WO2021249521A1 - 阳离子可染聚酯组合物及其制备方法和应用 - Google Patents

阳离子可染聚酯组合物及其制备方法和应用 Download PDF

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WO2021249521A1
WO2021249521A1 PCT/CN2021/099564 CN2021099564W WO2021249521A1 WO 2021249521 A1 WO2021249521 A1 WO 2021249521A1 CN 2021099564 W CN2021099564 W CN 2021099564W WO 2021249521 A1 WO2021249521 A1 WO 2021249521A1
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polyester composition
formula
sulfonate
cationic dyeable
esterification
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PCT/CN2021/099564
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English (en)
French (fr)
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胡永佳
文金淼
陈彬彬
望月克彦
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东丽纤维研究所（中国）有限公司
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Priority to CN202180028470.7A priority Critical patent/CN115362210B/zh
Priority to JP2022575227A priority patent/JP2023529387A/ja
Publication of WO2021249521A1 publication Critical patent/WO2021249521A1/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
    • C08G63/78—Preparation processes
    • 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
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent

Definitions

  • the invention relates to a cationic dyeable polyester composition and a preparation method and application thereof. Specifically, it relates to a cationic dyeable polyester composition with a low content of insoluble compounds and diethylene glycol and a small increase in filtration pressure during spinning.
  • Polyester resins due to their excellent mechanical properties and chemical properties, are widely used in industrial fields such as clothing, industrial fibers, magnetic tapes, surface coating films, and tire radial wires and mesh wires.
  • the isophthalic acid component containing sulfonate group represented by isophthalic acid-5-sodium sulfonate is used as a comonomer to prepare copolymerized modification.
  • Cationic dyeable polyester, or isophthalic acid component containing sulfonate group and polyethylene glycol are used together for copolymerization modification, but sulfonate group is prone to physical crosslinking in polyester, resulting in When the inherent viscosity (IV) of polyester is not high, the melt viscosity increases significantly, resulting in lower strength of the final yarn; limiting its application in some fields that require higher strength.
  • the copolyester obtained after modification with the isophthalic acid component containing the sulfonate group has a rapid rise in filtration pressure during melt spinning, making it difficult to perform stable production.
  • Japanese Patent Laid-open No. 5-25708 discloses a modified polyester fiber, which is polymerized by blocking cationic components, polyether and glycol components at the end. Ester modification, the cationic groups in the modified polyester obtained are mainly connected to the end of the molecular chain, and there are no interactive physical cross-linking groups in the molecular chain, which greatly reduces the viscosity of the polyester and the obtained cationic polyester fiber is stronger.
  • the existing polyester modified with the isophthalic acid component of the sulfonate group has been greatly improved.
  • the terminal blocking cationic component used in this patent has a carboxylic acid group, and direct addition will cause the problem of high DEG.
  • the object of the present invention is to provide a polyester composition having excellent cationic dyeability and high strength by suppressing the amount of insoluble compounds in the polymer, and a preparation method thereof, thereby suppressing the increase in filtration pressure during polyester spinning .
  • the cationic dyeable polyester composition is mainly composed of aromatic dicarboxylic acid structural units and ethylene glycol structural units.
  • the polyester composition contains the sulfonate group as shown in formula 1, and the content of the sulfonate group as shown in formula 1 accounts for 1000-5000 ppm of the total polyester composition, preferably 1000-5000 ppm in terms of sulfur element. 3500ppm; the content of the compound shown in formula 2 is equivalent to 10.0 mol% or less of the total sulfonate group shown in formula 1 in terms of sulfur element, preferably 5.0 mol% or less; the content of diethylene glycol in the polyester composition Relative to the total amount of the polyester composition, 0.8-5.0% by weight;
  • Y is an alkyl group, phenyl group or alkylbenzene having 2 to 20 carbon atoms, and Z and M are Li ion, Na ion or K ion, respectively.
  • the present invention also discloses a preparation method of the cationic dyeable polyester composition.
  • the oligomer is obtained by esterification or transesterification reaction of aromatic dicarboxylic acid or its esterified derivative and ethylene glycol, and then The obtained oligomer is polymerized to obtain a polyester composition.
  • an esterification liquid obtained by reacting a sulfonate compound and ethylene glycol as shown in formula 3 and an alkali metal compound are added, and the esterification reaction rate of the esterification liquid is above 95,
  • Y is an alkyl group having 2 to 20 carbon atoms, a phenyl group, or an alkylbenzene
  • Z is a Li ion, a Na ion, or a K ion.
  • the added amount of the esterification liquid is preferably 1000-3500 ppm of the total polyester composition based on sulfur element in the esterification liquid.
  • the alkali metal compound is preferably one or more of lithium acetate, potassium hydroxide or sodium hydroxide, and the addition amount thereof is based on the alkali metal element therein, preferably 10 to 1000 ppm relative to the total amount of the polyester composition.
  • the esterification liquid obtained by reacting the sulfonate compound represented by Formula 3 with ethylene glycol is preferably added after the polymerization reaction starts.
  • the polymer of the present invention has excellent cationic dyeability and strength, and the content of diethylene glycol and insoluble compounds is small, which can inhibit the increase of filtration pressure during spinning.
  • cationic dyeable components containing sulfonate groups such as isophthalic acid-5-sulfonate
  • polyesters to impart cationic dyeability to polyesters.
  • the sulfonate groups are distributed in the middle of the polyester molecular chain, the sulfonate groups are prone to physical cross-linking in the polyester, resulting in an increase in the viscosity of the polyester and a decrease in strength. At the same time, it will also lead to poor hydrolysis resistance of the polyester.
  • the cationic dyeable ingredient used in the present invention is a sulfonate compound as shown in formula 3.
  • Y is an alkyl group having 2 to 20 carbon atoms, a phenyl group, or an alkylbenzene
  • Z is a Li ion, a Na ion, or a K ion.
  • the sulfonate compound shown in formula 3 only contains one hydroxyl reactive group.
  • the sulfonate compound is mainly attached to the end of the molecular chain, and there is no interactive physical crosslinking group in the middle of the molecular chain, so It can ensure that the obtained polyester composition has a higher molecular weight and better strength.
  • the sulfonate compound represented by formula 3 can specifically exemplify sodium 2-carboxybenzenesulfonate, potassium 2-carboxybenzenesulfonate, sodium 3-carboxybenzenesulfonate, lithium 3-carboxybenzenesulfonate, Sodium 4-carboxybenzene sulfonate, 2-sodium sulfonate methyl benzoate, 3-sodium sulfonate methyl benzoate, 4-sodium sulfonate methyl benzoate, 2-sodium sulfonate ethyl benzoate, 2- Potassium sulfonate ethylene glycol benzoate, 3-sodium sulfonate ethyl benzoate, 4-sulfonate sodium ethylene benzoate, 3-sulfonate lithium ethylene benzoate, etc., among which 3-carboxyl is preferred Sodium benzene sulfonate.
  • polyester composition containing the sulfonate compound as shown in formula 3 with cationic dyeable ingredients contains the sulfonate group as shown in formula 1,
  • Y is an alkyl group having 2 to 20 carbon atoms, a phenyl group, or an alkylbenzene
  • Z is a Li ion, a Na ion, or a K ion.
  • the content of the sulfonate group shown in formula 1 in the polyester composition of the present invention accounts for 1000-5000 ppm of the polyester composition in terms of sulfur element.
  • the content of the sulfonate group as shown in formula 1 in the polyester composition is less than 1000 ppm, the resulting product is difficult to achieve a satisfactory color concentration in the subsequent dyeing process; when the sulfonate group as shown in formula 1 in the polyester composition
  • the content of the acid salt group is higher than 5000 ppm, the growth of the polyester molecular chain will be inhibited, the polymerization system will terminate before the target viscosity is reached, and a polyester composition with good physical properties cannot be obtained.
  • the content of the sulfonate group shown in Formula 1 preferably accounts for 1000-3500 ppm of the polyester composition in terms of sulfur.
  • the alkali metal compound can be potassium hydroxide, sodium hydroxide, magnesium hydroxide, lithium hydroxide, magnesium acetate, potassium acetate , Lithium acetate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium hexametaphosphate, etc. Among them, lithium acetate, potassium hydroxide, and sodium hydroxide are preferred.
  • the alkali metal compound may be added alone or mixed.
  • the content of diethylene glycol in the polyester composition of the present invention exceeds 5.0% by weight, which will cause the thermal oxidation resistance of the polyester composition to deteriorate, and at the same time, the regularity of the polyester composition deteriorates, and the creep of the fiber is irreversible in the later period. Partial increase; if the content of diethylene glycol in the polyester composition is less than 0.8wt%, the structure of the polyester composition will become compact, affecting the combination of dyes and dyeable positions, and further affecting the uniformity and stability of dyeing sex.
  • the addition amount of the alkali metal compound is preferably 10 to 1000 ppm based on the alkali metal element in the total amount of the polyester composition.
  • the addition amount of the alkali metal compound is too much, the too much alkali metal compound will make the color tone of the polyester composition worse; when the addition amount of the metal alkali compound is too low, the generation of diethylene glycol cannot be effectively suppressed.
  • alkali metal compound will react with the sulfonate compound shown in formula 3 to produce the compound shown in formula 2.
  • M and Z are Li ion, Na ion, or K ion, respectively, and Y is an alkyl group having 2 to 20 carbon atoms, a phenyl group, or an alkylbenzene.
  • the compound represented by formula 2 is insoluble in the polyester composition and will become a foreign body in the melt spinning stage, which will increase the filter pressure during melt spinning, shorten the filter replacement cycle in the spinning process, and increase the spinning cost. . Therefore, in order to achieve good spinnability of the polyester composition and reduce spinning costs, the present invention adds the sulfonate compound as shown in formula 3 in the form of an esterified liquid with ethylene glycol, and The terminal carboxyl group value is reduced by increasing the reaction rate, thereby reducing the reaction probability of the alkali metal compound and the sulfonate compound shown in formula 3, so that the content of the compound shown in formula 2 in the polyester composition is calculated as sulfur element relative to the formula 10.0 mol% or less, preferably 5.0 mol% or less of the total amount of sulfonate groups shown in 1.
  • ester compound formed by the sulfonate compound shown in Formula 3 and ethylene glycol is shown in Formula 4.
  • Y is an alkyl group having 2 to 20 carbon atoms, a phenyl group, or an alkylbenzene
  • Z is a Li ion, a Na ion, or a K ion.
  • the addition amount of the esterification liquid is 1000-5000 ppm based on the sulfur element in the esterification liquid relative to the total amount of the polyester composition.
  • the addition amount of the esterification solution is less than 1000ppm, it is difficult for the resulting product to achieve a satisfactory color concentration in the subsequent dyeing process; when the addition amount of the esterification solution is higher than 5000ppm, the growth of the polyester molecular chain will be inhibited, resulting in The phenomenon of polymerization heading, the obtained polyester composition has a small molecular weight and poor physical properties.
  • the addition amount of the esterification liquid is preferably 1000-3500 ppm based on the sulfur element in the esterification liquid relative to the total amount of the polyester composition.
  • the method for preparing the cationic dyeable polyester composition of the present invention is as follows: firstly, the oligomer is obtained by esterification or transesterification reaction of aromatic dicarboxylic acid or its esterified derivative and ethylene glycol, and then the obtained low polymer The polymer undergoes polymerization reaction to obtain a polyester composition. At any stage before the polyester composition is obtained, the esterification liquid obtained by reacting the sulfonate compound and ethylene glycol as shown in formula 3 and the alkali metal compound are added, and the esterification reaction rate of the esterification liquid is 95 %above,
  • Y is an alkyl group having 2 to 20 carbon atoms, a phenyl group, or an alkylbenzene
  • Z is a Li ion, a Na ion, or a K ion.
  • the esterification rate of the esterification solution is above 95%. If the esterification rate of the esterification solution is less than 95%, a large amount of the compound shown in formula 2 will be generated, and the filtration pressure during melt spinning will increase. Shorten the replacement cycle of the filter in the spinning project, which greatly increases the cost.
  • the esterification liquid obtained by reacting the sulfonate compound shown in Formula 3 with ethylene glycol can be added at any stage before obtaining the polyester composition, such as the esterification or transesterification reaction stage, the polymerization reaction process, and the like.
  • the esterified liquid obtained by reacting the sulfonate compound shown in Formula 3 with ethylene glycol is preferably after the start of the polymerization reaction. Add to.
  • the aromatic dicarboxylic acid or its esterified derivative of the present invention can be terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimethyl terephthalate, dimethyl isophthalate, Dimethyl naphthalate, dimethyl phthalate, etc., of which terephthalic acid or dimethyl terephthalate are preferred.
  • the esterification reaction may be carried out in an esterification reaction tank where oligomers are pre-existing, while continuously adding a slurry of ethylene glycol and aromatic dicarboxylic acid in a molar ratio of 1.05 to 1.50, while performing the esterification reaction; It is also possible to carry out the esterification reaction after all the ethylene glycol and the aromatic dicarboxylic acid are added in the esterification reaction tank where the oligomer is pre-existed before the esterification reaction starts.
  • the molar ratio of ethylene glycol and the aromatic dicarboxylic acid esterified derivative can be adjusted to be in the range of 1.50-2.50 to control the appropriate transesterification reaction rate.
  • the transesterification reaction catalyst may be various well-known catalysts, such as metal oxides such as cobalt, magnesium, manganese, titanium, or their acetates, and they may be used in combination or alone.
  • the polymerization catalyst used in the preparation method of the cationic dyeable polyester composition may be various known polymerization catalysts.
  • antimony compounds, germanium compounds, titanium compounds, etc. These catalysts can be used in combination or individually.
  • polyester composition of the present invention in addition to aromatic dicarboxylic acids, aliphatic diols, and sulfonate groups as shown in formula 1, other copolymers, such as polyethers or fatty acids, can also be added.
  • Family dibasic acid Since the compound shown in formula 2 has a certain solubility in polyether or aliphatic dibasic acid, the copolymerization of polyether or aliphatic dibasic acid in the polyester composition can effectively reduce the compound shown in formula 2 in polyether The amount of precipitation in the ester composition further improves the polymerization filter pressure.
  • the addition of polyether or aliphatic dibasic acid can also impart low-temperature dyeing properties to the polyester composition.
  • the polyether can be polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.
  • the aliphatic dibasic acid can be cyclohexanedicarboxylic acid, isophthalic acid, succinic acid, adipic acid, and glutaric acid. Sour etc. Among them, polyethylene glycol or cyclohexane dicarboxylic acid is preferred.
  • the molecular weight of the polyethylene glycol is preferably 600-6000 g/mol, more preferably 600-3000 g/mol.
  • the addition amount of the polyether or aliphatic dibasic acid is preferably 0.5 to 10.0% by weight, and more preferably 0.5 to 5.0% by weight relative to the total amount of the polyester composition.
  • esterification and polymerization reaction device for the production of the cationic dyeable polyester composition of the present invention various commonly used reaction devices can be used.
  • the preparation process of the cationic dyeable polyester composition it is preferable to perform solid phase polymerization after the polymerization reaction is completed.
  • the conditions of the solid-phase polymerization are not particularly limited, and the usual reaction conditions in this field can be used.
  • the polyester product obtained by the polymerization reaction may be subjected to pre-crystallization treatment, and solid-phase polymerization is carried out under the conditions of a reaction temperature of 200-240°C, a reaction pressure of 1000 Pa or less, and a reaction time of 100 hours to obtain the final polyester. combination.
  • the cationic dyeable polyester composition of the present invention has good physical properties, excellent dyeability, and good dye stability of the polyester composition. And by controlling the amount of the terminal carboxyl groups of the cationic dyeable component esterification solution, the content of insoluble foreign matter in the polyester composition is low, the foreign matter during polyester melt spinning is less, and the filtration pressure rises during the spinning process. The replacement cycle of the filter is long and the cost is low.
  • the measuring method and evaluation method of each index of the present invention are as follows:
  • the sulfur content in the polymer was quantitatively analyzed by the SEM-EDX element analyzer.
  • the polyester composition was spun to obtain a stretched yarn, and then the stretched fibers obtained were double-threaded to make a sock tube under the condition of 22 gauge.
  • the sock tube was dyed (Blue.TR) 3% owf, Dyeing for 60 minutes in a 130°C hot water bath with acetic acid 0.5ml/l, sodium acetate 0.2g/l, bath ratio 1:100. After the dyed samples are overlapped into an opaque state, the color is measured with a spectrophotometer (Datacolor 650 manufactured by Datacolor Asia Pacific (H.K.) Ltd.) under the CEI standard light source D65 and 10° angle conditions to obtain L*.
  • a spectrophotometer Datacolor 650 manufactured by Datacolor Asia Pacific (H.K.) Ltd.
  • Diethylene glycol in isophthalic acid diethylene glycol sulfonate solution Weigh 0.5g sample into 10ml adipic acid, measure by LC, and determine the content of diethylene glycol by internal standard method.
  • Diethylene glycol in polyester Weigh 0.5g sample, add ethanolamine and heat to dissolve, add 10ml adipic acid, measure by LC, and determine the content of diethylene glycol by internal standard method.
  • the strength and elongation are measured in accordance with JIS L1013: 2010 (Testing Methods for Long Fibers in Chemical Fibers) 8.8.1.
  • the terephthalic acid (PTA) and ethylene glycol (EG) are mixed uniformly and put into the reaction kettle, and the esterification reaction is carried out at 240-260°C. After the esterification reaction is over, the reaction product is transferred to the polycondensation kettle, and the esterification solution with the esterification rate of 99% is added, and then the lithium acetate solution is added, and then the catalyst antimony trioxide and the heat stabilizer trimethyl phosphate are added.
  • the polymerization reaction is carried out at °C ⁇ 290°C. After the polymer reaches the required viscosity, it is discharged and pelletized to obtain the required polyester composition.
  • the intrinsic viscosity IV of the polyester composition is 0.64dl/g
  • the filtration pressure difference of the polyester is 0.20MPa/h
  • the DEG value is 2.5%.
  • the chips are melt-spun at 290°C to obtain cationic dyeable polyester yarn.
  • the content of sulfur in the fiber was 2450 ppm, and the content of sulfur in the dissolved aqueous solution after hot water treatment was 4.7 ppm, accounting for 0.19% of the total sulfur content of the polyester composition.
  • the fiber's strength and elongation product is 24 and the blue dye concentration is 3.0% o.w.f, the L value after dyeing is 25.
  • the reaction rate of the sulfonate esterification solution shown in formula 3 was changed, that is, the terminal carboxyl group value of the sulfonate esterification solution was changed, and other conditions were the same as in Example 1 to prepare a cationic dyeable polyester composition. See Table 1 for specific physical properties.
  • solid-phase polymerization is carried out under the conditions of a reaction temperature of 230°C, a reaction pressure of 50 Pa, and a reaction time of 80 hours or less.
  • the other conditions are the same as in Example 1 to prepare a cationic dyeable polyester composition.
  • the specific physical properties are shown in Table 2. .
  • Comparative Example 1 due to the direct addition of unesterified sodium 3-carboxybenzene sulfonate, the amount of insoluble compounds shown in formula 2 in the polyester composition was too much, and the foreign matter in the final polyester melt filter pressure test More, the filter pressure difference ⁇ Pa is larger, and the spinning is more unstable.
  • the non-esterified sodium 3-carboxybenzene sulfonate monomer was directly added, and no alkali metal compound was added.
  • the other conditions were the same as in Example 1 to prepare the cationic dyeable polyester. See Table 3 for specific physical properties.
  • the sodium 3-carboxybenzene sulfonate undergoes esterification, the reaction rate is low and the amount of terminal carboxyl groups is large, resulting in too much insoluble compound as shown in formula 2 in the polyester composition, and finally the polyester is melted and filtered. There are more foreign bodies during the pressure test, the filter pressure difference ⁇ Pa is larger, and the spinning is more unstable.
  • the addition amount of the sulfonate is too low, the dyeability will be poor and the desired hue will not be dyed. If the addition amount of the sulfonate is too high, the resulting polyester composition will have a small molecular weight, poor physical properties, and low yarn strength.

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Abstract

本申请公开了一种阳离子可染聚酯组合物及其制备方法。所述阳离子可染聚酯组合物主要由芳香族二元羧酸单元和乙二醇单元构成。在聚酯组合物反应过程中添加磺酸盐化合物和乙二醇反应得到的酯化液以及碱金属化合物，所述酯化液的酯化反应率在95％以上。所得聚酯组合物中不溶性的化合物含量低，异物少，可纺性好，纺丝过程中滤压上升少、滤网的更换周期长、成本低。

Description

阳离子可染聚酯组合物及其制备方法和应用 技术领域
本发明涉及一种阳离子可染聚酯组合物及其制备方法和应用。具体的，涉及一种不溶性化合物和二甘醇含量少、纺丝时的滤压上升小的阳离子可染聚酯组合物。
背景技术
聚酯树脂，由于其具有优异的机械力学性能和化学特性，被广泛应用于衣料、产业用纤维，磁带、表面涂层用薄膜，以及轮胎子午线、网线等工业领域。
在作为衣料纤维使用的时候，为了提高聚酯的染色性，以间苯二甲酸-5-磺酸钠为代表的含有磺酸盐基团的间苯二甲酸成分被作为共聚单体制得共聚改性阳离子可染聚酯，或者含有磺酸盐基团的间苯二甲酸成分和聚乙二醇等一起使用进行共聚改性，但是磺酸盐基团在聚酯中容易发生物理交联，导致聚酯在固有粘度(IV)不高的情况下熔融粘度明显上升，导致最终所得到的纱线强度较低；限制了其在一些对强度要求较高的领域的应用。
另外，使用含有磺酸盐基团的间苯二甲酸成分改性后得到的共聚酯在进行熔融纺丝时，滤压上升快，很难进行稳定生产。
为了改善磺酸盐基团所产生的增粘现象以及滤压问题，日本专利特开平5-25708公开了一种改性聚酯纤维，通过使用末端封锁阳离子成分、聚醚以及二醇成分进行聚酯改性，所得改性聚酯中的阳离子基团主要接在分子链末端，分子链中间没有相互作用的物理交联基团，大大降低了聚酯的粘度，获得的阳离子聚酯纤维强度较现有磺酸盐基团的间苯二甲酸成分改性的聚酯有大幅度提高。但是该专利中使用的末端封锁阳离子成分具有羧酸基团，直接添加会导致DEG高的问题存在。
发明内容
本发明的目的在于提供一种通过抑制聚合物中不溶性化合物的量，制得具有优异阳离子可染性、高强度的聚酯组合物及其制备方法，从而抑制聚酯纺丝时的滤压上升。
本发明的技术解决方案：
阳离子可染聚酯组合物，主要由芳香族二元羧酸结构单元和乙二醇结构单元 构成。该聚酯组合物中含有如式1所示磺酸盐基团，且如式1所示磺酸盐基团的含量以硫元素计占聚酯组合物总量的1000～5000ppm，优选1000～3500ppm；如式2所示的化合物的含量以硫元素计相当于式1所示磺酸盐基团总量的10.0mol％以下，优选5.0mol％以下；该聚酯组合物中二甘醇含量相对于聚酯组合物总量为0.8～5.0wt％；
Figure PCTCN2021099564-appb-000001
式1和式2中，Y为碳原子数2～20的烷基、苯基或烷基苯，Z和M分别为Li离子、Na离子或K离子。
本发明还公开了一种上述阳离子可染聚酯组合物的制备方法，首先由芳香族二元羧酸或其酯化衍生物与乙二醇经过酯化或酯交换反应得到低聚物，然后将所得低聚物进行聚合反应得到聚酯组合物。在得到所述聚酯组合物之前的任意阶段添加由如式3所示磺酸盐化合物和乙二醇反应得到的酯化液，以及碱金属化合物，所述酯化液的酯化反应率在95％以上，
Figure PCTCN2021099564-appb-000002
式3中，Y为碳原子数2～20的烷基、苯基或烷基苯，Z为Li离子、Na离子或K离子。
所述酯化液的添加量优选以酯化液中硫元素计占聚酯组合物总量的1000～3500ppm。
所述碱金属化合物优选醋酸锂、氢氧化钾或氢氧化钠中的一种或几种，其添加量以其中碱金属元素计优选相对于聚酯组合物总量的10～1000ppm。
所述如式3所示磺酸盐化合物和乙二醇反应得到的酯化液优选在聚合反应开始以后添加。
本发明所述的聚合物具有优异阳离子可染性和强度，且其中二甘醇和不溶性化合物含量少，可以抑制纺丝时滤压的上升。
具体实施方式
现有技术中，一般通过在聚酯中共聚含有磺酸盐基团的阳离子可染成分，如间苯二甲酸-5-磺酸盐等，从而赋予聚酯阳离子可染性能。但是，由于磺酸盐基 团分布在聚酯分子链的中间，磺酸盐基团在聚酯中容易发生物理交联，导致聚酯的粘度上升、强度降低。同时，也会导致聚酯的耐水解性变差。
为了克服上述问题，本发明所使用的阳离子可染成分为如式3所示的磺酸盐化合物，
Figure PCTCN2021099564-appb-000003
式3中，Y为碳原子数2～20的烷基、苯基或烷基苯，Z为Li离子、Na离子或K离子。
所述如式3所示的磺酸盐化合物仅含有一个羟基反应基团，在聚酯中该磺酸盐化合物主要接在分子链末端，分子链中间没有相互作用的物理交联基团，因此能保证获得的聚酯组合物具有较高的分子量和较好的强度。
所述如式3所示的磺酸盐化合物，具体可以举例的有2-羧基苯磺酸钠、2-羧基苯磺酸钾、3-羧基苯磺酸钠、3-羧基苯磺酸锂、4-羧基苯磺酸钠、2-磺酸钠苯甲酸甲酯、3-磺酸钠苯甲酸甲酯、4-磺酸钠苯甲酸甲酯、2-磺酸钠苯甲酸乙酯、2-磺酸钾苯甲酸乙二醇酯、3-磺酸钠苯甲酸乙酯、4-磺酸钠苯甲酸乙二醇酯、3-磺酸锂苯甲酸乙二醇酯等，其中优选3-羧基苯磺酸钠。
添加了阳离子可染成分如式3所示磺酸盐化合物的聚酯组合物中，含有如式1所示磺酸盐基团，
Figure PCTCN2021099564-appb-000004
式1中，Y为碳原子数2～20的烷基、苯基或烷基苯，Z为Li离子、Na离子或K离子。
本发明所述聚酯组合物中如式1所示磺酸盐基团的含量，以硫元素计占聚酯组合物的1000～5000ppm。当聚酯组合物中如式1所示磺酸盐基团的含量低于1000ppm时，所得产品在后续的染色过程中难以达到满意的色彩浓度；当聚酯组合物中如式1所示磺酸盐基团的含量高于5000ppm时，会抑制聚酯分子链的增长，聚合体系还未达到目标粘度就终止聚合，不能获得物性良好的聚酯组合物。从染色性以及聚酯组合物物性综合考虑，所述如式1所示磺酸盐基团的含量优选以硫元素计占聚酯组合物的1000～3500ppm。
虽然如式3所示单羧基磺酸盐化合物的使用可以提高聚酯组合物的分子量和强度，但是也容易导致二甘醇含有量的增加，聚酯组合物的耐热氧化性能变差。 为了抑制二甘醇的增加，本发明在聚酯组合物中添加了碱性化合物，所述碱金属化合物可以是氢氧化钾、氢氧化钠、氢氧化镁、氢氧化锂、醋酸镁、醋酸钾、醋酸锂、碳酸钾、碳酸钙、碳酸镁、六偏磷酸钠等，其中优选醋酸锂、氢氧化钾、氢氧化钠。所述碱金属化合物可以单独添加，也可以混合添加。
本发明所述聚酯组合物中二甘醇含量超过5.0wt％，会导致聚酯组合物的耐热氧化性能变差，同时使聚酯组合物的规整性变差，后期纤维的蠕变不可逆部分增加；如果所述聚酯组合物中二甘醇的含量低于0.8wt％，聚酯组合物的结构会变得紧密，影响染料和可染位置的结合，进一步影响染色的均匀性和稳定性。
因此，为了保证本发明聚酯组合物中二甘醇含量在合适的范围之内，所述碱金属化合物的添加量以其中碱金属元素计优选相对于聚酯组合物总量的10～1000ppm。当碱金属化合物的添加量太多时，过多的碱金属化合物会使聚酯组合物的色调变差；当金属碱化合物的添加量太低时，不能有效的抑制二甘醇的生成。
然而，所述碱金属化合物会和如式3所示磺酸盐化合物反应，生成如式2所示化合物，
Figure PCTCN2021099564-appb-000005
式2中，M和Z分别为Li离子、Na离子或者K离子，Y为碳原子数2～20的烷基、苯基或烷基苯。
所述如式2所示化合物不溶于聚酯组合物，在熔融纺丝阶段会成为异物，使得熔融纺丝时的滤压上升，缩短纺丝工程中的滤网更换周期，增加了纺丝成本。因此，为了使得聚酯组合物达到良好的可纺性、减少纺丝成本，本发明在添加如式3所示磺酸盐化合物时，以其和乙二醇的酯化液的形式添加，并通过提高反应率来降低末端羧基值，从而降低碱金属化合物和如式3所示磺酸盐化合物的反应几率，使得聚酯组合物中如式2所示化合物的含量以硫元素计相对于式1所示磺酸盐基团总量的10.0mol％以下，优选5.0mol％以下。
具体的，如式3所示磺酸盐化合物和乙二醇所形成的酯化物如式4所示，
Figure PCTCN2021099564-appb-000006
式4中，Y为碳原子数2～20的烷基、苯基或烷基苯，Z为Li离子、Na离子或者K离子。
所述酯化液的添加量以酯化液中硫元素计相对于聚酯组合物总量为1000～ 5000ppm。当酯化液的添加量量低于1000ppm时，所得产品在后续的染色过程中难以达到满意的色彩浓度；当酯化液的添加量高于5000ppm时，会抑制聚酯分子链的增长，造成聚合打头现象，所得聚酯组合物的分子量小，物性不良。从染色性以及聚酯组合物物性综合考虑，所述酯化液的添加量以酯化液中硫元素计相对于聚酯组合物总量优选1000～3500ppm。
本发明所述阳离子可染聚酯组合物的制备方法为，首先由芳香族二元羧酸或其酯化衍生物与乙二醇经过酯化或酯交换反应得到低聚物，然后将所得低聚物进行聚合反应得到聚酯组合物。在得到所述聚酯组合物之前的任意阶段添加由如式3所示磺酸盐化合物和乙二醇反应得到的酯化液以及碱金属化合物，所述酯化液的酯化反应率在95％以上，
Figure PCTCN2021099564-appb-000007
式3中，Y为碳原子数2～20的烷基、苯基或烷基苯，Z为Li离子、Na离子或K离子。
所述酯化液的酯化率在95％以上，如果所述酯化液的酯化率低于95％，会导致如式2所示化合物的大量生成，熔融纺丝时的滤压上升，缩短纺丝工程中的滤网更换周期，大大的增加了成本。
所述如式3所示磺酸盐化合物和乙二醇反应得到的酯化液可以在得到所述聚酯组合物之前的任意阶段添加，比如酯化或者酯交换反应阶段、聚合反应过程中等。为了获得更高的聚合度以及抑制易容出的磺酸盐类低聚物的产生，所述如式3所示磺酸盐化合物和乙二醇反应得到的酯化液优选在聚合反应开始以后添加。
本发明所述芳香族二元羧酸或其酯化衍生物可以是对苯二甲酸、间苯二甲酸酸、萘二甲酸甲酸、对苯二甲酸二甲酯、间苯二甲酸二甲酯、萘二甲酸二甲酯、邻苯二甲酸二甲酯等，其中优选对苯二甲酸或对苯二甲酸二甲酯。
所述酯化反应，可以是在预先存在低聚物的酯化反应槽中，一边连续添加摩尔比为1.05～1.50的乙二醇和芳香族二元羧酸的浆料，一边进行酯化反应；也可以是在预先存在低聚物的酯化反应槽中，在酯化反应开始前，将乙二醇和芳香族二元羧酸全部添加后，然后再进行酯化反应。
所述酯交换反应，可以通过调整乙二醇和芳香族二元羧酸酯化衍生物的摩尔比为在1.50～2.50范围内，以控制合适的酯交换反应速度。
所述酯交换反应催化剂可以是各种公知的催化剂，例如钴、镁、锰、钛等金属的氧化物或者其醋酸盐，可以混合使用也可以单独使用。
所述阳离子可染聚酯组合物制备方法中使用的聚合催化剂可以是公知的各种聚合催化剂。例如锑化合物、锗化合物、钛化合物等。这些催化剂可以混合使用也可以单独使用。
在本发明所述聚酯组合物中，除了芳香族二元羧酸、脂肪族二元醇以及如式1所示磺酸盐基团外，还可以添加其他的共聚物质，如聚醚或者脂肪族二元酸。由于如式2所示化合物在聚醚或者脂肪族二元酸中有一定的溶解性，通过在聚酯组合物中共聚聚醚或者脂肪族二元酸可有效减少如式2所示化合物在聚酯组合物中的析出量，从而进一步改善聚合滤压。另外通过添加聚醚或者脂肪族二元酸还可以赋予聚酯组合物低温染色性能。所述聚醚可以是聚乙二醇、聚丙二醇、聚丁二醇等，所述脂肪族二元酸可以是环己烷二甲酸、间苯二甲酸、丁二酸、己二酸，戊二酸等。其中优选聚乙二醇或者环己烷二甲酸。所述聚乙二醇分子量优选600～6000g/mol，更优选600～3000g/mol。相对于聚酯组合物总量，聚醚或者脂肪族二元酸的添加量优选0.5～10.0wt％，更优选0.5～5.0wt％。
本发明的阳离子可染聚酯组合物制造用酯化及聚合反应装置，可以使用各种通常使用的反应装置。
为了进一步提高本发明阳离子可染聚酯组合物的耐热性和强度，在阳离子可染聚酯组合物的制备过程中，优选在聚合反应结束后再进行固相聚合。
对固相聚合的条件不做特别的限定，本领域的通常反应条件都可以。具体的，可以是将聚合反应得到的聚酯产物经预结晶处理后，在反应温度为200～240℃，反应压力1000Pa以下，反应时间100小时以下的条件下进行固相聚合以得到最终聚酯组合物。
本发明的阳离子可染聚酯组合物的物性良好，染色性优良，聚酯组合物的染色稳定性好。且通过控制阳离子染料可染成分酯化液的末端羧基的量，从而使得聚酯组合物中不溶性异物的含量低，聚酯熔融纺丝时的异物较少，纺丝过程中滤压上升少、滤网的更换周期长、成本低。
本发明各项指标的测定方法及评价方法如下：
(1)特性粘度(IV)
将聚酯组合物切片0.8g溶于10ml邻氯苯酚溶液中，在水浴温度为25±0.2℃条件下，使用乌氏粘度计来测定其特性粘度。
(2)不溶性化合物中硫元素含量
称取2g试样，用30ml六氟异丙醇进行溶解，然后使用4μm的滤纸将溶解液进行过滤，对滤纸上的硫元素的含量通过SEM-EDX进行定量分析。
(3)聚酯组合物中硫元素含量分析
通过SEM-EDX元素分析仪对聚合物中硫元素含量进行定量分析。
(4)染色稳定性评价
将聚酯组合物进行纺丝得到延伸丝，然后将得到的延伸纤维进行2根并丝，在22针距条件下制得袜筒，将此袜筒在染料(Blue.TR)3％owf、醋酸0.5ml/l、醋酸钠0.2g/l、浴比1:100的130℃的热水浴中染色60分。染色后的样品重叠成不透光状后用分光测色计(Datacolor Asia Pacific(H.K.)Ltd.制造的Datacolor 650)在CEI标准光源D65、10°角条件下进行测色得出L*。
(5)酯化液反应率的计算(羧基含量的测试)
称取0.5g试样用10ml邻甲酚溶解，用0.2mol/l的氢氧化钠通过电位滴定仪器测试羧基量。
(6)二甘醇测试
间苯二甲酸二乙二醇磺酸盐溶液中的二甘醇：称取0.5g试样加入10ml己二酸，通过LC测定，并通过内标法确定二甘醇含量。
聚酯中的二甘醇：称取0.5g试样加入乙醇胺加热溶解，加入10ml己二酸，通过LC测定，并通过内标法确定二甘醇含量。
(7)耐热性评价方法
称取8g的切片放入试管中，将其在300℃氮气下保温3小时进行加热处理，分别测试加热处理前后切片的羧基含量。如果加热处理前后羧基含量ΔCOOH(加热处理前COOH-加热处理后COOH)值大的话就表示聚酯的耐热性比较差。
(8)滤压差ΔPa
使用滤压测试用小型过滤性实验机进行测试。在一定的吐出量条件下，使阳离子可染聚酯通过滤网，滤网孔径为5μm，测试温度为聚酯的熔点+25℃，吐出量为10g/min，开始进料后30min时滤网前的压力记为初压Pa1，从初压开始的1小时后记录终了压力Pa2，则1小时的滤压上升值为ΔPa＝Pa2－Pa1。ΔPa越小则表示聚酯中异物越少，纺丝越稳定。
(9)纤维的强伸度积
强度和伸度测定参照JIS L1013：2010(化学纤维中长纤维实验方法)8.8.1 的基准算出。通过ORIENTEC Co.,RTC-1225A强伸度试验机测出强度和伸度，强伸度积＝强度×(伸度) 0.5。
下面将从列举的实施例和比较例对本发明的优点进行详细的说明。本发明并不限于下述的实施例。
实施例1
将对苯二甲酸(PTA)、乙二醇(EG)混合均匀后投入到反应釜中，于240～260℃进行酯化反应。酯化反应结束后，将反应产物移入缩聚釜，加入酯化率在99％的酯化液，然后再添加醋酸锂溶液，之后添加催化剂三氧化二锑以及热稳定剂磷酸三甲酯，于260℃～290℃进行聚合反应。待聚合物达到需要粘度后吐出、切粒，得到所需要的聚酯组合物。聚酯组合物的特性粘度IV为0.64dl/g,聚酯的滤压差为0.20MPa/h，DEG值在2.5％。
将上述切片在290℃进行熔融纺丝得到阳离子可染聚酯纱线。纤维中硫元素含量为2450ppm，热水处理后溶出水溶液中硫元素含量为4.7ppm，占聚酯组合物总的硫元素含量的0.19％。纤维的强伸度积为24，蓝色染料浓度3.0％o.w.f时，染色后的L值为25。
实施例2
变更芳香族二元羧酸或其酯化衍生物的种类，其它条件同实施例1制备得到阳离子可染聚酯组合物。具体物性见表1。
实施例3～6
变更如式3所示磺酸盐的添加量，其它条件同实施例1制备得到阳离子可染聚酯组合物。具体物性见表1。
实施例7
变更如式3所示磺酸盐酯化液的反应率，也就是变更磺酸盐酯化液的末端羧基值，其它条件同实施例1制备得到阳离子可染聚酯组合物。具体物性见表1。
实施例8～12
变更碱金属化合物醋酸锂的添加量，其它条件同实施例1制备得到阳离子可染聚酯组合物。具体物性见表1和表2。
实施例13～14
变更碱金属化合物的种类，其它条件同实施例1制备得到阳离子可染聚酯组合物。具体物性见表2。
实施例15～16
变更如式3所示磺酸盐的种类，其它条件同实施例1制备得到阳离子可染聚酯组合物。具体物性见表2。
实施例17
聚合反应结束后，在反应温度为230℃，反应压力50Pa，反应时间80小时以下的条件下进行固相聚合，其它条件同实施例1制备得到阳离子可染聚酯组合物，具体物性见表2。
比较例1
直接添加磺酸盐3-羧基苯磺酸钠，其它条件同实施例1制备得到阳离子可染聚酯。具体物性见表3。
比较例1中，由于直接添加了未酯化的3-羧基苯磺酸钠，导致聚酯组合物中如式2所示的不溶性化合物的量太多，最终聚酯熔融滤压测试时的异物较多，滤压差ΔPa比较大、纺丝越不稳定。
比较例2
直接添加未酯化的3-羧基苯磺酸钠单体，不添加碱金属化合物，其它条件同实施例1制备得到阳离子可染聚酯。具体物性见表3。
由于直接添加了未酯化的3-羧基苯磺酸钠单体，末端的羧基较多，整个聚合物体系呈酸性条件，在不加入DEG抑制剂碱金属化合物条件下，容易生成过多的二甘醇，二甘醇会导致聚合物的耐热性变差，而且容易导致聚合物出现打头现象，从而聚酯的最终IV较低。
比较例3
添加反应率在99％的磺酸盐酯化液，但是不加入碱金属化合物，其它条件同实施例1制备得到阳离子可染聚酯。具体物性见表3。
虽然是反应率在99％的酯化液，游离的酸性离子较少，但是由于过量EG较多，在不加入DEG抑制剂碱金属化合物条件下，还是容易生成过多的二甘醇，二甘醇会导致聚合物的耐热性变差，最终聚酯的物性差。
比较例4～6
变更磺酸盐酯化液的反应率，其它条件同实施例1制备得到阳离子可染聚酯组合物。具体物性见表3。
虽然是3-羧基苯磺酸钠经过酯化，但是由于反应率较低，末端羧基量很大，导致聚酯组合物中如式2所示的不溶性化合物的量太多，最终聚酯熔融滤压测试时的异物较多，滤压差ΔPa比较大、纺丝越不稳定。
比较例7～8
变更如式3所示磺酸盐的添加量，其它条件同实施例1制备得到阳离子可染聚酯组合物。具体物性见表3。
磺酸盐的添加量过低，会导致染色性很差，染不出需要的色调。磺酸盐的添加量过高，会导致所得聚酯组合物的分子量小，物性不良，纱线的强度太低。
Figure PCTCN2021099564-appb-000008
Figure PCTCN2021099564-appb-000009
Figure PCTCN2021099564-appb-000010
Figure PCTCN2021099564-appb-000011

Claims (9)

  1. 阳离子可染聚酯组合物，主要由芳香族二元羧酸结构单元和脂肪族二元醇结构单元构成，其特征是：该聚酯组合物中含有如式1所示磺酸盐基团，且如式1所示磺酸盐基团的含量以硫元素计占聚酯组合物总量的1000～5000ppm；如式2所示化合物的含量以硫元素计相当于式1所示磺酸盐基团总量的10.0mol％以下；该聚酯组合物中二甘醇含量相对于聚酯组合物总量为0.8～5.0wt％；
    Figure PCTCN2021099564-appb-100001
    Figure PCTCN2021099564-appb-100002
    式1和式2中，Y为碳原子数2～20的烷基、苯基或烷基苯，Z和M分别为Li离子、Na离子或K离子。
  2. 根据权利要求1所述的阳离子可染聚酯组合物，其特征是：所述如式1所示磺酸盐基团的含量以硫元素计占聚酯组合物总量的1000～3500ppm。
  3. 根据权利要求1或2所述的阳离子可染聚酯组合物，其特征是：所述如式2所示的化合物的含量以硫元素计相当于式1所示磺酸盐基团总量的5.0mol％以下。
  4. 权利要求1所述阳离子可染聚酯组合物的制备方法，首先由芳香族二元羧酸或其酯化衍生物与脂肪族二元醇经过酯化或酯交换反应得到低聚物，然后将所得低聚物进行聚合反应得到聚酯组合物，其特征是：在得到所述聚酯组合物之前的任意阶段添加由如式3所示磺酸盐化合物和乙二醇反应得到的酯化液，以及碱金属化合物，所述酯化液的酯化反应率在95％以上，
    Figure PCTCN2021099564-appb-100003
    式3中，Y为碳原子数2～20的烷基、苯基或烷基苯，Z为Li离子、Na离子或K离子。
  5. 根据权利要求4所述阳离子可染聚酯组合物的制备方法，其特征是：所述酯化液的添加量以酯化液中硫元素计占聚酯组合物总量的1000～3500ppm。
  6. 根据权利要求4或5所述阳离子可染聚酯组合物的制备方法，其特征是： 所述碱金属化合物为醋酸锂、氢氧化钾或氢氧化钠中的一种或几种。
  7. 根据权利要求4或5所述阳离子可染聚酯组合物的制备方法，其特征是：所述碱金属化合物的添加量以其中碱金属元素计为相对于聚酯组合物总量的10～1000ppm。
  8. 根据权利要求4或5所述阳离子可染聚酯组合物的制备方法，其特征是：所述如式3所示磺酸盐化合物和乙二醇反应得到的酯化液在聚合反应开始以后添加。
  9. 根据权利要求1所述阳离子可染聚酯在纤维中的应用。
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