CN1283690C - Dyeingable dalk coloured copolyester and its preparation method - Google Patents
Dyeingable dalk coloured copolyester and its preparation method Download PDFInfo
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- CN1283690C CN1283690C CN 200310125429 CN200310125429A CN1283690C CN 1283690 C CN1283690 C CN 1283690C CN 200310125429 CN200310125429 CN 200310125429 CN 200310125429 A CN200310125429 A CN 200310125429A CN 1283690 C CN1283690 C CN 1283690C
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- terephthalic acid
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- ethylene glycol
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000005886 esterification reaction Methods 0.000 claims abstract description 41
- 230000032050 esterification Effects 0.000 claims abstract description 35
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 27
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 79
- 239000000975 dye Substances 0.000 claims description 20
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- -1 terephthalic acid dipropylene glycol ester Chemical class 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005809 transesterification reaction Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- NMYFVWYGKGVPIW-UHFFFAOYSA-N 3,7-dioxabicyclo[7.2.2]trideca-1(11),9,12-triene-2,8-dione Chemical group O=C1OCCCOC(=O)C2=CC=C1C=C2 NMYFVWYGKGVPIW-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical group OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 229960004249 sodium acetate Drugs 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001639 calcium acetate Substances 0.000 claims description 2
- 229960005147 calcium acetate Drugs 0.000 claims description 2
- 235000011092 calcium acetate Nutrition 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- BCBHDSLDGBIFIX-UHFFFAOYSA-N 4-[(2-hydroxyethoxy)carbonyl]benzoic acid Chemical group OCCOC(=O)C1=CC=C(C(O)=O)C=C1 BCBHDSLDGBIFIX-UHFFFAOYSA-N 0.000 abstract 1
- 150000001462 antimony Chemical class 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- CAZNPELDCQMQFT-UHFFFAOYSA-N propane-1,1-diol;terephthalic acid Chemical group CCC(O)O.OC(=O)C1=CC=C(C(O)=O)C=C1 CAZNPELDCQMQFT-UHFFFAOYSA-N 0.000 abstract 1
- 150000003608 titanium Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- 229920000728 polyester Polymers 0.000 description 12
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 7
- 238000005453 pelletization Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229920004935 Trevira® Polymers 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004044 disperse dyeing Methods 0.000 description 1
- 230000009429 distress Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical class [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical group COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to easily dyeable dark colored copolyester and a preparation method thereof. The copolyester contains the following substances of the proportion by weight: 35.0 to 90.0% of bis2 hydroxyethyl terephthalate repeating unit and 5.0 to 50.0% of terephthalic acid propanediol repeating unit, and the rest is polyalkylene glycol whose average molecular weight is from 500 to 10000. The preparation method is characterized in that under the existence of titanium series and/or antimony series catalysts, two or more than two dibasic alcohol monomer mixed materials carry out direct esterification with terephthalic acid (TPA), or carry out ester interchange with dimethyl terephthalate (DMT); obtained esterified substances carry out a polycondensation reaction with polyalkylene glycol, which obtains a copolyester product. The preparation method of the present invention has the advantages of reasonable design, easy realization of industrial production and lower production cost, and the dark color dyeing performance of the prepared copolyester is good.
Description
Technical field
The present invention relates to the raw material of synthon, specifically is a kind of dark copolyesters and preparation method thereof that easily dyes, and the fiber of this co-polyester production has the good dark performance of dying.
Background technology
As everyone knows, the conventional polyester fiber can not be carried out dyeing at normal pressure, can only adopt high-temperature pressure dyeing, and be difficult for dying dark color, its these characteristics have not only limited its application in a lot of fields, and as when wool blended, dyeing high temperature can make wool feel variation etc., and carry out high-temperature pressure dyeing to the having relatively high expectations of dyeing installation, increased production cost virtually.Domestic and international many companies adopt several different methods that normal polyester has been carried out modification in succession at this situation, to improve its dyeing behavior.The method that generally adopts is for adding the cationic raw material that dyes at present, successively develop cation dyeable polyester (CDP), cationic dyestuff normal-pressure easy-to-dye polyester (ECDP), having solved the PET fiber can only be with the problem of disperse dyeing or high-temperature pressure dyeing.But the preparation method of CDP or ECDP introduces 5-sodium sulfonate-dimethyl isophthalate (SIPM) or 5-sodium sulfonate-ethylene isophthalate (SIPE), wherein sulfonic acid group (SO in polyester
3Na) sulfonate ion that comes out of disassociation easily with macromolecular chain on positron partly form stronger bonding entanglement point, make that polymer melt condenses easily, gelation, thereby cause melt viscosity to rise, easy obstruction spinning jet during spinning influences spinning property.
World patent WO01/36722, U.S. Pat 6,291,066B1 and US6,454,982B1 has all described a kind of method for preparing polyoxyethylene glycol (PEG) modified poly ester, proposed by adopting the poly ethyldiol modified dyeing ability that improves polyester, but a large amount of ehter bonds have been introduced in the adding of PEG in macromolecular chain, cause the thermotolerance of polyester and scale resistance significantly to descend, melt-spinning is very difficult, thereby further has influence on distortion, resultant yarn, weave and following process such as fabric post-treatment.
Mention a kind of trevira that easily dyes among the Japanese Patent JP2001-192933, be for solution relate to traditional trevira with contain the problem that exists in the textile fabric of the PET of dying raw material in distress, promptly prepare a kind of have chromatophilia can modified poly ester.This polyester is the multipolymer of Poly(Trimethylene Terephthalate) (PTT) and PET, and the mole ratio range of ethylene glycol and propylene glycol was from 99: 1 to 1: 99 in its molecular structure.Though this copolyesters chromatophilia can be relatively good, is difficult for dying dark color, and for improving its chromatophilia, PTT content is higher, and production cost is higher.
Summary of the invention
The technical issues that need to address of the present invention are, provide a kind of and easily dye dark color, and even dyeing, the modified copolymer ester material that colour fastness is high.
Another technical problem that the present invention need solve is that the preparation method of the lower above-mentioned copolyesters of a kind of production cost is provided.
Patent just can effectively address the above problem by introducing the method that a kind of new dibasic alcohol component and EG, PTA and polyalkylene glycol carry out polyreaction jointly.
The present invention easily dyes dark copolyesters, it is characterized in that containing therein the following material of weight percent:
Ethylene glycol terephthalate repeating unit 35.0～90.0,
Trimethylene terephthalate repeat units 5.0～50.0,
Molecular-weight average is its surplus of polyalkylene glycol of 500～10000.
The characteristics that the Poly(Trimethylene Terephthalate) dyeing behavior is good improve the copolyesters dyeability, and the adding of polyalkylene glycol further makes the structure of copolyesters become loose, and dye uptake improves greatly.
As preferably, the limiting viscosity of copolyesters is 0.35～1.00.
As preferably, wherein also contain the following material of weight percent≤3: anti-ether agent and/or antioxidant and/or toning agent and/or thermo-stabilizer and/or promotor.
Wherein, anti-ether agent such as sodium-acetate 100PPM etc., antioxidant 1010 is 200PPM etc., and toning agent is Cobaltous diacetate 100PPM, and thermo-stabilizer is trimethyl phosphite 99 200PPM etc.
The present invention easily dyes the preparation method of dark copolyesters, it is characterized in that having titanium system and/or antimony-based catalyst to exist down, two or more dibasic alcohol monomer batch mixing and terephthalic acid (TPA) carry out direct esterification, perhaps carry out transesterify with dimethyl terephthalate (DMT) (DMT), carboxylate that obtains and polyalkylene glycol carry out polycondensation and get product; Wherein, catalyzer is Sb, Ti, Ge, the mixture of one or more of Sn compound.
The above-mentioned preparation method who easily dyes dark copolyesters has two technology circuits of direct esterification and ester-interchange method, and each processing step is:
One, direct esterification route:
1) batch mixing: in the direct esterification, the monomeric mole of terephthalic acid and dibasic alcohol proportioning is respectively: with ethylene glycol be 1: 1.05～2.0, with 1, ammediol is 1: 1.05～2.50, adds catalyzer simultaneously;
2) esterification: temperature is that 200～290 ℃, pressure are 0.0～0.5Mpa, by a kind of the carrying out in the following processing step: a) terephthalic acid and ethylene glycol, 1, ammediol monomer directly and terephthalic acid carry out esterification; B) terephthalic acid respectively with ethylene glycol, 1, the ammediol monomer carries out direct esterification reaction; C) with bishydroxyethyl terephthalate monomer and terephthalic acid and 1, the ammediol monomer carries out the direct esterification reaction; D) terephthalic acid dipropylene glycol ester monomer and terephthalic acid, ethylene glycol monomer are carried out the direct esterification reaction;
3) polycondensation: the carboxylate that obtains adds polycondensation catalyst, system 0.1～0.01Mpa, 220～270 ℃ down and polyalkylene glycol carry out precondensation; Be decompressed to gradually≤130pa, be warming up to 255～295 ℃, finish polycondensation and get product;
Wherein, catalyzer is Sb, Ti, and Ge, one or more of Sn compound, as antimony acetate, weisspiessglanz, antimony glycol, titanous oxalate, tetrabutyl titanate, germanium oxides etc. can be used as esterifying catalyst or transesterification catalyst or polycondensation catalyst.
Two, transesterify route:
1) batch mixing: in the ester-interchange method, the mole proportioning of dimethyl terephthalate (DMT) and ethylene glycol is 1: 1.10～2.0, dimethyl terephthalate (DMT) and 1, and the mole proportioning of ammediol is 1: 1.05～2.50, adds catalyzer simultaneously;
2) transesterify: under 200～240 ℃, carry out;
3) polycondensation and catalyzer are with the direct esterification route.
As preferably, in polycondensation, can use promotor, promotor is one or more the mixture in Cobaltous diacetate, manganese acetate, magnesium acetate, calcium acetate, the sodium-acetate.
Polyalkylene glycol also can add before esterification or before the transesterify, makes easy to operate.
Preparation method of the present invention is reasonable in design, realize suitability for industrialized production easily, and production cost is lower; It is relatively good that the copolyesters of preparation dyes dark performance.
Specific embodiments
Below will the invention will be further described by specific embodiment.
In an embodiment, the limiting viscosity of gained modified copolyester section adopts Ubbelohde viscometer to test, and solvent is 25 ℃ phenol and a tetrachloroethane mixture, phenol: tetrachloroethane=1: 1 (weight ratio).
Embodiment 1, and a of direct esterification route---monomer is mixed method
Batch mixing: with 2.711mol terephthalic acid (PTA), 2.928mol ethylene glycol (EG) and 0.325mol1, after ammediol (PDO) mixed together, add in the reaction system, add the antimony acetate catalyzer of aequum simultaneously; Under 220～240 ℃, pressure 0.3Mpa, carry out esterification; The tetrabutyl titanate catalyzer that adds 0.054mol polyalkylene glycol (molecular weight is 1000) and aequum after esterification finishes again, first precondensation after 1.5 hours under rough vacuum, temperature of reaction system is heated to 265 ℃ and carry out polycondensation under the 50Pa high vacuum, after finishing, polycondensation stops to stir, product through the Cast Strip, pelletizing, finally obtain limiting viscosity and be 0.55 copolyester section.
Embodiment 2, the b of direct esterification route---the BHET+BHPT method:
To add reaction system after 1.0mol terephthalic acid (PTA), 1.3mol ethylene glycol (EG) and the aequum antimonous oxide catalyzer mixed together, carry out esterification under 220～240 ℃, pressure 0.3Mpa, esterification obtains carboxylate bishydroxyethyl terephthalate (BHET) after finishing.
With 1.0mol terephthalic acid (PTA), 2.0mol 1, add reaction system after ammediol (PDO) and the aequum titanium isopropylate catalyzer mixed together, carry out esterification under 220～240 ℃, pressure 0.3Mpa, esterification obtains carboxylate terephthalic acid dipropylene glycol ester (BHPT) after finishing.
With BHET, BHPT with add in the reaction system again after 0.02mol polyalkylene glycol (molecular weight is 5000) mixes, add aequum titanium isopropylate catalyzer simultaneously, precondensation is after 1.5 hours under rough vacuum, temperature of reaction system is heated to 265 ℃ and carry out polycondensation under the 50Pa high vacuum, after finishing, polycondensation stops to stir, product through the Cast Strip, pelletizing, finally obtain limiting viscosity and be 0.62 copolyester section.
Embodiment 3, the c of direct esterification route---BHET (esterification products of PTA and EG)+PTA+PDO method:
With 2.440mol terephthalic acid (PTA), 4.145mol after ethylene glycol (EG) mixed together, add in the reaction system, the antimony acetate catalyzer that adds aequum simultaneously, at 220～240 ℃, carry out esterification under the pressure 0.3Mpa, obtain carboxylate bishydroxyethyl terephthalate (BHET), esterification adds the 0.27mol terephthalic acid after finishing again, 0.539mol 1, ammediol (PDO), 0.067mol the tetrabutyl titanate catalyzer of polyalkylene glycol (molecular weight is 1000) and aequum, precondensation is after 1.5 hours under rough vacuum, temperature of reaction system is heated to 265 ℃ and carry out polycondensation under the 50Pa high vacuum, after finishing, polycondensation stops to stir, product is through the Cast Strip, pelletizing finally obtains limiting viscosity and is 0.64 copolyester section.
Embodiment 4, the d of direct esterification route---BHPT (PTA and 1, ammediol esterification products)+PTA+EG method:
With 1.440mol terephthalic acid (PTA), 2.880mol 1, after ammediol (PDO) mixed together, add in the reaction system, the antimony acetate catalyzer that adds aequum simultaneously, at 220～240 ℃, carry out esterification under the pressure 0.3Mpa, obtain carboxylate terephthalic acid dipropylene glycol ester (BHPT), esterification adds 1.27mol terephthalic acid (PTA) after finishing again, 1.778mol ethylene glycol (EG), 0.056mol the tetrabutyl titanate catalyzer of polyalkylene glycol (molecular weight is 2500) and aequum, precondensation is after 1.5 hours under rough vacuum, temperature of reaction system is heated to 265 ℃ and carry out polycondensation under the 50Pa high vacuum, after finishing, polycondensation stops to stir, product is through the Cast Strip, pelletizing finally obtains limiting viscosity and is 0.58 copolyester section.
Embodiment 5: one of transesterify route
With the 2.711mol dimethyl terephthalate (DMT), 2.928mol ethylene glycol and 0.325mol 1, after ammediol (PDO) mixed together, add in the reaction system, the antimony acetate catalyzer that adds aequum simultaneously, at 180 ℃, carry out transesterification reaction under the normal pressure, the titanium isopropylate catalyzer that adds 0.067mol polyalkylene glycol (molecular weight is 1000) and aequum after transesterification reaction finishes again, precondensation is after 1.5 hours under rough vacuum, temperature of reaction system is heated to 265 ℃ and carry out polycondensation under the 50Pa high vacuum, after finishing, polycondensation stops to stir, product is through the Cast Strip, pelletizing finally obtains limiting viscosity and is 0.56 copolyester section.
Embodiment 6～8: two, three, four of transesterify route
Change the monomers terephthalic acid among the embodiment 2～4 (TPA) into monomers dimethyl terephthalate (DMT), the pressurization esterification changes the normal pressure transesterification reaction into, and other reaction conditions is basic identical.
Comparative Examples 1:
After 2.711mol terephthalic acid and 2.625mol ethylene glycol mixed together, add in the reaction system, the antimony acetate catalyzer that adds aequum simultaneously, at 220～240 ℃, carry out esterification under the pressure 0.3Mpa, the tetrabutyl titanate catalyzer that adds 0.054mol polyalkylene glycol (molecular weight is 1000) and aequum after esterification finishes again, precondensation is after 1.5 hours under rough vacuum, temperature of reaction system is heated to 265 ℃ and carry out polycondensation under the 50Pa high vacuum, after finishing, polycondensation stops to stir, product is through the Cast Strip, pelletizing finally obtains limiting viscosity and is 0.50 copolyester section.
Comparative Examples 2:
With the 2.711mol terephthalic acid, 2.928mol ethylene glycol and 0.325mol 1, after the ammediol mixed together, add in the reaction system, the antimony acetate catalyzer that adds aequum simultaneously, at 220～240 ℃, carry out esterification under the pressure 0.3Mpa, the tetrabutyl titanate catalyzer that adds aequum after esterification finishes again, precondensation is after 1.5 hours under rough vacuum, temperature of reaction system is heated to 265 ℃ and carry out polycondensation under the 50Pa high vacuum, after finishing, polycondensation stops to stir, product is through the Cast Strip, pelletizing finally obtains limiting viscosity and is 0.58 copolyester section.
The multipolymer section of the foregoing description and Comparative Examples preparation is tested through carry out spinning property after the thorough drying on small-sized spinning-drawing machine, verified its spinning property, test-results sees Table 1; Adopt dispersed dye, measure the Apparent Depth K/S value of fiber and fabric respectively under 120～130 ℃ of temperature, find that its K/S value improves about 30～50% than conventional polyester, concrete outcome sees Table 1.
Table 1 experimental test result
| Sample number into spectrum | Limiting viscosity [η]/dL/g | Fusing point Tm/ ℃ | Spinning property | The K/S value | The ethylene glycol terephthalate repeating unit accounts for % | Trimethylene terephthalate repeat units accounts for % | Polyalkylene glycol accounts for % |
| Embodiment 1 | 0.55 | 245～251 | Better | 25.74 | 80 | 10.7 | 9.3 |
| Embodiment 2 | 0.64 | 252～260 | Good | 30.82 | 38.5 | 41.4 | 20.1 |
| Embodiment 3 | 0.58 | 243～250 | Generally | 24.08 | 79.3 | 9.4 | 11.3 |
| Embodiment 4 | 0.62 | 255～258 | Good | 29.16 | 35.8 | 43.6 | 20.6 |
| Embodiment 5 | 0.56 | 247～254 | Better | 28.50 | 80 | 10.7 | 9.3 |
| Embodiment 6 | 0.63 | 249～253 | Good | 30.91 | 38.5 | 41.4 | 20.1 |
| Embodiment 7 | 0.45 | 238～246 | Difference | 25.87 | 79.3 | 9.4 | 11.3 |
| Embodiment 8 | 0.57 | 250～259 | Good | 32.46 | 35.8 | 43.6 | 20.6 |
| Comparative Examples 1 | 0.50 | 241～247 | Generally | 19.72 | - | - | - |
| Comparative Examples 2 | 0.58 | 253～261 | Generally | 23.54 | - | - | - |
Titanium system of the present invention and antimony-based catalyst are meant disclosed Sb before the applying date, Ti, Ge, the mixture of one or more in the Sn compound.Anti-ether agent and/or antioxidant and/or toning agent and/or thermo-stabilizer and/or promotor all are disclosed auxiliary agent before the applying date.
Claims (7)
1, a kind ofly easily dye dark copolyesters, it is characterized in that containing therein the following repeating unit of weight percent:
Ethylene glycol terephthalate repeating unit 35.0～90.0,
Trimethylene terephthalate repeat units 5.0～50.0,
Molecular-weight average is its surplus of polyalkylene glycol of 500～10000.
2, according to claim 1ly easily dye dark copolyesters, it is characterized in that its limiting viscosity is 0.35～1.00.
3, according to claim 1 and 2ly easily dye dark copolyesters, it is characterized in that also containing the following material of weight percent≤3.0: anti-ether agent and/or antioxidant and/or toning agent and/or thermo-stabilizer and/or promotor.
4, the preparation method who easily dyes dark copolyesters as claimed in claim 1 is characterized in that,
1) batch mixing: in the direct esterification, the monomeric mole of terephthalic acid and dibasic alcohol proportioning is respectively: with ethylene glycol be 1: 1.05～2.0, with 1, ammediol is 1: 1.05～2.50, adds catalyzer simultaneously;
In the ester-interchange method, the mole proportioning of dimethyl terephthalate (DMT) and ethylene glycol is 1: 1.10～2.0, dimethyl terephthalate (DMT) and 1, and the mole proportioning of ammediol is 1: 1.05～2.50, adds catalyzer simultaneously;
2) esterification: temperature is that 200～290 ℃, pressure are 0.0～0.5Mpa, and by a kind of the carrying out in the following processing step: a) terephthalic acid and ethylene glycol and 1, ammediol monomer directly carry out esterification; B) terephthalic acid respectively with ethylene glycol, 1, the ammediol monomer carries out direct esterification reaction; C) with bishydroxyethyl terephthalate monomer and terephthalic acid and 1, the ammediol monomer carries out the direct esterification reaction; D) terephthalic acid dipropylene glycol ester monomer and terephthalic acid and ethylene glycol monomer are carried out the direct esterification reaction;
Or transesterify: under 200～240 ℃, carry out;
3) polycondensation: the carboxylate that obtains adds polycondensation catalyst, system 0.1～0.01Mpa, 220～270 ℃ down and polyalkylene glycol carry out precondensation; Be decompressed to gradually≤130pa, be warming up to 255～295 ℃, finish polycondensation and get product;
Wherein, catalyzer is Sb, Ti, and Ge, the mixture of one or more of Sn compound is as esterifying catalyst or transesterification catalyst or polycondensation catalyst.
5, the preparation method who easily dyes dark copolyesters according to claim 4 is characterized in that in the polycondensation, and using promotor, promotor is one or more mixture in Cobaltous diacetate, manganese acetate, magnesium acetate, calcium acetate, the sodium-acetate.
6, the preparation method who easily dyes dark copolyesters according to claim 4 is characterized in that polyalkylene glycol adds before esterification or before the transesterify.
7, the preparation method who easily dyes dark copolyesters according to claim 5 is characterized in that polyalkylene glycol adds before esterification or before the transesterify.
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| CN108610477B (en) * | 2018-05-21 | 2020-04-17 | 东华大学 | Method for inhibiting polymerization side reaction |
| CN114591496B (en) * | 2022-01-11 | 2023-10-24 | 浙江恒逸石化研究院有限公司 | Preparation method of rigid copolyester |
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