CN110964184A - Oligomer containing sulfonate group and preparation method and application thereof - Google Patents
Oligomer containing sulfonate group and preparation method and application thereof Download PDFInfo
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- CN110964184A CN110964184A CN201811154039.3A CN201811154039A CN110964184A CN 110964184 A CN110964184 A CN 110964184A CN 201811154039 A CN201811154039 A CN 201811154039A CN 110964184 A CN110964184 A CN 110964184A
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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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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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
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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
Abstract
The invention discloses an oligomer containing sulfonate groups, a preparation method and application thereof. The molecular chain of the oligomer comprises an isophthalic acid-5-sulfonate unit, a terephthalic acid unit, a dihydric alcohol unit and a polyethylene glycol unit. The oligomer phase containing sulfonate groups can be stored at normal temperature, does not have crystal precipitation, has good compatibility with polyester, can be added into polyester to improve the cationic dyeing property of the polyester, and has the advantages of little increase of filtration pressure of subsequent polyester melt spinning, long replacement period of a filter screen in spinning engineering and low cost.
Description
Technical Field
The invention relates to an oligomer containing a sulfonate group, which contains an isophthalic acid-5-sulfonate structural unit, a terephthalic acid structural unit, a diol structural unit and a polyethylene glycol 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, Japanese patent laid-open Nos. 2000-355831, 2003-301328 and Chinese patent CN204999829U all disclose that cationic dyeability is imparted to the final polyester by adding isophthalic acid-5-sulfonate or dimethyl isophthalate-5 sulfonate to the polymerization reaction of the polyester. However, the technical solutions disclosed in the above patents all have the influence of foreign matters formed on the filtration pressure of the later polyester spinning due to the self-polymerization of the isophthalic acid-5-sulfonate or dimethyl isophthalate-5 sulfonate monomer and the poor compatibility with the polyester.
Meanwhile, cationic modifier monomers such as dimethyl isophthalate-5-sodium Sulfonate (SIPM) and diethylene glycol isophthalate-5-sodium Sulfonate (SIPE) have poor stability, and crystals can be separated out after the monomers are placed at normal temperature for a period of time. Therefore, the storage temperature of the cationic modifier monomer needs to be above a certain value, increasing the transportation and storage costs.
Disclosure of Invention
The invention aims to provide an oligomer containing sulfonate groups and a preparation method thereof, wherein the oligomer can improve the cationic dyeability of polyester. The oligomer phase containing sulfonate groups can be stored at normal temperature, no crystal is separated out, the compatibility with polyester is good, the filtration pressure rise of subsequent polyester melt spinning is less, the replacement period of a filter screen in the spinning engineering is long, and the cost is low.
The technical solution of the invention is as follows:
an oligomer containing sulfonate groups comprises an isophthalic acid-5-sulfonate unit shown as a formula 1, a terephthalic acid unit shown as a formula 2, a dihydric alcohol unit shown as a formula 3 and a polyethylene glycol unit shown as a formula 4 in a molecular chain, wherein the number average molecular weight of the polyethylene glycol unit is 100-2000 g/mol; (ii) a The number average molecular weight of the oligomer is 1000-3000 g/mol;
-OCH2CH2OCH2CH2……OCH2CH2-a compound of the formula 4,
in the formula 1, X is sodium ion, potassium ion or lithium ion, and in the formula 3, n is an integer of 2-6.
The molar ratio of the isophthalic acid-5-sulfonate unit to the terephthalic acid unit is preferably 1: 0.1 to 30.0; the molar ratio of the total amount of moles of the isophthalic acid-5-sulfonate unit and the terephthalic acid unit to the diol unit is preferably 1: 1.3 to 2.0.
The mole ratio of the repeating structural unit of the polyethylene glycol to the isophthalic acid-5-sulfonate unit is preferably 0.5-10.0.
The invention also discloses a preparation method of the oligomer containing sulfonate groups, which comprises the steps of adding 5-sulfoisophthalate or an esterified product thereof, terephthalic acid or an esterified product thereof, linear chain dihydric alcohol with 2-6 carbon atoms and polyethylene glycol into a reaction kettle, adding a catalyst, and reacting at 150-240 ℃ for 1-5 hours to obtain the oligomer containing sulfonate groups with the number average molecular weight of 1000-3000 g/mol; the sulfonate is sodium sulfonate, potassium sulfonate or lithium sulfonate.
The molar ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the terephthalic acid or the esterified product thereof is preferably 1: 0.1 to 30; the molar ratio of the total amount of the isophthalic acid-5-sulfonate or the ester thereof and the terephthalic acid or the ester thereof to the linear diol having 2 to 6 carbon atoms is preferably 1: 1.3 to 20.0.
The molar ratio of the polyethylene glycol repeating unit structure to the S component is 0.5-10.0.
The oligomer containing sulfonate groups is easy to store, has good compatibility with polyester, can be added into polyester to improve the cationic dyeing property of the polyester, and has little filtration pressure rise, long service life of components and low cost in subsequent processing such as spinning.
Detailed Description
In the general art, cationic dyes that impart dyeability to polyesters are copolymerized in polyesters isophthalic acid-5-sulfonate or esterified derivatives thereof. 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 above problems, the present application provides an oligomer containing a sulfonate group, wherein a molecular chain of the compound containing a sulfonate group comprises four structural units, i.e., an isophthalic acid-5-sulfonate structural unit shown in formula 1, a terephthalic acid structural unit shown in formula 2, a diol unit shown in formula 3, and a polyethylene glycol unit shown in formula 4,
-OCH2CH2OCH2CH2……OCH2CH2-a compound of the formula 4,
in the formula 1, X is sodium ion, potassium ion or lithium ion, and in the formula 3, n is an integer of 2-6.
Compared with the prior art, the oligomer containing the sulfonate group introduces a terephthalic acid structural unit into a molecular chain, so that the compatibility of the oligomer containing the sulfonate group and polyester is improved. Meanwhile, due to the introduction of the benzene ring structure, the steric hindrance in molecules and among molecules of the oligomer containing the sulfonate group is increased, so that the mutual attraction of the oligomer containing the sulfonate group is reduced, the agglomeration of the oligomer containing the sulfonate group is effectively inhibited, the generation of foreign matters in the polyester is reduced, and the spinning filtration pressure of the subsequent cationic dyeable polyester is improved.
The number average molecular weight of the oligomer containing sulfonate groups is 1000-3000 g/mol. If the number average molecular weight of the oligomer containing sulfonate groups is more than 3000g/mol, the viscosity of the oligomer containing sulfonate groups is too high, which reduces the dispersibility of the oligomer containing sulfonate groups in polyester, causes the oligomer containing sulfonate groups to be condensed, increases foreign matters in polyester, and finally influences the spinning filtration pressure of subsequent cationic dyeable polyester. The number average molecular weight of the oligomer containing sulfonate groups is preferably 1000 to 2000 g/mol.
In the molar ratio of the isophthalic acid-5-sulfonate unit to the terephthalic acid unit, the molar amount of the isophthalic acid-5-sulfonate unit is 1, when the amount of the terephthalic acid unit is too small, the compatibility of the oligomer containing sulfonate groups and the polyester is poor, and when the isophthalic acid-5-sulfonate unit and the terephthalic acid unit are added into the polyester, the oligomer containing sulfonate groups 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 terephthalic acid unit is too large, the sulfonate group-containing oligomer has good compatibility with the polyester and is not likely to generate foreign matters when added to the polyester, but when the sulfonate group-containing oligomer has a reduced concentration of the isophthalic acid-5-sulfonate unit, the amount of the sulfonate group-containing oligomer added to the polyester is increased, which not only increases the cost, but also has a poor cationic dyeability effect of the polyester. The molar ratio of the isophthalic acid-5-sulfonate unit and the terephthalic acid unit in the present invention is preferably 1: 0.1 to 30.0, more preferably 1: 0.5 to 20.0.
In the molar ratio of the total mole of the isophthalic acid-5-sulfonate unit and the terephthalic acid unit to the diol unit, the total mole of the isophthalic acid-5-sulfonate unit and the terephthalic acid unit is 1, when the diol unit is too low, the number average molecular weight of the generated oligomer containing sulfonate groups is too large, and when the oligomer containing sulfonate groups is added into the polyester, the oligomer containing sulfonate groups is not favorably dispersed, so that the oligomer is coagulated, foreign matters in the polyester are increased, and the spinning filtration pressure of the cationic dyeable polyester is finally influenced. The molar ratio of the total amount of moles of the isophthalic acid-5-sulfonate unit and the terephthalic acid unit to the diol unit in the present invention is preferably 1: 1.3 to 2.0, more preferably 1: 1.5 to 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.
A substance synthesized by an isophthalic acid-5-sulfonate unit, a terephthalic acid unit and a dihydric alcohol unit shown as a formula 3 has the defect that crystals are precipitated when the substance is stored at normal temperature, like cation dyeable modifier monomers such as SIPE and SIPM.
In order to solve the technical problems, the low polymer of the invention is copolymerized with polyethylene glycol, so that the precipitation of crystal substances under the condition of normal-temperature storage of the low polymer is improved, and the dyeing effect of the cation dyeable polyester added with the low polymer of the invention can be improved.
The number average molecular weight of the polyethylene glycol unit in the sulfonate group-containing oligomer is 100-2000 g/mol. When the number average molecular weight of the polyethylene glycol unit is more than 2000g/mol, the polyethylene glycol can be copolymerized into the oligomer only by increasing the reaction temperature of esterification or ester exchange, the formation of byproducts can be increased, the chroma of the oligomer is darker, and the chroma of the finally cationic dyeable polyester is also influenced; when the number average molecular weight of the polyethylene glycol unit is less than 100/mol, the effect of improving the precipitation of crystals of the oligomer under normal temperature storage is not obvious, and the dyeing property of the cation dyeable polyester added with the oligomer can not be further improved.
When the content of the polyethylene glycol unit is too low, the effect of improving the precipitation of crystals of the oligomer under normal-temperature storage is not achieved, and simultaneously, the precipitation of the crystals is not causedThe dyeing property of the cationic dyeable polyester added with the low polymer can be further improved; when the content of the polyethylene glycol unit is too high, the light resistance of the cationic dyeable polyester to which the oligomer of the present invention is added is poor. The content of the polyethylene glycol unit in the present invention is preferably 0.5 to 10.0, more preferably 1.0 to 5.0, in terms of a molar ratio of the repeating structural unit of polyethylene glycol to the isophthalic acid-5-sulfonate unit. The repeating structural unit of the polyethylene glycol is CH2CH2And O. For example, if the number average molecular weight of polyethylene glycol is 1000g/mol and the number of moles thereof is 1mol, the number of moles of the repeating structural unit of polyethylene glycol is 22.7 mol.
The invention also provides a preparation method of the oligomer containing the sulfonate group, which comprises the following specific steps: adding m-phthalic acid-5-sulfonate or an esterified substance thereof, terephthalic acid or an esterified substance thereof and linear chain dihydric alcohol with 2-6 carbon atoms into an esterification reaction kettle, then adding a catalyst, and reacting at 150-240 ℃ for 1-5 hours to obtain an oligomer containing a sulfonate group with the number average molecular weight of 100-4000 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 150-240 ℃, when the reaction temperature is lower than 150 ℃, 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 oligomer containing sulfonate groups, so that when the oligomer containing sulfonate groups is added into polyester, foreign matters in the polyester are increased, and the spinning filtration pressure of the cationic 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 invention is 1-5 hours, and when the reaction time is less than 1 hour, 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 terephthalic acid or the esterified product thereof, the molar amount of the isophthalic acid-5-sulfonate or the esterified product thereof is 1, when the amount of the terephthalic acid or the esterified product thereof is too small, the compatibility between the oligomer containing the sulfonate group and the polyester is poor, and when the terephthalic acid or the esterified product thereof is added to the polyester, the oligomer containing the sulfonate group is aggregated, so that foreign matters in the polyester are increased, and the spinning filtration pressure of the cation-dyeable polyester is finally influenced; when the amount of terephthalic acid or its esterified product is too large, the sulfonate group-containing oligomer has good compatibility with the polyester and is not likely to generate foreign matters when added to the polyester, but when the sulfonate group-containing oligomer has a reduced concentration of isophthalic acid-5-sulfonate unit, the amount of the sulfonate group-containing oligomer added to the polyester is increased, which not only increases the cost but also deteriorates the cationic dyeability effect of the polyester. The molar ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the terephthalic acid or the esterified product thereof is preferably 1: 0.1 to 30.0, more preferably 1: 0.5 to 20.0.
In the molar ratio of the total mole amount of the isophthalic acid-5-sulfonate or the esterified product thereof and the terephthalic acid or the esterified product thereof to the diol, the total mole amount of the isophthalic acid-5-sulfonate or the esterified product thereof and the terephthalic acid or the esterified product thereof is 1, when the addition amount of the diol is too low, the number average molecular weight of the generated oligomer containing sulfonate groups is too large, and when the diol is added into the polyester, the oligomer containing sulfonate groups is not favorably dispersed, so that the oligomer is coagulated, 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 concentrations of the isophthalic acid-5-sulfonate or its esterified product and the terephthalic acid or its esterified product in the system are too low to be favorable for the production. The molar ratio of the total molar amount of the isophthalic acid-5-sulfonate or the esterified product thereof and the terephthalic acid or the esterified product thereof to the diol is preferably 1: 1.3 to 20.0, more preferably 1: 1.5 to 15.0.
One of the uses of the sulfonate group-containing oligomers 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. Because the oligomer containing the sulfonate group contains a terephthalic acid structural unit, the compatibility with the polyester can be improved, and the performance of the final cationic dyeable polyester is not negatively influenced.
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 sulfonate group-containing oligomer 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 by the esterification reaction, and is preferably added before the polymerization reaction is completed by the esterification reaction. 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 sulfonate group-containing oligomer may be present in the polyester in an amount of 0.05 to 5.00% by weight, calculated as elemental sulfur, based on the total amount of the final cationic-dyeable polyester. In addition to the sulfonate group-containing oligomer, other additives may be used in combination with the polyester to improve the properties of the polyester, such as the addition of polyethylene glycol to further improve the antistatic properties of the polyester.
The oligomer containing sulfonate groups 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 oligomer containing sulfonate group
By H1NMR nuclear magnetic testing of oligomers containing sulfonate groups, the molar ratio of the abovementioned units being determined by the ratio of the area of the characteristic peak of the hydrogen element on benzene in the terephthalic acid unit and the area of the peak of the characteristic peak of the hydrogen element on benzene in the isophthalic acid-5 sulfonate unit, and the area of the peak of the characteristic peak of the hydrogen element on the alkyl radical in the linear diol.
(4) Molecular weight of oligomer containing sulfonate group
0.5g of the sulfonate group-containing oligomer was taken, dissolved in chloroform, filtered, and the molecular weight of the sulfonate group-containing substance 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 oligomer containing a sulfonate group 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 oligomer (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.
Example 1
Sulfonate group-containing oligomer: adding m-phthalic acid-5 sodium sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the m-phthalic acid-5 sodium sulfonate to the terephthalic acid is 1: 0.1. Simultaneously adding 1, 4-butanediol, wherein the molar ratio of the total amount of the isophthalic acid-5 sodium sulfonate and the terephthalic acid to the 1, 4-butanediol is 1: 1.3, and adding PEG with the number average molecular weight of 1000g/mol, wherein the molar ratio of the repeating structural unit of the PEG to the isophthalic acid-5 sodium sulfonate is 3.6. The stirrer was started and 500ppm of tetrabutyl titanate was added. The temperature is raised to 150 ℃ for 1hr after 150min at room temperature. And (4) after the time is up, stopping the reaction, cooling and discharging to obtain the oligomer containing the sulfonate group. The number average molecular weight of the sulfonate group-containing oligomer was 1500g/mol, wherein isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 0.1 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.3 (molar ratio).
Cationic dyeable polyester: terephthalic acid and 1, 4-butanediol are uniformly mixed and then put into a reaction kettle, and tetrabutyl titanate serving as a catalyst accounting for titanium and accounting for 0.1wt% of the esterification reactant is added to carry out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared low polymer containing sulfonate groups and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing substance in the cationic dyeable polyester accounts for 0.5wt% of the final cationic dyeable polyester in terms of sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Example 2
Sulfonate group-containing oligomer: adding dimethyl isophthalate-5 sodium sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the two is 1: 30.0. Simultaneously adding 1, 4-butanediol, the molar ratio of the total amount of the sodium sulfoisophthalate-5 and the terephthalic acid to the 1, 4-butanediol is 1: 30.0, and adding PEG with the number average molecular weight of 1000g/mol, wherein the molar ratio of the PEG repeating structural unit to the sodium sulfoisophthalate-5 is 0.5. The stirrer was started and 800ppm sodium acetate was added. The temperature is raised to 250 ℃ for 1hr after 200min at room temperature. And (4) after the time is up, stopping the reaction, cooling and discharging to obtain the oligomer containing the sulfonate group. The number average molecular weight of the sulfonate group-containing oligomer was 1150g/mol, wherein isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit was 1: 30.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) and 1, 4-butanediol unit in a molar ratio of 1: 2.0.
Cationic dyeable polyester: uniformly mixing terephthalic acid, 1, 4-butanediol and the prepared oligomer containing the sulfonate group, putting the mixture into a reaction kettle, adding tetrabutyl titanate serving as a catalyst, wherein the tetrabutyl titanate is 0.1wt% of the esterification reactant relative to the titanium element, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding a thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing substance in the cationic dyeable polyester accounts for 0.5wt% of the final cationic dyeable polyester in terms of sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Example 3
Sulfonate group-containing oligomer: oligomer containing sulfonate group was prepared in the same manner as in example 1 except that the molar ratio of sodium dimethyl isophthalate-5 sulfonate to terephthalic acid was changed to 1: 15.0 and the molar ratio of PEG to sodium dimethyl isophthalate-5 sulfonate was changed to 10.0. The number average molecular weight of the sulfonate group-containing oligomer was 2300g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 15.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.3 (molar ratio).
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing material in the cationic-dyeable polyester accounted for 5.0wt% of the final cationic-dyeable polyester in terms of elemental sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Example 4
Sulfonate group-containing oligomer: the molar ratio of sodium sulfoisophthalate-5 to terephthalic acid was changed to 1: 20.0. The sulfonate group-containing oligomer was obtained in the same manner as in example 1. The number average molecular weight of the sulfonate group-containing oligomer was 2500g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 20.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.3 (molar ratio).
Cationic dyeable polyester: the preparation method is the same as example 1, and the specific physical properties are shown in Table 1.
Example 5
Sulfonate group-containing oligomer: adding dimethyl isophthalate-5-sodium sulfonate and dimethyl terephthalate into an esterification kettle, wherein the molar ratio of the two is 1: 10.0. Simultaneously, 1, 4-butanediol, the molar ratio of the total amount of sodium sulfoisophthalate-5 and dimethyl terephthalate to the 1, 4-butanediol is 1: 1.3. PEG with the number average molecular weight of 1000g/mol is added, wherein the molar ratio of the PEG repeating structural unit to the dimethyl isophthalate-5-sodium sulfonate is 3.6. The stirrer was started and 700ppm tetraethyl titanate was added. The temperature is increased to 180 ℃ for 3hr after 160min at room temperature. And (4) after the time is up, stopping the reaction, cooling and discharging to obtain the oligomer containing the sulfonate group. The number average molecular weight of the sulfonate group-containing oligomer was 2500g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 10 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.3 (molar ratio).
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing substance in the cationic dyeable polyester accounts for 2wt% of the final cationic dyeable polyester in terms of sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Example 6
Sulfonate group-containing oligomer: adding sodium m-phthalic acid monomethyl ester-5 sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the sodium m-phthalic acid monomethyl ester to the terephthalic acid is 1: 10.0. Simultaneously, the molar ratio of the total amount of the ethylene glycol, the sodium monomethyl isophthalate-5 sulfonate and the terephthalic acid to the ethylene glycol is 1: 10.0. PEG with the number average molecular weight of 1000g/mol is added, wherein the molar ratio of the PEG repeating structural unit to the isophthalic acid monomethyl ester-5-sodium sulfonate is 3.6. The stirrer was started and 800ppm of lithium acetate was added. The temperature is raised to 180 ℃ for 3hr after 150min at room temperature. And (4) after the time is up, stopping the reaction, cooling and discharging to obtain the oligomer containing the sulfonate group. The number average molecular weight of the sulfonate group-containing oligomer was 1500g/mol, wherein isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 10.0 (molar ratio); (5-sodium sulfoisophthalate units + terephthalic acid units): (molar ratio) ethylene glycol units: 1: 2.0.
Cationic dyeable polyester: adding dihydroxy ethyl terephthalate into an esterification reaction tank, keeping the temperature at 250 ℃, gradually adding terephthalic acid and ethylene glycol slurry into an esterification reaction layer within 4 hours, and then carrying out esterification reaction for 1 hour. And finally transferring the obtained esterification reactant into a polycondensation reaction kettle. The esterification reaction product was maintained at 250 ℃ under normal pressure, and the above prepared sulfonate group-containing substance was added in an amount of 0.5wt% based on the sulfur content and the weight of the final polyester, and after 5 minutes of stirring, phosphoric acid corresponding to 50ppm of the final polyester in terms of phosphorus atom was added, and after 5 minutes, antimony trioxide corresponding to 250ppm of the final polyester in terms of antimony atom was added. And after a certain stirring degree is reached, introducing nitrogen into the reaction system to return to normal pressure, and stopping the polycondensation reaction to obtain the cationic dyeable polyester. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Example 7
Sulfonate group-containing oligomer: adding diethylene glycol isophthalate-5-sodium sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the two is 1: 10.0. Simultaneously adding 1, 3-propanediol, the molar ratio of the total amount of the isophthalic acid diethylene glycol ester-5-sodium sulfonate and the terephthalic acid to the 1, 3-propanediol is 1: 1.3, and adding PEG with the number average molecular weight of 600g/mol, wherein the molar ratio of the PEG repeating structural unit to the isophthalic acid diethylene glycol ester-5-sodium sulfonate is 3.6. The stirrer was started and 500ppm of antimony trioxide was added. The temperature is raised to 180 ℃ for 2hr after 150min at room temperature. And (4) after the time is up, stopping the reaction, cooling and discharging to obtain the oligomer containing the sulfonate group. The number average molecular weight of the sulfonate group-containing oligomer was 2500g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 10.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) 1, 3-propanediol unit in a molar ratio of 1: 1.3.
Cationic dyeable polyester: terephthalic acid and 1, 3-propanediol are uniformly mixed and then put into a reaction kettle, and tetrabutyl titanate serving as a catalyst accounting for titanium and accounting for 0.1wt% of the esterification reactant is added to carry out esterification reaction at 235 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 260 ℃. And (3) after the polymer reaches the required viscosity, discharging and granulating to obtain the required cationic dyeable polyester. The copolymerized sulfonate group-containing material in the cationic dyeable polyester accounted for 0.5wt% of the final polyester, calculated as elemental sulfur. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 1.
Example 8
1, 3-propanediol was changed to 1, 5-pentanediol and the other conditions were the same as in example 7. Specific physical properties are shown in table 1.
Example 9
1, 3-propanediol was changed to 1, 6-hexanediol, and the number average molecular weight of PEG was 2000g/mol, under the same conditions as in example 7. Specific physical properties are shown in table 2.
Example 10
Sulfonate group-containing oligomer: adding sodium m-phthalic acid monomethyl ester-5 sulfonate and terephthalic acid monomethyl ester into an esterification kettle, wherein the molar ratio of the sodium m-phthalic acid monomethyl ester to the terephthalic acid monomethyl ester is 1: 10.0. Simultaneously adding ethylene glycol, wherein the molar ratio of the total amount of the sodium monomethyl isophthalate-5 sulfonate and the monomethyl terephthalate to the ethylene glycol is 1: 2.0, and adding PEG with the number average molecular weight of 1000g/mol, wherein the molar ratio of the PEG repeating structural unit to the sodium monomethyl isophthalate-5-sulfonate is 3.6. The stirrer was started and zinc acetate 700ppm was added. The temperature is increased to 180 ℃ for 3hr after 160min at room temperature. And (4) after the time is up, stopping the reaction, cooling and discharging to obtain the oligomer containing the sulfonate group. The number average molecular weight of the sulfonate group-containing oligomer was 1100g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit was 1: 10 (molar ratio); (5-sodium sulfoisophthalate units + terephthalic acid units): (molar ratio) ethylene glycol units: 1: 2.0.
Cationic dyeable polyester: adding dihydroxy ethyl terephthalate into an esterification reaction tank, keeping the temperature at 250 ℃, gradually adding terephthalic acid and ethylene glycol slurry into an esterification reaction layer within 4 hours, and then carrying out esterification reaction for 1 hour. And finally transferring the obtained esterification reactant into a polycondensation reaction kettle. The esterification reaction product was maintained at 250 ℃ under normal pressure, and the above prepared sulfonate group-containing substance was added in an amount of 0.5wt% based on the sulfur content and the weight of the final polyester, and after 5 minutes of stirring, phosphoric acid corresponding to 50ppm of the final polyester in terms of phosphorus atom was added, and after 5 minutes, antimony trioxide corresponding to 250ppm of the final polyester in terms of antimony atom was added. And after a certain stirring degree is reached, introducing nitrogen into the reaction system to return to normal pressure, and stopping the polycondensation reaction to obtain the cationic dyeable polyester. The cationic dyeable polyester is melt spun at 280 ℃ to obtain polyester fiber. Specific physical properties are shown in table 2.
Example 11
Sulfonate group-containing oligomer: adding diethyl isophthalate-5-sodium sulfonate and monoethyl terephthalate into an esterification kettle in a molar ratio of 1: 10.0. Simultaneously adding 1, 4-butanediol, wherein the molar ratio of the total amount of the sodium sulfoisophthalate-5 and the monoethyl terephthalate to the 1, 4-butanediol is 1: 1.5, and adding PEG with the number average molecular weight of 1000g/mol, wherein the molar ratio of the PEG repeating structural unit to the sodium sulfoisophthalate-5 is 3.6. The stirrer was started and 700ppm tetraethyl titanate was added. The temperature is increased to 180 ℃ for 3hr after 160min at room temperature. And (4) after the time is up, stopping the reaction, cooling and discharging to obtain the oligomer containing the sulfonate group. The number average molecular weight of the sulfonate group-containing oligomer was 1300g/mol, where isophthalic acid-5-sodium sulfonate unit to terephthalic acid unit is 1: 10.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.5 (molar ratio).
Cationic dyeable polyester: the preparation method is the same as example 1, and the specific physical properties are shown in Table 2.
Example 12
Sulfonate group-containing oligomer: adding diethyl isophthalate-5-sodium sulfonate and diethyl terephthalate into an esterification kettle, wherein the molar ratio of the two is 1: 10.0. Simultaneously adding 1, 4-butanediol, wherein the molar ratio of the total amount of the sodium sulfoisophthalate-5 and the diethyl terephthalate to the 1, 4-butanediol is 1: 1.4, and adding PEG with the number average molecular weight of 1000g/mol, wherein the molar ratio of the PEG repeating structural unit to the sodium sulfoisophthalate-5 is 3.6. The stirrer was started and 700ppm tetraethyl titanate was added. The temperature is increased to 180 ℃ for 3hr after 160min at room temperature. And (4) after the time is up, stopping the reaction, cooling and discharging to obtain the oligomer containing the sulfonate group. The number average molecular weight of the sulfonate group-containing oligomer was 1700g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 10 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.4 (molar ratio).
Cationic dyeable polyester: the preparation method is the same as example 1, and the specific physical properties are shown in Table 2.
Example 13
Diethyl isophthalate-5-sulfonate was replaced with lithium isophthalate-5-sulfonate under the same conditions as in example 12. Specific physical properties are shown in table 2.
Example 14
Diethyl isophthalate-5-sulfonate was replaced with potassium isophthalate-5-sulfonate under the same conditions as in example 12. Specific physical properties are shown in table 2.
Example 15
Sulfonate group-containing oligomer: the molar ratio of sodium sulfoisophthalate-5 to diethyl terephthalate was changed to 1: 15.0, and the molar ratio of the total amount of sodium sulfoisophthalate-5 and diethyl terephthalate to 1, 4-butanediol was changed to 1: 1.5. The oligomer containing sulfonate groups was prepared under the same conditions as in example 12. The number average molecular weight of the sulfonate group-containing oligomer was 1500g/mol, wherein isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 15.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.5 (molar ratio).
Cationic dyeable polyester: the preparation method is the same as example 1, and the specific physical properties are shown in Table 2.
Example 16
Sulfonate group-containing oligomer: adding m-phthalic acid-5 sodium sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the m-phthalic acid-5 sodium sulfonate to the terephthalic acid is 1: 0.02. Simultaneously adding 1, 4-butanediol, wherein the molar ratio of the total amount of the isophthalic acid-5 sodium sulfonate and the terephthalic acid to the 1, 4-butanediol is 1: 1.5, and adding PEG with the number average molecular weight of 1000g/mol, wherein the molar ratio of the PEG repeating structural unit to the isophthalic acid diethyl ester-5-sodium sulfonate is 3.6. The stirrer was started and 500ppm of tetrabutyl titanate was added. The temperature is raised to 150 ℃ for 1hr after 150min at room temperature. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the substance containing the sulfonate group. The sulfonate group-containing material had a number average molecular weight of 1000g/mol, where isophthalic acid-5-sodium sulfonate unit to terephthalic acid unit is 1: 1.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) to 1, 4-butanediol unit: 1: 1.5 (molar ratio).
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (4) after the polymer reaches the required viscosity, discharging and granulating to obtain the required copolyester. The copolymerized sulfonate group-containing material in the copolyester accounts for 0.5wt% of the final polyester in terms of sulfur element. The polyester is melt-spun at 280 ℃ to obtain the polyester fiber. Specific physical properties are shown in table 3.
Example 17
Sulfonate group-containing oligomer: adding m-phthalic acid-5 sodium sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the m-phthalic acid-5 sodium sulfonate to the terephthalic acid is 1: 15.00. Simultaneously adding 1, 4-butanediol, wherein the molar ratio of the total amount of the isophthalic acid-5 sodium sulfonate and the terephthalic acid to the 1, 4-butanediol is 1: 1.0, and adding PEG with the number average molecular weight of 1000g/mol, wherein the molar ratio of the PEG repeating structural unit to the isophthalic acid diethyl ester-5-sodium sulfonate is 3.6. The stirrer was started and 500ppm of tetrabutyl titanate was added. The temperature is raised to 150 ℃ for 1hr after 150min at room temperature. And (4) after the time is up, stopping the reaction, cooling and spitting to obtain the substance containing the sulfonate group. The sulfonate group-containing material had a number average molecular weight of 1000g/mol, where m-phthalic acid-5-sodium sulfonate unit to terephthalic acid unit is 1: 15.00 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) and 1, 4-butanediol unit in a molar ratio of 1: 1.0.
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (4) after the polymer reaches the required viscosity, discharging and granulating to obtain the required copolyester. The copolymerized sulfonate group-containing material in the copolyester accounts for 0.5wt% of the final polyester in terms of sulfur element. The polyester is melt-spun at 280 ℃ to obtain the polyester fiber. Specific physical properties are shown in table 3.
Comparative example 1
Uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding a thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (4) after the polymer reaches the required viscosity, discharging and granulating to obtain the required copolyester. The polyester is melt-spun at 280 ℃ to obtain the polyester fiber. Specific physical properties are shown in table 3.
Ordinary polybutylene terephthalate has poor dyeability.
Comparative example 2
Uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst into tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding dibutylene glycol-5-sodium sulfonate isophthalate and trimethyl phosphate serving as a heat stabilizer, and carrying out polycondensation reaction at 250 ℃. And (4) after the polymer reaches the required viscosity, discharging and granulating to obtain the required copolyester. The copolymerized sulfonate-containing salts in the copolyester account for 0.5wt% of the final polyester in terms of sulfur element. The polyester is melt-spun at 280 ℃ to obtain the polyester fiber. Specific physical properties are shown in table 3.
Although the dyeability of the cationic dyeable polyester obtained by directly adding the butanediol isophthalate-5-sulfonic acid sodium salt monomer to the reaction of polybutylene terephthalate is improved, the filtration pressure during spinning is increased, and the spinnability of the polyester is poor.
Comparative example 3
Sulfonate group-containing oligomer: adding m-phthalic acid-5 sodium sulfonate and terephthalic acid into an esterification kettle, wherein the molar ratio of the m-phthalic acid-5 sodium sulfonate to the terephthalic acid is 1: 15.0. Simultaneously adding 1, 4-butanediol, wherein the molar ratio of the total amount of the isophthalic acid-5 sodium sulfonate and the terephthalic acid to the 1, 4-butanediol is 1: 1.0, and adding PEG with the number average molecular weight of 10000g/mol, wherein the molar ratio of the PEG repeating structural unit to the isophthalic acid-5 sodium sulfonate is 3.6. The stirrer was started and 500ppm of tetrabutyl titanate was added. The temperature is raised to 150 ℃ for 4hr after 150min at room temperature. And (4) after the time is up, stopping the reaction, cooling and discharging to obtain the oligomer containing the sulfonate group. The number average molecular weight of the sulfonate group-containing oligomer was 3000g/mol, where isophthalic acid-5-sodium sulfonate unit: terephthalic acid unit is 1: 15.0 (molar ratio); (5-sodium sulfoisophthalate unit + terephthalic acid unit) and 1, 4-butanediol unit in a molar ratio of 1: 1.0.
Cationic dyeable polyester: uniformly mixing terephthalic acid and 1, 4-butanediol, putting into a reaction kettle, adding a catalyst into tetrabutyl titanate accounting for titanium element and accounting for 0.1wt% of an esterification reactant, and carrying out esterification reaction at 225 ℃. After the esterification reaction is finished, transferring the reaction product into a polycondensation kettle, adding the prepared sulfonate group-containing substance and thermal stabilizer trimethyl phosphate, and carrying out polycondensation reaction at 250 ℃. And (4) after the polymer reaches the required viscosity, discharging and granulating to obtain the required copolyester. The copolymerized sulfonate group-containing material in the copolyester accounts for 0.5wt% of the final polyester in terms of sulfur element. The polyester is melt-spun at 280 ℃ to obtain the polyester fiber. Specific physical properties are shown in table 3.
Since the data molecular weight of the sulfonate group-containing oligomer is more than 3000g/mol, the spinnability of the final cationic dyeable polyester is poor, and the filtration pressure during spinning is obviously increased.
Comparative example 4
The procedure of example 5 was followed except that no PEG was added during the synthesis of the sulfonate group-containing oligomer.
Since no PEG was added, the amount of crystals precipitated from the sulfonate group-containing oligomer was large, and the coloring properties of the final cationic-dyeable polyester were poor.
In tables 1 to 3, A represents an isophthalic acid-5-sulfonate unit, B represents a terephthalic acid unit, C represents a diol unit, and D represents a repeating structural unit of polyethylene glycol.
Abbreviations for respective substances in tables 1 to 3 represent:
SSIA: the sodium sulfoisophthalic acid-5 has been described,
SIPM: dimethyl isophthalate-5 sodium sulfonate,
SIPSM: the isophthalic acid monomethyl ester-5 sodium sulfonate,
SIPE, sodium diethylene glycol isophthalate-5-sulfonate,
SIPD is sodium sulfoisophthalate-5,
SSIL lithium 5-sulfoisophthalate,
SSIK potassium phthalate-5-sulfonate,
EGM: a diol unit represented by the formula 5,
PDM: a diol unit represented by the formula 6,
BDM: a diol unit represented by the formula 7,
TDM: a diol unit represented by the formula 8,
HDM is a diol unit represented by the formula 9.
Claims (9)
1. An oligomer comprising sulfonate groups, characterized by: the molecular chain of the oligomer comprises an isophthalic acid-5-sulfonate unit shown as a formula 1, a terephthalic acid unit shown as a formula 2, a dihydric alcohol unit shown as a formula 3 and a polyethylene glycol unit shown as a formula 4, wherein the number average molecular weight of the polyethylene glycol unit is 100-2000 g/mol; the number average molecular weight of the oligomer is 1000-3000 g/mol;
-OCH2CH2OCH2CH2……OCH2CH2- in the formula (4), the first and second groups,
in the formula 1, X is sodium ion, potassium ion or lithium ion, and in the formula 3, n is an integer of 2-6.
2. The sulfonate group-containing oligomer of claim 1, wherein: the mol ratio of the isophthalic acid-5-sulfonate unit to the terephthalic acid unit is 1: 0.1 to 30.0.
3. The sulfonate group-containing oligomer according to claim 1 or 2, characterized in that: the molar ratio of the total mole of the isophthalic acid-5-sulfonate unit and the terephthalic acid unit to the mole of the diol unit shown in the formula 3 is 1: 1.3 to 2.0.
4. The sulfonate group-containing oligomer according to claim 1 or 2, characterized in that: the molar ratio of the repeating structural unit of the polyethylene glycol to the isophthalic acid-5-sulfonate unit is 0.5-10.0.
5. A method for preparing the sulfonate group-containing oligomer of claim 1, wherein: adding 5-sulfoisophthalic acid or an esterified product thereof, terephthalic acid or an esterified product thereof, linear chain dihydric alcohol with 2-6 carbon atoms and polyethylene glycol into a reaction kettle, then adding a catalyst, and reacting at 150-240 ℃ for 1-5 hours to obtain an oligomer containing a sulfonate group with the number average molecular weight of 1000-3000 g/mol; the sulfonate is sodium sulfonate, potassium sulfonate or lithium sulfonate.
6. The method for preparing an oligomer having a sulfonate group according to claim 5, wherein: the mol ratio of the isophthalic acid-5-sulfonate or the esterified product thereof to the terephthalic acid or the esterified product thereof is 1: 0.1 to 30.0.
7. The method for producing the sulfonate group-containing oligomer according to claim 5 or 6, wherein: the molar ratio of the total amount of the isophthalic acid-5-sulfonate or the esterified product thereof to the terephthalic acid or the esterified product thereof to the linear diol having 2-6 carbon atoms is 1: 1.3 to 2.0.
8. The method for producing the sulfonate group-containing oligomer according to claim 5 or 6, wherein: the molar ratio of the repeating structural unit of the polyethylene glycol to the isophthalic acid-5-sulfonate or the esterified product thereof is 0.5-10.0.
9. Use of an oligomer containing a sulfonate group as defined in 1 in a polyester.
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| CN112029149A (en) * | 2020-09-16 | 2020-12-04 | 贺州学院 | Polyester water-soluble polymer modifier for calcium carbonate surface modification and preparation method thereof |
| CN114163625A (en) * | 2021-11-23 | 2022-03-11 | 中国纺织科学研究院有限公司 | Cationic dyeable polyester and preparation method thereof |
| CN115362210A (en) * | 2020-06-12 | 2022-11-18 | 东丽纤维研究所（中国）有限公司 | Cationic dyeable polyester composition, preparation method and application thereof |
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| CN115362210A (en) * | 2020-06-12 | 2022-11-18 | 东丽纤维研究所（中国）有限公司 | Cationic dyeable polyester composition, preparation method and application thereof |
| CN112029149A (en) * | 2020-09-16 | 2020-12-04 | 贺州学院 | Polyester water-soluble polymer modifier for calcium carbonate surface modification and preparation method thereof |
| CN114163625A (en) * | 2021-11-23 | 2022-03-11 | 中国纺织科学研究院有限公司 | Cationic dyeable polyester and preparation method thereof |
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