CN113683762B - Functional master batch and preparation method and application thereof - Google Patents

Functional master batch and preparation method and application thereof Download PDF

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Publication number
CN113683762B
CN113683762B CN202111237273.4A CN202111237273A CN113683762B CN 113683762 B CN113683762 B CN 113683762B CN 202111237273 A CN202111237273 A CN 202111237273A CN 113683762 B CN113683762 B CN 113683762B
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functional
esterification
master batch
reaction
temperature
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CN113683762A (en
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吉鹏
王华平
王朝生
徐毅明
徐虎明
谢伟
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Poly Plastic Masterbatch Suzhou Co ltd
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Poly Plastic Masterbatch Suzhou Co ltd
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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
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
    • C08G63/6956—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to a functional master batch and a preparation method and application thereof, wherein a mixture containing an esterification product and a functional prepolymer is subjected to polycondensation reaction to prepare the functional master batch; the esterification product is prepared by esterification reaction of dibasic acid and dihydric alcohol, and the end group of the esterification product is hydroxyl; the preparation process of the functional prepolymer comprises the following steps: firstly, carrying out esterification reaction on a phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane in a molar ratio of 1: 1.05-1.20 until the esterification rate is 95-99%, and introducing polycarbodiimide for further reaction to prepare a functional prepolymer, wherein the phosphorus-containing flame retardant contains two terminal carboxyl groups; the number average molecular weight of the prepared functional master batch is higher; blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber, wherein the mechanical strength retention rate of the polyester fiber after high-temperature and high-pressure dyeing is more than 95%; the preparation method is simple; the functional master batch has good crystallization property.

Description

Functional master batch and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polyester, relates to a functional master batch, a preparation method and application thereof, and particularly relates to a flame-retardant functional master batch for high-strength polyester fibers and a preparation method thereof.
Background
Polyester fibers are a textile base material, and among them, PET polyester fibers are a variety represented. However, the conventional polyester fiber has a limit oxygen index of 20%, belongs to flammable materials, and can release a large amount of heat and form molten drops to cause human injury in the combustion process. And as a textile raw material, the polyester fiber has high requirements on the mechanical property, so that the polyester fiber usually has both the mechanical property and the flame retardant property in various application fields of textiles.
At present, in order to realize that polyester fibers and products have better mechanical properties and flame retardant properties, technical means including polymerization modification (such as patent application CN110528109A, patent CN102199807B and the like), blending modification (such as patent application CN 105177754A), blending (such as patent application CN 110359152A), coating finishing (such as patent CN 105178011B) and the like are mainly formed. However, through analysis, the blending technology does not change the original flammable property of the polyester fiber, and the coating after-finishing method has the problem of easy falling off, and the like, and although the polyester fiber developed by the copolymerization or blending method has better flame retardance, the existing data does not explain the performance change of the developed flame-retardant polyester fiber and products in the post-processing process, especially in the post-alkali weight reduction process.
The performance change of the flame-retardant polyester fiber in the alkali weight reduction is correspondingly developed by the technical personnel in the field, and when the alkali weight reduction treatment is carried out, the flame-retardant polyester fabric is compared with the common polyester fabric, so that the influence of the alkali dosage, the treatment time and the accelerator dosage on the weight reduction rate of the flame-retardant polyester fabric is much larger than that of the common polyester fabric, and the fabric strength is obviously reduced.
Aiming at polyester fibers with large quantity and wide range, the problem which needs to be solved urgently by current research is solved if the flame retardance of the polyester fibers is effectively improved and the performance reduction caused by the post-processing process is avoided.
Disclosure of Invention
The invention aims to solve the problem that the flame-retardant polyester fiber prepared by a copolymerization or blending method in the prior art is obviously reduced in mechanics in the post-processing (including alkali decrement and dyeing and finishing) process, and provides a functional master batch, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing functional master batch, carry on the condensation polymerization to react and make functional master batch in mixture containing esterification product and functional prepolymer;
the esterification product is prepared by esterification reaction of dibasic acid and dihydric alcohol, and the end group of the esterification product is hydroxyl;
the preparation process of the functional prepolymer comprises the following steps: firstly, carrying out esterification reaction on a phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane with a molar ratio of 1: 1.05-1.20 until the esterification rate is 95-99%, and then introducing polycarbodiimide for further reaction to prepare a functional prepolymer, wherein the phosphorus-containing flame retardant contains two carboxyl-terminated groups, the molar ratio of the hydroxyl-terminated polysiloxane to the phosphorus-containing flame retardant is 1.05-1.20: 1, so that the prepolymer formed by the reaction of the phosphorus-containing flame retardant and the phosphorus-containing flame retardant is terminated by the hydroxyl groups, the reaction can basically react the carboxyl groups in the phosphorus-containing flame retardant to ensure that the content of the carboxyl groups is extremely low, the residual carboxyl groups in the phosphorus-containing flame retardant are further reacted with the subsequently introduced polycarbodiimide, and the esterification rate of the phosphorus-containing flame retardant and the hydroxyl-terminated polysiloxane is 95-99%, so that the polycarbodiimide is excessive relative to the residual carboxyl groups, and the polycarbodiimide which does not react with the carboxyl groups can react with the carboxyl groups generated in the hydrolysis process of polyester in the post-processing process to generate stable ureide, thereby inhibiting the hydrolysis and providing the polyester with certain hydrolysis resistance;
because the functional prepolymer is terminated by hydroxyl, after the functional prepolymer and the esterification product terminated by the dihydric alcohol are mixed, the functional prepolymer and the esterification product can carry out ester exchange reaction (the polycondensation reaction is essentially ester exchange reaction, the hydroxyl-terminated parts of the two substances carry out ester exchange reaction, and small molecules are removed to increase the molecular weight), thereby preparing the functional master batch.
As a preferred technical scheme:
according to the preparation method of the functional master batch, the mixture containing the esterification product and the functional prepolymer also contains a heat stabilizer and an antioxidant.
The preparation method of the functional master batch comprises the following specific steps:
(1) performing esterification reaction;
carrying out esterification reaction on dibasic acid and dihydric alcohol according to a certain molar ratio until the specified water yield is reached to obtain an esterification product;
(2) preparing a functional prepolymer;
carrying out esterification reaction on the phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane under the action of an esterification catalyst, and introducing polycarbodiimide for further reaction after the esterification reaction is finished to prepare a functional prepolymer;
(3) performing polycondensation reaction;
and mixing the esterification product, the functional prepolymer, the heat stabilizer and the antioxidant according to a certain proportion, and then carrying out polycondensation reaction to obtain the functional master batch.
The preparation method of the functional master batch comprises the following steps of (1), wherein the molar ratio of the dibasic acid to the dihydric alcohol is 1: 1.1-2.0;
the dibasic acid is more than one of terephthalic acid and isophthalic acid; the dihydric alcohol is more than one of ethylene glycol, propylene glycol, butanediol and pentanediol;
the temperature of the esterification reaction is 200-260 ℃, the pressure is 0.01-0.5 MPa, and the specified water yield is 94-98% of the theoretical water yield; because the esterification reaction of the dibasic acid and the dihydric alcohol is a reversible equilibrium reaction, the esterification product generated by the reaction and water belong to a positive reaction, and in order to realize the continuous positive reaction, the temperature and the time of the reaction need to be met and the water generated by the reaction needs to be removed; the esterification reaction of the dibasic acid and the dihydric alcohol needs to be over the boiling point of the dihydric alcohol, wherein the boiling point of the glycol is close to 200 ℃, and the boiling points of other related dihydric alcohols are higher than that of the glycol; therefore, the reaction is controlled to be more than 200 ℃, although the increase of the reaction temperature can accelerate the esterification reaction, but the reaction is also accompanied with the generation of series side reactions, in the invention, when the esterification reaction is increased to exceed 260 ℃, the side reactions of self-condensation between dihydric alcohols to form ether are increased, and the esterification mainly comprises the side reactions; the water yield reaction is the esterification reaction degree, the esterification rate is improved extremely limitedly by continuously prolonging the reaction time after the esterification reaction reaches a certain degree, and meanwhile, the side reaction becomes more and more dominant; thus, the esterification, i.e.the water output, is stopped after a certain degree of progress.
According to the preparation method of the functional master batch, in the step (2), the mass ratio of the polycarbodiimide to the hydroxyl-terminated polysiloxane is 0.05-0.20: 1; the addition amount of the esterification catalyst is 100-400 ppm of the mass of the hydroxyl-terminated polysiloxane;
the phosphorus-containing flame retardant is DDP ([ (6-oxo-6H-dibenzo [ c, e ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid); the number average molecular weight of the hydroxyl-terminated polysiloxane is 1000-5000 g/mol; the number average molecular weight of the polycarbodiimide is 1000-5000 g/mol; the esterification catalyst is methyl benzene sulfonic acid;
the temperature of the esterification reaction is 180-240 ℃; the further reaction temperature is 220-260 ℃ and the time is 0.5-1.5 h.
According to the preparation method of the functional master batch, in the step (3), the mass ratio of the esterification product to the functional prepolymer is 5: 5-2: 8; the addition amount of the heat stabilizer is 50-500 ppm of the mass of the functional prepolymer; the addition amount of the antioxidant is 50-500 ppm of the mass of the functional prepolymer;
the heat stabilizer is more than one of trimethyl phosphate, alkyl phosphodiester and tri (nonylphenyl) phosphite ester; the antioxidant is more than one of antioxidant 1010, antioxidant 168 and antioxidant 616;
the polycondensation reaction is divided into two stages of pre-polycondensation reaction and final polycondensation reaction; the temperature of the pre-polycondensation reaction is 240-270 ℃, the pressure is 0.5-1.0 KPa, the time is 0.5-2.5 h, and the stirring speed is 5-15 rpm; the temperature of the final polycondensation reaction is 260-280 ℃, the pressure is 20-200 Pa, and the time is 1.0-5.0 h; the polycondensation reaction is a process for increasing molecular weight, the reaction mechanism in the process is a reversible equilibrium reaction, and the polycondensation reaction needs certain reaction temperature, catalyst and reaction time; the temperature of the polycondensation reactants in the invention is above the melting point of the esterification product, so the temperature is higher than a certain temperature, namely 240 ℃, but the polycondensation reaction is always in an increased state when the polycondensation temperature is not higher, the polycondensation reaction is controlled within a certain range, otherwise the polyester is thermally decomposed; in the invention, the vacuum degree in the pre-polycondensation stage is less than that in the final polycondensation stage, and the content of oxygen possibly remained in the pre-polycondensation stage is higher than that in the final polycondensation, so the temperature control is lower than that in the final polycondensation.
The invention also provides a functional master batch which is prepared by adopting the method of any one of the above; the number average molecular weight of the functional master batch is 10000-20000 g/mol, the molecular weight distribution index is 2.0-3.0, and the dynamic viscosity is 50-100 Pa.s;
the number average molecular weight and molecular weight distribution are based on GPC measurements;
the dynamic viscosity is 10-20 ℃ above the melting point of the polymer to be tested, and the shear rate is 50s-1The results were tested under the conditions.
The invention also provides the application of the functional master batch, the polyester fiber is prepared by melt spinning after the functional master batch and the polyester are blended, although the functional master batch and the polyester can generate a certain ester exchange reaction in the melt spinning process, the blending time is short, and the ester exchange reaction degree is not high; the products obtained by melt spinning can be POY (polyester pre-oriented yarn), FDY (fully drawn yarn), short fibers, non-woven fabrics and the like; the mechanical strength retention rate of the polyester fiber after high-temperature and high-pressure dyeing is more than 95%, namely the mechanical strength reduction rate of the fiber after high-temperature and high-pressure dyeing is less than 5%;
the specific process of the high-temperature high-pressure dyeing comprises the following steps: the fibers were first added to disperse blue 284 (CAS 71872-43-0, formula C) at 40 ℃ and pH 517H19N5O6S) dispersing dye liquor, heating the dye liquor to 125 ℃ at a heating rate of 2 ℃/min, wherein the temperature is a dyeing transition temperature, the dyeing rate is rapidly increased, the heating rate is strictly controlled to ensure that the dye is uniformly dyed, continuously keeping the temperature, dyeing for 60min under the pressure of 0.176MPa, finally slowly cooling to room temperature, carrying out post-treatment such as reduction cleaning and water washing, and thoroughly removing flooding to improve the color fastness and glossiness of the product.
As a preferred technical scheme:
in the application, the content of the functional master batch in the blend (i.e. the product obtained by blending the functional master batch and the polyester) is 2.0-10.0 wt% (i.e. the mass addition amount of the functional master batch is 2.0-10.0 wt% of the sum of the mass addition amounts of the functional master batch and the polyester); the polyester fiber has a skin-core structure, wherein the skin layer is the functional master batch, and the core layer is the polyester; the functional master batch has excellent flow characteristic and obvious shear thinning, and the fiber prepared by melt spinning after being blended with polyester forms a micro-phase structure, wherein the functional master batch is distributed on the skin layer of the fiber, and the polyester is distributed on the core layer of the fiber, so that the finally obtained fiber has a skin-core structure.
The application of the polyester fiber has the advantages that the inherent viscosity of the polyester fiber without the oil silk is reduced by less than or equal to 0.01 dL/g; LOI (low index of inertia) of the polyester fiber is more than or equal to 30% after high-temperature and high-pressure dyeing; compared with a comparison sample, the viscous flow activation energy (the viscous flow activation energy is a physical quantity describing the viscosity-temperature dependence of a material and is defined as the minimum energy required by a flow unit (namely a chain segment for a high polymer material) for overcoming a potential barrier and jumping to a nearby cavity from an original position) of the polyester fiber is reduced by 10-30% in the flow process, the spinning temperature is reduced by 5-20 ℃, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added;
the 'no-oil-silk intrinsic viscosity reduction' refers to the fiber intrinsic viscosity at the stage of testing the no-oil-silk, and the method adopts an Ubbelohde viscometer to test;
"viscous flow activation energy" (Eeta) is a measure of the degree to which a polymer fluid is sensitive to temperature; the more flexible the polymer molecular chain, the lower E eta; when the molecular chain contains benzene rings, polar groups or larger side groups, the flexibility of the molecular chain is greatly reduced, and the E eta of the polymer is increased; the greater E eta, the greater the sensitivity of the viscosity of the polymer fluid to temperature, and the poorer the spinnability; in a smaller temperature range, the viscosity of the polymer fluid is related to temperature by the Arrheniuus equation, i.e., η = Aexp (E η/RT) where a is a constant; e eta is viscous flow activation energy, kJ/mol; eta is apparent viscosity, Pa · s; t is absolute temperature, K; r is a gas constant of 8.314J/(mol.K); drawing Ln eta and 1/T under different shear rates, and obtaining LnA (intercept of a straight line) and E eta/R (slope of the straight line) after linear fitting, thereby solving the viscous flow activation energy of the melt under different shear rates;
the spinning in the invention is melt spinning, which is realized by completely melting the polymer in a hot processing mode and then realizing the flow through a certain pressure, and the fluidity of the melt is influenced by the molecular structure of the melt and the external factors such as the melting temperature and the like play an important role; the flow of the melt is realized in a certain range, the resistance in the melt flow is increased when the temperature is lower, the fluidity is poor, and the quality of the melt is reduced (the molecular weight of the melt is reduced and the color is poor along with the prolonging of the time) when the melt stays in a pipeline for a long time; therefore, the melt must be controlled to spin above the minimum temperature; the spinning temperature is reduced by 5-20 ℃, which is a reduction value relative to the lowest spinning temperature of a reference sample (namely, the lower limit of the spinning temperature applicable to the reference sample under the condition of ensuring spinnability).
The principle of the invention is as follows:
analysis shows that the main reasons of the obvious mechanical reduction of the flame-retardant polyester fiber and the flame-retardant polyester product prepared by the conventional copolymerization or blending method in the post-processing process, particularly in the alkali weight loss process, are as follows: (1) the crystallinity of the fiber is influenced by flame retardant components contained in the macromolecular chain of the flame-retardant polyester fiber, and alkali liquor easily enters the interior of the fiber, so that hydrolysis of ester groups in the macromolecular chain is facilitated, and performance is reduced; (2) the residual carboxyl functional groups in the flame-retardant polyester fiber can accelerate the degradation of the polyester matrix under the high-temperature alkaline environment.
The invention solves the problem that the mechanical property of the flame-retardant polyester fiber prepared by the copolymerization or blending method in the prior art is obviously reduced in the post-processing (including alkali decrement and dyeing and finishing) process by preparing the functional master batch, blending the functional master batch with the polyester and then carrying out melt spinning to prepare the polyester fiber. The method comprises the following steps:
in the prior art, the dehumidification of the functional master batches and the polyester is carried out in a heating mode, namely, the moisture is removed by a negative pressure suction mode above a certain temperature. The functional master batch and the polyester must have good crystallization performance, otherwise, the functional master batch and the polyester are bonded into blocks at the drying temperature and cannot be used. The polycarbodiimide in the functional master batch can play a role in heterogeneous nucleation (the polycarbodiimide introduced in the invention can have a certain chemical reaction with carboxyl in a matrix and has a certain binding force with the matrix, so that the function of heterogeneous nucleation can be played), the high-proportion copolymerized functional master batch can have crystallinity, the requirements of drying, no bonding and the like can be met, and the problem of performance reduction caused by hydrolysis of ester groups in a macromolecular chain when alkali liquor enters the fiber can be reduced.
In the alkali weight reduction treatment process of the conventional polyester fiber, ester bonds on the molecular weight of polyester are easy to be hydrolyzed and broken under an alkaline environment, so that the molecular weight is reduced; compared with the conventional polyester, the phosphorus-containing copolyester formed in the prior art is more prone to ester bond and phosphorus-oxygen bond breakage under the alkali weight reduction environment, so that the molecular weight and the flame retardant property are reduced; the ester bond is broken, the breaking of the ester bond is the reverse reaction of the esterification reaction, the esterification reaction is the chemical reaction of hydroxyl and carboxyl to form the ester bond, and the breaking of the ester bond is the formation of the hydroxyl and the carboxyl; the polycarbodiimide in the functional master batch can react with the carboxyl generated in the hydrolysis process of the polyester to generate stable ureide, so that the continuation of the hydrolysis is inhibited, and certain hydrolysis resistance of the polyester is provided; meanwhile, the polycarbodiimide contains a plurality of functional groups, so that the polycarbodiimide not only can play a role in end capping, but also can play a role in chain extension to a certain extent, thereby realizing the control of the molecular weight of the polyester, and greatly reducing the performance reduction caused by the hydrolysis reaction of the fiber under the action of strong alkali due to the reduction of the carboxyl content;
the functional master batch also contains linear hydroxyl terminated polysiloxane, so that the hydrophobicity of the fiber can be improved, and the combination of water molecules and ester bonds is hindered in the alkali decrement process, thereby reducing the hydrolysis reaction of the ester bonds.
In addition, the functional components are introduced into the polyester in a functional master batch mode, the master batch is of a macromolecular type, the structure of the polyester is basically not changed, the master batch and the polyester are similar to a blending system, and the blending mode does not influence the macromolecular chains of the polyester.
In addition, the functional master batch added in the invention has the advantages of promoting the fluidity and reducing the problem of quality reduction (especially molecular weight reduction) of polyester in forming processing, because the functional master batch contains linear hydroxyl terminated polysiloxane, the fluidity is good, the functional master batch plays a role in plasticizing melt in fiber forming, and the flow activation energy of polyester melt is reduced, thereby reducing the spinning temperature.
In addition, the polysiloxane and the phosphorus flame retardant have a synergistic effect, so that the flame retardant property of the polyester fiber is greatly improved, and for the linear hydroxyl-terminated polysiloxane used in the invention, the polysiloxane is grafted into the polyester molecular chain through active groups at two ends or side groups of the molecular chain, so that the functional master batch has a better flame retardant effect, because: firstly, the silicon-oxygen bond energy in the organosilicon is about 452kJ/mol, and the carbon-carbon bond energy in the polymer is generally 318-352 kJ/mol, and the polysiloxane has better thermal stability and low heat release rate in the thermal decomposition process, wherein the heat release rate is usually 60-150 kW/m2Toxic or corrosive gas can not be released, smoke is less, polysiloxane has higher thermal stability, oxidation stability, hydrophobicity and good flexibility, and polysiloxane is introduced into polyester to play a condensed phase flame retardant mechanism, namely, the flame retardant effect of the polysiloxane is realized by generating a cracking carbon layer and improving the oxidation resistance of the carbon layer; after polysiloxane is introduced into the phosphorus-containing flame retardant polyester, the polysiloxane can migrate to the surface of the material to form a high-molecular gradient material of which the surface is an organic silicon flame retardant enrichment layer; once burned, an inorganic oxygen-and heat-insulating protective layer containing Si bonds and/or Si-C bonds, which is peculiar to polysiloxane, is formed; the flame retardant can not only prevent the combustion decomposition products from escaping, but also inhibit the thermal decomposition of the high polymer material, thereby achieving the purposes of flame retardance, low smoke, low toxicity and the like; secondly, the flame retardance of the fiber product has a direct relation with the actual content of phosphorus flame retardants, especially phosphorus, in the fiber; although the actual phosphorus content and the addition amount in the polyester and the fiber modified by the existing phosphorus flame retardant are basically consistent, the polyester or the fiber is not a final product, and the fiber needs subsequent processes such as dyeing, finishing, alkali reducing amount treatment and the like; after the existing polyester fiber modified by the phosphorus-containing flame retardant is subjected to the processes, the phosphorus content loss is extremely serious and is obviously lower than the addition amount, so that the flame retardant effect is reduced; the polysiloxane introduced in the invention can realize that the loss of the flame retardant in the processes of dyeing, finishing, alkali reduction treatment and the like of the flame-retardant polyester fiber is low, so that the flame-retardant polyester fiber modified by the phosphorus flame retardant without the polysiloxane has the flame-retardant enhancement effect.
Advantageous effects
(1) According to the preparation method of the functional master batch, the method is simple and the prepared functional master batch has good performance by selecting special raw materials and controlling the reaction flow;
(2) the functional master batch disclosed by the invention has good crystallization performance, and does not have crystallization performance due to the introduction of a high proportion of copolymerization components, so that the practical application value is ensured;
(3) the application of the functional master batch in the polyester fiber can effectively avoid the problem of performance reduction of the polyester fiber in the post-processing process;
(4) the application of the functional master batch can realize the adjustment of the fiber performance by regulating the addition amount, has the characteristics of simplicity and flexibility, and is favorable for popularization and application.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of functional master batches comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: terephthalic acid;
a dihydric alcohol: ethylene glycol;
phosphorus-containing flame retardants: DDP;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 1000 g/mol;
polycarbodiimide having a number average molecular weight of 1000 g/mol;
esterification catalyst: (ii) methyl benzene sulfonic acid;
thermal stabilizer: trimethyl phosphate;
antioxidant: an antioxidant 1010;
(2) performing esterification reaction;
carrying out esterification reaction on dibasic acid and dihydric alcohol according to the molar ratio of 1:1.1, wherein the temperature of the esterification reaction is 200 ℃, the pressure is 0.5MPa, and an esterification product is obtained until the water yield reaches 95 percent of the theoretical water yield, and the end group of the esterification product is hydroxyl;
(3) preparing a functional prepolymer;
carrying out esterification reaction on a phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane with a molar ratio of 1:1.05 under the action of an esterification catalyst at the temperature of 180 ℃ until the esterification rate is 95%, introducing polycarbodiimide, and further reacting for 1.5 hours at the temperature of 220 ℃ to obtain a functional prepolymer; wherein the mass ratio of the polycarbodiimide to the hydroxyl-terminated polysiloxane is 0.05: 1; the addition amount of the esterification catalyst is 100ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product, the functional prepolymer, the heat stabilizer and the antioxidant, performing a pre-polycondensation reaction for 2.5 hours under the conditions of temperature of 240 ℃, pressure of 1KPa and stirring speed of 5rpm, and performing a final polycondensation reaction for 5 hours under the conditions of temperature of 260 ℃ and pressure of 200Pa to obtain functional master batches; wherein the mass ratio of the esterification product to the functional prepolymer is 5: 5; the addition amount of the heat stabilizer is 50ppm of the mass of the functional prepolymer; the addition amount of the antioxidant is 50ppm of the mass of the functional prepolymer;
the number average molecular weight of the prepared functional master batch is 20000g/mol, the molecular weight distribution index is 2, and the dynamic viscosity is 100 Pa.s.
Blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%.
The polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the inherent viscosity of the polyester fiber without the oil silk is reduced to 0.001 dL/g; the mechanical strength of the polyester fiber is 4.8cN/dtex, and the LOI is 32%; after high-temperature and high-pressure dyeing, the mechanical strength retention rate is 95%, and the LOI is 31%; compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 10 percent, the spinning temperature is reduced by 5 ℃, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The specific process of high-temperature high-pressure dyeing comprises the following steps: the fibers were first added to disperse blue 284 (CAS 71872-43-0, formula C) at 40 ℃ and pH 517H19N5O6S) dispersing dye liquor, heating the dye liquor to 125 ℃ at the temperature rise rate of 2 ℃/min, continuously maintaining the temperature, and keeping the pressure of 0.176MPaDyeing for 60min under force, finally slowly cooling to room temperature, and carrying out post-treatment such as reduction cleaning, water washing and the like to thoroughly remove loose color so as to improve the color fastness and glossiness of the product.
Comparative example 1
A method for preparing a functional masterbatch, which is substantially the same as example 1, except that the esterification reaction in step (3) is performed with a phosphorus-containing flame retardant (DDP) and a diol (ethylene glycol), and comparative example 1 is equivalent to replacing the hydroxyl-terminated polysiloxane of step (3) in example 1 with the diol (ethylene glycol).
Blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%.
The polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the inherent viscosity of the polyester fiber without the oil silk is reduced to 0.02 dL/g; the mechanical strength of the polyester fiber is 3.5cN/dtex, and the LOI is 30%; after high-temperature and high-pressure dyeing (the specific process is the same as that of example 1), the mechanical strength retention rate is 80%, and the LOI is 26%; compared with a reference sample, the viscous flow activation energy and the spinning temperature of the polyester fiber are not reduced, and the preparation process of the reference sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
Comparing example 1 with comparative example 1, it can be seen that after hydroxyl-terminated polysiloxane is replaced by dihydric alcohol (ethylene glycol), the flame retardant property of the fiber is reduced, the mechanical property is reduced, the viscous flow activation energy and the spinning temperature are improved, and after high-temperature and high-pressure dyeing, the mechanical strength retention rate of the fiber is reduced, and the flame retardant property is reduced. The reason is that the introduction of the hydroxyl-terminated polysiloxane of the embodiment 1 has an enhancement effect on the flame retardant property of the phosphorus flame retardant, the hydroxyl-terminated polysiloxane has better thermal stability, meanwhile, the heat release rate is low in the thermal decomposition process, toxic or corrosive gas can not be released, the smoke is less, the hydroxyl-terminated polysiloxane is introduced into the polyester to play a condensed phase flame retardant mechanism, namely, the flame retardant effect is realized by generating a cracked carbon layer and improving the oxidation resistance of the carbon layer, and the purposes of flame retardance, low smoke, low toxicity and the like are achieved; meanwhile, the hydroxyl-terminated polysiloxane has good hydrophobicity, and the fiber can reduce the effect of water molecules, ester bonds and other easily-hydrolyzed functional groups in dyeing, so that the reduction of flame retardance and mechanical property caused in the fiber dyeing process is reduced; in addition, the hydroxyl-terminated polysiloxane has the advantages of promoting the fluidity and reducing the problem of quality reduction (especially molecular weight reduction) of polyester in forming processing, because the functional master batch contains the linear hydroxyl-terminated polysiloxane, the fluidity is good, the function of plasticizing melt in fiber forming is realized, the flow activation energy of the polyester melt is reduced, and the spinning temperature is reduced.
Comparative example 2
A preparation method of functional master batch, which is basically the same as the embodiment 1, and is different from the step (3) only in that the step (3) is as follows: carrying out esterification reaction on a phosphorus-containing flame retardant (same as example 1) and hydroxyl-terminated polysiloxane (same as example 1) in a molar ratio of 1:1.05 under the action of an esterification catalyst (same as example 1) at the temperature of 180 ℃ until the esterification rate is 95%, and then reacting for 1.5h at the temperature of 220 ℃ to obtain a functional prepolymer; wherein the addition amount of the esterification catalyst is 100ppm based on the mass of the hydroxyl-terminated polysiloxane.
Blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%.
The polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the inherent viscosity of the polyester fiber without the oil silk is reduced to 0.005 dL/g; the mechanical strength of the polyester fiber is 4.0cN/dtex, and the LOI is 32%; after high-temperature and high-pressure dyeing (the specific process is the same as that of example 1), the mechanical strength retention rate is 75%, and the LOI is 25%; compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 10 percent, the spinning temperature is reduced by 5 ℃, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
Comparing example 1 with comparative example 2, it can be seen that the mechanical properties of the fiber are reduced after the polycarbodiimide is omitted, and the mechanical strength retention rate and the flame retardant property of the fiber are reduced after the fiber is dyed at high temperature and high pressure. This is because polycarbodiimide can react with carboxyl group formed in the hydrolysis process of polyester to form stable ureide, thereby inhibiting the continuation of hydrolysis and providing polyester with a certain hydrolysis resistance; meanwhile, the polycarbodiimide contains a plurality of functional groups, so that the polycarbodiimide not only can play a role in end capping, but also can play a role in chain extension to a certain extent, thereby realizing the control of the molecular weight of the polyester, and greatly reducing the reduction of the performance caused by the hydrolysis reaction of the fiber under the action of strong alkali. The polycarbodiimide plays a positive role in the aspects of maintaining the mechanical strength of the dyed fiber and inhibiting the reduction of the flame retardant property.
Example 2
A preparation method of functional master batches comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: isophthalic acid;
a dihydric alcohol: propylene glycol;
phosphorus-containing flame retardants: DDP;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 2000 g/mol;
polycarbodiimide having a number average molecular weight of 2000 g/mol;
esterification catalyst: (ii) methyl benzene sulfonic acid;
thermal stabilizer: an alkyl phosphodiester;
antioxidant: an antioxidant 168;
(2) performing esterification reaction;
carrying out esterification reaction on dibasic acid and dihydric alcohol according to the molar ratio of 1:1.2, wherein the temperature of the esterification reaction is 210 ℃, the pressure is 0.45MPa, and an esterification product is obtained until the water yield reaches 96% of the theoretical water yield, and the end group of the esterification product is hydroxyl;
(3) preparing a functional prepolymer;
carrying out esterification reaction on a phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane with a molar ratio of 1:1.1 under the action of an esterification catalyst at the temperature of 190 ℃ until the esterification rate is 96%, introducing polycarbodiimide, and further reacting for 1.4h at the temperature of 230 ℃ to obtain a functional prepolymer; wherein the mass ratio of the polycarbodiimide to the hydroxyl-terminated polysiloxane is 0.08: 1; the addition amount of the esterification catalyst is 150ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product, the functional prepolymer, the heat stabilizer and the antioxidant, performing a pre-polycondensation reaction for 2 hours under the conditions of the temperature of 245 ℃, the pressure of 0.9KPa and the stirring speed of 7rpm, and performing a final polycondensation reaction for 4 hours under the conditions of the temperature of 265 ℃ and the pressure of 180Pa to obtain functional master batches; wherein the mass ratio of the esterification product to the functional prepolymer is 4: 6; the adding amount of the heat stabilizer is 100ppm of the mass of the functional prepolymer; the addition amount of the antioxidant is 90ppm of the mass of the functional prepolymer;
the number average molecular weight of the prepared functional master batch is 18000g/mol, the molecular weight distribution index is 2.2, and the dynamic viscosity is 80 Pa.s.
Blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%.
The polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the inherent viscosity of the polyester fiber without the oil silk is reduced to 0.004 dL/g; the mechanical strength of the polyester fiber is 4.5cN/dtex, and the LOI is 32%; after high-temperature and high-pressure dyeing, the mechanical strength retention rate is 96%, and the LOI is 31%; compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 13%, the spinning temperature is reduced by 8 ℃, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The specific process of high-temperature high-pressure dyeing comprises the following steps: the fibers were first added to disperse blue 284 (CAS 71872-43-0, formula C) at 40 ℃ and pH 517H19N5O6S) dispersing dye liquor, heating the dye liquor to 125 ℃ at the heating rate of 2 ℃/min, keeping the temperature, dyeing for 60min under the pressure of 0.176MPa, finally slowly cooling to room temperature, carrying out post-treatment such as reduction cleaning and water washing, and thoroughly removing loose color so as to improve the color fastness and glossiness of the product.
Example 3
A preparation method of functional master batches comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: terephthalic acid;
a dihydric alcohol: butanediol;
phosphorus-containing flame retardants: DDP;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 2500 g/mol;
polycarbodiimide having a number average molecular weight of 4000 g/mol;
esterification catalyst: (ii) methyl benzene sulfonic acid;
thermal stabilizer: tris (nonylphenyl) phosphite;
antioxidant: an antioxidant 616;
(2) performing esterification reaction;
carrying out esterification reaction on dibasic acid and dihydric alcohol according to the molar ratio of 1:1.3, wherein the temperature of the esterification reaction is 220 ℃, the pressure is 0.4MPa, and an esterification product is obtained until the water yield reaches 95 percent of the theoretical water yield, and the end group of the esterification product is hydroxyl;
(3) preparing a functional prepolymer;
carrying out esterification reaction on a phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane with a molar ratio of 1:1.13 under the action of an esterification catalyst at the temperature of 200 ℃ until the esterification rate is 98%, introducing polycarbodiimide, and further reacting for 1.2h at the temperature of 240 ℃ to obtain a functional prepolymer; wherein the mass ratio of the polycarbodiimide to the hydroxyl-terminated polysiloxane is 0.1: 1; the addition amount of the esterification catalyst is 200ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product, the functional prepolymer, the heat stabilizer and the antioxidant, performing a pre-polycondensation reaction for 1.8h under the conditions of the temperature of 250 ℃, the pressure of 0.8KPa and the stirring speed of 9rpm, and performing a final polycondensation reaction for 3.5h under the conditions of the temperature of 270 ℃ and the pressure of 150Pa to obtain functional master batches; wherein the mass ratio of the esterification product to the functional prepolymer is 3: 7; the addition amount of the heat stabilizer is 150ppm of the mass of the functional prepolymer; the addition amount of the antioxidant is 160ppm of the mass of the functional prepolymer;
the prepared functional master batch has the number average molecular weight of 17000g/mol, the molecular weight distribution index of 2.3 and the dynamic viscosity of 70Pa & s.
Blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%.
The polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the inherent viscosity of the polyester fiber without the oil silk is reduced to 0.005 dL/g; the mechanical strength of the polyester fiber is 4.4cN/dtex, and the LOI is 33%; after high-temperature and high-pressure dyeing, the mechanical strength retention rate is 96.5%, and the LOI is 32%; compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 15%, the spinning temperature is reduced by 9 ℃, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The specific process of high-temperature high-pressure dyeing comprises the following steps: the fibers were first added to disperse blue 284 (CAS 71872-43-0, formula C) at 40 ℃ and pH 517H19N5O6S) dispersing dye liquor, heating the dye liquor to 125 ℃ at the heating rate of 2 ℃/min, keeping the temperature, dyeing for 60min under the pressure of 0.176MPa, finally slowly cooling to room temperature, carrying out post-treatment such as reduction cleaning and water washing, and thoroughly removing loose color so as to improve the color fastness and glossiness of the product.
Example 4
A preparation method of functional master batches comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: isophthalic acid;
a dihydric alcohol: pentanediol;
phosphorus-containing flame retardants: DDP;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 3000 g/mol;
a polycarbodiimide having a number average molecular weight of 4500 g/mol;
esterification catalyst: (ii) methyl benzene sulfonic acid;
thermal stabilizer: an alkyl phosphodiester;
antioxidant: an antioxidant 616;
(2) performing esterification reaction;
carrying out esterification reaction on dibasic acid and dihydric alcohol according to the molar ratio of 1:1.4, wherein the temperature of the esterification reaction is 230 ℃, the pressure is 0.3MPa, and an esterification product is obtained until the water yield reaches 94% of the theoretical water yield, and the end group of the esterification product is hydroxyl;
(3) preparing a functional prepolymer;
carrying out esterification reaction on a phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane with a molar ratio of 1:1.15 under the action of an esterification catalyst at the temperature of 210 ℃ until the esterification rate reaches 97%, introducing polycarbodiimide, and further reacting for 0.9h at the temperature of 250 ℃ to obtain a functional prepolymer; wherein the mass ratio of the polycarbodiimide to the hydroxyl-terminated polysiloxane is 0.12: 1; the addition amount of the esterification catalyst is 250ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product, the functional prepolymer, the heat stabilizer and the antioxidant, performing a pre-polycondensation reaction for 1.6 hours under the conditions of the temperature of 255 ℃, the pressure of 0.7KPa and the stirring speed of 11rpm, and performing a final polycondensation reaction for 3 hours under the conditions of the temperature of 274 ℃ and the pressure of 130Pa to obtain functional master batches; wherein the mass ratio of the esterification product to the functional prepolymer is 2: 8; the addition amount of the heat stabilizer is 200ppm of the mass of the functional prepolymer; the addition amount of the antioxidant is 200ppm of the mass of the functional prepolymer;
the number average molecular weight of the prepared functional master batch is 15000g/mol, the molecular weight distribution index is 2.4, and the dynamic viscosity is 65 Pa.s.
Blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%.
The polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the inherent viscosity of the polyester fiber without the oil silk is reduced to 0.006 dL/g; the mechanical strength of the polyester fiber is 4.3cN/dtex, and the LOI is 32%; after high-temperature and high-pressure dyeing, the mechanical strength retention rate is 97%, and the LOI is 31%; compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 18 percent, the spinning temperature is reduced by 10 ℃, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The specific process of high-temperature high-pressure dyeing comprises the following steps: the fibers were first added to disperse blue 284 (CAS 71872-43-0, formula C) at 40 ℃ and pH 517H19N5O6S) dispersing dye liquor, heating the dye liquor to 125 ℃ at the heating rate of 2 ℃/min, keeping the temperature, dyeing for 60min under the pressure of 0.176MPa, finally slowly cooling to room temperature, carrying out post-treatment such as reduction cleaning and water washing, and thoroughly removing loose color so as to improve the color fastness and glossiness of the product.
Example 5
A preparation method of functional master batches comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: a mixture of terephthalic acid and isophthalic acid in a mass ratio of 1: 1;
a dihydric alcohol: a mixture of ethylene glycol and propylene glycol in a mass ratio of 1: 1;
phosphorus-containing flame retardants: DDP;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 3500 g/mol;
polycarbodiimide having a number average molecular weight of 3000 g/mol;
esterification catalyst: (ii) methyl benzene sulfonic acid;
thermal stabilizer: a mixture of trimethyl phosphate and alkyl diester phosphate in a mass ratio of 1: 1;
antioxidant: a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1: 1;
(2) performing esterification reaction;
carrying out esterification reaction on dibasic acid and dihydric alcohol according to the molar ratio of 1:1.5, wherein the temperature of the esterification reaction is 240 ℃, the pressure is 0.2MPa, and an esterification product is obtained until the water yield reaches 95 percent of the theoretical water yield, and the end group of the esterification product is hydroxyl;
(3) preparing a functional prepolymer;
carrying out esterification reaction on a phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane with a molar ratio of 1:1.17 under the action of an esterification catalyst at 220 ℃ until the esterification rate reaches 96%, introducing polycarbodiimide, and further reacting for 0.5h at 260 ℃ to obtain a functional prepolymer; wherein the mass ratio of the polycarbodiimide to the hydroxyl-terminated polysiloxane is 0.15: 1; the addition amount of the esterification catalyst is 300ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product, the functional prepolymer, the heat stabilizer and the antioxidant, performing a pre-polycondensation reaction for 1.3 hours under the conditions of temperature of 260 ℃, pressure of 0.6KPa and stirring speed of 13rpm, and performing a final polycondensation reaction for 2 hours under the conditions of temperature of 277 ℃ and pressure of 110Pa to obtain functional master batches; wherein the mass ratio of the esterification product to the functional prepolymer is 4: 6; the addition amount of the heat stabilizer is 350ppm of the mass of the functional prepolymer; the addition amount of the antioxidant is 370ppm of the mass of the functional prepolymer;
the prepared functional master batch has the number average molecular weight of 14500g/mol, the molecular weight distribution index of 2.5 and the dynamic viscosity of 60 Pa.s.
Blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%.
The polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the inherent viscosity of the polyester fiber without the oil silk is reduced to 0.007 dL/g; the mechanical strength of the polyester fiber is 4.2cN/dtex, and the LOI is 32%; after high-temperature and high-pressure dyeing, the mechanical strength retention rate is 98%, and the LOI is 31%; compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 20%, the spinning temperature is reduced by 12 ℃, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The specific process of high-temperature high-pressure dyeing comprises the following steps: the fibers were first added to disperse blue 284 (CAS 71872-43-0, formula C) at 40 ℃ and pH 517H19N5O6S) dispersing dye liquor, heating the dye liquor to 125 ℃ at the heating rate of 2 ℃/min, keeping the temperature, dyeing for 60min under the pressure of 0.176MPa, finally slowly cooling to room temperature,and carrying out post-treatment such as reduction cleaning, water washing and the like to thoroughly remove loose color so as to improve the color fastness and glossiness of the product.
Example 6
A preparation method of functional master batches comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: terephthalic acid;
a dihydric alcohol: ethylene glycol;
phosphorus-containing flame retardants: DDP;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 4000 g/mol;
polycarbodiimide having a number average molecular weight of 3500 g/mol;
esterification catalyst: (ii) methyl benzene sulfonic acid;
thermal stabilizer: an alkyl phosphodiester;
antioxidant: an antioxidant 168;
(2) performing esterification reaction;
carrying out esterification reaction on dibasic acid and dihydric alcohol according to the molar ratio of 1:1.7, wherein the temperature of the esterification reaction is 250 ℃, the pressure is 0.1MPa, and an esterification product is obtained until the water yield reaches 98% of the theoretical water yield, and the end group of the esterification product is hydroxyl;
(3) preparing a functional prepolymer;
carrying out esterification reaction on a phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane with a molar ratio of 1:1.19 under the action of an esterification catalyst at 230 ℃ until the esterification rate is 99%, introducing polycarbodiimide, and further reacting for 0.7h at 255 ℃ to obtain a functional prepolymer; wherein the mass ratio of the polycarbodiimide to the hydroxyl-terminated polysiloxane is 0.19: 1; the addition amount of the esterification catalyst is 350ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product, the functional prepolymer, the heat stabilizer and the antioxidant, performing a pre-polycondensation reaction for 0.8h under the conditions of a temperature of 265 ℃, a pressure of 0.5KPa and a stirring speed of 14rpm, and performing a final polycondensation reaction for 1.5h under the conditions of a temperature of 280 ℃ and a pressure of 70Pa to obtain functional master batches; wherein the mass ratio of the esterification product to the functional prepolymer is 3: 7; the addition amount of the heat stabilizer is 500ppm of the mass of the functional prepolymer; the addition amount of the antioxidant is 500ppm of the mass of the functional prepolymer;
the number average molecular weight of the prepared functional master batch is 12000g/mol, the molecular weight distribution index is 2.6, and the dynamic viscosity is 55 Pa.s.
Blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%.
The polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the inherent viscosity of the polyester fiber without the oil silk is reduced to 0.008 dL/g; the mechanical strength of the polyester fiber is 4cN/dtex, and the LOI is 33%; after high-temperature and high-pressure dyeing, the mechanical strength retention rate is 98.5%, and the LOI is 31%; compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 22 percent, the spinning temperature is reduced by 14 ℃, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The specific process of high-temperature high-pressure dyeing comprises the following steps: the fibers were first added to disperse blue 284 (CAS 71872-43-0, formula C) at 40 ℃ and pH 517H19N5O6S) dispersing dye liquor, heating the dye liquor to 125 ℃ at the heating rate of 2 ℃/min, keeping the temperature, dyeing for 60min under the pressure of 0.176MPa, finally slowly cooling to room temperature, carrying out post-treatment such as reduction cleaning and water washing, and thoroughly removing loose color so as to improve the color fastness and glossiness of the product.
Example 7
A preparation method of functional master batches comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: isophthalic acid;
a dihydric alcohol: propylene glycol;
phosphorus-containing flame retardants: DDP;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 5000 g/mol;
polycarbodiimide having a number average molecular weight of 5000 g/mol;
esterification catalyst: (ii) methyl benzene sulfonic acid;
(2) performing esterification reaction;
carrying out esterification reaction on dibasic acid and dihydric alcohol according to the molar ratio of 1:2, wherein the temperature of the esterification reaction is 260 ℃, the pressure is 0.01MPa, and an esterification product is obtained until the water yield reaches 96% of the theoretical water yield, and the end group of the esterification product is hydroxyl;
(3) preparing a functional prepolymer;
carrying out esterification reaction on a phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane with a molar ratio of 1:1.2 under the action of an esterification catalyst at the temperature of 240 ℃ until the esterification rate is 98%, introducing polycarbodiimide, and further reacting for 1h at the temperature of 245 ℃ to obtain a functional prepolymer; wherein the mass ratio of the polycarbodiimide to the hydroxyl-terminated polysiloxane is 0.2: 1; the addition amount of the esterification catalyst is 400ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product and the functional prepolymer, firstly carrying out pre-polycondensation reaction for 0.5h under the conditions of temperature of 270 ℃, pressure of 0.5KPa and stirring speed of 15rpm, and then carrying out final polycondensation reaction for 1h under the conditions of temperature of 280 ℃ and pressure of 20Pa to obtain functional master batch; wherein the mass ratio of the esterification product to the functional prepolymer is 2: 8;
the prepared functional master batch has the number average molecular weight of 10000g/mol, the molecular weight distribution index of 3 and the dynamic viscosity of 50Pa & s.
Blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%.
The polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the inherent viscosity of the polyester fiber without the oil silk is reduced to 0.01 dL/g; the mechanical strength of the polyester fiber is 3.5cN/dtex, and the LOI is 30%; after high-temperature and high-pressure dyeing, the mechanical strength retention rate is 95%, and the LOI is 28%; compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 10 percent, the spinning temperature is reduced by 5 ℃, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The specific process of high-temperature high-pressure dyeing comprises the following steps: the fibers were first added to disperse blue 284 (CAS 71872-43-0, formula C) at 40 ℃ and pH 517H19N5O6S) dispersing dye liquor, heating the dye liquor to 125 ℃ at the heating rate of 2 ℃/min, keeping the temperature, dyeing for 60min under the pressure of 0.176MPa, finally slowly cooling to room temperature, carrying out post-treatment such as reduction cleaning and water washing, and thoroughly removing loose color so as to improve the color fastness and glossiness of the product.

Claims (10)

1. A preparation method of functional master batches is characterized in that a mixture containing an esterification product and a functional prepolymer is subjected to polycondensation reaction to prepare the functional master batches;
the esterification product is prepared by esterification reaction of dibasic acid and dihydric alcohol, and the end group of the esterification product is hydroxyl;
the preparation process of the functional prepolymer comprises the following steps: firstly, carrying out esterification reaction on a phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane in a molar ratio of 1: 1.05-1.20 until the esterification rate is 95-99%, and then introducing polycarbodiimide for further reaction to prepare a functional prepolymer, wherein the phosphorus-containing flame retardant is DDP.
2. The method of claim 1, wherein the mixture of the esterification product and the functional prepolymer further comprises a thermal stabilizer and an antioxidant.
3. The preparation method of the functional master batch according to claim 2, which is characterized by comprising the following specific steps:
(1) performing esterification reaction;
carrying out esterification reaction on dibasic acid and dihydric alcohol according to a certain molar ratio until the specified water yield is reached to obtain an esterification product;
(2) preparing a functional prepolymer;
carrying out esterification reaction on the phosphorus-containing flame retardant and hydroxyl-terminated polysiloxane under the action of an esterification catalyst, and introducing polycarbodiimide for further reaction after the esterification reaction is finished to prepare a functional prepolymer;
(3) performing polycondensation reaction;
and mixing the esterification product, the functional prepolymer, the heat stabilizer and the antioxidant according to a certain proportion, and then carrying out polycondensation reaction to obtain the functional master batch.
4. The method for preparing the functional master batch according to claim 3, wherein in the step (1), the molar ratio of the dibasic acid to the dihydric alcohol is 1: 1.1-2.0;
the dibasic acid is more than one of terephthalic acid and isophthalic acid; the dihydric alcohol is more than one of ethylene glycol, propylene glycol, butanediol and pentanediol;
the temperature of the esterification reaction is 200-260 ℃, the pressure is 0.01-0.5 MPa, and the specified water yield is 94-98% of the theoretical water yield.
5. The preparation method of the functional master batch according to claim 3, wherein in the step (2), the mass ratio of the polycarbodiimide to the hydroxyl-terminated polysiloxane is 0.05-0.20: 1; the addition amount of the esterification catalyst is 100-400 ppm of the mass of the hydroxyl-terminated polysiloxane;
the number average molecular weight of the hydroxyl-terminated polysiloxane is 1000-5000 g/mol; the number average molecular weight of the polycarbodiimide is 1000-5000 g/mol; the esterification catalyst is methyl benzene sulfonic acid;
the temperature of the esterification reaction is 180-240 ℃; the further reaction temperature is 220-260 ℃ and the time is 0.5-1.5 h.
6. The preparation method of the functional masterbatch according to claim 3, wherein in the step (3), the mass ratio of the esterification product to the functional prepolymer is 5: 5-2: 8; the addition amount of the heat stabilizer is 50-500 ppm of the mass of the functional prepolymer; the addition amount of the antioxidant is 50-500 ppm of the mass of the functional prepolymer;
the heat stabilizer is more than one of trimethyl phosphate, alkyl phosphodiester and tri (nonylphenyl) phosphite ester; the antioxidant is more than one of antioxidant 1010, antioxidant 168 and antioxidant 616;
the polycondensation reaction is divided into two stages of pre-polycondensation reaction and final polycondensation reaction; the temperature of the pre-polycondensation reaction is 240-270 ℃, the pressure is 0.5-1.0 KPa, the time is 0.5-2.5 h, and the stirring speed is 5-15 rpm; the temperature of the final polycondensation reaction is 260-280 ℃, the pressure is 20-200 Pa, and the time is 1.0-5.0 h.
7. A functional master batch is characterized by being prepared by the method of any one of claims 1 to 6; the functional master batch has the number average molecular weight of 10000-20000 g/mol, the molecular weight distribution index of 2.0-3.0 and the dynamic viscosity of 50-100 Pa.s.
8. The use of the functional masterbatch according to claim 7, wherein the functional masterbatch is blended with polyester and then melt-spun to obtain polyester fiber; the mechanical strength retention rate of the polyester fiber after high-temperature and high-pressure dyeing is more than 95%.
9. The application of claim 8, wherein the content of the functional master batch in the blend is 2.0-10.0 wt%; the polyester fiber has a skin-core structure, wherein the skin layer is the functional master batch, and the core layer is the polyester.
10. The use of claim 9, wherein the polyester fiber has an inherent filament-free viscosity drop of 0.01dL/g or less; the LOI of the polyester fiber is more than or equal to 30 percent after high-temperature and high-pressure dyeing.
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