CN102453246B - A kind of copolyesters and its production and use - Google Patents
A kind of copolyesters and its production and use Download PDFInfo
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- CN102453246B CN102453246B CN201010529354.7A CN201010529354A CN102453246B CN 102453246 B CN102453246 B CN 102453246B CN 201010529354 A CN201010529354 A CN 201010529354A CN 102453246 B CN102453246 B CN 102453246B
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000835 fiber Substances 0.000 claims abstract description 13
- 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 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 4
- 125000003827 glycol group Chemical group 0.000 claims abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 polyoxyethylene Polymers 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 125000001118 alkylidene group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 5
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 4
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000007520 diprotic acids Chemical class 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000004043 dyeing Methods 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 9
- 230000000704 physical effect Effects 0.000 abstract description 5
- 229920004935 Trevira® Polymers 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 abstract description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000000975 dye Substances 0.000 description 17
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000032050 esterification Effects 0.000 description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229960003330 pentetic acid Drugs 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004258 Ethoxyquin Substances 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940077744 antacid containing magnesium compound Drugs 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000004044 disperse dyeing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093500 ethoxyquin Drugs 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 235000019285 ethoxyquin Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- HHCCNQLNWSZWDH-UHFFFAOYSA-N n-hydroxymethanimine oxide Chemical compound O[N+]([O-])=C HHCCNQLNWSZWDH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a kind of copolyesters and its production and use, form in the dicarboxylic acid component of copolyesters, terephthalic acid structural unit content is more than 90mol%, form in the glycol component of copolyesters, the content of ethylene glycol structure unit is 70 ~ 99mol%, have the content of the aliphatic dihydroxy alcohol structural unit of structure shown in formula 1 is 1 ~ 15mol%, also containing polyethylene glycol structures unit in copolyesters.HO-(XO)
a-M-O-(YO)
b-H formula 1.Copolyesters of the present invention makes fiber by known method, and then formation fabric, obtained finished product has good dyeability and high heat resistance for dispersed dye at normal temperatures and pressures, thus has not only reduced great number facility investment and running cost that high-temperature pressure dyeing brings but also maintained the physical property of trevira excellence.
Description
Technical field
The present invention relates to a kind of copolyesters and its production and use, specifically a kind of polyester with the normal pressure disperse dye dyeable function of high heat resistance.
Background technology
Polyethylene terephthalate in polyester has outstanding performance, is widely used in the field such as fiber, film, particularly dress ornament, industry goods, materials and equipments field.
Dyeing process according to the different trevira of purposes has a lot, but it is tight that common polyester exists molecular chain, the constitutional featuress such as degree of crystallinity is high, make it and easily dye unlike natural fiber, when use disperse dyeing, need high temperature, the high pressure of 130 DEG C.Dye under the condition of high temperature and high pressure, except increasing facility investment, also can increase running cost.
The problem improving the dyeing behavior of trevira has had have studied of long time.Wherein, improving polymer property by copolymerization technology is one of main means.
Disclose in Chinese patent CN1534114A by means of only with alkoxide 2-methyl isophthalic acid, 3-third diol copolymer forms the method for polyester, although but dyeing behavior can be improved still in higher level, to obtain better dyeing behavior, the addition of copolymer composition must be increased, the fusing point which results in copolyesters declines too much, thermotolerance is deteriorated, crystal property is deteriorated simultaneously, these all cause fiber to be restricted in the course of processing, and the feel of fiber can be caused to become, and hardening, greatly limit the application of fibre product.Disclose a kind of modified polyester fiber in patent JK56-26006 and improve dyeability by the method for adding sulfonic acid group and polyalkylene glycol monomer in the polyester, but the dyestuff that the fiber that this kind of polyester is made uses then need be promoted to cationoid reaction dyestuff by general dispersed dye, cause production cost to increase.
Summary of the invention
The object of the present invention is to provide a kind of good heat resistance, copolyesters that under normal temperature and pressure, dyeing behavior is good, cost is low and its production and use.
Copolyesters in the present invention, form in the dicarboxylic acid component of copolyesters, terephthalic acid structural unit content is more than 90mol%; Form in the glycol component of copolyesters, the content of ethylene glycol structure unit is 70 ~ 99mol%, the content of the aliphatic dihydroxy alcohol structural unit of structure shown in formula 1 is 1 ~ 15mol%; Also containing polyethylene glycol structures unit in copolyesters;
HO-(XO)
a-M-O-(YO)
b-H formula 1
Wherein, X and Y is separately selected from the straight-chain alkyl-sub-or branched alkylidene with 2 ~ 4 carbon atoms; A and b is separately the integer of 0 ~ 6, and at least one not to be 0, M be band side chain of a and b and carbonatoms is the alkylidene group of less than 6.
Said band side chain and the alkylidene group that carbonatoms is less than 6 is 2-methyl trimethylene, 2,2-dimethyl-trimethylene, 2-methyl isophthalic acid, 4-butylidene, 2,3-dimethyl-tetramethylene, 2-methyl isophthalic acid, 5-pentylidene.Preferred 2-methyl isophthalic acid, 3 propylidene.Select 2-methyl isophthalic acid, during 3 propylidene, its dyeability and thermotolerance are all fine.
The aliphatic dihydroxy alcohol of structure shown in formula 1 be preferably diethyl oxidation 2-methyl isophthalic acid, ammediol, its structure as shown in Equation 2:
formula 2
Form in the glycol component of copolyesters, the content of the aliphatic dihydroxy alcohol structural unit of structure shown in formula 1 is preferably 1 ~ 10mol%.Be difficult to the dyeing behavior obtaining expecting when content is below 1%, then there will be polymer performance when content is more than 10% and decline, poor processability, the situation of restriction fiber applications.
In order to improve the physical property of dyeing behavior and raising fiber, the present invention also with the addition of polyalkylene glycol monomer in copolymerization process, because the submissive chain structure of polyoxyethylene glycol makes dyestuff more easily disperse, the 2-methyl isophthalic acid of diethyl oxidation is reduced while improving fiber dyeing performance, ammediol usage quantity, thus decrease the fusing point caused due to copolymer composition and decline too much, crystallinity deterioration, the situation that fibrous physical property is deteriorated.
The molecular weight of polyalkylene glycol monomer is 1000 ~ 10000g/mol.The addition of polyoxyethylene glycol is 1 ~ 10wt% of copolyesters total amount, if not within the scope of this, then the thermotolerance of multipolymer can decline, and spinning property is deteriorated, and easily occurs a phenomenon of wafing.
The production method of copolyesters of the present invention in the scope of mol ratio 1/1.12 ~ 1/1.9, first prepares low-molecular weight polymer by diprotic acid and ethylene glycol, carry out high temperature 250 ~ 290 degree of high vacuum polycondensations afterwards and obtain polymkeric substance, the aliphatic dihydroxy alcohol of structure shown in formula 1 and polyoxyethylene glycol can add in any stage before polymkeric substance spues.
Copolyesters of the present invention can be prepare low-molecular weight polymer by terephthalic acid and ethylene glycol through esterification, also can prepare low-molecular weight polymer with dimethyl terephthalate (DMT) and ethylene glycol through transesterification reaction, then low-molecular weight polymer carries out the polycondensation of high temperature high vacuum.Various catalyzer can be used in esterification, transesterify and esterification.
The catalyzer of the catalyzer of the transesterification reaction that the present invention uses in esterification reaction process or bunching reaction, specifically refer to calcium acetate, the calcium cpds such as calcium chloride, magnesium acetate, magnesium chloride, the magnesium compounds such as magnesiumcarbonate, ANTIMONY TRIOXIDE SB 203 99.8 PCT, the antimony compoundss such as antimony acetate, germanium oxide, the germanium compounds such as germanium chloride, tetrabutyl titanate, the titanium metal alkoxide of titanium isopropylate etc., ethylenediamine tetraacetic acid (EDTA), hydroxyethyliminodiacetic acid, diethylene-triamine pentaacetic acid, triethylenetetramine six acetic acid, or as the polyvalent carboxylic acid of sequestrant and/or the titanium complex body of hydroxycarboxylic acid and/or nitrogenous carboxyl.Sequestrant refers to the hydroxy carboxylic acids of phthalic acid, three sour three monooctyl esters, trimesic acid, hemimellitic acid, pyromellitic acid anhydride etc.; Or contain ethylenediamine tetraacetic acid (EDTA), NTP, carboxyl imido oxalic acid, carboxymethyl imido grpup dipropionic acid, diethylene-triamine pentaacetic acid, triethylenetetramine six acetic acid, imines two acetic acid, imido grpup dipropionic acid, 2-hydroxyethyl-imido grpup acetic acid, 2-hydroxyethyl-imido grpup dipropionic acid, the 2-methoxy ethyl-imido grpup acetic acid of nitronic acid.
Copolyesters of the present invention manufactures by batchwise polymerization method or continuous polymerization.
Copolyesters of the present invention can also add known matting agent, anti ultraviolet agent, thermo-stabilizer etc. does not affect invention effect of the present invention.
In addition, copolyesters of the present invention makes fiber by known method, and then formation fabric, obtained finished product has good dyeability for dispersed dye at normal temperatures and pressures, thus reduces great number facility investment and running cost that high-temperature pressure dyeing brings, trevira of the present invention simultaneously, while same excellent dyeability energy, physical property is high, reduces the poor heat resistance because copolymerization units causes, fusing point is low, the problem that crystallinity is low.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.These embodiments are only not used in for illustration of the present invention and limit the scope of the invention.
The present invention writes a Chinese character in simplified form TPA containing the diprotic acid of more than terephthalic acid 90mol%; Ethylene glycol is abbreviated as EG; The 2-methyl isophthalic acid of ethoxyquin, ammediol is abbreviated as EOMPO; Polyoxyethylene glycol is abbreviated as PEG.
Embodiment 1
Bishydroxyethyl terephthalate is added esterification groove, keep temperature 250 DEG C, pressure 1.2 × 10
5pa, joined esterification layer by the EG slurry of TPA and 3.54kg of 8.25kg gradually, then carries out the esterification of 1 hour in 4 hours.Finally from the reactant of esterification obtained, get 10.2kg joins polycondensation layer.
Esterification reaction product is remained on 250 DEG C, under normal pressure, add the stirring being equivalent to add after polyester 2wt%PEG1000 stirs five minutes the EOMPO being equivalent to whole glycol component 5mol% amount in gained polyester and carrying out 30 minutes.Then add the phosphoric acid that phosphorus atom amount is equivalent to polymkeric substance 18ppm, after 5 minutes, add the antimonous oxide that antimony atoms amount is equivalent to polymkeric substance 230ppm, and cobalt atom amount is equivalent to the Cobaltous diacetate of polymkeric substance 15ppm.The ethylene glycol slurry containing Titanium particles that Titanium particles amount is equivalent to polymkeric substance 0.3wt% is added after 5 minutes.Start decompression after 5 minutes, heat up.Temperature by 250 DEG C rise to 290 DEG C, Pressure Drop is to 40Pa.Outlet temperature, resulting pressure is reached after 90 minutes.After arriving certain stirring extent, in reaction system, import nitrogen be back to normal pressure, stop polycondensation.Polymkeric substance is that strip spues, section after cooling in the sink.The intrinsic viscosity of resulting polymers is 0.67.
Make its moisture rate remain on 50ppm the chip drying obtained, then melt-spinning under the spinning temperature of 290 DEG C, batches under the pulling speed of 3000m.The undrawn yarn obtained stretches under the condition of draft temperature 90 DEG C, stretching ratio 1.65 times, then batches after heat setting type at 130 DEG C, obtains the drawn yarn of 56dtex/24f.
The silk obtained is carried out cylinder volume, carries out staining evaluation by following condition.With high temperature dyeing trier URMINI-COLOR (the small-sized staining agent of infrared rays (TEXAM technical study manufacture) mixing treating liquid, dyeing under the condition of 95 DEG C × 30min.Now the medicament for the treatment of solution used is as follows.
Dianix Blue E-Plus (manufacture of De Sida company, dispersed dye) 5owf%
NIKKA SUNSALT (manufacture of solar corona chemical company, levelling agent) 1g/l
Acetic acid (pH adjusting agent) 0.5g/l
After dyeing, the medicament preparation treatment solution below using under the condition of 80 DEG C × 20min, carries out reduction clearing.
Sodium hydroxide 0.6g/l
Sodium bisulfite 2g/l
Then, cylinder is compiled thing washing, air-dry after be used as assess sample.Sample is overlapped into spectral photometric colour measuring meter (Datacolor 650 that Datacolor Asia Pacific (H.K.) Ltd. manufactures) colour examining after 8 layers, L*=26.1.L* refers to the lightness in L*, a* and b* color specification system, and the less dyeability of numerical value is better.
In addition, after carrying out 180 degree of heat setting type process of 2 minutes to assess sample, touch the soft degree of assess sample by hand, feel is hardening, is evaluated as difference, soft not hardening, is evaluated as good, falls between, and is evaluated as general.
Also can clearly be seen that from comparative example below, with do not compare with the polyethylene terephthalate of EOMPO with PEG copolymerization, while copolyesters of the present invention dyeability excellence at ambient pressure, fibrous physical property is excellent equally, there is not the situation that feel is deteriorated.Each embodiment and comparative example result are summed up as shown in table 1.
Comparative example 1
Do not add PEG1000, other are with embodiment 1.Being compiled by obtained cylinder and recording L* value after thing dyes under 95 DEG C of dyeing temperatures is 30.0.
Comparative example 2
Do not add EOMPO and PEG1000, all the other conditions are with embodiment 1.Being compiled by obtained cylinder and recording L* value after thing dyes under 95 DEG C of dyeing temperatures is 37.5.
Comparative example 3
EOMPO addition is 15mol%, does not add PEG, and all the other conditions are with embodiment 1.Being compiled by obtained cylinder and recording L* value after thing dyes under 95 degree of dyeing temperatures is 25.
Embodiment 2
Make PEG1000 into PEG4000, all the other conditions are with embodiment 1.Being compiled by obtained cylinder and recording L* value after thing dyes under 95 DEG C of dyeing temperatures is 25.7.
Embodiment 3
Make PEG1000 into PEG10000, all the other conditions are with embodiment 1.Being compiled by obtained cylinder and recording L* value after thing dyes under 95 DEG C of dyeing temperatures is 27.
Embodiment 4
Change EOMPO addition into 6.5mol%, PEG4000 addition changes 1wt% into, and all the other conditions are with embodiment 1.Being compiled by obtained cylinder and recording L* value after thing dyes under 95 DEG C of dyeing temperatures is 26.4.
Embodiment 5
Change EOMPO addition into 2mol%, PEG1000 addition is 5wt%, and all the other conditions are with embodiment 1.Being compiled by obtained cylinder and recording L* value after thing dyes under 95 DEG C of dyeing temperatures is 25.8.
Embodiment 6
Change the addition of EOMPO into 3mol%, all the other conditions are with embodiment 1.Being compiled by obtained cylinder and recording L* value after thing dyes under 95 DEG C of dyeing temperatures is 29.
Embodiment 7
Change the addition of EOMPO into 8mol%, all the other conditions are with embodiment 1.Being compiled by obtained cylinder and recording L* value after thing dyes under 95 DEG C of dyeing temperatures is 25.3.
Embodiment 8
Change the addition of PEG1000 into 10wt%, all the other conditions are with embodiment 1.Being compiled by obtained cylinder and recording L* value after thing dyes under 95 DEG C of dyeing temperatures is 25.0.
Table 1:
| EOMPO(mol％) | PEG(wt％) | L* value | Feel | |
| Comparative example 1 | 5 | 0 | 30 | Good |
| Comparative example 2 | 0 | 0 | 37.5 | Good |
| Comparative example 3 | 15 | 0 | 25 | Difference |
| Embodiment 1 | 5 | 2(PEG1000) | 26.1 | Good |
| Embodiment 2 | 5 | 2(PEG4000) | 25.7 | Good |
| Embodiment 3 | 5 | 2(PEG10000) | 27 | Good |
| Embodiment 4 | 6.5 | 1(PEG4000) | 26.4 | Generally |
| Embodiment 5 | 2 | 5(PEG1000) | 25.8 | Good |
| Embodiment 6 | 3 | 2(PEG1000) | 29 | Good |
| Embodiment 7 | 8 | 2(PEG1000) | 25.3 | Generally |
| Embodiment 8 | 2 | 10(PEG1000) | 25 | Good |
Claims (5)
1. a copolyesters, is characterized in that: form in the dicarboxylic acid component of copolyesters, terephthalic acid structural unit content is more than 90mol%; Form in the glycol component of copolyesters, the content of ethylene glycol structure unit is 70 ~ 99mol%, the content of the aliphatic dihydroxy alcohol structural unit of structure shown in formula 1 is 1 ~ 15mol%; Also containing polyethylene glycol structures unit in copolyesters;
formula 1
Wherein, X and Y is separately selected from the straight-chain alkyl-sub-or branched alkylidene with 2 ~ 4 carbon atoms; A and b is separately the integer of 0 ~ 6, and at least one not to be 0, M be band side chain of a and b and carbonatoms is the alkylidene group of less than 6;
The molecular weight of described polyethylene glycol structures unit is 1000 ~ 10000g/mol, and it accounts for 1 ~ 10wt% of copolyesters total amount.
2. copolyesters according to claim 1, is characterized in that: form in the glycol component of copolyesters, the content of the aliphatic dihydroxy alcohol structural unit of structure shown in formula 1 is 1 ~ 10mol%.
3. copolyesters according to claim 1 and 2, is characterized in that: the aliphatic dihydroxy alcohol of structure shown in formula 1 is the 2-methyl isophthalic acid of diethyl oxidation, ammediol, its structure as shown in Equation 2:
Formula 2.
4. the preparation method of a copolyesters according to claim 1, it is characterized in that in the scope of mol ratio 1/1.12 ~ 1/1.9, first preparing low-molecular weight polymer by diprotic acid and ethylene glycol, carry out high temperature 250 ~ 290 degree of high vacuum polycondensations afterwards and obtain polymkeric substance, the aliphatic dihydroxy alcohol of structure shown in formula 1 and the polyoxyethylene glycol any stage before polymkeric substance spues adds.
5. a copolyesters according to claim 1 is preparing the application in fiber.
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