阅读说明：本技术 含阳离子成分的化合物及其制备方法和用途 (Compound containing cation component and preparation method and application thereof ) 是由 吴亚薇 陈彬彬 成娟 望月克彦 于 2019-02-01 设计创作，主要内容包括：本发明公开了一种含阳离子成分的化合物及其制备方法和用途。该化合物的分子链中包括的间苯二甲酸-5-磺酸盐结构单元,数均分子量为350～2500g/mol的双酚A聚氧乙烯醚结构单元,及二元醇结构单元。该含阳离子成分的化合物可在常温下保存,不会有结晶物析出,并且与聚酯的相容性好,后续聚酯熔融纺丝滤压上升少、纺丝工程中滤网的更换周期长、成本低。(The invention discloses a compound containing a cation component, a preparation method and application thereof. The molecular chain of the compound comprises an isophthalic acid-5-sulfonate structural unit, a bisphenol A polyoxyethylene ether structural unit with the number average molecular weight of 350-2500 g/mol and a dihydric alcohol structural unit. The compound containing the cationic component can be stored at normal temperature, does not precipitate crystals, has good compatibility with polyester, and has the advantages of little filtration pressure rise of subsequent polyester melt spinning, long replacement period of a filter screen in the spinning engineering and low cost.)

1. A compound containing a cationic component, characterized by: the molecular chain of the compound comprises an isophthalic acid-5-sulfonate structural unit shown as a formula 1, a bisphenol A polyoxyethylene ether structural unit shown as a formula 2 and having a number average molecular weight of 350-2500 g/mol, and a dihydric alcohol structural unit shown as a formula 3, wherein the number average molecular weight of the compound containing a cation component is 900-4000 g/mol;

in the formula 1, the compound is shown in the specification,

in the formula (2), the first and second groups,

in the formula 3, the first step is,

in the formula 1, X is sodium ion, potassium ion or lithium ion; in the formula 2, n and m are integers of 1-50 respectively, n + m is more than or equal to 2 and less than or equal to 50, and y is an integer of 2-6.

2. The cationic moiety-containing compound according to claim 1, wherein: the mol ratio of the isophthalic acid-5-sulfonate structural unit to the bisphenol A polyoxyethylene ether structural unit is 1: 0.1-2.0.

3. The cationic moiety-containing compound according to claim 1 or 2, characterized in that: the mol ratio of the isophthalic acid-5-sulfonate structural unit to the diol structural unit shown as the formula 3 is 1: 0.5-2.0.

4. A method for preparing the cationic component-containing compound according to claim 1, characterized by: adding m-phthalic acid-5-sulfonate or an esterified product thereof, bisphenol A polyoxyethylene ether and linear chain dihydric alcohol with 2-6 carbon atoms into a reaction kettle, then adding a catalyst, and reacting at 170-240 ℃ for 2-5 hours to obtain a compound containing a cationic component with the number average molecular weight of 900-4000 g/mol; the sulfonate is sodium sulfonate, potassium sulfonate or lithium sulfonate.

5. The method for preparing a compound of a cationic component according to claim 4, wherein: the molar ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the bisphenol A polyoxyethylene ether is 1: 0.1-5.0.

6. The method for producing the cationic component-containing compound according to claim 4 or 5, characterized in that: the mol ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the linear chain dihydric alcohol with the carbon number of 2-6 is 1: 2.0-20.0.

7. Use of the cationic moiety-containing compound of claim 1 in polyesters.

Technical Field

The invention relates to a compound containing a cationic component, which contains an isophthalic acid-5-sulfonate structural unit, a bisphenol A polyoxyethylene ether structural unit and a dihydric alcohol structural unit, and a preparation method and application thereof.

Background

The polyester has excellent physical and mechanical properties, but the polyester has poor dyeing effect because the molecular chain structure of the polyester is compact, the crystallinity and the orientation degree are higher, the polarity is smaller, the hydrophilicity is poor, and gaps which can properly contain dye molecules do not exist among long-chain molecules of the polyester.

Among the methods for improving the cationic dyeing effect of polyesters, the copolymerization of a third monomer, isophthalic acid-5-sulfonate, terephthalic acid-5-sulfonate or their esterified derivatives, in polyesters is most commonly used. For example, in patent specification Hei 11-238518, the prepared sulfonate is added into polyester to achieve the effect of cationic dyeing, but the sulfonate monomer self-polymerizes and has poor compatibility with the polyester, so that foreign matters formed have influence on the later-stage polyester spinning filtration pressure.

In patent 200880001148.X, polyester copolymer containing sulfonate compound and polyethylene glycol is synthesized to improve dyeability, but linear diol is used in the polyester copolymer, and the synthesized polyester copolymer has large molecular weight, which is poor in compatibility with polyester after being added in polyester polymerization, resulting in foreign matter formation and affecting spinning filtration pressure.

Disclosure of Invention

The invention aims to provide a compound containing a cationic component, which can improve the cationic dyeability of polyester and inhibit foreign matters, and a preparation method and application thereof. The compound containing the cationic component has good compatibility with polyester, the filtration pressure rise of subsequent polyester melt spinning is less, the replacement period of a filter screen in spinning engineering is long, the cost is low, and the compound phase containing the cationic component can be stored at normal temperature without crystal precipitation.

The technical solution of the invention is as follows:

a compound containing a cationic component comprises an isophthalic acid-5-sulfonate structural unit shown as a formula 1, a bisphenol A polyoxyethylene ether structural unit shown as a formula 2 and having a number average molecular weight of 350-2500 g/mol, and a dihydric alcohol structural unit shown as a formula 3, wherein the number average molecular weight of the compound containing the cationic component is 900-4000 g/mol;

in the formula 1, the compound is shown in the specification,

in the formula (2), the first and second groups,

in the formula 3, the first step is,

in the formula 1, X is sodium ion, potassium ion or lithium ion; in the formula 2, n and m are integers of 1-50 respectively, n + m is more than or equal to 2 and less than or equal to 50, and y is an integer of 2-6.

The preferable molar ratio of the isophthalic acid-5-sulfonate structural unit to the bisphenol A polyoxyethylene ether structural unit is 1: 0.1-2.0. The mol ratio of the isophthalic acid-5-sulfonate structural unit to the diol structural unit shown as the formula 3 is preferably 1: 0.5-2.0.

The preparation method of the compound containing the cationic component comprises the steps of adding isophthalic acid-5-sulfonate or an esterified product thereof, bisphenol A polyoxyethylene ether and linear chain dihydric alcohol with 2-6 carbon atoms into a reaction kettle, adding a catalyst, and reacting at 170-240 ℃ for 2-5 hours to obtain the compound containing the cationic component with the number average molecular weight of 900-4000 g/mol; the sulfonate is sodium sulfonate, potassium sulfonate or lithium sulfonate.

The preferable molar ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the bisphenol A polyoxyethylene ether is 1: 0.1-5.0. The mol ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the linear chain dihydric alcohol with the carbon number of 2-6 is preferably 1: 2.0-20.0.

The compound containing the cationic component can be applied to the preparation of polyester, has good compatibility with the polyester, little filtration pressure rise of subsequent polyester melt spinning, long replacement period of a filter screen in spinning engineering and low cost, and can be stored at normal temperature without crystal precipitation.

Detailed Description

In the general art, isophthalic acid-5-sulfonate or its esterified derivative is copolymerized in polyester in order to impart cationic dyeability to polyester. However, the isophthalic acid-5-sulfonate or the esterified derivative thereof has poor compatibility with polyester, and self-polymerization reaction is easy to occur in the polymerization process, so that the filtration pressure in the polyester preparation process and the subsequent processing process is increased, yarn breakage is easy to occur, and the strength of the prepared yarn is low.

In order to solve the problems, the application provides a compound containing a cationic component, wherein a molecular chain of the compound comprises an isophthalic acid-5-sulfonate structural unit shown as a formula 1, a bisphenol A polyoxyethylene ether structural unit shown as a formula 2 and having a number average molecular weight of 350-2500 g/mol, and a dihydric alcohol structural unit shown as a formula 3, and the number average molecular weight of the compound containing the cationic component is 900-4000 g/mol;

in the formula 1, the compound is shown in the specification,

in the formula (2), the first and second groups,

in the formula 3, the first step is,

in the formula 1, X is sodium ion, potassium ion or lithium ion; in the formula 2, n and m are integers of 1-50 respectively, n + m is more than or equal to 2 and less than or equal to 50, and y is an integer of 2-6.

Compared with the prior art, the compound containing the cationic component introduces a bisphenol A polyoxyethylene ether structural unit in a molecular chain, and improves the compatibility of the compound containing the cationic component and polyester through the bisphenol A with a benzene ring. Meanwhile, due to the introduction of the benzene ring structure, the steric hindrance in molecules and among molecules of the compound containing the cationic components is increased, so that the mutual attraction of the compound containing the cationic components is reduced, the agglomeration of the compound containing the cationic components is effectively inhibited, the generation of foreign matters in the polyester is reduced, and the subsequent spinning filtration pressure of the cationic dyeable polyester is improved.

The number average molecular weight of the structural unit of the bisphenol A polyoxyethylene ether is 350-2500 g/mol. If the number average molecular weight of the structural unit of bisphenol A polyoxyethylene ether is more than 2500g/mol, the compatibility of the compound containing the cationic component and the polyester is poor when the compound is added into the polyester for use; if the number average molecular weight of the structural unit of the bisphenol A polyoxyethylene ether is less than 350g/mol, the effect of improving the precipitation of crystal substances of the compound containing the cationic component under the condition of normal-temperature storage is not obvious, and the dyeing property of the cationic dyeable polyester added with the compound containing the cationic component cannot be further improved.

The number average molecular weight of the compound containing the cation component is 900-4000 g/mol. If the number average molecular weight of the cationic component-containing compound is more than 4000g/mol, the cationic component-containing compound has too high a viscosity, which reduces its dispersibility in the polyester, causes the cationic component-containing compound to coagulate, increases foreign matters in the polyester, and finally affects the spinning filtration pressure of the subsequent cationic-dyeable polyester. The number average molecular weight of the cation component-containing compound is preferably 1000 to 3000 g/mol.

In the molar ratio of the isophthalic acid-5-sulfonate unit to the bisphenol A polyoxyethylene ether structural unit, the molar amount of the isophthalic acid-5-sulfonate unit is 1, when the bisphenol A polyoxyethylene ether structural unit is too small, the compatibility of a compound containing a cationic component and polyester is poor, and when the compound containing the cationic component is added into the polyester, the compound containing the cationic component is coagulated, so that foreign matters in the polyester are increased, and the spinning filtration pressure of the cationic dyeable polyester is influenced finally; when the number of the bisphenol A polyoxyethylene ether structural units is too large, although the compatibility of the compound containing the cationic component and the polyester is good, and foreign matters are not easy to generate when the compound containing the cationic component is added into the polyester, the concentration of the isophthalic acid-5-sulfonate unit is reduced, when the compound containing the cationic component is added into the polyester, the addition amount of the compound containing the cationic component is increased, the cost is increased, and the cationic dyeable effect of the polyester is not good. The mol ratio of the isophthalic acid-5-sulfonate structural unit to the bisphenol A polyoxyethylene ether structural unit is preferably 1: 0.1-2.0.

In the molar ratio of the isophthalic acid-5-sulfonate unit to the diol unit shown in the formula 3, the molar weight of the isophthalic acid-5-sulfonate unit is 1, when the diol unit shown in the formula 3 is too low, the number average molecular weight of the generated compound containing the cationic component is too large, and when the compound containing the cationic component is added into the polyester, the compound containing the cationic component is not favorably dispersed, so that the compound containing the cationic component is coagulated, foreign matters in the polyester are increased, and the spinning filtration pressure of the cationic dyeable polyester is finally influenced. The mol ratio of the isophthalic acid-5-sulfonate structural unit to the diol structural unit shown as the formula 3 is preferably 1: 0.5-2.0, more preferably 1: 1.0-2.0, and most preferably 1: 1.5-2.0.

The dihydric alcohol unit shown as the formula 3 is a straight chain dihydric alcohol unit with 2-6 carbon atoms, and can be selected according to the category of target polyester. When the dye is used for dyeing modification of polyethylene terephthalate cation, the diol unit can be selected from glycol; when the dye is used for dyeing modification of polybutylene terephthalate cation, butanediol can be selected as the diol unit.

The invention also provides a preparation method of the compound containing the cation component, which comprises the following steps: adding m-phthalic acid-5-sulfonate or an esterified product thereof, bisphenol A polyoxyethylene ether and linear chain dihydric alcohol with 2-6 carbon atoms into a reaction kettle, then adding a catalyst, and reacting at 170-240 ℃ for 2-5 hours to obtain a compound containing a cationic component with the number average molecular weight of 900-4000 g/mol; the sulfonate is sodium sulfonate, potassium sulfonate or lithium sulfonate.

The above-mentioned catalyst is not particularly limited in the present invention, and is generally used as an esterification catalyst. Such as titanium-based catalysts: tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, tert-butyl titanate, and the like; acetate catalyst: lithium acetate, sodium acetate, zinc acetate, manganese acetate, calcium acetate, and the like; metal oxide catalyst: zinc oxide, tin oxide, stannous oxide, antimony trioxide, and the like.

The isophthalic acid-5-sulfonate ester is small molecular weight sulfonate such as isophthalic acid-5-sulfonate, isophthalic acid dimethyl ester-5-sulfonate, isophthalic acid monomethyl ester-5 sulfonate, isophthalic acid monoethyl ester-5-sulfonate, isophthalic acid diethylene glycol ester-5-sulfonate, isophthalic acid dibutylene glycol-5-sulfonate and the like; the terephthalic acid ester is micromolecular aromatic dicarboxylic acid ester such as dimethyl terephthalate, diethyl terephthalate, monomethyl terephthalate, monoethyl terephthalate and the like.

The reaction temperature of the method is 170-240 ℃, when the reaction temperature is lower than 170 ℃, the reaction is incomplete because of too low reaction temperature, and the obtained product contains a large amount of m-phthalic acid-5-sulfonate or an esterified substance thereof which do not participate in the reaction besides the compound containing the cation component, so that when the compound is added into polyester, foreign matters in the polyester are increased, and the spinning filtration pressure of the cation-dyeable polyester is influenced; when the reaction temperature is higher than 240 ℃, the formation of an isophthalic acid-5-sulfonate or an esterified product thereof self-polymer is promoted due to the overhigh temperature, the self-polymer has low compatibility with the polyester, and when the self-polymer is added into the polyester, foreign matters in the polyester are increased, so that the spinning filtration pressure of the cation dyeable polyester is influenced.

The reaction time of the method is 2-5 hours, and when the reaction time is less than 2 hours, the reaction is incomplete. When the reaction time is longer than 5 hours, the production efficiency is influenced, and long-time reaction can not only cause the generation of diol oligomer, but also influence the physical properties of the cation dyeable polyester; meanwhile, the long-time reaction can also cause the formation of an isophthalic acid-5-sulfonate or an esterified product of the isophthalic acid-5-sulfonate to form an autopolymer, and the autopolymer has low compatibility with the polyester and can influence the spinning filtration pressure of the cation dyeable polyester.

In the molar ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the bisphenol A polyoxyethylene ether, the molar amount of the isophthalic acid-5-sulfonate or the esterified product thereof is 1, when the bisphenol A polyoxyethylene ether is too little, the compatibility of a compound containing a cationic component and polyester is poor, and when the bisphenol A polyoxyethylene ether is added into the polyester, the compound containing the cationic component is coagulated, so that foreign matters in the polyester are increased, and the spinning filtration pressure of the cationic dyeable polyester is influenced finally; when the amount of the bisphenol A polyoxyethylene ether is too large, the compatibility of the compound containing the cationic component with the polyester is good, and foreign matters are not easily generated when the compound containing the cationic component is added to the polyester, but the concentration of the unit of isophthalic acid-5-sulfonate is reduced, and when the compound containing the cationic component is added to the polyester, the addition amount of the compound containing the cationic component is increased, so that not only the cost is increased, but also the cationic dyeable effect of the polyester is not good. The mol ratio of the m-phthalic acid-5-sulfonate or the esterified product thereof to the bisphenol A polyoxyethylene ether is preferably 1: 0.1-5.0.

In the molar ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the linear diol with 2-6 carbon atoms, when the addition total amount of the linear diol with 2-6 carbon atoms is too low, the number average molecular weight of the generated compound containing the cationic component is too large, and when the linear diol with 2-6 carbon atoms is added into the polyester, the compound containing the cationic component is not favorably dispersed, so that the coagulation is caused, foreign matters in the polyester are increased, and the spinning filtration pressure of the cationic dyeable polyester is finally influenced; when the amount of the diol to be added is too large, the concentration of the isophthalic acid-5-sulfonate or its ester in the system is too low, which is disadvantageous in production. The molar ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the total amount of the linear dihydric alcohol having 2 to 6 carbon atoms added is preferably 1: 2.0 to 20.0, and more preferably 1: 2.0 to 15.0.

One of the uses of the cationic component-containing compounds of the present invention is to add them to polyesters to impart cationic dyeability to the polyesters. The polyester may be polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, and the like. The linear diol having 2 to 6 carbon atoms may be ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, or the like, depending on the type of the polyester.

The method for synthesizing the cationic-dyeable polyester is not particularly limited, and may be a direct polymerization method or an ester exchange method depending on the raw material, or a batch polymerization method or a continuous polymerization method depending on the polymerization process. According to the conventional polyester preparation method, the reaction temperature, pressure and catalyst can be selected properly in the esterification or ester exchange reaction stage and the polycondensation reaction stage. For example, the catalyst may be an antimony catalyst, a titanium-based catalyst, an alkali metal catalyst, or the like. Depending on the desired function, a heat stabilizer, a delustering agent, a toner, and the like may be added to the polyester.

The cationic component-containing compound of the present invention may be added in the esterification stage of the polyester direct polymerization method, or may be added before the polymerization reaction is completed, preferably before the polymerization reaction is completed. The addition may be carried out before the completion of the polymerization reaction in the transesterification process, and preferably before the completion of the polymerization reaction in the esterification process. The content of the cationic component-containing compound in the polyester may be 0.05 to 5.00% by weight, calculated as elemental sulphur, relative to the total amount of the final cationic dyeable polyester. In addition to the cationic component-containing compound, other additives may be used in combination with the polyester to improve the properties of the polyester, for example, polyethylene glycol may be added to further improve the antistatic properties of the polyester.

The compound containing the cationic component has the characteristics of easy storage and good compatibility with polyester. The cation dyeable polyester prepared by using the above-mentioned additive has the advantages of bright color, firm dyeing degree and the like which are generally obtained by using isophthalic acid-5-sulfonate or an esterified monomer thereof, and also has the advantages of low foreign matter content and good spinnability.

The present invention will be described in more detail by way of examples. The physical property parameters in the examples were measured by the following methods.

(1) Dyeing property of cation dyeable polyester

First, a tubular knitted fabric was prepared from a cationic dyeable polyester fiber, and then dyed using a commercial cationic blue dye CB546 (1% owf) and a leveling assistant YK91 with a dyeing assistant of 1g/L, YL15 with a dyeing assistant of 1g/L at 120 ℃ for 60 minutes at a bath ratio of 1: 30, and then dyed at 80 ℃ with 0.6 g/L of sodium hydroxide and 2 g/L of sodium hydrogen sulfite. The tubular knitted fabric was treated under the conditions for 20 minutes, washed with water and dried with air, and the brightness L value of the fabric was measured, and the lower the L value, the better the dyeing effect.

(2) Differential filtration pressure Δ Pa

The test was carried out using a small filterability tester for filter pressure test. Under the condition of a certain discharge quantity, enabling the cation-dyeable polyester to pass through a filter screen, wherein the aperture of the filter screen is 5 mu m, the testing temperature is the melting point + 25 ℃ of the polyester, the discharge quantity is 10g/min, the pressure before the filter screen is recorded as initial pressure Pa1 at 30min after the feeding is started, the final pressure Pa2 is recorded after 6hr from the initial pressure, and the filter pressure rise value of 6hr is delta Pa-2-Pa 1. The smaller Δ Pa means that the foreign matter in the polyester is smaller and the spinning is more stable.

(3) The content of each structural unit in the compound containing the cation component

By H¹NMR Nuclear magnetic testing of the cationic component-containing compound, the molar ratio of each unit being determined by the ratio of the peak area of the characteristic peak of the hydrogen element on benzene in the isophthalic acid-5 sulfonate unit and the peak area of the characteristic peak of the hydrogen element on the alkyl group in the linear diol.

(4) Molecular weight of compound containing cationic component

0.5g of the compound containing the cationic component was taken, dissolved in chloroform, filtered, and the molecular weight of the compound containing the cationic component was measured by Gel Permeation Chromatography (GPC).

(5) Sulfur element content in polyester

After 5g of the copolyester was pressed into a sheet, the intensity of the element was measured using a fluorescent X-ray analyzer, and the result was converted using a detection line previously made from a sample having a known sulfur content.

(6) Precipitation ratio of crystals

100g of the compound containing the cationic component was taken out and left at room temperature for 1 month, followed by filtration, and the resulting solid matter was vacuum-dried for 5 hours and weighed, and the ratio of the weight of the solid matter to the weight of the compound (100 g) taken out before was the precipitation ratio of the crystal.

The technical solutions of the present invention are described in more detail below by way of specific embodiments, but the present invention is not limited to these embodiments.