CN102276806A - Preparation method of polyterephthalic acid ethane diacid butanediol copolyester - Google Patents
Preparation method of polyterephthalic acid ethane diacid butanediol copolyester Download PDFInfo
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Abstract
The invention discloses a preparation method of polyterephthalic acid ethane diacid butanediol copolyester. The polyterephthalic acid ethane diacid butanediol copolyester is prepared from oxalate serving as a comonomer, terephthalic acid and ester thereof, and 1,4-butanediol. In the polyterephthalic acid ethane diacid butanediol copolyester, the melting point is 180 to 220 DEG C and the intrinsic viscosity is 0.7 to 1.5 dL/g. The polyterephthalic acid ethane diacid butanediol copolyester has biodegradability. The preparation method is simple. Costs of raw materials are low. The performance of the polyterephthalic acid ethane diacid butanediol copolyester is similar to the performance of polybutylece terephthalate (PBT). The polyterephthalic acid ethane diacid butanediol copolyester can be applied to manufacturing fiber, films and other plastic products.
Description
Technical field
The invention belongs to polyester art, be specifically related to a kind of preparation method of poly terephthalic acid oxalic acid butyleneglycol copolyesters.
Background technology
Polybutylene terephthalate (PBT) engineering plastics are with good comprehensive performances such as its excellent mechanical property, electrical property, resistance toheat, processing characteristicies and be celebrated, along with industrial expansions such as automotive industry, electronic apparatus industry, optical fiber cables, driven the development of PBT engineering plastics, its demand is enlarged rapidly.In addition, the application in fiber, film field also constantly enlarges.But polybutylene terephthalate does not possess the natural degradation performance, is difficult for the application scenario of recovery at some, just because of the above-mentioned excellent properties of polybutylene terephthalate, causes some white pollutions to exist.
In order to improve the biodegradability of PBT, usually with aliphatic polyester or aliphatic diacid and alcohol acid etc. and PBT copolymerization.Openly report PBT/PBS/PEG ternary block copolymerization (2002 as Zhang Yong, Liu Fengxiang etc.; the chemistry journal; 60 12 phases of volume; 2225-2231); Guo Baohua, Ding Huige etc. openly report the PBST atactic polyester (2003, SCI, 24 the volume 12 phases; 2312-2316), its multipolymer all has the biodegradable performance.CN200610116114 and CN200610118400 also disclose the method that the PBST random copolymers prepares fiber.But in the copolyesters building-up process, butyleneglycol easily forms tetrahydrofuran (THF), Succinic Acid and easily forms Succinic anhydried, causes vacuum system easily to be stopped up, and makes that the copolyesters preparation is difficult.
Oxalic acid is the simplest aliphatic diacid, and with terephthalic acid, 1, the copolyesters that the copolymerization of 4-butyleneglycol forms will produce certain biodegradability, and other performance is suitable with polybutylene terephthalate.But directly use oxalic acid as comonomer,, be difficult to direct copolymerization because the acidity of oxalic acid is stronger.
Now, the coal-ethylene glycol technology has obtained to break through also industrial applications, and as described in CN90101447, CN95116136, CN02111624 and CN03114989, the core of this technology is the CO synthesis of oxalic ester by gaseous catalysis.Therefore, a large amount of suitability for industrialized production cheapnesss and the high barkite of purity become possibility.The present invention be exactly with a kind of cheap, barkite that can a large amount of suitability for industrialized production as comonomer and terephthalic acid and ester, 1 thereof, the 4-butyleneglycol prepares poly terephthalic acid oxalic acid butyleneglycol copolyesters.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, purpose of the present invention is exactly as comonomer and terephthalic acid and ester, 1 thereof with a kind of barkite cheap, suitability for industrialized production in a large number, the 4-butyleneglycol prepares copolyesters, and the preparation method of poly terephthalic acid oxalic acid butyleneglycol copolyesters is provided.The present invention adopts known melt-polycondensation to prepare copolyesters, promptly both can be interrupter method, also can be continuous processing.Aspect raw material, both can be the transesterify route, also can be the direct esterification route.Further improve the molecular weight of copolyesters if desired, can reach by methods such as solid-phase tack producing, chain extension tackifies.
Purpose of the present invention can reach by following measure:
A kind of preparation method of poly terephthalic acid oxalic acid butyleneglycol copolyesters comprises the steps:
A, the two hydroxy butyl esters of preparation terephthalic acid and two hydroxy butyl esters of oxalic acid and oligopolymer:
With terephthalic acid, 1,4-butyleneglycol and barkite directly carry out transesterify and esterification; Perhaps
With barkite and 1, the 4-butyleneglycol carries out earlier transesterification reaction separately, ester exchange offspring again with terephthalic acid and 1, the 4-butyleneglycol carries out esterification; Perhaps
With barkite and 1, the ester exchange offspring of 4-butyleneglycol and terephthalic acid and 1, the esterification products of 4-butyleneglycol mixes; Perhaps
With terephthalate, 1,4-butyleneglycol and barkite directly carry out transesterification reaction;
B, the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of oxalic acid and oligopolymer are carried out polyreaction, preparation poly terephthalic acid oxalic acid butyleneglycol copolyesters.
Terephthalate among the present invention is preferably dimethyl terephthalate (DMT).As the comonomer---barkite that improves biodegradable performance, can be dimethyl oxalate, oxalic acid diethyl ester, dipropyl oxalate etc., be preferably dimethyl oxalate and oxalic acid diethyl ester.Barkite can add in any stage of pulling an oar to prepolymerization.The barkite that adds both can directly add with the form of barkite, also can be earlier with 1, and the form that the 4-butanediol ester is exchanged into the two hydroxy butyl esters of oxalic acid adds.
In the steps A, the integral molar quantity of acid and ester, it is the integral molar quantity of terephthalic acid, terephthalate and barkite, with 1, the ratio of the integral molar quantity of 4-butyleneglycol is 1: 1.0～2.5, wherein the molar weight of barkite account for terephthalic acid, terephthalate and barkite integral molar quantity (i.e. the acid and the integral molar quantity of ester) 2～80%.
In the steps A, when barkite and 1,4-butyleneglycol carry out transesterification reaction separately, barkite and 1, the mol ratio of 4-butyleneglycol is 1: 1.8～3.0.Terephthalic acid and 1, the esterification products of 4-butyleneglycol are with barkite and 1, and the mol ratio of the ester exchange offspring of 4-butyleneglycol is 0.25～49: 1.
The method for preparing two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of oxalic acid and oligopolymer (perhaps preparing two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of oxalic acid) in the steps A has four kinds of selections, and wherein oligopolymer comprises the oligopolymer of the two hydroxy butyl ester oligopolymer of terephthalic acid, the two hydroxy butyl ester oligopolymer of oxalic acid or two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of oxalic acid.
First method is a terephthalic acid, 1,4-butyleneglycol and barkite directly carry out the preparation of transesterify and esterification, and its reaction conditions is: temperature is 140～280 ℃, preferred 150～260 ℃, more preferably 160～240 ℃, pressure is-0.088～0.3MPa (gauge pressure).
Second method is earlier with barkite and 1, after the 4-butyleneglycol carries out transesterification reaction separately earlier, ester exchange offspring again with terephthalic acid and 1, the 4-butyleneglycol carries out esterification and prepares.Wherein the transesterification reaction condition is: 140～250 ℃ of temperature, be preferably 150～230 ℃, and more preferably 160～220 ℃, normal pressure, catalyzer are selected metal acetate salt for use, as manganese acetate, magnesium acetate etc.; Ester exchange offspring and terephthalic acid and 1,4-butyleneglycol carry out the esterification condition and are: 150～280 ℃ of temperature, preferred 160～240 ℃, pressure-0.088～0.3MPa (gauge pressure).
The third method for directly with barkite and 1, the ester exchange offspring of 4-butyleneglycol (oxalic acid two hydroxy butyl esters) and terephthalic acid and 1, the esterification products of 4-butyleneglycol (terephthalic acid pair hydroxy butyl esters) mixing.
The 4th kind of method is: terephthalate, 1,4-butyleneglycol and barkite are directly carried out the transesterification reaction preparation, and temperature of reaction is 160～240 ℃, and normal pressure, catalyzer are metal acetate salt, as manganese acetate, magnesium acetate etc.
When polyreaction (step B), temperature of reaction is 220 ℃～300 ℃, is preferably 220 ℃～270 ℃, most preferably is 240 ℃～265 ℃, and vacuum tightness is＜150Pa (absolute pressure).In the melt phase polycondensation process, need to use polycondensation catalyst (also being polymerizing catalyst), described polycondensation catalyst preferably contains one or more in the compound of Sb, Ti, Ge, Sn or Al, as antimony glycol, tetrabutyl titanate etc., it adds total amount is 5～700ppm of final resulting copolyesters amount, and polymerizing catalyst can add in raw material pulping to any stage before the prepolymerization.Esterification generally need not catalyzer, needs acetate catalyst when carrying out transesterify separately, as manganese acetate, magnesium acetate etc.
In order to improve the use properties of copolyesters, available other a small amount of dicarboxylic acid substitutes the part terephthalic acid, as in terephthalic acid or terephthalate, can there be 0.1～10% terephthalic acid or terephthalate to adopt other dicarboxylic acid or dicarboxylic ester to replace, described other dicarboxylic acid or dicarboxylic ester are selected from m-phthalic acid, isophthalic acid ester, phthalic acid, phthalic ester, 2, the 6-naphthalic acid, 4,4 '-the phenylbenzene dioctyl phthalate, 4,4 '-the phenylbenzene dicarboxylic acid esters, 4,4 '-the diphenyl ether dioctyl phthalate, 4,4 '-the diphenyl ether dicarboxylic acid esters, 5-sodium sulfo isophthalate, 5-sodium sulfonate-isophthalic acid ester, 1, the 4-Succinic Acid, 1, the 4-succinate, 1, the 6-hexanodioic acid, 1, the 6-adipic acid ester, sebacic acid, sebate, in 1,4 cyclohexanedicarboxylic acid or the 1,4 cyclohexanedicarboxylic acid ester one or more.
In order to improve the use properties of copolyesters, also available other small amounts of diol substitutes part 1, the 4-butyleneglycol, as 1, in the 4-butyleneglycol, can have 0.1～10% 1, the 4-butyleneglycol adopts other glycol to replace, described other glycol are selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, in ammediol, 1,3 butylene glycol, 1,4 cyclohexane dimethanol, glycol ether, triglycol, polyoxyethylene glycol, polypropylene glycol or the polyoxy tetramethylene glycol one or more.
Also can add other auxiliary agents among the preparation method of the present invention.During as polyreaction in order to improve the thermostability of copolyesters, can use phosphonium stabilizer and oxidation inhibitor, phosphonium stabilizer can be one or more of phosphoric acid, phosphorous acid, Hypophosporous Acid, 50, polyphosphoric acid, phosphate n-butyl, p isopropylbenzoic acid ester, triethyl phosphate, trimethyl phosphite 99, triphenylphosphate etc., oxidation inhibitor can be one or more in oxidation inhibitor 1222, the antioxidant 1010 etc., and phosphorus content is about 5～50ppm in the copolyesters.And, can also use 1,3, polyfunctional compounds such as 5-benzenetricarboxylic acid, trimellitic acid, trimellitic acid 1,2-anhydride, pyromellitic acid, pyromellitic acid acid anhydride, trimethylolethane, TriMethylolPropane(TMP), Pehanorm, glycerine, tetramethylolmethane improve the melt strength of copolyesters of the present invention as copolymer composition, these polyfunctional compounds can use a kind separately, also can more than 2 kinds and use.
The poly terephthalic acid oxalic acid butyleneglycol copolyesters of the present invention preparation, the fusing point of this copolyesters are that 180～220 ℃, intrinsic viscosity are 0.7～1.5dL/g, are atactic polyester, have biodegradability, and its repeated structural unit is as follows:
In the said structure formula, m+n=1, n=0.02～0.80.When n＜0.02, the copolyesters biodegradability is not obvious; When n＞0.80, can make high-molecular weight poly terephthalic acid oxalic acid butyleneglycol copolyesters, but this moment, the copolyesters weathering resistance was relatively poor, very easily decomposed under field conditions (factors), made copolyesters lose use value.
Adopt the situation of other dicarboxylic acid among the corresponding preparation method, in the said structure formula, keeping under the constant situation of n value, in order to improve the use properties of copolyesters, available other a small amount of dicarboxylic acid substitutes the part terephthalic acid.These dicarboxylic acid comprise: m-phthalic acid, phthalic acid, 2,6-naphthalic acid, 4,4 '-phenylbenzene dioctyl phthalate, 4,4 '-diphenyl ether dioctyl phthalate, 5-sodium sulfo isophthalate, 1,4-Succinic Acid, 1, dicarboxylic acid such as 6-hexanodioic acid, sebacic acid, 1,4 cyclohexanedicarboxylic acid can also be the derivatives of the ester of these dicarboxylic acid formation.These dicarboxylic acid can use a kind separately, also can more than 2 kinds and use.Behind these dicarboxylic acid of copolymerization, copolyesters still keeps biodegradability, but the fusing point of copolyesters will further reduce.
Adopt the situation of other glycol among the corresponding preparation method, in the said structure formula, keeping under the constant situation of n value, in order to improve the use properties of copolyesters, available other small amounts of diol substitutes part 1,4-butyleneglycol.These glycol comprise: ethylene glycol, 1,2-propylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 1, polyether glycols such as two pure and mild polyoxyethylene glycol such as 3-butyleneglycol, 1,4 cyclohexane dimethanol, glycol ether, triglycol, polypropylene glycol, polyoxy tetramethylene glycol.These glycol can use a kind separately, also can more than 2 kinds and use.Behind these glycol of copolymerization, copolyesters still keeps biodegradability, but the fusing point of copolyesters will further reduce.
In poly terephthalic acid oxalic acid butyleneglycol copolyesters structure, can also there be the structure of part polyfunctional compound, to improve the melt strength of copolyesters of the present invention, these polyfunctional compounds can use a kind separately, also can more than 2 kinds and use.Concrete polyfunctional compound is as 1,3,5-benzenetricarboxylic acid, trimellitic acid, trimellitic acid 1,2-anhydride, pyromellitic acid, pyromellitic acid acid anhydride, trimethylolethane, TriMethylolPropane(TMP), Pehanorm, glycerine, tetramethylolmethane etc.
And then, in the preparation method of copolyesters of the present invention, can add indigo plant as the tone conditioning agent and be conditioning agent and/or red be conditioning agent.The tone conditioning agent can be a dyestuff, also can be cobalt salt.According to purpose, can use a kind or multiple.
The copolyesters that uses among the present invention also can contain a spot of other functional additive, for example UV light absorber, fire retardant, white dyes, matting agent, static inhibitor, antiseptic-germicide, opening agent etc. as required.
Poly terephthalic acid oxalic acid butyleneglycol copolyesters by the present invention makes can be used as the manufacturing of fiber, film and plastic products thereof, and goods have biodegradability.
The poly terephthalic acid oxalic acid butyleneglycol copolyesters of the present invention preparation has biodegradability, and the preparation method is simple, raw materials cost is cheap, product performance and PBT difference are less.Described copolyesters is compared with polybutylene terephthalate, has fusing point (Tm) and descends, and improves biodegradability simultaneously.
Embodiment
Embodiment 1
In batch reactor, add 182 parts of terephthalic acids (mass parts), 420 part 1, the 4-butyleneglycol, 194 parts of dimethyl oxalates, 0.12 part antimonous oxide and 0.18 part of tetrabutyl titanate, at 190～240 ℃, esterification and transesterify under the normal pressure, treat to finish when aquifer yield reaches theoretical water outlet 95% esterification, after adding 0.028 part of trimethyl phosphite 99, change over to and have the biconical polymeric kettle that disk stirs, decompression heats up gradually, and post polymerization still vacuum reached 90Pa (absolute pressure) in 45 minutes, and temperature of reaction maintains 240～250 ℃, finish polyreaction again when reaching specified power of agitator after the polymerization in 180 minutes, eliminate vacuum with nitrogen, through water-cooled, pelletizing can get a kind of poly terephthalic acid oxalic acid butyleneglycol copolyesters.The intrinsic viscosity 1.255dL/g of this copolyesters, end carboxyl 20.3mol/ ton, 183 ℃ of fusing points, form and aspect L 66, a-0.6, b 4.6.The PBT that does not have modification, its Tm are 228 ℃.
Embodiment 2
In batch reactor, add 330 parts of terephthalic acids, 320 part 1, the 4-butyleneglycol, 12.5 part dimethyl oxalate, 0.12 part antimonous oxide and 0.18 part of tetrabutyl titanate, at 190～240 ℃, esterification and transesterify under the normal pressure, treat to finish when aquifer yield reaches theoretical water outlet 95% esterification, after adding 0.028 part of trimethyl phosphite 99, change over to and have the biconical polymeric kettle that disk stirs, decompression heats up gradually, and post polymerization still vacuum reached 90Pa in 45 minutes, and temperature of reaction maintains 240～250 ℃, finish polyreaction again when reaching specified power of agitator after the polymerization in 160 minutes, eliminate vacuum with nitrogen, through water-cooled, pelletizing can get a kind of poly terephthalic acid oxalic acid butyleneglycol copolyesters.The intrinsic viscosity 0.960dL/g of this copolyesters, end carboxyl 22.5mol/ ton, 221 ℃ of fusing points, form and aspect L 68.0, a-0.8, b 3.2.
Embodiment 3
83 parts of dimethyl oxalates and 130 part 1, the 4-butyleneglycol, 0.07 a part manganese acetate at first carries out transesterify under 150～220 ℃, and then with 272 parts of terephthalic acids, 255 part 1, the 4-butyleneglycol, 0.12 part antimonous oxide and 0.18 part of tetrabutyl titanate, at 190～240 ℃, esterification under the normal pressure, treat to finish when aquifer yield reaches theoretical water outlet 95% esterification, after adding 0.025 part of triethyl phosphate, change the biconical polymeric kettle that has the disk stirring over to, decompression heats up gradually, post polymerization still vacuum reached 90Pa in 45 minutes, temperature of reaction maintains 240～250 ℃, finishes polyreaction again when reaching specified power of agitator after the polymerization in 170 minutes, eliminates vacuum with nitrogen, through water-cooled, pelletizing can get a kind of poly terephthalic acid oxalic acid butyleneglycol copolyesters.The intrinsic viscosity 1.128dL/g of this copolyesters, end carboxyl 22.2mol/ ton, 205.0 ℃ of fusing points, form and aspect L 64, a 0.4, b 5.
Embodiment 4
In batch reactor, add 344 parts of dimethyl terephthalate (DMT), 410 part 1,4-butyleneglycol glycol, 53 parts of dimethyl oxalates, 0.18 part of manganese acetate is used nitrogen replacement three times, transesterification reaction under 160～240 ℃ of normal pressures treats to finish when methyl alcohol measures famous dictum stoichiometric 99% transesterification reaction.Add 0.020 part of phosphoric acid then, after 0.12 part antimony glycol and 0.18 part of tetrabutyl titanate stir, change over to and have the biconical polymeric kettle that disk stirs, decompression heats up gradually, and post polymerization still vacuum reached 90Pa in 45 minutes, 240～250 ℃ of temperature of reaction, finish polyreaction again when reaching specified power of agitator after 165 minutes, eliminate vacuum with nitrogen, through water-cooled, pelletizing can get a kind of poly terephthalic acid oxalic acid butyleneglycol copolyesters.The intrinsic viscosity 0.992dL/g of this copolyesters, end carboxyl 23.2mol/ ton, 209.8 ℃ of fusing points, form and aspect L 68.0, a 0.6, b 3.5.
Claims (10)
1. the preparation method of a poly terephthalic acid oxalic acid butyleneglycol copolyesters is characterized in that comprising the steps:
A, the two hydroxy butyl esters of preparation terephthalic acid and two hydroxy butyl esters of oxalic acid and oligopolymer:
With terephthalic acid, 1,4-butyleneglycol and barkite directly carry out transesterify and esterification; Perhaps
With barkite and 1, the 4-butyleneglycol carries out earlier transesterification reaction separately, ester exchange offspring again with terephthalic acid and 1, the 4-butyleneglycol carries out esterification; Perhaps
With barkite and 1, the ester exchange offspring of 4-butyleneglycol and terephthalic acid and 1, the esterification products of 4-butyleneglycol mixes; Perhaps
With terephthalate, 1,4-butyleneglycol and barkite directly carry out transesterification reaction;
B, the two hydroxy butyl esters of terephthalic acid and the two hydroxy butyl esters of oxalic acid and oligopolymer are carried out polyreaction, preparation poly terephthalic acid oxalic acid butyleneglycol copolyesters.
2. the preparation method of poly terephthalic acid oxalic acid butyleneglycol copolyesters according to claim 1, it is characterized in that in the steps A, the integral molar quantity and 1 of acid and ester, the ratio of the integral molar quantity of 4-butyleneglycol is 1: 1.0～2.5, the molar weight of barkite accounts for acid and 2～80% of ester integral molar quantity; Wherein said acid and ester are terephthalic acid, terephthalate and barkite.
3. the preparation method of poly terephthalic acid oxalic acid butyleneglycol copolyesters according to claim 1, it is characterized in that in the steps A that barkite and 1,4-butyleneglycol carry out in the transesterification reaction separately, barkite and 1, the mol ratio of 4-butyleneglycol are 1: 1.8～3.0; Terephthalic acid and 1, the esterification products of 4-butyleneglycol are with barkite and 1, and the mol ratio of the ester exchange offspring of 4-butyleneglycol is 0.25～49: 1.
4. the preparation method of poly terephthalic acid oxalic acid butyleneglycol copolyesters according to claim 1, it is characterized in that terephthalic acid, 1, when 4-butyleneglycol and barkite directly carried out transesterify and esterification, temperature of reaction was 160～240 ℃, and pressure is-0.088～0.3MPa (gauge pressure); When terephthalate, 1,4-butyleneglycol and barkite were directly carried out transesterification reaction, temperature of reaction was 160～240 ℃, and catalyzer is a metal acetate salt.
5. the preparation method of poly terephthalic acid oxalic acid butyleneglycol copolyesters according to claim 1 is characterized in that barkite and 1, and when the 4-butyleneglycol carried out transesterification reaction separately, temperature of reaction was 140～250 ℃, and catalyzer is a metal acetate salt; Barkite and 1, the ester exchange offspring of 4-butyleneglycol and terephthalic acid and 1, when the 4-butyleneglycol carried out esterification, temperature of reaction was 160～240 ℃, pressure is-0.088～0.3MPa (gauge pressure) MPa.
6. the preparation method of poly terephthalic acid oxalic acid butyleneglycol copolyesters according to claim 1, the temperature of reaction that it is characterized in that polyreaction are 220 ℃～270 ℃, vacuum tightness＜150Pa (absolute pressure); Polymerizing catalyst is selected from one or more in the compound that contains Sb, Ti, Ge, Sn or Al.
7. according to the preparation method of arbitrary described poly terephthalic acid oxalic acid butyleneglycol copolyesters in the claim 1～6, it is characterized in that terephthalate is a dimethyl terephthalate (DMT), described barkite is dimethyl oxalate or oxalic acid diethyl ester.
8. the preparation method of poly terephthalic acid oxalic acid butyleneglycol copolyesters according to claim 7, the fusing point that it is characterized in that the poly terephthalic acid oxalic acid butyleneglycol copolyesters that makes is 180～220 ℃, intrinsic viscosity is 0.7～1.5dL/g, and its main repeating structure is as follows:
Wherein, m+n=1, n=0.02～0.80.
9. the preparation method of poly terephthalic acid oxalic acid butyleneglycol copolyesters according to claim 1, it is characterized in that in described terephthalic acid or the terephthalate, there are 0.1～10% terephthalic acid or terephthalate to adopt other dicarboxylic acid or dicarboxylic ester to replace, described other dicarboxylic acid or dicarboxylic ester are selected from m-phthalic acid, isophthalic acid ester, phthalic acid, phthalic ester, 2, the 6-naphthalic acid, 4,4 '-the phenylbenzene dioctyl phthalate, 4,4 '-the phenylbenzene dicarboxylic acid esters, 4,4 '-the diphenyl ether dioctyl phthalate, 4,4 '-the diphenyl ether dicarboxylic acid esters, 5-sodium sulfo isophthalate, 5-sodium sulfonate-isophthalic acid ester, 1, the 4-Succinic Acid, 1, the 4-succinate, 1, the 6-hexanodioic acid, 1, the 6-adipic acid ester, sebacic acid, sebate, 1, in 4-cyclohexane cyclohexanedimethanodibasic or the 1,4 cyclohexanedicarboxylic acid ester one or more; Described 1, in the 4-butyleneglycol, have 0.1～10% 1, the 4-butyleneglycol adopts other glycol to replace, described other glycol are selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, 2-methyl isophthalic acid, ammediol, 2,2-dimethyl-1, ammediol, 2-ethyl-2-butyl-1, ammediol, 1, in 3-butyleneglycol, 1,4 cyclohexane dimethanol, glycol ether, triglycol, polyoxyethylene glycol, polypropylene glycol or the polyoxy tetramethylene glycol one or more.
10. the preparation method of poly terephthalic acid oxalic acid butyleneglycol copolyesters according to claim 1, also add stablizer when it is characterized in that polyreaction, oxidation inhibitor or polyfunctional compound, described stablizer is selected from phosphoric acid, phosphorous acid, Tripyrophosphoric acid, trimethyl phosphite 99, in triphenylphosphate or the triethyl phosphate one or more, described oxidation inhibitor is oxidation inhibitor 1222 or antioxidant 1010, described polyfunctional compound is selected from 1,3, the 5-benzenetricarboxylic acid, trimellitic acid, trimellitic acid 1,2-anhydride, pyromellitic acid, the pyromellitic acid acid anhydride, trimethylolethane, TriMethylolPropane(TMP), Pehanorm, in glycerine or the tetramethylolmethane one or more.
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| WO2021129393A1 (en) * | 2019-12-26 | 2021-07-01 | 东丽先端材料研究开发（中国）有限公司 | Polyester resin, polyester resin composition, and molded product thereof |
| CN114262503A (en) * | 2021-12-20 | 2022-04-01 | 山东哈工生物科技有限公司 | Completely biodegradable heat shrinkable film material, completely biodegradable heat shrinkable film and preparation method |
| CN115058235A (en) * | 2022-06-17 | 2022-09-16 | 东方宝麟科技发展(北京)有限公司 | Degradable knot temporary plugging fiber material for oil and gas fields and preparation method thereof |
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| CN103225176A (en) * | 2013-04-24 | 2013-07-31 | 徐双喜 | Preparation method for completely biodegradable aliphatic polyester spunbond non-woven fabric |
| CN107881581A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of direct electrospinning method for preparing for thering is light superelevation to wash high tenacity polyester staple fiber by force |
| CN107881581B (en) * | 2016-09-29 | 2021-12-07 | 中国石油化工股份有限公司 | Direct spinning preparation method of bright ultrahigh-strength polyester high-tenacity polyester staple fiber |
| CN109576813A (en) * | 2017-09-28 | 2019-04-05 | 中国石化仪征化纤有限责任公司 | A kind of preparation method of low melting point PBT copolyester fiber |
| WO2021129393A1 (en) * | 2019-12-26 | 2021-07-01 | 东丽先端材料研究开发（中国）有限公司 | Polyester resin, polyester resin composition, and molded product thereof |
| CN111155198A (en) * | 2020-01-17 | 2020-05-15 | 西安工程大学 | Preparation method of antibacterial polyester fiber |
| CN111155198B (en) * | 2020-01-17 | 2022-09-30 | 西安工程大学 | Preparation method of antibacterial polyester fiber |
| CN115477742A (en) * | 2021-10-19 | 2022-12-16 | 源创核新(北京)新材料科技有限公司 | Preparation method of end group modified polyoxalate |
| CN115477742B (en) * | 2021-10-19 | 2023-12-15 | 源创核新(北京)新材料科技有限公司 | Preparation method of terminal group modified polyoxalate |
| CN114262503A (en) * | 2021-12-20 | 2022-04-01 | 山东哈工生物科技有限公司 | Completely biodegradable heat shrinkable film material, completely biodegradable heat shrinkable film and preparation method |
| CN115058235A (en) * | 2022-06-17 | 2022-09-16 | 东方宝麟科技发展(北京)有限公司 | Degradable knot temporary plugging fiber material for oil and gas fields and preparation method thereof |
| CN115058235B (en) * | 2022-06-17 | 2023-09-29 | 东方宝麟科技发展(北京)有限公司 | Degradable rope knot temporary plugging fiber material for oil and gas field and preparation method thereof |
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