CN102585187B - Modified copolyester and preparation method as well as application thereof - Google Patents

Modified copolyester and preparation method as well as application thereof Download PDF

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CN102585187B
CN102585187B CN 201110458505 CN201110458505A CN102585187B CN 102585187 B CN102585187 B CN 102585187B CN 201110458505 CN201110458505 CN 201110458505 CN 201110458505 A CN201110458505 A CN 201110458505A CN 102585187 B CN102585187 B CN 102585187B
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modified copolyester
acid
sodium sulfonate
ammediol
potassium
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CN102585187A (en
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顾利霞
付昌飞
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Donghua University
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Abstract

The invention relates to modified copolyester and a preparation method as well as application thereof. The modified copolyester comprises the following monomers: terephthalic acid, ethylene glycol, benzene-m binary acid binary ester-5-sodium sulfonate or potassium, 2-methyl-1, 3-propylene glycol and 1, 3-propylene glycol, molar ratios of which are 1:1.1-2.4: 0.015-0.07:0.04-0.20:0.02-0.10. The preparation method comprises the following steps of: polymerizing the five monomers, after the reaction is ended, discharging, pelletizing and drying to obtain the modified copolyester. The modified copolyester is used for chip spinning or directly spinning to prepare short fibers or filaments. The fibers of the copolyester prepared by the invention have very good dyeability of cationic dyes; the dye-uptake of the fibers is more than 95%; and the fibers of the copolyester are spirally curly after being subjected to ordinary pressure boiling dyeing or boiling water treatment or dry heat treatmentand have the unique styles of soft touch feeling, good rebound resilience, super bulkiness and the like.

Description

A kind of modified copolyester and its preparation method and application
Technical field
The invention belongs to copolyesters and its preparation method and application field, particularly a kind of modified copolyester and its preparation method and application.
Background technology
Textile industry is one of mainstay industry of Chinese national economy, trevira is most widely used in the textile industry, the textile fibres of output maximum, China's polyester filament was 1,790 ten thousand tons in 2010, account for 73% of world's polyester filament ultimate production, 8,950,000 tons of polyester staple fibers account for 66% of world's polyester staple fiber ultimate production, occupy first place in the world in continuous 12 years.Though but China is production of polyester big country, be polyester technology weak nation, the product homoorganicity is particularly thorny, and differential functionalized polyester fiber species is few, and external differential fibre accounts for 50%, and China has only 30%.The development trend of taking the dress material demand is: (1) is comfortable: generally slim and graceful, bulk, dangle, flexible, visually color and luster gracefulness, soft, the sense that has levels of gloss are soft, plentiful, smooth, nice and cool in the sense of touch; (2) environmental protection, energy-conservation, low-carbon (LC).
Benzene sulfonic acid sodium salt between adding (or potassium) class modified monomer carries out modification, existing many reports and research.The dyeing behavior of this class copolyesters (be called for short CDP) has improvement, but defectiveness still.Owing to when CDP needs that natural fiber such as cationic dye capable of dyeing and cotton wool silk fiber crops carries out blend dyeing under the High Temperature High Pressure, can influence the natural fiber performance.In addition, copolyesters ECDP and HCDP that the atmospheric cation dye chromophil also occurred.But the spinning instability of ECDP, the poor heat resistance of fiber.Copolyesters HCDP and the fiber of atmospheric cation dye chromophil, its polyreaction are difficult to control, and the molecular weight that increase polymkeric substance is very difficult, makes fiber process be difficult to carry out, and mechanical properties decrease, and production cost is than higher, and influence further enlarges produces.
Summary of the invention
Technical problem to be solved by this invention provides a kind of modified copolyester and its preparation method and application, and the fiber of this copolyesters has extraordinary cationic dye capable of dyeing, and dye uptake can reach more than 95%; The fiber of this copolyesters is after boiling dyeing at normal pressure or boiling water treating or dry heat treatment, and the shape that curls in the shape of a spiral gives that the fiber sense of touch is soft, rebound resilience good, super individual style such as fluffy.
A kind of modified copolyester of the present invention, the monomer of described modified copolyester comprises: mol ratio is 1: 1.1~2.4: 0.015~0.07: 0.04~0.20: 0.02~0.10 terephthalic acid, ethylene glycol, isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium, 2-methyl isophthalic acid, ammediol and 1, ammediol.Its structural formula is as follows:
Figure BDA0000127803170000021
The monomer of described modified copolyester comprises: mol ratio is 1: 11~2.4: 0.015~0.05: 0.05~0.20: 0.025~0.10 terephthalic acid, ethylene glycol, isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium, 2-methyl isophthalic acid, ammediol and 1, ammediol.
The monomer of described modified copolyester comprises: mol ratio is 1: 11~2.4: 0.02~0.05: 0.05~0.15: 0.025~0.075 terephthalic acid, ethylene glycol, isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium, 2-methyl isophthalic acid, ammediol and 1, ammediol.
The monomer of described modified copolyester comprises: mol ratio is 1: 11~2.4: 0.03~0.04: 0.05~0.10: 0.025~0.05 terephthalic acid, ethylene glycol, isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium, 2-methyl isophthalic acid, ammediol and 1, ammediol.
Described isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium are ethylene isophthalate-5-sodium sulfonate, ethylene isophthalate-5-potassium sulfonate, m-phthalic acid propylene glycol ester-5-sodium sulfonate, m-phthalic acid propylene glycol ester-5-potassium sulfonate, m-phthalic acid butanediol ester-5-sodium sulfonate or m-phthalic acid pentadiol ester-5-sodium sulfonate.
The intrinsic viscosity of described modified copolyester is 0.4~0.7, is recorded by the capillary viscosity method, and fusing point is 200 ℃~240 ℃.
The preparation method of a kind of modified copolyester of the present invention comprises:
Go up synthetic copolyester at continuous polymerization device (comprising: first esterifying kettle, second esterifying kettle and polycondensation vessel): adding ethylene glycol and terephthalic acid carry out esterification in first esterifying kettle, and temperature of reaction is 240 ℃~270 ℃, and the time is 2~4h; Then, enter second esterifying kettle, add isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium, 2-methyl isophthalic acid, ammediol and 1, the further esterification of ammediol, temperature of reaction is 240 ℃~270 ℃, the time is 1~3h; Subsequently, enter polycondensation vessel, add the catalyzer of terephthalic acid monomers weight 0.01%~0.08% and the thermo-stabilizer of terephthalic acid monomers weight 0.02%~0.06%, temperature of reaction is 270 ℃~300 ℃, time is 2~4h, and reaction finishes back discharging, pelletizing, is drying to obtain modified copolyester;
Wherein terephthalic acid, ethylene glycol, isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium, 2-methyl isophthalic acid, ammediol and 1, the mol ratio of ammediol is 1: 1.1~2.4: 0.015~0.07: 0.04~0.20: 0.02~0.10.
Described catalyzer is to contain in Zn, Sb, Mn, Ca or the Co compound one or more.
Described thermo-stabilizer is trimethyl phosphite 99 or triphenylphosphate.
In the synthetic the present invention of Large Scale and Continuous polymerization unit, must be according to the method described above, preferred composition, feed way, strict control esterification, condensation temperature and time, solve above gordian technique, could guarantee to obtain the copolyesters of good spinning property.
In the synthetic the present invention of Large Scale and Continuous polymerization unit, its advantage be can industrial mass produce continuously, melt can directly be spun into staple fibre or long filament.And cost is low, and the copolyesters molecular weight is higher, even structure, good product quality, good spinnability.
The application of a kind of modified copolyester of the present invention is used for chip spinning or direct fabrics and makes staple fibre or long filament; Wherein, spinning technology parameter is: 270~320 ℃ of spinning screw temperature, spinning speed 800~4200m/min, 70~160 ℃ of drawing temperatures, 1~4 times of drafting multiple.
Copolyesters of the present invention also can adopt interrupter method, carries out chip spinning then at batchwise polymerization equipment.
Copolyesters of the present invention has been introduced the pending methyl group group again when introducing the isophthalic sulfonate groups in its macromolecular chain.Because the volume effect of pendant methyl has reduced this kind copolyesters crystal property and second-order transition temperature, make that copolyester flock can be for the cationic dye capable of dyeing dark color under the boiling dyeing at normal pressure condition, and do not need alkaline purification that beautiful in colour, chromatogram is extensive.
Especially, the present invention adopts specific isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium as the 3rd comonomer, the 2-methyl isophthalic acid, the ammediol monomer is as the 4th comonomer, with 1, the ammediol monomer obtains novel copolymerized ester as the 5th comonomer, this novel copolymerized ester spin fiber have the special performance of potential crimp.After boiling water treating, boiling dyeing at normal pressure, heated dry air were handled, the number in the curling cycle of its 25mm reached more than 10, gave fiber softening, fluffy individual style.
The cationic dyestuff normal-pressure easy-to-dye performance of copolyester fiber of the present invention and potential crimp performance come from the structural changes of the macromolecular main chain that specific the 4th monomer that adopts and the 4th monomer (2-methyl isophthalic acid, ammediol and 1, ammediol) cause.
The monomethyl side chain is randomly introduced in the macromolecular chain of copolyesters, the irregularity that has caused macromolecular chain, the average chain length of crystallizable PET reduces in the molecular chain, and it is regular and closely build lattice to have hindered in the copolyesters PET segment, degree of crystallinity is low in the polymkeric substance, grain-size is little, molecular structure is loose, has guaranteed that dyeing course middle-jiao yang, function of the spleen and stomach ionic dye molecule is easy to be diffused into fibrous inside and dyes seat (SIP) combination, thereby has obtained the dyeing behavior of cationic dyestuff normal-pressure easy-to-dye.
And, existence-CH in the macromolecular chain 2-CH 2-CH 2The spirrillum conformation of-unit for rotating freely, the molecule chain flexibility increases.Because-CH 2-CH (CH 3)-CH 2The existence of monomethyl side chain in the-unit has aggravated the irregularity of macromolecular chain, helps further to strengthen flexible.In boiling dyeing at normal pressure or boiling water treating or dry heat treatment process, because temperature is higher than its second-order transition temperature, these two structural units are adjusted to the minimum spirrillum conformation of energy in the macromolecular main chain, different with the plane prionodont conformation of PET, macromolecular chain is the three-dimensional crimp state as spring, it is curved that fiber is rendered as helical coil on the macroscopic view, gives that the fiber sense of touch is soft, rebound resilience good, super individual style such as fluffy.
Copolyester fiber of the present invention can be dyed dark color with cationic dyestuff under 95~100 ℃ of normal pressures under the condition of boiling dyeing at normal pressure, its dye uptake is more than 95%, and the number in the curling cycle of every 25mm is more than 10.
Copolyester fiber of the present invention is under the pretension of 0.1cN/dtex, and behind the boiling water treating 5min, the number in the curling cycle of every 25mm is more than 10.
Copolyester fiber of the present invention is under the pretension of 0.1cN/dtex, and behind the processing 10min, the number in the curling cycle of every 25mm is more than 10 in 160 ℃ of heated dry airs.
Beneficial effect
The present invention is the 3rd comonomer with isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium, with the 2-methyl isophthalic acid, ammediol is the 4th comonomer, with 1, ammediol is the 5th comonomer, obtained a kind of novel modified copolyester, the fiber of this copolyesters has extraordinary cationic dye capable of dyeing, and dye uptake can reach more than 95%, and beautiful in colour, chromatogram is extensive; The fiber of this copolyesters is after boiling dyeing at normal pressure or boiling water treating or dry heat treatment, and the shape that curls in the shape of a spiral gives that the fiber sense of touch is soft, rebound resilience good, super individual style such as fluffy.And this copolyesters can also be with the method preparation of successive polymerization and direct fabrics or chip spinning; Its preparation process does not have particular requirement to equipment, and is with low cost, easily realizes suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
In embodiments of the present invention, the material that adopts and the abbreviation of title thereof are expressed as follows:
Terephthalic acid: PTA;
Ethylene glycol: EG;
The 2-methyl isophthalic acid, ammediol: MPO;
1, ammediol: PDO;
Isophthalic diprotic acid second diester-5-sodium sulfonate: SIPE;
Dimethyl isophthalate-5-sodium sulfonate: SIPM;
This copolyesters is also referred to as Ao Sika, abbreviates OSKA as;
Embodiment 1
Adopt continuous polymerization device, first esterifying kettle adds 1 ton of PTA, 600 kilograms of EG, add 0.2 kilogram The catalytic antimony trioxide and 0.2 kilogram triphenylphosphate simultaneously, carry out esterification, temperature of reaction is 260 ℃, behind the reaction 3h, material changes second esterifying kettle over to, injects the MPO of the 4mol% that is equivalent to PTA simultaneously, the PDO and the SIPE that is equivalent to the 1.5mol% of PTA that are equivalent to the 2mol% of PTA, further esterification, 250 ℃ of temperature of reaction, behind the reaction 2h, material changes polycondensation vessel over to, 270 ℃ of temperature of reaction, be decompressed to vacuum tightness gradually less than 130Pa, behind the polycondensation 3h, discharging, pelletizing, be drying to obtain the copolyester section OSKA1 of modification.OSKA1 slicing characteristics viscosity number is 0.615,233.3 ℃ of fusing points.
Embodiment 2
Adopt continuous polymerization device, first esterifying kettle adds 1 ton of PTA, 410 kilograms of EG, add 0.32 kilogram The catalytic antimony trioxide and 0.6 kilogram triphenylphosphate simultaneously, carry out esterification, temperature of reaction is 260 ℃, behind the reaction 3h, material changes second esterifying kettle over to, injects the MPO of the 20mol% that is equivalent to PTA simultaneously, the PDO and the SIPM that is equivalent to the 7mol% of PTA that are equivalent to the 4mol% of PTA, further esterification, 252 ℃ of temperature of reaction, behind the reaction 2h, material changes polycondensation vessel over to, 286 ℃ of temperature of reaction, be decompressed to vacuum tightness gradually less than 130Pa, behind the polycondensation 3h, discharging, pelletizing, be drying to obtain the copolyester section OSKA2 of modification.OSKA2 slicing characteristics viscosity number is 0.543,234.2 ℃ of fusing points.
Embodiment 3
Adopt continuous polymerization device, first esterifying kettle adds 1 ton of PTA, 450 kilograms of EG, add 0.1 kilogram The catalytic antimony trioxide and 0.2 kilogram triphenylphosphate simultaneously, carry out esterification, temperature of reaction is 260 ℃, behind the reaction 3h, material changes second esterifying kettle over to, injects the MPO of the 10mol% that is equivalent to PTA simultaneously, the PDO and the SIPE that is equivalent to the 3mol% of PTA that are equivalent to the 5mol% of PTA, further esterification, 250 ℃ of temperature of reaction, behind the reaction 2h, material changes polycondensation vessel over to, 270 ℃ of temperature of reaction, be decompressed to vacuum tightness gradually less than 130Pa, behind the polycondensation 3h, discharging, pelletizing, be drying to obtain the copolyester section OSKA3 of modification.OSKA3 slicing characteristics viscosity number is 0.588,230.1 ℃ of fusing points.
Embodiment 4
The OSKA copolyester section places in the vacuum drum moisture eliminator, vapor pressure 0.2Mpa, and vacuum tightness≤100Kpa, 100 ℃ of temperature, time 8h obtains water ratio and can spin section less than the drying of 50PPM.
Embodiment 5
Dry sliced with OSKA1 is raw material, fusion high-speed spinning FDY, extruder temperature: 270 ℃; Spinning speed: 4200m/min, spinning specification 110dtex/72F, 90 ℃ of hot-rolling 1 temperature, 125 ℃ of hot-rolling 2 temperature, drafting multiple: 2.64 times.
The fibre breakage intensity 2.63cN/dtex of spinning, extension at break 30%.At 95 ℃, the dye uptake of Cationic Bright Yellow 7GL dyestuff is 96.5%, and the curling number of cycles of the every 25mm of the fiber after the dyeing is 11.
Embodiment 6
Dry sliced with OSKA2 is raw material, fusion high-speed spinning FDY, extruder temperature: 300 ℃; Spinning speed: 4000m/min, spinning specification 67dtex/48F, 95 ℃ of hot-rolling 1 temperature, 122 ℃ of hot-rolling 2 temperature, drafting multiple: 2.5 times.
The fibre breakage intensity 2.78cN/dtex of spinning, extension at break 26%.At 100 ℃, the dye uptake of cationic yellow x-8gl dyestuff is 96.8%.The fiber of spinning is under the pretension of 0.1cN/dtex, and behind the boiling water treating 5min, the curling number of cycles of every 25mm is 13.
Embodiment 7
Dry sliced with OSKA3 is raw material, fusion high-speed spinning POY, extruder temperature: 273 ℃: spinning speed: 2800m/min, spinning specification 130dtex/72f, breaking tenacity 1.68cN/dtex, extension at break 117%.With spin POY flat lead temperature of heat plate: 80 ℃, 160 ℃ of hot plate temperatures, ratio of drawing 1.72 makes the flat silk that leads.
Putting down and leading a specification is 83.3dtex/72f, breaking tenacity 2.96cN/dtex, extension at break 32%.At 95 ℃, the dye uptake of the blue X-BL dyestuff of positively charged ion is 97.5%.The flat silk that leads is handled 10min in 160 ℃ of heated dry airs under the pretension of 0.1cN/dtex, the curling number of cycles of every 25mm is 12.
Embodiment 8
Adopt continuous polymerization device, first esterifying kettle adds 1 ton of PTA, 800 kilograms of EG, add 0.2 kilogram The catalytic antimony trioxide and 0.4 kilogram triphenylphosphate simultaneously, carry out esterification, temperature of reaction is 260 ℃, and behind the reaction 3h, material changes second esterifying kettle over to, inject the MPO of the 10mol% that is equivalent to PTA simultaneously, the PDO and the SIPE that is equivalent to the 1.8mol% of PTA that are equivalent to the 5mol% of PTA, further esterification, 253 ℃ of temperature of reaction are behind the residence time 1.5h, reactant enters precondensation still I, 275 ℃ of temperature of reaction, the reaction times is 0.5h, enters precondensation still II, temperature of reaction is 270 ℃, reaction times is 1h, and the final minification temperature of reaction is 268 ℃, and the reaction times is 2.5h, copolyesters melt viscosity 0.580,228 ℃ of fusing points.Directly spin staple fibre 3.33detx * 38mm, winding speed 800m/min, preliminary draft 1.02, first stretch ratio, 2.85, the second stretch ratios 1.12, draw speed 180m/min, 65 ℃ of stretch baths, drawing temperature is 80 ℃ for the second time, 80 ℃, 80 ℃, 75 ℃ and 75 ℃ of the lax temperature in each district.
The fibre number 3.24dt of spinning, breaking tenacity 3.2cN/dt, elongation 30%.At 95-100 ℃, the dye uptake of cationic pink X-FG dyestuff is 97.5%.Under the pretension of 0.1cN/dtex, handle 10min in 160 ℃ of heated dry airs, the curling number of cycles of every 25mm is 12.

Claims (7)

1. modified copolyester, it is characterized in that: the monomer of described modified copolyester comprises: mol ratio is terephthalic acid, ethylene glycol, isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium, the 2-methyl isophthalic acid of 1:1.1~2.4:0.03~0.04:0.05~0.10:0.025~0.05, ammediol and 1, ammediol.
2. a kind of modified copolyester according to claim 1, it is characterized in that: described isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium are ethylene isophthalate-5-sodium sulfonate, ethylene isophthalate-5-potassium sulfonate, m-phthalic acid propylene glycol ester-5-sodium sulfonate, m-phthalic acid propylene glycol ester-5-potassium sulfonate, m-phthalic acid butanediol ester-5-sodium sulfonate or m-phthalic acid pentadiol ester-5-sodium sulfonate.
3. a kind of modified copolyester according to claim 1, it is characterized in that: the intrinsic viscosity of described modified copolyester is 0.4~0.7, fusing point is 200 ℃~240 ℃.
4. the preparation method of a modified copolyester comprises:
Adding ethylene glycol and terephthalic acid carry out esterification in first esterifying kettle, and temperature of reaction is 240 ℃~270 ℃, and the time is 2~4h; Then, enter second esterifying kettle, add isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium, 2-methyl isophthalic acid, ammediol and 1, the further esterification of ammediol, temperature of reaction is 240 ℃~270 ℃, the time is 1~3h; Subsequently, enter polycondensation vessel, add the catalyzer of terephthalic acid monomers weight 0.01%~0.08% and the thermo-stabilizer of terephthalic acid monomers weight 0.02%~0.06%, temperature of reaction is 270 ℃~300 ℃, time is 2~4h, and reaction finishes back discharging, pelletizing, is drying to obtain modified copolyester;
Wherein terephthalic acid, ethylene glycol, isophthalic diprotic acid dibasic ester-5-sodium sulfonate or potassium, 2-methyl isophthalic acid, ammediol and 1, the mol ratio of ammediol is 1:1.1~2.4:0.03~0.04:0.05~0.10:0.025~0.05.
5. the preparation method of a kind of modified copolyester according to claim 4 is characterized in that: described catalyzer is to contain in Zn, Sb, Mn, Ca or the Co compound one or more.
6. the preparation method of a kind of modified copolyester according to claim 4, it is characterized in that: described thermo-stabilizer is trimethyl phosphite 99 or triphenylphosphate.
7. the application of a modified copolyester as claimed in claim 1 is characterized in that: described modified copolyester is used for chip spinning or direct fabrics make staple fibre or long filament; Wherein, spinning technology parameter is: 270~320 ℃ of spinning screw temperature, spinning speed 800~4200m/min, 70~160 ℃ of drawing temperatures, 1~4 times of drafting multiple.
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CN105734711A (en) * 2016-03-30 2016-07-06 中润科技股份有限公司 X-like moisture conducting and preserving polyester POY (PRE-ORIENTED YARN) and manufacture method thereof
CN107746457B (en) * 2017-10-19 2020-10-27 浙江恒逸高新材料有限公司 Preparation method of PET copolyester
CN111304781B (en) * 2020-03-12 2022-05-24 浙江恒逸石化研究院有限公司 Preparation method of moisture-absorbing and sweat-releasing ECDP fiber
CN113445147B (en) * 2021-01-14 2022-06-17 浙江光乾纺织有限公司 Double-yarn air-spliced polyester staple fiber with high color fastness and preparation method thereof

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CN101613466A (en) * 2009-07-17 2009-12-30 东华大学 The copolyester section and the preparation thereof of the aliphatic dihydroxy alcohol modification of band side chain
CN102120816A (en) * 2011-01-25 2011-07-13 东华大学 Polyester chip modified by blend with side chain aliphatic diol and preparation method thereof

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CN101613466A (en) * 2009-07-17 2009-12-30 东华大学 The copolyester section and the preparation thereof of the aliphatic dihydroxy alcohol modification of band side chain
CN102120816A (en) * 2011-01-25 2011-07-13 东华大学 Polyester chip modified by blend with side chain aliphatic diol and preparation method thereof

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