrocarbon is selected from one or more the mixture in methylene dichloride, trichloromethane, tetracol phenixin or 1,2-ethylene dichloride.
Described precipitation agent is selected from one or more the mixture in methyl alcohol, ethanol, ether, acetone or ethyl acetate.
The NaOH alkaline aqueous solution that described alkaline aqueous solution concentration is 0.05%～5%, the NaOH alkaline aqueous solution that preferred concentration is 0.1%～2%.
The HCl acidic aqueous solution that described acidic aqueous solution concentration is 0.05%～5%, the HCl acidic aqueous solution that preferred concentration is 0.1%～2%.
Compared with the existing technology, tool has the following advantages and beneficial effect in the present invention:
1, aromatic copolyester of the present invention has excellent flame retardant resistance, ultraviolet-shielding type, higher molecular weight and mechanical property etc. preferably, to meet the various requirement of different field to required polymer product performance.
2, the present invention, by utilizing phase transition interface polycondensation to prepare aromatic copolyester, compares with traditional interfacial polycondensation, and present method has added a kind of organic quaternary ammonium salt as catalyzer in reaction system, and polycondensation speed is obviously accelerated, and has reduced production cost.
3, the present invention is by phase transition interfacial polycondensation, aromatic series diacid chloride and aliphatics diacid chloride and the random copolymerization of aromatic series phenols are obtained to aromatic copolyester, compare with traditional polyarylester, the polymkeric substance that present method obtains is owing to there being the existence of aliphatics unit, increase the kindliness of molecular chain, by regulating the ratio of each copolymerization component, make the thermal property second-order transition temperature T of the aromatic copolyester obtaining
gchange continuously within the specific limits with processing temperature.Meeting under the prerequisite that actual use temperature requires, the processing temperature of suitable reduction aromatic copolyester, can greatly improve the processing characteristics of polymkeric substance, reduces production costs.
4, the present invention is by phase transition interfacial polycondensation, aromatic series diacid chloride and aliphatics diacid chloride and the random copolymerization of aromatic series phenols are obtained to aromatic copolyester, compare with traditional semi-aromatic polyester, owing to there being the existence of Wholly aromatic polyester unit, the polymkeric substance that the present invention obtains has good flame retardant resistance and ultraviolet-shielding type, has very large advantage for the use of outdoor and inflammable occasion.
Embodiment
Below in conjunction with illustrated embodiment, the present invention is further illustrated.
In the embodiment providing below, adopt following detection method:
Adopt differential scanning calorimeter Perkin Elmer DSC7, under following type of heating, measure second-order transition temperature T
gwith melt temperature T
m
Scanning, with 50 DEG C/min, is warmed up to 350 DEG C from-10 DEG C for the first time;
Scanning, with 10 DEG C/min, cools to-10 DEG C from 350 DEG C for the second time;
Scanning, with 20 DEG C/min, is warmed up to 350 DEG C from-10 DEG C for the third time.
Adopt the logarithmic specific concentration viscosity (η of Ubbelohde viscometer to polymkeric substance
inh) test:
Polymkeric substance is dissolved in the sym.-tetrachloroethane, phenol mixed solvent of 50v/50v, is made into 0.5% solution, in the Water Tank with Temp.-controlled of 30 ± 0.1 DEG C with determination of ubbelohde viscometer, by η
inh=C
-1lint
1/ t
0calculate.In formula, C is polymer concentration (0.5g/dL), t
1for the time that polymers soln is flowed through in Ubbelodhe viscometer, t
0the time of flowing through in Ubbelodhe viscometer for solvent.
Embodiment 1
(1) by the sodium hydroxide of 7.2g, 13.7g 2,2-bis-(4-hydroxy phenyl) propane (dihydroxyphenyl propane), 0.2g cetyl trimethylammonium bromide, 500mL distilled water join in the there-necked flask that whipping appts and thermometer are housed, and stir and make it dissolve formation dihydroxyphenyl propane water white transparency alkaline aqueous solution.
(2) 6.3g Adipoyl Chloride, 3.5g p-phthaloyl chloride, 3.5g m-phthaloyl chloride are dissolved in 500mL dichloromethane solution and obtain organic solution.
(3) (750rpm) obtains step (2) under agitation condition organic solution slowly splashes in the aqueous solution that step (1) obtains through 0.5h, reacts 2.5h, stopped reaction at 10 DEG C; Reaction system is poured under intense agitation in the methanol solution of 3L and precipitated, utilize Büchner funnel vacuumizing filtration to remove reaction solvent water, methylene dichloride and precipitation agent methanol, utilize respectively 1%NaOH alkaline aqueous solution, the 0.5%HCl aqueous solution and distilled water solution to clean throw out, remove successively unreacted acyl chlorides and dicarboxylic acid monomer, residual NaOH, the salt NaCl of generation.Finally, by products therefrom dry 10h in the vacuum drying oven of 80 DEG C, obtain semi-aromatic aromatic copolyester poly terephthalic acid-co-m-phthalic acid (25%)-co-hexanodioic acid (50%) dihydroxyphenyl propane ester.
Products therefrom is carried out to the test of DSC and Ubbelohde viscosity, test result is: intrinsic viscosity=0.87dl/g, second-order transition temperature T
g=127 DEG C, decomposition temperature T
d=464 DEG C.
Embodiment 2
(1) by the potassium hydroxide of the sodium hydroxide of 4g, 2.8g, 13.1g 4,4-dihydroxy phenyl thioether, 0.1g benzyl trimethyl ammonium chloride, 500mL distilled water join in the there-necked flask that whipping appts and thermometer are housed, and stir and make it dissolve formation water white transparency alkaline aqueous solution.
(2) 6.3g Adipoyl Chloride, 3.5g p-phthaloyl chloride, 3.5g m-phthaloyl chloride are dissolved in 500mL chloroform soln and obtain organic solution.
(3) (800rpm) obtains step (2) under agitation condition organic solution slowly splashes in the aqueous solution that step (1) obtains through 0.5h, reacts 1.5h, stopped reaction at 20 DEG C; Reaction system is poured under intense agitation in the acetone soln of 3L and precipitated, utilize Büchner funnel vacuumizing filtration to remove reaction solvent water, trichloromethane and precipitation agent acetone, utilize respectively 0.5%NaOH alkaline aqueous solution, the 1%HCl aqueous solution and distilled water solution to clean throw out, remove successively unreacted acyl chlorides and diprotic acid, residual NaOH, the salt NaCl of generation.Finally, by products therefrom dry 16h in the vacuum drying oven of 60 DEG C, obtain semi-aromatic aromatic copolyester poly terephthalic acid-co-m-phthalic acid (25%)-co-hexanodioic acid (50%) 4,4-dihydroxy phenyl thioether ester.
Products therefrom is carried out to the test of DSC and Ubbelohde viscosity, test result is: intrinsic viscosity=0.86dl/g, second-order transition temperature T
g=124 DEG C, decomposition temperature T
d=446 DEG C.
Embodiment 3
(1) by the potassium hydroxide of 10.2g, 13.7g 2,2-bis-(4-hydroxy phenyl) propane (dihydroxyphenyl propane), 0.15g phenyl trimethyl ammonium chloride, 450mL distilled water join in the there-necked flask that whipping appts and thermometer are housed, and stir and make it dissolve formation dihydroxyphenyl propane water white transparency alkaline aqueous solution.
(2) 10.9g sebacoyl chloride, 1.8g p-phthaloyl chloride, 1.8g m-phthaloyl chloride are dissolved in 500mL carbon tetrachloride solution and obtain organic solution.
(3) (900rpm) obtains step (2) under agitation condition organic solution slowly splashes in the aqueous solution that step (1) obtains through 0.5h, reacts 2.5h, stopped reaction at 10 DEG C; Reaction system is poured under intense agitation in the diethyl ether solution of 3L and precipitated, utilize Büchner funnel vacuumizing filtration to remove reaction solvent water, tetracol phenixin and precipitation agent ether, utilize respectively 1.5%NaOH alkaline aqueous solution, the 1%HCl aqueous solution and distilled water solution to clean throw out, remove successively unreacted acyl chlorides and dicarboxylic acid monomer, residual NaOH, the salt NaCl of generation.Finally, by products therefrom dry 10h in the vacuum drying oven of 80 DEG C, obtain semi-aromatic aromatic copolyester poly terephthalic acid-co-m-phthalic acid (12.5%)-co-sebacic acid (75%) dihydroxyphenyl propane ester.
Products therefrom is carried out to the test of DSC and Ubbelohde viscosity, test result is: intrinsic viscosity=0.79dl/g, second-order transition temperature T
g=47 DEG C, decomposition temperature T
d=414 DEG C.
Embodiment 4
(1) by the sodium hydroxide of 8.4g, 6.9g 2,2-bis-(4-hydroxy phenyl) propane (dihydroxyphenyl propane), 10.2g 2,2-bis-(4-hydroxy phenyl) HFC-236fa (bisphenol AF), 0.1g Tetrabutyl amonium bromide, 0.1g cetyl trimethylammonium bromide, 600mL distilled water join in the there-necked flask that whipping appts and thermometer are housed, and stir and make it dissolve formation dihydroxyphenyl propane and bisphenol AF water white transparency alkaline aqueous solution.
(2) 2.7g succinic chloride, 3.2g Adipoyl Chloride, 5.3g p-phthaloyl chloride, 5.3g m-phthaloyl chloride are dissolved in to 550mL1, in 2-dichloroethane solution, obtain organic solution.
(3) (800rpm) obtains step (2) under agitation condition organic solution slowly splashes in the aqueous solution that step (1) obtains through 0.5h, reacts 1h, stopped reaction at 30 DEG C; Reaction system is poured under intense agitation in the ethanolic soln of 3L and precipitated, utilize Büchner funnel vacuumizing filtration to remove reaction solvent water, 1,2-ethylene dichloride and precipitation agent ethanol, utilize respectively 1%NaOH alkaline aqueous solution, the 1%HCl aqueous solution and distilled water solution to clean throw out, remove successively unreacted acyl chlorides and dicarboxylic acid monomer, residual NaOH, the salt NaCl of generation.Finally, by products therefrom dry 10h in the vacuum drying oven of 80 DEG C, obtain semi-aromatic aromatic copolyester poly terephthalic acid-co-m-phthalic acid (37.5%)-co-succinic acid (12.5%)-co-hexanodioic acid (12.5%) dihydroxyphenyl propane-bisphenol AF (50%) ester.
Products therefrom is carried out to the test of DSC and Ubbelohde viscosity, test result is: intrinsic viscosity=0.89dl/g, second-order transition temperature T
g=155 DEG C, decomposition temperature T
d=503 DEG C.
Embodiment 5
(1) by the sodium hydroxide of 7.2g, 20.4g 2,2-bis-(4-hydroxy phenyl) HFC-236fa (bisphenol AF), 0.25g cetyl trimethylammonium bromide, 450mL distilled water join in the there-necked flask that whipping appts and thermometer are housed, and stir and make it dissolve formation bisphenol AF water white transparency alkaline aqueous solution.
(2) 13g Adipoyl Chloride is dissolved in 550mL dichloromethane solution and obtains organic solution.
(3) (1000rpm) obtains step (2) under agitation condition organic solution slowly splashes in the aqueous solution that step (1) obtains through 0.5h, reacts 1.5h, stopped reaction at 25 DEG C; Reaction system is poured under intense agitation in the ethyl acetate solution of 3L and precipitated, utilize Büchner funnel vacuumizing filtration to remove reaction solvent water, methylene dichloride and precipitation agent ethyl acetate, utilize respectively 0.5%NaOH alkaline aqueous solution, the 1%HCl aqueous solution and distilled water solution to clean throw out, remove successively unreacted acyl chlorides and dicarboxylic acid monomer, residual NaOH, the salt NaCl of generation.Finally, by products therefrom dry 10h in the vacuum drying oven of 80 DEG C, obtain the poly-hexanodioic acid bisphenol AF ester of semi-aromatic aromatic copolyester.
Products therefrom is carried out to the test of DSC and Ubbelohde viscosity, test result is: intrinsic viscosity=0.79dl/g, second-order transition temperature T
g=108 DEG C, decomposition temperature T
d=435 DEG C.
Control Example
(1) by the sodium hydroxide of 7.2g, 13.7g 2,2-bis-(4-hydroxy phenyl) propane (dihydroxyphenyl propane), 0.2g cetyl trimethylammonium bromide, 500mL distilled water join in the there-necked flask that whipping appts and thermometer are housed, and stir and make it dissolve formation dihydroxyphenyl propane water white transparency alkaline aqueous solution.
(2) 7g p-phthaloyl chloride, 7g m-phthaloyl chloride are dissolved in 500mL chloroform soln and obtain organic solution.
(3) (700rpm) obtains step (2) under agitation condition organic solution slowly splashes in the aqueous solution that step (1) obtains through 0.5h, reacts 2h, stopped reaction at 15 DEG C; Reaction system is poured under intense agitation in the methanol solution of 3L and precipitated, utilize Büchner funnel vacuumizing filtration to remove reaction solvent water, trichloromethane and precipitation agent methanol, utilize respectively 1%NaOH alkaline aqueous solution, the 1.5%HCl aqueous solution and distilled water solution to clean throw out, remove successively unreacted acyl chlorides and dicarboxylic acid monomer, residual NaOH, the salt NaCl of generation.Finally, by products therefrom dry 10h in the vacuum drying oven of 80 DEG C, obtain all aromatic aromatic copolyester poly terephthalic acid-co-m-phthalic acid (50%) dihydroxyphenyl propane ester.
Products therefrom is carried out to the test of DSC and Ubbelohde viscosity, test result is: intrinsic viscosity=0.92dl/g, second-order transition temperature T
g=178 DEG C, decomposition temperature T
d=526 DEG C.
By implementation process and the detected result of each embodiment, known preparation method of the present invention is by regulating the ratio of each copolymerization component, especially the ratio of binary aliphatic acyl chlorides and aromatic dicarboxylic acyl chlorides, can obtain glass transition temperature Tg and processing temperature continually varying aromatic copolyester within the specific limits, meet the diversity requirement of different environments for use to sample.In addition, the processing temperature of reduction aromatic copolyester that can also be suitable, greatly improves the processing characteristics of polymkeric substance, reduces production costs.
The above-mentioned description to embodiment is can understand and apply the invention for the ease of those skilled in the art.Person skilled in the art obviously can easily make various amendments to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from improvement and the amendment that category of the present invention makes all should be within protection scope of the present invention.
Claims (10)
1. an aromatic copolyester, is characterized in that: this aromatic copolyester has following repeated structural unit,
Wherein:
or
R2 is
with
with
Or
with
n＝50～500，m＝2～10；
The preparation method of described aromatic copolyester comprises the following steps,
(1) bisphenol cpd, alkali and phase transition interfacial polycondensation catalyzer organic quaternary ammonium salt are joined in distilled water, form the water white transparency aqueous solution of bisphenol cpd;
(2), by the mixture of aromatic dimethyl chloride and aliphatics diacid chloride, join the transparent organic solution of dissolving formation acyl chlorides in halogenated hydrocarbon solvent;
(3) under the condition that is 600～1200rpm at rotating speed, stir, the organic solution that above-mentioned steps (2) is configured is added drop-wise in the aqueous solution of step (1), after 10～30 DEG C of reaction 0.5～3h, and stopped reaction; Reaction soln is poured fast into precipitating in the precipitation agent of vigorous stirring, precipitating product cleans with alkaline aqueous solution, acidic aqueous solution and distilled water respectively, Büchner funnel vacuumizing filtration, and 50～100 DEG C of dry 8～16h of vacuum drying oven, obtain aromatic copolyester product;
Described bisphenol cpd and the mol ratio of alkali are 1:2～1:4; The mol ratio of described bisphenol cpd and phase transition interfacial polycondensation catalyzer organic quaternary ammonium salt is 1:0.001～1:0.1; The mol ratio of described aromatic dimethyl chloride and aliphatics diacid chloride is 1:9～1:0.1; Described bisphenol cpd and the mol ratio of acyl chlorides are 1:1～1:1.5; Described precipitation agent and the volume ratio of halohydrocarbon are 1:1～1:10.
2. a preparation method for aromatic copolyester claimed in claim 1, is characterized in that: the method comprises the following steps,
(1) bisphenol cpd, alkali and phase transition interfacial polycondensation catalyzer organic quaternary ammonium salt are joined in distilled water, form the water white transparency aqueous solution of bisphenol cpd;
(2), by the mixture of aromatic dimethyl chloride and aliphatics diacid chloride, join the transparent organic solution of dissolving formation acyl chlorides in halogenated hydrocarbon solvent;
(3) under the condition that is 600～1200rpm at rotating speed, stir, the organic solution that above-mentioned steps (2) is configured is added drop-wise in the aqueous solution of step (1), after 10～30 DEG C of reaction 0.5～3h, and stopped reaction; Reaction soln is poured fast into precipitating in the precipitation agent of vigorous stirring, precipitating product cleans with alkaline aqueous solution, acidic aqueous solution and distilled water respectively, Büchner funnel vacuumizing filtration, and 50～100 DEG C of dry 8～16h of vacuum drying oven, obtain aromatic copolyester product;
The mol ratio of described aromatic dimethyl chloride and aliphatics diacid chloride is 1:9～1:0.1.
3. the preparation method of aromatic copolyester according to claim 2, is characterized in that: described bisphenol cpd and the mol ratio of alkali are 1:2～1:4; The mol ratio of described bisphenol cpd and phase transition interfacial polycondensation catalyzer organic quaternary ammonium salt is 1:0.001～1:0.1; Described bisphenol cpd and the mol ratio of acyl chlorides are 1:1～1:1.5; Described precipitation agent and the volume ratio of halohydrocarbon are 1:1～1:10.
4. the preparation method of aromatic copolyester according to claim 2, it is characterized in that: described bisphenol cpd is selected from 4,4-dihydroxy phenyl thioether, 2, the mixture of one or more in 2-bis-(4-hydroxy phenyl) propane or 2,2-bis-(4-hydroxy phenyl) HFC-236fa; Described alkali is selected from one or both mixture of sodium hydroxide or potassium hydroxide.
5. the preparation method of aromatic copolyester according to claim 2, is characterized in that: described phase transition interfacial polycondensation catalyzer organic quaternary ammonium salt is selected from one or more the mixture in cetyl trimethylammonium bromide, benzyl trimethyl ammonium chloride, phenyl trimethyl ammonium chloride or Tetrabutyl amonium bromide.
6. the preparation method of aromatic copolyester according to claim 2, is characterized in that: described aromatic dimethyl chloride is selected from a kind of in p-phthaloyl chloride or m-phthaloyl chloride or their mixture; Described aliphatics diacid chloride is selected from one or more the mixture in succinic chloride, glutaryl chlorine, Adipoyl Chloride, pimeloyl chloride, suberoyl chlorine, azelaoyl chloride, sebacoyl chloride, undecane diacid chloride or dodecane diacid chloride.
7. the preparation method of aromatic copolyester according to claim 2, is characterized in that: described halohydrocarbon is selected from one or more the mixture in methylene dichloride, trichloromethane, tetracol phenixin or 1,2-ethylene dichloride.
8. the preparation method of aromatic copolyester according to claim 2, is characterized in that: described precipitation agent is selected from one or more the mixture in methyl alcohol, ethanol, ether, acetone or ethyl acetate.
9. the preparation method of aromatic copolyester according to claim 2, is characterized in that: the NaOH alkaline aqueous solution that described alkaline aqueous solution concentration is 0.05%～5%.
10. the preparation method of aromatic copolyester according to claim 2, is characterized in that: the HCl acidic aqueous solution that described acidic aqueous solution concentration is 0.05%～5%.
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| CN104497290B (en) * | 2014-11-13 | 2016-08-24 | 哈尔滨工业大学无锡新材料研究院 | Optics fluorine-containing copolyesters, optical thin film and manufacture method thereof |
| CN104497292B (en) * | 2014-12-12 | 2016-09-14 | 东华大学 | A kind of multi-functional copolyesters of antifouling fire-retardant anti-molten droplet and preparation method thereof |
| CN105418906B (en) * | 2015-12-18 | 2017-07-07 | 佛山市南海高拓包装材料有限公司 | The method and carborane polyarylate of a kind of room temperature synthesis carborane polyarylate |
| CN113896870B (en) * | 2020-06-22 | 2023-05-05 | 比亚迪股份有限公司 | Polyester and preparation method and application thereof |
| CN114075328B (en) * | 2020-08-17 | 2024-04-09 | 万华化学集团股份有限公司 | Phosphorus-containing flame-retardant copolyarylester and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049109A (en) * | 1988-12-27 | 1991-02-13 | 联合碳化工业气体技术公司 | Semipermeable partition based on specified tetrabromobisphenol type polyesters |
| CN1944488A (en) * | 2006-10-27 | 2007-04-11 | 四川大学 | Bisphenol type poly arylate and its preparing method and use |
-
2010
- 2010-12-07 CN CN201010576677.1A patent/CN102558518B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049109A (en) * | 1988-12-27 | 1991-02-13 | 联合碳化工业气体技术公司 | Semipermeable partition based on specified tetrabromobisphenol type polyesters |
| CN1944488A (en) * | 2006-10-27 | 2007-04-11 | 四川大学 | Bisphenol type poly arylate and its preparing method and use |
Non-Patent Citations (2)
| Title |
|---|
| 相转移催化法合成双酚A型聚芳酯的研究;蔡明中等;《化学世界》;19931231(第6期);第261页第1段到第263页第1段 * |
| 蔡明中等.相转移催化法合成双酚A型聚芳酯的研究.《化学世界》.1993,(第6期),第261页第1段到第263页第1段. |
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