WO2011038671A1 - 一种共聚酯及其制备方法和用途 - Google Patents

一种共聚酯及其制备方法和用途 Download PDF

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Publication number
WO2011038671A1
WO2011038671A1 PCT/CN2010/077393 CN2010077393W WO2011038671A1 WO 2011038671 A1 WO2011038671 A1 WO 2011038671A1 CN 2010077393 W CN2010077393 W CN 2010077393W WO 2011038671 A1 WO2011038671 A1 WO 2011038671A1
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Prior art keywords
copolyester
mol
content
structural unit
acid
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PCT/CN2010/077393
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English (en)
French (fr)
Inventor
李旭
吴亚薇
杨娟
青山雅俊
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东丽纤维研究所（中国）有限公司
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Priority to CN2010800430724A priority Critical patent/CN102648231A/zh
Priority to KR1020127010597A priority patent/KR101739402B1/ko
Priority to US13/499,080 priority patent/US20120202964A1/en
Priority to JP2012531224A priority patent/JP5720059B2/ja
Publication of WO2011038671A1 publication Critical patent/WO2011038671A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters

Definitions

  • the present invention relates to a copolyester, a process for the preparation thereof and use thereof, and more particularly to a polyester obtained by copolymerization with an aliphatic diol monomer having a side chain and having 6 or less carbon atoms.
  • Polyethylene terephthalate in polyester has outstanding performance and is widely used in the fields of fiber and film, especially in the field of clothing and industrial materials.
  • polyester fibers There are many dyeing methods for polyester fibers depending on the application.
  • ordinary polyesters have structural characteristics such as tight molecular chain and high crystallinity, so that they are not easily dyed like natural fibers, and require high temperature and high pressure of 130 ° C when dyeing with disperse dyes. Dyeing under high temperature and high pressure conditions will increase operating costs in addition to increasing equipment investment.
  • Ciba Patent No. CN101063236A, CN1534114A discloses a method for forming a polyester by copolymerization only with a diol having a side chain. Although the dyeing property is improved, the brightness value L* after dyeing is still high, if the diol copolymerization unit is increased. Amount, although it can improve the dyeing performance, but the amount of glycol is increased, resulting in The crystallinity of the polymer is lowered, which in turn leads to a fiber shrinkage rate during dry heat treatment of the fiber during use, resulting in a hard texture of the fabric, which greatly limits the fiber versatility.
  • Patent JK56-26006 discloses a modified polyester fiber which improves the dyeability by adding a sulfonic acid group and a polyethylene glycol monomer to the polyester, but the fiber made of such a polyester is used.
  • the dyes need to be upgraded from general disperse dyes to cationic reactive dyes, resulting in increased production costs.
  • the object of the present invention is to provide a copolyester with good dyeing performance and low cost under normal temperature and normal pressure, a preparation method and use thereof.
  • the terephthalic acid structural unit content of the dibasic acid component constituting the copolyester is 90 mol% or more, and the content of the ethylene glycol structural unit in the glycol component constituting the copolyester is The content of the aliphatic diol structural unit having 70 to 99 mol% and having a side chain and having 6 or less carbon atoms is 1 to 30 mol%, and the copolyester further contains a polyethylene glycol structural unit.
  • the aliphatic diol having a side chain and having 6 or less carbon atoms in the present invention is 2-methyl-1,3 propanediol, 2,2-dimethyl-1,3 propanediol, and 2-methyl-1. 4-butanediol, 2,3-dimethyl-1,4-butanediol, 2-methyl-1,5-pentanediol, 1,2-propanediol. 2-Methyl-1,3 propanediol is preferred, and the dyeability of the copolyester is good at this time.
  • the copolymerization amount of the aliphatic diol having a side chain and having 6 or less carbon atoms must be an aliphatic diol structural unit having a side chain and having a carbon number of 6 or less in the diol component constituting the copolyester.
  • the content is from 1 to 30 mol%. Within this range, the dyeability of the copolyester is good.
  • a preferred range is from 6 to 20 mol%.
  • the present invention also adds a polyethylene glycol monomer during the copolymerization reaction. Because the compliant chain structure of polyethylene glycol makes the dye easier to disperse, and the addition of polyethylene glycol can reduce the tightness of the structure of the polyester fiber and lower the dyeing temperature.
  • the polyethylene glycol monomer has a molecular weight of from 1,000 to 10,000 g/mol.
  • the amount of polyethylene glycol added is 1 to 30% by weight based on the total amount of the copolyester. If it is not within this range, the heat resistance of the copolymer is lowered, and the spinnability is deteriorated, and the phenomenon of fluttering is likely to occur.
  • the dyeing ability of the fiber is improved, and the crystallization property of the polyester is seriously reduced, so that the dry heat shrinkage rate of the polyester fiber is not greatly increased when used, and the fabric is used.
  • the feel did not change much and did not become a factor limiting its application.
  • the copolyester of the present invention is prepared by copolymerizing 100 parts by weight of a dibasic acid, 56-93.4 parts by weight of a diol and 1.15 to 35 parts by weight of polyethylene glycol, and the dibasic acid is prepared.
  • the content of the terephthalic acid is 90% by mole or more
  • the content of the ethylene glycol in the glycol is 70 to 99% by mole
  • the content of the aliphatic diol having a side chain and having 6 or less carbon atoms is 1 to 30% by mole.
  • the molar ratio of the dibasic acid to the diol is 1:1.5 to 2.5.
  • the catalyst for the transesterification reaction or the catalyst for the polycondensation reaction used in the esterification reaction of the present invention specifically refers to a calcium compound such as calcium acetate or calcium chloride, a magnesium compound such as magnesium acetate, magnesium chloride or magnesium carbonate, and antimony trioxide.
  • a ruthenium compound such as ruthenium acetate, a ruthenium compound such as ruthenium oxide or ruthenium chloride, a titanium alkoxide such as tetrabutyl orthotitanate or tetraisopropyl titanate, ethylenediaminetetraacetic acid or hydroxyethyliminodiacetic acid.
  • diethylenetriaminepentaacetic acid triethylenetetramine hexaacetic acid, or a titanium complex of a polyvalent carboxylic acid and/or a hydroxycarboxylic acid and/or a nitrogen-containing carboxyl group as a chelating agent.
  • the chelating agent refers to a hydroxycarboxylic acid such as phthalic acid, trioctyl triacetate, trimesic acid, benzotricarboxylic acid, pyromellitic dianhydride or the like; or ethylenediaminetetraacetic acid or NTP containing a nitrogen carboxylic acid.
  • carboxyiminodiacetic acid carboxymethyliminodipropionic acid, diethylenetriaminepentaacetic acid, triethylenetetramine hexaacetic acid, imine diacetic acid, imidodipropionic acid, 2-hydroxyethyl Base-iminoacetic acid, 2-hydroxyethyl-iminodipropionic acid, 2-methoxyethyl-iminoacetic acid.
  • the copolyester of the present invention can be produced by a direct polymerization method or a DMT method. It can also be produced by a batch polymerization method or a continuous polymerization method.
  • the copolyester of the present invention can be formed into fibers by a known method, thereby forming a woven fabric, and the finished product has good dyeability against disperse dyes under normal temperature and pressure, thereby reducing the high amount of high temperature and high pressure dyeing. Equipment investment and operating costs. At the same time, the fiber product has excellent physical properties and wide versatility.
  • the present invention contains terephthalic acid containing more than 90 mol% of terephthalic acid, TPA; ethylene glycol is abbreviated as EG; 2-methyl-1,3-propanediol is abbreviated as MPO; and polyethylene glycol is abbreviated as PEG.
  • TPA terephthalic acid containing more than 90 mol% of terephthalic acid
  • EG ethylene glycol
  • MPO 2-methyl-1,3-propanediol
  • PEG polyethylene glycol
  • Dihydroxyethyl terephthalate was added to the esterification reaction tank to maintain a temperature of 250 ° C and a pressure of 1.2 ⁇ 10 5 Pa. 8.25 kg of TPA and 3.54 kg of EG slurry were gradually added to the esterification reaction layer within 4 hours. Further, an esterification reaction was carried out for 1 hour. Finally, 10.2 kg of the obtained esterification reaction was added to the polycondensation reaction layer.
  • the esterification reaction product was kept at 250 ° C under normal pressure, and after stirring for 5 minutes with the addition of 1 wt% of PEG 1000 of the polyester, MPO in an amount equivalent to 10 mol% of all the glycol components in the obtained polyester was added and stirred for 30 minutes. Then, phosphoric acid having an amount of phosphorus equivalent to 18 ppm of the polymer was added, and after 5 minutes, antimony trioxide corresponding to 230 ppm of the polymer was added, and cobalt acetate having an atomic weight equivalent to 15 ppm of the polymer was added. After a further 5 minutes, an ethylene glycol slurry containing titanium oxide particles in an amount corresponding to 0.3% by weight of the polymer was added.
  • the obtained chips were dried to maintain a water content of 50 ppm, and then melt-spun at a spinning temperature of 290 ° C, and taken up at a pulling speed of 3000 m.
  • the obtained undrawn yarn was stretched under the conditions of a stretching temperature of 90 ° C and a draw ratio of 1.65 times, and then heat-set at 130 ° C and then taken up to obtain a drawn yarn of 56 dtex / 24 f.
  • the obtained silk was subjected to tube knitting, and dyeing was evaluated under the following conditions.
  • the treatment liquid was stirred and dyed under the conditions of 95 ° C ⁇ 30 min by a high-temperature dyeing tester UR, MINI-COLOR (infrared micro-staining agent (manufactured by TEXAM Technology Co., Ltd.).
  • the chemicals of the treatment liquid used at this time are as follows.
  • Dianix Blue E-Plus (Destinating, Disperse Dyes) 5owf%
  • the treatment liquid was prepared using the following agent under the conditions of 80 ° C ⁇ 20 min, and subjected to reduction washing.
  • the cartridge was washed with water and dried to be used as an evaluation sample.
  • L* refers to the brightness in the L*, a*, and b* color systems, and the smaller the value, the better the dyeability.
  • the dry heat shrinkage rate of the fiber is also measured, and the measurement method is as follows: taking the fiber length of 10 m, winding it into 10 turns, and measuring the heat at a temperature of 160 ° for 15 minutes.
  • the length of the fiber based on the reduction in the length of the fiber and the percentage of the original fiber length, gives the percentage of dry heat shrinkage of the fiber. Since the dry heat shrinkage rate of the PET polyester is usually about 8% to 10%, if the shrinkage ratio becomes too large, the fiber feel is hardened, and the application thereof is greatly restricted.
  • fibers having a dry heat shrinkage ratio of 15% or less are referred to as excellent physical properties
  • fibers having 18% or less are referred to as good physical properties
  • fibers having 18% or more are referred to as poor physical properties.
  • Example 2 No PEG 1000 was added, and the other was the same as in Example 1.
  • the obtained tubular knitted fabric was dyed at a dyeing temperature of 95 ° C and found to have an L* value of 30.0 and a good dry heat shrinkage ratio.
  • Example 2 MPO and PEG1000 were not added, and the remaining conditions were the same as in Example 1.
  • the obtained tubular braid was dyed at a dyeing temperature of 95 ° C and the L* value was 37.5, and the dry heat shrinkage rate was excellent.
  • PEG1000 was changed to PEG4000, and the other conditions were the same as in Example 1.
  • the obtained tubular knitted fabric was dyed at a dyeing temperature of 95 ° C and found to have an L* value of 25.7 and a good dry heat shrinkage ratio.
  • the MPO was changed to DMPO (2,2-dimethyl-1,3 propanediol), and the other conditions were the same as in Example 1.
  • the obtained package was dyed at a dyeing temperature of 95 ° C and found to have an L* value of 28.4.
  • the dry heat shrinkage rate is good.
  • the MPO was replaced with EPED (2-methyl-1,5-pentanediol), and the other conditions were the same as in Example 1.
  • the obtained package was dyed at a dyeing temperature of 95 ° C and found to have an L* value of 29.2.
  • the dry heat shrinkage rate is good.
  • the MPO was changed to 1,2-PDO (1,2-propanediol), and the other conditions were the same as in Example 1.
  • the obtained package was dyed at a dyeing temperature of 95 ° C and found to have an L* value of 29.0.
  • the dry heat shrinkage rate is good.
  • the amount of MPO added was changed to 3 mol%, and the other conditions were the same as in Example 1.
  • the obtained package was dyed at a dyeing temperature of 95 ° C and found to have an L* value of 30.0. Excellent dry heat shrinkage rate.
  • the amount of MPO added was changed to 20 mol%, and the other conditions were the same as in Example 1.
  • the resulting package was dyed at a dyeing temperature of 95 ° C and found to have an L* value of 25.2.
  • the dry heat shrinkage rate is good.
  • the addition amount of PEG1000 was changed to 10% by weight, and the other conditions were the same as in Example 1.
  • the obtained package was dyed at a dyeing temperature of 95 ° C and found to have an L* value of 25.0.
  • the dry heat shrinkage rate is good.
  • the addition amount of PEG4000 was changed to 20% by weight, and the other conditions were the same as in Example 1.
  • the obtained package was dyed at a dyeing temperature of 95 ° C and found to have an L* value of 27.3.
  • the dry heat shrinkage rate is good.
  • Example 1 The amount of MPO added in Example 1 was changed to 8 mol%, the amount of PEG 1000 added was changed to 3 wt%, and the spinning of Example 1 was carried out to obtain undrawn yarn, and the undrawn yarn was stretched at 90 ° C and the draw ratio was 1.65 times.
  • the film was stretched under the conditions of the film, and then taken up by heat setting at 160 ° C to obtain a drawn yarn of 56 dtex / 24 f.
  • the tubular fabric was dyed at a dyeing temperature of 95 ° C and found to have an L* value of 25.7. Excellent dry heat shrinkage rate.
  • Example 1 The amount of MPO added in Example 1 was changed to 5 mol%, the amount of PEG 1000 added was changed to 4 wt%, and the spinning of Example 1 was carried out to obtain undrawn yarn, and the undrawn yarn was stretched at 90 ° C and the draw ratio was 1.65 times.
  • the film was stretched under the conditions of the film, and then taken up by heat setting at 160 ° C to obtain a drawn yarn of 56 dtex / 24 f.
  • the tubular fabric was dyed at a dyeing temperature of 95 ° C and found to have an L* value of 25.5. Excellent dry heat shrinkage rate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Description

一种共聚酯及其制备方法和用途
说明书
一种共聚酯及其制备方法和用途
技术领域
本发明涉及一种共聚酯及其制备方法和用途，具体地说是与带侧链且碳原子数为6以下的脂肪族二元醇单体共聚而制得的聚酯。
背景技术
聚酯中的聚对苯二甲酸乙二醇酯拥有突出的性能，广泛应用于纤维、薄膜等领域，特别是服饰、产业资材领域。
根据用途不同聚酯纤维的染色方法有很多， 但是普通的聚酯存在分子链紧密，结晶度高等结构特征，使得其并不像天然纤维容易进行染色，在使用分散染料染色的时候，需要130℃的高温、高压。在高温与高压的条件下进行染色，除了增加设备投资外，也会增加操作成本。
提高聚酯纤维的染色性能的课题已经有很长的时间的研究了。其中，通过共聚合技术来改善聚合物特性是主要的手段之一。
中国专利CN101063236A、CN1534114A中公开了仅通过与带侧链的二元醇共聚形成聚酯的方法，虽然染色性能提高，但是染色后明度值L*仍然较高，若对增加二元醇共聚单元的量，虽然可以提高染色性能，但是，提高二元醇的量，导致了 聚合物结晶性下降，进而导致了纤维在使用过程中，干热处理时纤维收缩率变大，得到织物手感变硬，大大限制了纤维泛用性。
专利JK56-26006中公开了一种改性聚酯纤维通过在聚酯中添加磺酸基团和聚乙二醇单体的方法来提高可染性，但这类聚酯制成的纤维所使用的染料则需由一般的分散染料提升为阳离子反应性染料，导致生产成本增加。
发明内容
本发明的目的在于提供一种常温常压下染色性能好、成本低的共聚酯及其制备方法和用途。
本发明的技术解决方案如下：
本发明中的共聚酯，构成共聚酯的二元酸成分中，对苯二甲酸结构单元含量为90mol%以上，构成共聚酯的二元醇成分中，乙二醇结构单元的含量为70～99mol%、带侧链且碳原子数为6以下的脂肪族二元醇结构单元的含量为1～30mol%，共聚酯中还含有聚乙二醇结构单元。
本发明中带侧链且碳原子数为6以下的脂肪族二元醇为2-甲基-1，3丙二醇、2，2-二甲基-1，3丙二醇、2-甲基-1，4-丁二醇、2，3-二甲基-1，4-丁二醇、2-甲基-1，5-戊二醇、1,2-丙二醇。优选2-甲基-1，3丙二醇，此时共聚酯的染色性很好。
带侧链且碳原子数为6以下的脂肪族二元醇的共聚量必须是使得构成共聚酯的二元醇成分中带侧链且碳原子数为6以下的脂肪族二元醇结构单元的含量为1～30mol%。在此范围内的话，共聚酯的染色性很好。优选范围为6～20mol%。
为了提高染色性能，本发明还在共聚合反应过程中添加了聚乙二醇单体， 因为聚乙二醇的柔顺链结构使得染料更容易分散进去，且聚乙二醇的加入可以降低聚酯纤维结构的紧密度从而使染色温度降低。 聚乙二醇单体的分子量为1000～10000g/mol。聚乙二醇的添加量为共聚酯总量的1～30wt%，如果不在此范围内，则共聚物的耐热性会下降，且可纺性变差，容易出现飘丝现象。本发明中通过添加聚乙二醇成分，即提高了纤维的染色能力，同时避免了严重降低聚酯的的结晶性能，使聚酯纤维在使用时其干热收缩率没有大量的变大，织物手感没有太大变化，没有成为限制其应用的因素。
本发明的共聚酯的制备方法是由100重量份的二元酸、56～93.4重量份的二元醇和1.15～35重量份的聚乙二醇共聚制得共聚酯，且二元酸中对苯二甲酸含量为90mol%以上，二元醇中的乙二醇含量为70～99mol%、带侧链且碳原子数为6以下的脂肪族二元醇含量为1～30mol%。其中，二元酸和二元醇的摩尔比为1：1.5～2.5。
本发明在酯化反应过程中所使用的酯交换反应的催化剂或聚缩反应的催化剂，具体是指醋酸钙、氯化钙等钙化合物，醋酸镁、氯化镁、碳酸镁等镁化合物，三氧化锑、醋酸锑等锑化合物，氧化锗、氯化锗等锗化合物，正钛酸四丁酯、钛酸四异丙酯等的钛金属醇盐、乙二胺四乙酸、羟乙基亚氨基二乙酸、二乙撑三胺五乙酸、三乙撑四胺六乙酸，或是作为螯合剂的多价羧酸和／或羟基羧酸和／或含氮的羧基的钛复合体。螯合剂是指邻苯二甲酸、三酸三辛酯、均苯三甲酸、苯连三酸、均苯四甲酸二酐等的羟基羧基酸；或含氮羧酸的乙二胺四乙酸、NTP、羧基亚胺基二乙酸、羧甲基亚胺基二丙酸、二乙撑三胺五乙酸、三乙撑四胺六乙酸、亚胺二醋酸、亚胺基二丙酸、2-羟乙基-亚胺基乙酸、2-羟乙基-亚胺基二丙酸、2-甲氧基乙基-亚胺基乙酸。
本发明的共聚酯可通过直接聚合法或DMT法制造。还可以通过间歇聚合法或连续聚合法来制造。
另外，本发明的共聚酯可通过公知的方法做成纤维，进而形成织物，制得的成品在常温常压下针对分散染料具有良好的染色性，从而降低了高温高压染色带来的高额设备投资和操作成本。同时该纤维制品具有优异的物性，泛用性广。
具体实施方式
下面结合具体实施例，进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。
本发明含对苯二甲酸90mol%以上的二元酸简写TPA；乙二醇简写为EG；2-甲基-1，3-丙二醇简写为MPO；聚乙二醇简写为PEG。
实施例1
将对苯二甲酸双羟乙酯加入酯化反应槽，保持温度250℃、压力1.2×105Pa，将8.25kg的TPA和3.54kg的EG浆料在4小时内逐渐加入到酯化反应层，再进行1小时的酯化反应。最后从得到的酯化反应物中取10.2kg加入到缩聚反应层。
将酯化反应生成物保持在250℃、常压下，加入相当于聚酯1wt%PEG1000搅拌五分钟后加入相当于所得聚酯中全部二元醇成分10mol%量的MPO进行30分钟的搅拌。然后加入磷原子量相当于聚合物18ppm的磷酸，5分钟后加入锑原子量相当于聚合物230ppm的三氧化二锑，以及钴原子量相当于聚合物15ppm的醋酸钴。再过5分钟后加入氧化钛粒子量相当于聚合物0.3wt%的含氧化钛粒子的乙二醇浆料。5分钟后开始减压、升温。温度由250℃升至290℃、压力降至40Pa。90分钟后达到最终温度、最终压力。到达一定的搅拌程度后，向反应体系里导入氮气回至常压，停止缩聚反应。聚合物呈条状吐出，在水槽中冷却后切片。所得聚合物的固有粘度为0.67。
将得到的切片干燥使其水分率保持在50ppm，然后在290℃的纺丝温度下熔融纺丝，3000m的牵引速度下卷取。得到的未拉伸丝在拉伸温度90℃、拉伸倍率1.65倍的条件下进行拉伸，然后在130℃下热定型后卷取，得到56dtex/24f的拉伸丝。
将得到的丝进行筒编，用下述条件进行染色评价。用高温染色试验机UR・MINI-COLOR（红外线小型染色剂（TEXAM技术研究制造）在95℃×30min的条件下搅拌处理液、染色。此时所用处理液的药剂如下所示。
Dianix Blue E-Plus （德司达公司制造、分散染料） 5owf%
NIKKA SUNSALT （日华化学公司制造、匀染剂） 1g／l
醋酸 （pH调节剂） 0.5 g／l
染色后，在80℃×20min的条件下使用下面的药剂配制处理液，进行还原清洗。
氢氧化钠 0.6g／l
亚硫酸氢钠 2g／l
然后，将筒编物水洗、风干后用作评价样品。将样品重叠成8层后用分光测色计（Datacolor Asia Pacific(H.K.)Ltd.制造的Datacolor 650）测色，L*=26.1。L*是指L*、a*和b*表色系中的明度，数值越小染色性越好。
同时为了说明本发明聚酯纤维的泛用性，对纤维的干热收缩率也进行的测量，测量方法：取纤维10米长度，绕成10圈，温度160度下进行15分钟的热处理后测量纤维的长度，根据纤维长度的缩小值与纤维原长的百分比例，得到纤维干热收缩百分比率。由于通常PET聚酯的干热收缩率在8%-10%左右，若收缩率变的太大，则导致纤维手感变硬，大大限制其应用。本发明将干热收缩率在15%以下的纤维称为物性优，18%以下的纤维称为物性良，18%以上的纤维称为物性差。
从下面的比较例也可以清楚地看出，与没有与MPO和PEG共聚合的聚对苯二甲酸乙二醇酯相比，本发明的共聚酯在常压下的染色性得到了很大的改善。
比较例1
不添加PEG1000，其他同实施例1。将制得的筒编物在95℃染色温度下染色后测得L*值为30.0，干热收缩率良。
比较例2
不添加MPO和PEG1000，其余条件同实施例1。将制得的筒编物在95℃染色温度下染色后测得L*值为37.5，干热收缩率优。
实施例2
将PEG1000改成PEG4000，其余条件同实施例1。将制得的筒编物在95℃染色温度下染色后测得L*值为25.7，干热收缩率良。
实施例3
将PEG1000改成PEG10000, 其余条件同实施例1。将制得的筒编物在95℃染色温度下染色后测得L*值为28.1。干热收缩率良。
实施例4
将MPO换成DMPO(2，2-二甲基-1，3丙二醇)，其余条件同实施例1。将制得的筒编物在95℃染色温度下染色后测得L*值为28.4。干热收缩率良。
实施例5
将MPO换成EPED(2-甲基-1，5-戊二醇)，其余条件同实施例1。将制得的筒编物在95℃染色温度下染色后测得L*值为29.2。干热收缩率良。
实施例6
将MPO换成1,2-PDO(1,2-丙二醇)，其余条件同实施例1。将制得的筒编物在95℃染色温度下染色后测得L*值为29.0。干热收缩率良。
实施例7
将MPO的添加量改为3mol%，其余条件同实施例1。将制得的筒编物在95℃染色温度下染色后测得L*值为30.0。干热收缩率优。
实施例8
将MPO的添加量改为20mol%，其余条件同实施例1。将制得的筒编物在95℃染色温度下染色后测得L*值为25.2。干热收缩率良。
实施例9
将PEG1000的添加量改为10wt%，其余条件同实施例1。将制得的筒编物在95℃染色温度下染色后测得L*值为25.0。干热收缩率良。
实施例10
将PEG4000的添加量改为20wt%，其余条件同实施例1。将制得的筒编物在95℃染色温度下染色后测得L*值为27.3。干热收缩率良。
实施例11
将实施例1中MPO的添加量改为8mol%，PEG1000的添加量改为3wt%，同时实施例1纺丝得到未延伸丝，未拉伸丝在拉伸温度90℃、拉伸倍率1.65倍的条件下进行拉伸，然后在160℃下热定型后卷取，得到56dtex/24f的拉伸丝。同实施例1的评价方法，筒编物在95℃染色温度下染色后测得L*值为25.7。干热收缩率优。
实施例12
将实施例1中MPO的添加量改为5mol%，PEG1000的添加量改为4wt%，同时实施例1纺丝得到未延伸丝，未拉伸丝在拉伸温度90℃、拉伸倍率1.65倍的条件下进行拉伸，然后在160℃下热定型后卷取，得到56dtex/24f的拉伸丝。同实施例1的评价方法，筒编物在95℃染色温度下染色后测得L*值为25.5。干热收缩率优。

Claims (2)

  1. 权利要求书
    1 、一种共聚酯，其特征是：构成共聚酯的二元酸成分中，对苯二甲酸结构单元含量为90mol%以上；构成共聚酯的二元醇成分中，乙二醇结构单元的含量为70～99mol%、带侧链且碳原子数为6以下的脂肪族二元醇结构单元的含量为1～30mol%；共聚酯中还含有聚乙二醇结构单元。
    2 、根据权利要求1所述的共聚酯，其特征是：构成共聚酯的二元醇成分中，带侧链且碳原子数为6以下的脂肪族二元醇结构单元的含量为6～20mol%。
    3 、根据权利要求1或2所述的共聚酯，其特征是：所述带侧链且碳原子数为6以下的脂肪族二元醇为2-甲基-1，3-丙二醇。
    4 、根据权利要求1或2所述的共聚酯，其特征是：所述聚乙二醇结构单元的分子量为1000～10000g/mol。
    5 、根据权利要求1所述的共聚酯，其特征是：所述聚乙二醇结构单元总量占共聚酯总量的1～30wt%。
    6 、一种权利要求1所述的共聚酯的制备方法，其特征是：由100重量份的二元酸、56～93.4重量份的二元醇和1.15～35重量份的聚乙二醇共聚制得共聚酯，且二元酸中对苯二甲酸含量为90mol%以上，二元醇中的乙二醇含量为70～99mol%、带侧链且碳原子数为6以下的脂肪族二元醇含量为1～30mol%。
    7 、根据权利要求6所述的共聚酯的制备方法，其特征是：所述二元酸和二元醇的摩尔比为1：1.5～2.5。
    8 、一种权利要求1所述的共聚酯在制备纤维中的应用。
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KR102274423B1 (ko) * 2017-03-27 2021-07-06 도레이첨단소재 주식회사 터치감이 우수한 고발색성 폴리에스테르 섬유 및 이의 제조방법.
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KR102061805B1 (ko) * 2018-06-27 2020-01-03 도레이첨단소재 주식회사 열접착성 섬유용 폴리에스테르 조성물, 이를 통해 구현된 열접착성 복합섬유및 부직포
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