CN1746206A - Copoaromatic ether and preparation thereof - Google Patents
Copoaromatic ether and preparation thereof Download PDFInfo
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- CN1746206A CN1746206A CN 200510060698 CN200510060698A CN1746206A CN 1746206 A CN1746206 A CN 1746206A CN 200510060698 CN200510060698 CN 200510060698 CN 200510060698 A CN200510060698 A CN 200510060698A CN 1746206 A CN1746206 A CN 1746206A
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- CN
- China
- Prior art keywords
- aromatic copolyester
- structural unit
- diphenolic acid
- general formula
- diphenolic
- Prior art date
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- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title description 4
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 claims abstract description 66
- 125000003118 aryl group Chemical group 0.000 claims abstract description 56
- 229920001634 Copolyester Polymers 0.000 claims abstract description 54
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 30
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 239000008367 deionised water Substances 0.000 claims description 54
- 229910021641 deionized water Inorganic materials 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 54
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 30
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- -1 isophthaloyl Chemical group 0.000 claims description 21
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 14
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 11
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 claims description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 241000370738 Chlorion Species 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 2
- 229940006461 iodide ion Drugs 0.000 claims description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 238000012696 Interfacial polycondensation Methods 0.000 abstract 1
- 125000002252 acyl group Chemical group 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 63
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 52
- 238000006243 chemical reaction Methods 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical class CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003937 drug carrier Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- LQOBMKYCRQDMTN-UHFFFAOYSA-N 3-(2-ethylphenyl)pentan-3-amine;hydrochloride Chemical compound Cl.CCC1=CC=CC=C1C(N)(CC)CC LQOBMKYCRQDMTN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- FCTFGDVLBOGMPH-UHFFFAOYSA-N TOAC Chemical compound CC1(C)CC(N)(C(O)=O)CC(C)(C)N1[O] FCTFGDVLBOGMPH-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- XKDUZXVNQOZCFC-UHFFFAOYSA-N hexan-1-amine;hydron;chloride Chemical class Cl.CCCCCCN XKDUZXVNQOZCFC-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
A copolyester aryl and its production are disclosed. The copolyester aryl consists of bisphenol A structural unit, terephthalyl acyl structural unit, isophthalamic acyl structural unit, at least a diphenolic acid or diphenolic ester structural unit or diphenolic salt structural unit, or hung carboxy, carboxylic ester and carboxylic salt on side chain. The process is carried out by taking bisphenol monomer containing at least a diphenolic acid or its derivative and phthalchlorine monomer as raw material, taking quaternary ammonium salt as phase transfer catalyst, and interfacial polycondensation reacting under 10-50 Deg C. to obtain copolyester aryl. It achieves fast polymerization speed, short time, low temperature, more yield and molecular weight.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of aromatic copolyester and preparation method thereof, be specially a kind of aromatic copolyester that contains a kind of diphenolic acid or derivatives thereof structural unit at least and preparation method thereof.
Technical background
Polyarylester broadly is meant ester group
Two ends connect the polymkeric substance of aromatic ring, refer to the polyarylate resin that dihydroxyphenyl propane and terephthalic acid (or p-phthaloyl chloride) and m-phthalic acid (or m-phthaloyl chloride) make for polymerizable raw material industrial more, mostly are aromatic copolyester in the practical application.
At first industrialization of Japanese You Niqika (Unitika) company in 1973, trade(brand)name U-polymkeric substance, basic trade mark U-100.Aromatic ring density height in the polyarylester main chain, the thermotolerance height of resin, heat-drawn wire (1.8MPa) reaches 157～175 ℃, heat-resisting in addition weldering and heat aging performance are all excellent, flame retardant properties is good, and the deflection rebound resilience is good in than large-temperature range, can be at-70～180 ℃ of life-time service.Polyarylester is soluble in halohydrocarbon and phenols, and general organic chemicals, oils are stablized the ability diluted acid.
Though the polyarylester resistance toheat is good, melt viscosity is big, poor mobile performance, and processing characteristics is bad, and particularly thin-walled and big part goods are difficult to make.For the processibility of improving polyarylester and improve its performance, the investigator adopts means such as blend, filling, copolymerization that polyarylester has been carried out many-sided modification, has obtained the modification polyarylester material of various excellent performances, has satisfied the needs of different field.
Prepare the effective means that the polyarylester alloy is the polyarylester modification with other polymer blending, existing lot of documents is reported the preparation of polyarylester alloy both at home and abroad, for example domestic 02817350.3,89107822, patent disclosures such as external US4804707, US5034502, US5130383, US5043413, US6608147 the preparation method of various polyarylester alloys, obtained the polyarylester material of a series of different performances.
The another kind of method of polyarylester being carried out modification is to carry out copolymerization to obtain aromatic copolyester, introduces new structural unit or new functional group in polymer architecture, thereby obtains new performance.Patent US5149769, US6794463 etc. and Cai Mingzhong, Song Caisheng (Jiangxi Normal University's journal (natural science newspaper), 1994,18:21～24) reported and had substituent dihydroxyphenyl propane synthetic polyarylester, its melt temperature reduces and is convenient to processing, and erosion-resisting characteristics and flame retardant resistance etc. all has raising; Liaw D J, (J Polym Sci PartA:Polym chem:2000 such as Liaw BY, 38:4451～4456) react by other aromatic series phenol replacement dihydroxyphenyl propanes and phthalyl chloride, obtain a series of aromatic ester that easily contains intermingle with, improve polyarylester and be difficult to the dissolved characteristic, reduce second-order transition temperature, make polyarylester also can be applicable to the paint film material; Wang C H, (J Polyer Sci PartA:Polymerchem:1995,33:2027～2031) such as Nakamura S are mixed with dihydroxyphenyl propane with phthalyl chloride by other aliphatic dihydroxy alcohol and are reacted, obtain a series of flexible polyarylesters; Huang Hansheng (New Chemical Materials, 1995,8:28～31) has reported two kinds of novel polyarylesters of the Austrian Isovolta of company trade mark PAR15, PAR25, and this polyarylester has excellent optical, is applied to the parts that use in fields such as UV filtering film, aviation.
Owing to above-mentionedly aliphatic dihydroxy alcohol replaced part dihydroxyphenyl propane and phthalyl chloride react the flexible polyarylester that obtains, though solvability is improved greatly, but because the aliphatics ester group is positioned on the main chain, thereby its resistance toheat obviously reduces, how when introducing the aliphatics ester bond, to keep the good thermotolerance of polyarylester, await solving; How in polyarylester, to introduce polar functional group,, expand the application of polyarylester, also have very important practical value in frontiers such as polymer catalyst, sequestrant, pharmaceutical carrier, polyelectrolyte as carboxyl, carboxylate radical etc.
Summary of the invention
The object of the present invention is to provide a kind of aromatic copolyester and preparation method thereof.
The technical solution adopted in the present invention is as follows:
One, a kind of aromatic copolyester:
Comprise and contain structure of bisphenol A unit, paraphenylene terephthalamide's structural unit, isophthaloyl structural unit in its chain structure.Also contain the bis-phenol hydrochlorate structural unit shown in diphenolic acid shown in a kind of general structure (1) or diphenolic acid ester structure unit or the general structure (2) at least, contain carboxyl, carboxylic acid ester groups and the carboxylate salt of suspension on the side chain;
General formula (1) general formula (2)
Wherein, R is selected from a kind of (R preferentially be selected from H atom, methyl, ethyl, propyl group, butyl, tertiary butyl, hexyl, phenyl or the benzyl a kind of) in H atom, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, hexyl, octyl group, phenyl or the benzyl, M
+Be selected from a kind of of sodium ion, potassium ion or ammonium ion.
The summation of diphenolic acid, bis-phenol acid esters, bis-phenol hydrochlorate structural unit and the unitary mol ratio of structure of bisphenol A are 100: 0～1: 99 in its chain structure.
The mol ratio of paraphenylene terephthalamide's structural unit and isophthaloyl structural unit is 100: 0～0: 100 in its chain structure.
Two, a kind of preparation method of aromatic copolyester:
Biphenol monomer, phase-transfer catalyst and sour accepting agent are dissolved in the deionized water by 100: 0～10: 200～1000 molar ratio, constitute water, the phthalyl chloride monomer is dissolved in the organic solvent, constitute oil phase, the mol ratio of phthalyl chloride monomer and biphenol monomer is 100: 80～80: 100, the volume ratio of water and oil phase is 5: 1～1: 5, water is mixed with oil phase, stir, under 10 ℃～50 ℃ temperature, reacted 0.5～8 hour, the product that obtains drips dilute hydrochloric acid solution, regulating the pH value is 3～4, washing, precipitation, filter, last handling processes such as drying obtain aromatic copolyester.
Described biphenol monomer is selected from a kind of in the bis-phenol hydrochlorate shown in the diphenolic acid shown in dihydroxyphenyl propane, the general formula (3) or bis-phenol acid esters, the general formula (4) or any two kinds, R is selected from a kind of (R preferentially be selected from H atom, methyl, ethyl, propyl group, butyl, tertiary butyl, hexyl, phenyl or the benzyl a kind of) in H atom, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, hexyl, octyl group, phenyl or the benzyl, M in the general formula (4) in the general formula (3)
+Be selected from a kind of of sodium ion, potassium ion or ammonium ion; The mol ratio of the summation of diphenolic acid, bis-phenol acid esters, bis-phenol hydrochlorate and dihydroxyphenyl propane is 100: 0～1: 99 in the biphenol monomer.
General formula (3) general formula (4)
Described phthalyl chloride monomer is selected from a kind of or its mixture in p-phthaloyl chloride and the m-phthaloyl chloride, and the mol ratio of p-phthaloyl chloride and m-phthaloyl chloride is 100: 0～0: 100.
The general structure of described phase-transfer catalyst (5) is:
General formula (5)
Wherein, R
1, R
2Be selected from C
1～C
8A kind of (R in alkyl or the benzyl
1Preferentially be selected from a kind of in butyl, hexyl or the octyl group, R
2Preferentially be selected from a kind of in butyl, hexyl, octyl group or the benzyl); X
-A kind of in chlorion, bromide anion or the iodide ion.
Described sour accepting agent is selected from a kind of in sodium hydroxide, potassium hydroxide, sodium bicarbonate, yellow soda ash, triethylamine or the pyridine or any two kinds.
The organic solvent of described formation oil phase is selected from a kind of in methylene dichloride, chloroform, tetracol phenixin, vinyl trichloride, sym.-tetrachloroethane, toluene, oil of mirbane, dimethylbenzene, dichlorobenzene, naphthalene or the hexanaphthene or any two kinds.
The useful effect that the present invention has is: the preparation method of aromatic copolyester provided by the invention has the advantages that rate of polymerization is fast, polymerization time is short, polymerization temperature is low, polymer yield is high, molecular weight is big, and the aromatic copolyester that obtains has functional groups such as the carboxyl, carboxylicesters, carboxylate salt of suspension.With respect to the aromatic copolyester that contains the aliphatic carboxylic acid ester group on the main chain, the aromatic copolyester that contains the aliphatic carboxylic acid ester group of suspension on the side chain provided by the invention can keep the resistance toheat of polyarylester constant substantially; With respect to traditional polyarylester, contain the carboxyl of suspension and the aromatic copolyester of carboxylate salt on the side chain provided by the invention and given new performances such as polyarylester is water-soluble, strong polarity.Thereby, with respect to traditional polyarylester, novel copolymerized aromatic ester provided by the invention has new structure and performance, performance range is wide and adjustable, both can be used as the modification kind of traditional polyarylester, also can be used as polyarylester ionogen, water-soluble poly aromatic ester, support of the catalyst, sequestrant, pharmaceutical carrier etc., will enlarge the use range of traditional polyarylester.
Embodiment
Among the preparation method of aromatic copolyester provided by the present invention, the described polymerization following reaction times of normal temperature is short, is reflected at the aromatic copolyester that can obtain having pendant carboxy group, carboxylicesters or carboxylate salt functional group in 2 hours, and reaction yield can reach more than 90%.
Polymer intrinsic viscosity adopts Ubbelohde viscometer to measure under the condition of 30 ℃ of following concentration 0.5g/dl, and solvent is H
2SO
4Phenol/the tetrachloroethane of volume content 4.76% (3: 2, w/w).
The embodiment that the invention is further illustrated by the following examples, but be not limited to these cases.
Reference example 1:
Synthesizing of diphenolic acid methyl esters:
In three mouthfuls of reactors, diphenolic acid (DPA, 28.6g, 0.1mol), methyl alcohol (32g, 1mol), tosic acid (0.85g, 0.005mol), backflow stirring reaction 5h is after reaction finishes, adding entry precipitates, carry out recrystallization with methyl alcohol one water, obtain 133～134 ℃ of final product fusing points, productive rate 58.9%.
Reference example 2:
Synthesizing of diphenolic acid propyl ester:
In three mouthfuls of reactors, diphenolic acid (DPA, 10g, 35.0mmol), propyl alcohol (250ml) and the vitriol oil (1ml), reaction mixture reflux 8h, 100ml ether continuous extraction 4 times is poured in the 600ml water in cooling into, the combining extraction liquid drying, carry out recrystallization with toluene, 100～101 ℃ of final product fusing points, productive rate 84%.
Embodiment 1:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, stir, diphenolic acid is dissolved fully, and 25 ℃ of constant temperature add m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7 fast, 0.01mol, 2.03g) the 50ml dichloromethane solution, stir with the rotating speed of 400rpm, reacted 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 56.7%, and reduced viscosity is 0.558dl/g.
Embodiment 2:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 89.8%, and reduced viscosity is 0.827dl/g.
Embodiment 3:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.29g, 10mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 90.2%, and reduced viscosity is 0.829dl/g.
Embodiment 4:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst four hexyl ammonium chlorides (THAC, 0.154g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 90%, and reduced viscosity is 0.834dl/g.
Embodiment 5:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst four octyl group ammonium chlorides (TOAC, 0.191g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 90.6%, and reduced viscosity is 0.841dl/g.
Embodiment 6:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst Tetrabutyl amonium bromide (TBAB, 0.135g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 87.2%, and reduced viscosity is 0.818dl/g.
Embodiment 7:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst triethyl benzyl ammonia chloride (TEBAC, 0.097g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 84.8%, and reduced viscosity is 0.773dl/g.
Embodiment 8:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml toluene solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 83.2%, and reduced viscosity is 0.765dl/g.
Embodiment 9:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), diphenolic acid is dissolved fully, and 25 ℃ of constant temperature add m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7 fast, 0.01mol, 2.03g) the 50ml chloroformic solution, stir with the rotating speed of 400rpm, reacted 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 82.0%, and reduced viscosity is 0.791dl/g.
Embodiment 10:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.005mol, 1.432g), dihydroxyphenyl propane (BPA, 0.005mol, 1.142g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid, dihydroxyphenyl propane are dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 51.2%, and reduced viscosity is 0.826dl/g.
Embodiment 11:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.0001mol, 0.0286g), dihydroxyphenyl propane (BPA, 0.0099mol, 2.261g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid, dihydroxyphenyl propane are dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 92.3%, and reduced viscosity is 1.426dl/g.
Embodiment 12:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.After reaction finishes,, filter 100 ℃ of dry 12h of vacuum with deionized water, washing with acetone.The diphenolic acid sodium salt aromatic copolyester yield that obtains is 84.2%, and reduced viscosity is 0.775dl/g.
Embodiment 13:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.008mol, 2.290g), the diphenolic acid methyl esters (0.002mol, 0.600g), triethylamine (TEA, 0.05mol, 5.05g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.After reaction finishes,, filter 100 ℃ of dry 12h of vacuum with deionized water, washing with acetone.The aromatic copolyester yield that obtains is 46.3%, and reduced viscosity is 0.421dl/g.
Embodiment 14:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, add m-phthaloyl chloride (IPC, 0.01mol, 50ml dichloromethane solution 2.03g) fast, rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 88.4%, and reduced viscosity is 0.609dl/g, and Tg is 136 ℃.
Embodiment 15:
In three mouthfuls of reactors, and diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, and 25 ℃ of constant temperature add m-phthaloyl chloride (IPC fast, 0.005mol, 1.015g), p-phthaloyl chloride (TPC, 0.005mol, 1.015g) the 50ml dichloromethane solution, stir with the rotating speed of 400rpm, reacted 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 70.7%, and reduced viscosity is 0.779dl/g, and Tg is 168 ℃.
Embodiment 16:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, add p-phthaloyl chloride (TPC, 0.01mol, 50ml dichloromethane solution 2.03g) fast, rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The polyarylester yield that obtains is 82.3%, and reduced viscosity is 0.773dl/g, and Tg is 189 ℃.
Embodiment 17:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.008mol, 50ml dichloromethane solution 1.624g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 63.0%, and reduced viscosity is 0.896dl/g.
Embodiment 18:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.008mol, 2.290g), NaOH (0.024mol, 0.96g), deionized water 72ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.094g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 95.6%, and reduced viscosity is 0.413dl/g.
Embodiment 19:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 450ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 96.3%, and reduced viscosity is 1.03dl/g.
Embodiment 20:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 18ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 62.3%, and reduced viscosity is 0.319dl/g.
Embodiment 21:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.02mol, 0.8g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 79.4%, and reduced viscosity is 0.583dl/g.
Embodiment 22:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.10mol, 4g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 56.4%, and reduced viscosity is 0.417dl/g.
Embodiment 23:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 10 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 87.7%, and reduced viscosity is 0.793dl/g.
Embodiment 24:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 50 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 1 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 90.1%, and reduced viscosity is 0.829dl/g.
Embodiment 25:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 0.5 hour.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 87.6%, and reduced viscosity is 0.697dl/g.
Embodiment 26:
In three mouthfuls of reactors, diphenolic acid (DPA, 0.01mol, 2.863g), NaOH (0.03mol, 1.2g), deionized water 90ml, phase-transfer catalyst tetrabutylammonium chloride (TBAC, 0.117g, 4mol%/[DPA]), stir, diphenolic acid is dissolved fully, 25 ℃ of constant temperature, quick adding m-phthaloyl chloride/p-phthaloyl chloride (IPC/TPC=3: 7,0.01mol, 50ml dichloromethane solution 2.03g), rotating speed with 400rpm stirs, and reacts 8 hours.Reaction adds rare HCl solution regulator solution pH and is about 3 after finishing, and uses deionized water, washing with acetone then, filters 100 ℃ of dry 12h of vacuum.The aromatic copolyester yield that obtains is 89.5%, and reduced viscosity is 0.843dl/g.
Claims (9)
1, a kind of aromatic copolyester comprises and contains structure of bisphenol A unit, paraphenylene terephthalamide's structural unit, isophthaloyl structural unit in its chain structure; It is characterized in that: also contain the bis-phenol hydrochlorate structural unit shown in diphenolic acid shown in a kind of general structure (1) or diphenolic acid ester structure unit or the general structure (2) at least, contain carboxyl, carboxylic acid ester groups and the carboxylate salt of suspension on the side chain;
General formula (1) general formula (2)
Wherein, R is selected from a kind of in H atom, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, hexyl, octyl group, phenyl or the benzyl, M
+Be selected from a kind of of sodium ion, potassium ion or ammonium ion.
2, a kind of aromatic copolyester according to claim 1 is characterized in that: the summation of diphenolic acid, bis-phenol acid esters, bis-phenol hydrochlorate structural unit and the unitary mol ratio of structure of bisphenol A are 100: 0～1: 99 in its chain structure.
3, a kind of aromatic copolyester according to claim 1 is characterized in that: the mol ratio of paraphenylene terephthalamide's structural unit and isophthaloyl structural unit is 100: 0～0: 100 in its chain structure.
4, a kind of preparation method of aromatic copolyester, it is characterized in that: biphenol monomer, phase-transfer catalyst and sour accepting agent are dissolved in the deionized water by 100: 0～10: 200～1000 molar ratio, constitute water, the phthalyl chloride monomer is dissolved in the organic solvent, constitute oil phase, the mol ratio of phthalyl chloride monomer and biphenol monomer is 100: 80～80: 100, the volume ratio of water and oil phase is 5: 1～1: 5, water is mixed with oil phase, stir, under 10 ℃～50 ℃ temperature, reacted 0.5～8 hour, the product that obtains drips dilute hydrochloric acid solution, and regulating the pH value is 3～4, washing, precipitation, filter, last handling processes such as drying obtain aromatic copolyester.
5, the preparation method of a kind of aromatic copolyester according to claim 4, it is characterized in that: described biphenol monomer is selected from a kind of in the bis-phenol hydrochlorate shown in the diphenolic acid shown in dihydroxyphenyl propane, the general formula (3) or bis-phenol acid esters, the general formula (4) or any two kinds, R is selected from a kind of in H atom, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, hexyl, octyl group, phenyl or the benzyl, M in the general formula (4) in the general formula (3)
+Be selected from a kind of of sodium ion, potassium ion or ammonium ion; The mol ratio of the summation of diphenolic acid, bis-phenol acid esters, bis-phenol hydrochlorate and dihydroxyphenyl propane is 100: 0～1: 99 in the biphenol monomer.
General formula (3) general formula (4)
6, the preparation method of aromatic copolyester according to claim 4, it is characterized in that described phthalyl chloride monomer is selected from a kind of or its mixture in p-phthaloyl chloride and the m-phthaloyl chloride, the mol ratio of p-phthaloyl chloride and m-phthaloyl chloride is 100: 0～0: 100.
7, the preparation method of aromatic copolyester according to claim 4 is characterized in that the general structure (5) of described phase-transfer catalyst is:
General formula (5)
Wherein, R
1, R
2Be selected from C
1～C
8A kind of in alkyl or the benzyl; X
-A kind of in chlorion, bromide anion or the iodide ion.
8, the preparation method of aromatic copolyester according to claim 4 is characterized in that described sour accepting agent is selected from a kind of in sodium hydroxide, potassium hydroxide, sodium bicarbonate, yellow soda ash, triethylamine or the pyridine or any two kinds.
9, according to the preparation method of right 4 described aromatic copolyesters, the organic solvent that it is characterized in that described formation oil phase is selected from methylene dichloride, chloroform, tetracol phenixin, 1,1,2-trichloroethane, 1,1,2, a kind of in 2-tetrachloroethane, toluene, oil of mirbane, dimethylbenzene, dichlorobenzene, naphthalene or the hexanaphthene or any two kinds.
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| CN113861400A (en) * | 2021-10-29 | 2021-12-31 | 中国科学院长春应用化学研究所 | Hyperbranched polyarylester and preparation method thereof |
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| CN114479029A (en) * | 2022-01-26 | 2022-05-13 | 安徽理工大学 | Preparation method of bisphenol-B type polyarylate material |
| CN115850670A (en) * | 2022-11-21 | 2023-03-28 | 中国科学技术大学 | Preparation method of diphenolic acid polyaromatic ester material |
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| US4957996A (en) * | 1988-10-12 | 1990-09-18 | Hoechst Celanese Corporation | Preparation of polyarylate of improved color with cobalt salt |
| EP0513658A3 (en) * | 1991-05-14 | 1993-01-20 | Hoechst Aktiengesellschaft | Polyaryletherketone alloys |
| EP0569001A1 (en) * | 1992-05-05 | 1993-11-10 | Hoechst Aktiengesellschaft | Mixtures of liquid crystalline copolymers and polyarylates |
| US5714567A (en) * | 1996-02-15 | 1998-02-03 | Council Of Scientific & Ind. Research | Process for the preparation of aromatic polyesters |
| TWI295298B (en) * | 2000-08-29 | 2008-04-01 | Sumitomo Chemical Co | Liquid crystalline polyester and method for producing the same |
| CN1308380C (en) * | 2002-06-28 | 2007-04-04 | 罗福高技术薄膜股份有限公司 | Membranes made of cast polyarylate film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102898630A (en) * | 2011-07-27 | 2013-01-30 | 上海杰事杰新材料(集团)股份有限公司 | Copolyarylate and its preparation method |
| CN113861400A (en) * | 2021-10-29 | 2021-12-31 | 中国科学院长春应用化学研究所 | Hyperbranched polyarylester and preparation method thereof |
| CN113930058A (en) * | 2021-10-29 | 2022-01-14 | 中国科学院长春应用化学研究所 | Low-temperature thermoplastic plate composition and preparation method thereof |
| CN113930058B (en) * | 2021-10-29 | 2023-02-28 | 中国科学院长春应用化学研究所 | Low-temperature thermoplastic plate composition and preparation method thereof |
| CN114479029A (en) * | 2022-01-26 | 2022-05-13 | 安徽理工大学 | Preparation method of bisphenol-B type polyarylate material |
| CN115850670A (en) * | 2022-11-21 | 2023-03-28 | 中国科学技术大学 | Preparation method of diphenolic acid polyaromatic ester material |
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| CN100386360C (en) | 2008-05-07 |
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