CN109485838B - Copolymerization type high-fluidity cationic polyester master batch matrix material and preparation method thereof - Google Patents

Copolymerization type high-fluidity cationic polyester master batch matrix material and preparation method thereof Download PDF

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CN109485838B
CN109485838B CN201811193197.XA CN201811193197A CN109485838B CN 109485838 B CN109485838 B CN 109485838B CN 201811193197 A CN201811193197 A CN 201811193197A CN 109485838 B CN109485838 B CN 109485838B
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fluidity
chain segment
matrix material
branched structure
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CN109485838A (en
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王华平
吉鹏
王朝生
陈向玲
陈仕艳
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Donghua University
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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
    • 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
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

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Abstract

The invention relates to a copolymerization type high-fluidity cationic polyester master batch matrix material and a preparation method thereof, wherein the method comprises the following steps: uniformly mixing dibasic acid I, dibasic acid II and dihydric alcohol I, then carrying out esterification reaction, introducing a high-fluidity branched structure modifier after the esterification reaction is finished, carrying out pre-polycondensation reaction and final polycondensation reaction to obtain the copolymer type high-fluidity cationic polyester master batch matrix material, wherein the high-fluidity branched structure modifier is an esterified substance which is prepared by the reaction of branched structure acid or anhydride and the dihydric alcohol II and is terminated by hydroxyl. The melt index of the prepared product is 8-15 g/10min, and the viscosity is reduced by less than or equal to 0.02dL/g in the melt processing process. The preparation method has simple process and low cost; the prepared copolymerization type high-fluidity cationic polyester master batch matrix material has excellent fluidity, can effectively improve the phenomena of fiber broken filaments, broken ends and the like by mixing with polyester melt, and has high fiber dye uptake and color fastness and good wearing comfort.

Description

Copolymerization type high-fluidity cationic polyester master batch matrix material and preparation method thereof
Technical Field
The invention belongs to the field of polyester preparation, and relates to a copolymerization type high-fluidity cationic polyester master batch matrix material and a preparation method thereof.
Background
Polyester is a general term for polymers obtained by polycondensation of polyhydric alcohol and polybasic acid, mainly refers to polyethylene terephthalate (PET), and conventionally also includes linear thermoplastic resins such as polybutylene terephthalate (PBT) and polyarylate, and is a polymer with excellent performance and wide application, and has been widely used in the fields of fiber, plastic, film, and the like. With the demand for diversification of clothing fiber products, development of novel polyester fiber materials is more and more urgent.
The development direction of new products of polyester and fiber at present mainly comprises copolymerization modification, blending modification and surface coating finishing. Although polyester has high molecular chain arrangement regularity and good crystallinity, the dyeing process usually needs to be carried out under the conditions of high temperature and high pressure due to the lack of groups capable of effectively adsorbing small molecules (such as dyes and the like) in the structure, so that the energy consumption is high, and meanwhile, the color vividness of the product is low. Therefore, how to improve the dyeing performance of polyester fiber has been a hot spot of industry research.
The method for improving the dyeing property of the polyester fiber comprises a copolymerization modification method and a blending modification method. As for the copolymerization modification method, many existing documents disclose a method of introducing sodium bis (hydroxyethyl) isophthalate-5-sulfonate and polyester to form cationic copolyester in the polyester synthesis process, or further introducing polyethylene glycol with a certain chain segment length to further enhance the dyeing effect to form normal pressure cationic copolyester, and the principle is to enhance the adsorption capacity to dye small molecules by introducing sulfonate groups. Patent CN102094256B discloses a method for producing modified cationic polyester filament and its product, firstly preparing a modified cationic polyester, then melt spinning according to the characteristics of the modified cationic polyester to prepare pre-oriented yarn, and then false twisting the pre-oriented yarn under the special texturing process condition. Patent CN101580974B discloses a continuous production method of cation modified polyester and a continuous production system of modified polyester melt and side-cut slices using the method, which produce cation modified polyester melt and side-cut slices after continuous esterification and polycondensation, the polyester melt can be continuously extruded into a spinning system for spinning through a melt pressure conveying pipeline, the system comprises a two-stage esterification system, a pre-polycondensation reaction system, a final polycondensation reaction system, a melt conveying system, a spinning system and a side-cut slice production system which are connected in sequence, wherein the second esterification reactor adopts a horizontal chamber reactor specially designed for cation polyester production. The method can realize continuous production of the cation modified polyester and direct melt spinning. From the practical application effect, the fibers formed by the cationic copolyester or the normal-pressure cationic copolyester in the patent technology disclosed above can be dyed under the normal-pressure boiling dyeing condition, the dye-uptake rate is obviously improved, and the vividness of the prepared product is also improved. However, the following problems are present: the fluidity of the cationic copolyester formed by the copolymerization modification method is reduced sharply, and because the copolyester contains sulfonate groups, the fluidity of the cationic copolyester is poor due to strong acting force between the groups and large acting force on the inner walls of a reactor and a pipeline, and a certain difficulty is caused in cleaning the cationic polyester melt pipeline.
In terms of the blending modification method, the method for improving the polyester dyeing property by introducing a substance (such as master batch) into a polyester melt in a blending mode has the characteristic of strong flexibility, and particularly when the subsequent application requirements change, the blending modification method can realize quick switching through the change of the addition amount of the master batch, but if a master batch matrix material with a high content of dyeing modification components is prepared, the flow property of the prepared master batch matrix material is generally poor due to the poor flow property of the dyeing modification components represented by cationic modification component sulfonate at high concentration, the conventional method for improving the flow property of the matrix material has limited improvement on the flow property of the polyester master batch matrix material, so that the cost is increased, and other properties of the matrix material are influenced to a certain extent. Chinese patent CN104831404A discloses a cationic polyester FDY slub yarn and a production method thereof, wherein the cationic polyester FDY slub yarn is prepared by mixing a first PET slice with a cationic master batch mainly composed of materials such as isophthalic acid diethylene glycol ester-5-sodium sulfonate, a lubricant, an antioxidant, a dispersant, an ultraviolet absorbent and the like, and then spinning. CN104831403A discloses a trilobal profiled cationic FDY filament and a production method thereof, wherein a cationic master batch mainly composed of a lubricant, an antioxidant, a dispersant, an ultraviolet absorbent and a second PET slice is added into a first PET slice, so that the cationic master batch can be dyed by an anionic dye, and the trilobal profiled cationic FDY filament is prepared. The above patent technologies all use cation master batches to carry out blending modification on polyester, in order to improve the fluidity of the cation master batches, a certain proportion of lubricant is added into the master batches, the lubricant is a stearate substance, but the lubricant is an aliphatic linear chain segment and has limited promotion on the fluidity of sulfonate, and meanwhile, stearate is blended in a matrix, so that the compatibility with polyester is general, and the thermal stability in the processing process is uncertain.
Therefore, finding a high-fluidity modified component and developing a copolymerization type high-fluidity cationic polyester master batch matrix material based on the high-fluidity modified component to improve the fluidity of the polyester is a fundamental approach to solve the above problems.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a copolymerization type high-fluidity cationic polyester master batch matrix material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the molecular chain of the copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a dibasic acid I chain segment, a dibasic acid II chain segment, a dihydric alcohol I chain segment, a dihydric alcohol II chain segment and an M chain segment;
the dibasic acid I chain segment is more than one of dibasic acid chain segments used for synthesizing polyester except for isophthalic acid-5-sodium sulfonate;
the dibasic acid II chain segment is an isophthalic acid-5-sodium sulfonate chain segment;
the dihydric alcohol II chain segment is more than one of ethylene glycol chain segment, propylene glycol chain segment, butanediol chain segment, pentanediol chain segment, hexanediol chain segment, heptanediol chain segment, octanediol chain segment, nonanediol chain segment and decanediol chain segment;
the diol I chain segment is the same as the diol II chain segment or is more than one of the diol chain segments for synthesizing the polyester except the diol II;
the M chain segment is more than one of a pyromellitic acid chain segment, a cyclopentane tetracarboxylic acid chain segment, a benzophenone tetracarboxylic acid chain segment, a trimellitic acid chain segment and a trimellitic acid chain segment;
the melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 8-15 g/10min, and the viscosity is reduced by less than or equal to 0.02dL/g in the melt processing process. The existing preparation method of cation modified master batch is mainly based on granulation after physical mixing, the intrinsic viscosity of master batch matrix material is controlled within 0.45-0.50 dL/g, the number average molecular weight is 10000-12000 g/mol, and the viscosity is reduced to more than 0.05 dL/g. In order to improve the flow property, a stearate lubricant is generally required to be added, but the stearate lubricant is an aliphatic linear segment and has limited promotion on the fluidity of sulfonate, and meanwhile, the stearate is blended in a matrix, has general compatibility with polyester and poor thermal stability, and cannot meet the processing requirement of fine denier fibers, particularly superfine denier fibers. In the invention, a branched structure acid or anhydride chain segment (pyromellitic chain segment, cyclopentane tetracarboxylic acid chain segment, benzophenone tetracarboxylic acid chain segment, trimellitic acid chain segment and trimellitic acid chain segment) and an aliphatic flexible chain segment (dihydric alcohol II chain segment) are introduced into a copolyester molecular structure, the intrinsic viscosity is 0.55-0.65 dL/g, the melt molecular weight is improved, the fluidity is improved, the requirements of superfine denier fiber processing on a melt are met, the movement of the molecular chain can be promoted in the melting process, the flow property of a master batch matrix material is obviously improved, the residence time in a pipeline is greatly reduced, and the viscosity reduction is effectively controlled.
As a preferred technical scheme:
the copolymerization type high-fluidity cation polyester master batch base material has the number average molecular weight of 14000-20000 g/mol and the intrinsic viscosity of 0.55-0.65 dL/g.
The invention also provides a method for preparing the copolymerization type high-fluidity cationic polyester master batch base material, which comprises the steps of uniformly mixing the dibasic acid I, the dibasic acid II and the dibasic alcohol I, then carrying out esterification reaction, introducing the high-fluidity branched structure modifier after the esterification reaction is finished, and carrying out pre-polycondensation reaction and final polycondensation reaction to obtain the copolymerization type high-fluidity cationic polyester master batch base material;
the dibasic acid I is more than one of dibasic acids used for synthesizing polyester except for isophthalic acid-5-sodium sulfonate;
the dibasic acid II is isophthalic acid-5-sodium sulfonate;
the high-fluidity branched structure modifier is an ester which is prepared by the reaction of a branched structure acid or anhydride and dihydric alcohol II and is terminated by hydroxyl;
the branched structure acid or anhydride is more than one of pyromellitic anhydride, cyclopentane tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, trimellitic anhydride, trimellitic dianhydride, pyromellitic acid, cyclopentane tetracarboxylic acid, benzophenone tetracarboxylic acid, trimellitic acid and trimellitic acid;
the dihydric alcohol II is more than one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol and decanediol;
the dihydric alcohol I is the same as the dihydric alcohol II or is more than one of dihydric alcohols used for synthesizing polyester except the dihydric alcohol II.
The high-fluidity branched structure modifier selected by the invention has a branched structure (branched structure acid or anhydride), the reaction activity is higher, and acid with a branched structure (such as pyromellitic acid, cyclopentanetetracarboxylic acid, benzophenone tetracarboxylic acid, trimellitic acid or trimellitic acid) reacts with dihydric alcohol II in the esterification stage and is connected into a polyester molecular chain. Acid anhydride with a branched structure (such as pyromellitic anhydride, cyclopentane tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, trimellitic anhydride or trimellitic dianhydride) can be combined with water molecules generated by esterification reaction in the esterification process to form acid with a branched structure (such as pyromellitic acid, cyclopentane tetracarboxylic acid, benzophenone tetracarboxylic acid, trimellitic acid or trimellitic acid), and then the acid with a branched structure reacts with dihydric alcohol II to be connected into a polyester molecular chain.
As a preferred technical scheme:
the preparation conditions of the high-fluidity branched structure modifier, as described above, were: the temperature is 180-240 ℃, the pressure is normal pressure, the time is 2.5-4.0 h, the molar ratio of the branched structure acid or anhydride to the dihydric alcohol II is 1: 1.6-2.0, the catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 100-300 ppm of the mass of the branched structure acid or anhydride.
The preparation temperature of the high-fluidity branched structure modifier may be varied within a suitable range, but is not too high, and when the preparation temperature is too low, the esterification reaction rate of the branched structure acid or acid anhydride with the diol II is too low, resulting in that the unreacted monomer is mainly contained in the product. When the temperature is too high, the reaction rate of the glycol II self-polycondensation is accelerated, and the proportion of glycol II self-polycondensation byproducts in the product is increased sharply.
The preparation pressure of the high-fluidity branched structure modifier can be changed within a proper range, but is not too high, and too low preparation pressure (under the negative pressure condition) can cause the diol II monomer to be pumped out from the reaction system under the negative pressure condition, so that the esterification reaction cannot be continuously completed, and adverse effects are caused on pipelines. When the pressure is too high, on the one hand, more severe requirements are made on the pressure resistance of the reaction equipment, and on the other hand, the self-polycondensation by-products of the dihydric alcohol II are increased.
The preparation time of the high-fluidity branched structure modifier may be varied within a suitable range, but it is not preferable that the preparation time is too short, which may result in incomplete esterification reaction and unreacted monomers in the product. Too long a preparation time can cause side reactions such as thermal degradation and the like to occur when the product stays under high temperature conditions for too long.
When the high-fluidity branched structure modifier is prepared, the molar ratio of the branched structure acid or anhydride to the dihydric alcohol II can be changed within a proper range, but the molar ratio is not too high, and the problems of reduced esterification reaction rate, prolonged esterification reaction process and low efficiency can occur when the molar ratio of the branched structure acid or anhydride to the alcohol is too low. Too high a molar ratio may result in serious side reactions such as self-polycondensation of alcohol in the system, and waste of alcohol raw material.
When the high-fluidity branched structure modifier is prepared, the addition amount of the catalyst can be changed within a proper range, but the addition amount of the catalyst is not too high, and the esterification reaction is limited due to the fact that the addition amount of the catalyst is too low, the reaction rate is slow, and the efficiency is low. Too high catalyst addition can result in too rapid esterification reaction rate, harsh requirements on heat and mass transfer in the reaction process, and poor reaction controllability.
The method comprises the following specific steps:
(1) prepared slurry
Mixing and pulping dibasic acid I, dibasic acid II, dihydric alcohol I and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is prepared by compounding a titanium-silicon composite catalyst and a cobalt catalyst, and the titanium-silicon composite catalyst is prepared by loading a titanium catalyst on a silicon catalyst;
the titanium-based composite catalyst is adopted, so that the catalytic effect is ensured, and the final product can be improved, and other catalysts except the titanium-silicon-cobalt composite catalyst can be selected, but side reactions are increased and the color of the product is poor, so that the composite catalyst can realize higher catalytic activity and improve the color of the product;
the specific preparation method of the titanium composite catalyst comprises the following steps:
the titanium series composite catalyst is made of TiO2-SiO2The composite catalyst and the cobalt catalyst are mixed and added into a polymerization system according to a certain proportion. Wherein, TiO is obtained by adopting a sol-gel method2-SiO2The composite catalyst method comprises the following steps: proper amount of ethyl orthosilicate, ethanol, distilled water and nitric acid are added into a three-neck flask in sequence and mixed evenly. The three-neck flask is placed on a magnetic stirrer to be heated and refluxed, the heating temperature is set to be 65 ℃, the stirring speed is 820r/min, and the reflux is carried out for 2 hours. After the ethyl orthosilicate is completely hydrolyzed, 40.0g of tetrabutyl titanate is added into the three-neck flask and stirred for 20min, so that the tetrabutyl titanate and the reactants are uniformly mixed. And (3) dropwise adding a proper amount of distilled water slowly at a certain speed by using a constant-pressure burette. After the addition was complete, the mixture was refluxed at 65 ℃ for 2 hours. After the gel was formed, it was aged at room temperature for 12 h. Drying at 110 deg.C for 12h in a forced air drying oven, removing water and ethanol solvent in the reaction system, and grinding the dried solid in a mortar. Putting the ground powder into a muffle furnace, setting the baking temperature to be 500 ℃, starting timing when the temperature reaches the set temperature, and baking for 3 hours. After the roasting is finished, taking out the roasted material, naturally cooling the roasted material, and finally obtaining the TiO2-SiO2A composite catalyst;
(2) esterification reaction
Carrying out esterification reaction on the slurry;
(3) polycondensation reaction
Adding a high-fluidity branched structure modifier, a heat stabilizer and an antioxidant into the esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain the copolymerization type high-fluidity cationic polyester master batch matrix material. Although the invention can obtain the polycondensation product without adding a heat stabilizer and an antioxidant, the product is easy to generate side reactions such as thermal degradation, thermal oxidative degradation and the like due to long-term high-temperature conditions in the polycondensation process.
In the above method, the dibasic acid is one or more of terephthalic acid, isophthalic acid and furandicarboxylic acid, the diol I is one or more of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol and decylene glycol, the titanium-based catalyst is tetrabutyl titanate or metatitanic acid, the silicon-based catalyst is silica, the cobalt-based catalyst is cobalt acetate, the heat stabilizer is one or more of trimethyl phosphate, alkylphosphonic diester and tris (nonylphenyl) phosphite, and the antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant 616.
According to the method, in the step (1), the stirring speed of mixing and pulping is 5-25 rpm, and the time is 0.5-1.0 h; the dibasic acid I, the dibasic acid II, the dihydric alcohol I and other auxiliaries are mixed in the slurry preparation stage, so that the components can be uniformly dispersed in the system, and the subsequent uniform and stable participation in the esterification reaction is ensured. At the moment, only the material mixing stage is adopted, the system viscosity is low, and the material mixing process can be realized without overhigh stirring speed or overlong stirring time, so that the stirring speed is controlled to be 5-25 rpm, and the time is 0.5-1.0 h. The stirring speed and time of mixing and beating can be reduced adaptively but are not too high, and the effective mixing of materials cannot be realized by too low stirring speed and too low stirring time.
The molar ratio of the dibasic acid I to the dibasic acid II is 1: 4-3: 2; the ratio of the sum of the molar weight of the dibasic acid I and the molar weight of the dibasic acid II to the molar weight of the dibasic alcohol I is 1: 1.1-2.0, the addition amount of the titanium-based composite catalyst is 20-200 ppm of the sum of the mass of the dibasic acid I and the mass of the dibasic acid II, and the molar ratio of the titanium-based catalyst, the silicon-based catalyst and the cobalt-based catalyst in the titanium-based composite catalyst is 1: 0.1-10.
The reaction among the dibasic acid I, the dibasic acid II and the dibasic alcohol I belongs to the organic chemical reaction of alcohol acid, excessive dibasic alcohol I in a certain range can promote the reaction to be carried out in the positive direction, the ratio of the sum of the molar quantities of the dibasic acid I and the dibasic acid II to the molar quantity of the dibasic alcohol I can be reduced adaptively but is not too high, the dibasic alcohol I is too high, the waste of the dibasic alcohol I is caused, and the dibasic alcohol I can generate self-polycondensation side reaction under the high-temperature condition, so the molar ratio of the sum of the molar quantities of the dibasic acid I and the dibasic acid II to the dibasic alcohol I is controlled to be 1: 1.1-2.0. The addition amount of the titanium composite catalyst can be changed within a proper range but is not too large, the catalytic effect is reduced due to too low addition amount of the catalyst, the reaction time is prolonged, the efficiency is reduced, the reaction is too fast due to too high addition amount of the catalyst, the risk of 'implosion' is possible to occur, and the cost is increased.
According to the method, in the step (2), the temperature of the esterification reaction is 200-260 ℃, the pressure is 20-80 KPa, the time is 2-4 h, and the stirring speed is 5-20 rpm; the intrinsic viscosity of the esterification reaction product is 0.10-0.25 dL/g.
The esterification temperature is controlled to be 200-260 ℃, the temperature of the esterification reaction can be changed within a proper range, but the esterification reaction is not too high, the rate of the esterification reaction can be further accelerated by too high temperature, but the rate of side reaction can also be accelerated, and the heat requirement in the esterification reaction and the dissolving process cannot be met by too low temperature. The esterification reaction is slightly positive in pressure, and the pressure is controlled to be 20-80 kPa, because small molecular water is generated in the esterification process due to the reaction and has a certain positive pressure, the esterification reaction rate can be promoted to be increased. The pressure of the esterification reaction can be changed within a proper range, but the pressure is not too high, and the higher pressure can put higher requirements on an esterification reaction device.
The stirring speed of the invention is controlled at 5-20 rpm, at the moment, the viscosity of the slurry in the esterification reaction kettle is slightly increased compared with that in the pulping kettle, the stirring speed of the esterification reaction can be changed within a proper range, but the stirring speed is not too high, the mixing of the slurry cannot be realized at too low stirring speed, the requirement on a stirrer is higher at too high stirring speed, and the energy consumption is increased.
The esterification reaction time is determined according to the types of the dibasic acid I, the dibasic acid II and the dibasic alcohol I, the reaction time is 2-4 hours, the esterification rate is ensured to be more than 96%, the esterification reaction time can be changed within a proper range, but the reaction time is not too long, the sufficient reaction of the alcoholic acid functional group cannot be ensured due to too short esterification reaction time, and the esterification rate is difficult to further improve due to too long esterification reaction time and side reactions are increased.
The intrinsic viscosity of the esterification reaction product can be changed within a proper range, but is not too high, the low intrinsic viscosity of the esterification reaction product means low molecular weight, so that the esterification product is easy to be pumped into a vacuum pipeline when entering a polycondensation stage, and the high intrinsic viscosity means high molecular weight, so that the activity of the esterification reaction product and the dihydric alcohol II in the polycondensation stage can be reduced.
In the method, in the step (3), the temperature of the pre-polycondensation reaction is 220-270 ℃, the pressure is 0.5-1.0 KPa, the time is 0.5-2.5 h, the stirring speed is 5-15 rpm, the temperature of the final polycondensation reaction is 220-270 ℃, the pressure is 0-200 Pa, the time is 1.0-3.0 h, and the stirring speed is 5-10 rpm;
the pre-polycondensation reaction temperature is controlled to be 220-270 ℃, and can be changed within a proper range, but is not too high, because the pre-polycondensation reaction cannot be carried out due to too low reaction temperature, thermal degradation side reactions are increased in the pre-polycondensation reaction process due to too high reaction temperature, and the color of the formed product is poor.
The pre-polycondensation reaction pressure is controlled to be 0.5-1.0 KPa, compared with the final polycondensation vacuum degree, the pre-polycondensation reaction pressure can be changed in a proper range, but the pre-polycondensation reaction pressure is not too high, low viscosity prepolymer in the pre-polycondensation reaction can be pumped out due to too low pressure (namely, higher vacuum effect) to block a pipeline to cause polycondensation accidents, small molecules in the polycondensation reaction can not be removed due to too high pressure (namely, poorer vacuum effect), and the pre-polycondensation reaction can not be normally carried out.
The pre-polycondensation reaction time is controlled to be 0.5-2.5 h, can be changed within a proper range, but is not too long, the pre-polycondensation reaction time is too short, the reaction is insufficient, the pre-polycondensation reaction time is too long, thermal degradation side reactions in the pre-polycondensation reaction process at high temperature are increased, and the effective increase of the molecular weight cannot be realized.
The stirring speed of the pre-polycondensation reaction is 5-15 rpm, the viscosity of the material in the pre-polycondensation reaction process is higher than that of an esterification reaction product and lower than that of a final polycondensation reaction product, the stirring speed of the pre-polycondensation reaction can be changed within a proper range, but the stirring speed is not too high, the pre-polycondensation product with lower viscosity can be brought out together with dihydric alcohol under a vacuum environment due to the too high stirring speed, the reaction is not favorable, and the effect of uniformly stirring the material cannot be achieved due to the too low stirring speed.
The final polycondensation reaction temperature is controlled to be 220-270 ℃, the final polycondensation reaction temperature can be changed within a proper range, but the final polycondensation reaction temperature is not too high, the final polycondensation reaction cannot be carried out due to too low reaction temperature, thermal degradation side reactions are increased in the final polycondensation reaction process due to too high reaction temperature, and the color of the formed product is poor.
The final polycondensation reaction pressure is controlled to be 0-200 Pa, and can be changed within a proper range, but is not too high, the requirement on equipment is higher due to too low pressure (namely higher vacuum effect), small molecules in the polycondensation reaction cannot be removed due to too high pressure (namely poorer vacuum effect), and the final polycondensation reaction cannot be normally carried out.
The final polycondensation reaction time is controlled to be 1.0-3.0 h, the final polycondensation reaction time can be changed in a proper range, but the final polycondensation reaction time is not too long, the formed product cannot reach the spinning grade due to too short final polycondensation reaction time, the thermal degradation side reaction of the polymer under the high-temperature condition is obviously increased due to too long final polycondensation reaction time, and the number average molecular weight of the product is rapidly reduced due to thermal degradation after reaching the maximum number average molecular weight.
The stirring speed of the final polycondensation reaction is 5-10 rpm, the viscosity of materials in the final polycondensation reaction process is higher than that of a pre-polycondensation reaction product, the higher the viscosity of the product is, the harder the stirring is, the stirring speed of the final polycondensation reaction can be changed within a proper range, but the stirring speed is not too high, the stirring effect cannot be realized for a high-viscosity polymer system by using the too high stirring speed, and meanwhile, the motor is damaged due to too high current, and the uniform stirring effect of the materials cannot be realized by using the too low stirring speed.
The addition amount of the high-fluidity branched structure modifier is 1-20% of the mole fraction of the dibasic acid II in the slurry, the addition amount of the heat stabilizer is 0.001-0.02% of the mass sum of the dibasic acid I and the dibasic acid II, and the addition amount of the antioxidant is 0.001-0.03% of the mass sum of the dibasic acid I and the dibasic acid II.
The invention mechanism is as follows:
the invention introduces an isophthalic acid-5-sodium sulfonate chain segment and a high-fluidity branched structure modifier chain segment into a polyester molecular chain based on the principles of molecular structure design and copolymerization reaction, thereby preparing a cation polyester master batch matrix material with excellent flow property, wherein the high-fluidity branched structure modifier is a hydroxyl-terminated esterified substance formed by the reaction of a branched structure acid or anhydride and aliphatic dihydric alcohol (dihydric alcohol II), and is connected into the polyester molecular chain through ester exchange reaction; the aliphatic diol contained in the high-fluidity branched structure modifier has proper molecular weight and high reactivity, belongs to an aliphatic flexible chain segment, further improves the fluidity of polyester on the basis of ensuring full reaction, the chain segment length of the aliphatic diol is a key condition, if the chain segment is too long, the chain entanglement is increased, the fluidity is poor, and meanwhile, the reactivity is reduced due to too long chain segment, so that the aliphatic diol is difficult to be introduced into a polyester molecular chain through an ester exchange reaction process.
The branched structure acid or anhydride chain segment in the high-fluidity branched structure modifier and the aliphatic diol chain segment play a synergistic role, if only the branched structure acid or anhydride is added in the polycondensation stage, the branched structure acid or anhydride cannot react with an esterification reaction product formed by mixed dibasic acid (including dibasic acid II and dibasic acid I) and the dibasic alcohol I due to certain steric hindrance effect, because the molecular chain of the esterification reaction product formed by the mixed dibasic acid and the dibasic alcohol I is longer, the terminal hydroxyl of the longer molecular chain cannot form an effective alcohol acid organic chemical reaction with the branched structure acid or anhydride, so that the branched structure acid or anhydride exists in a matrix material in a carboxyl form, the carboxyl can cause very adverse effect on the thermal stability of the polymer, and the flow property of the matrix material cannot be effectively improved; if only the dihydric alcohol II is added in the polycondensation reaction stage, the reaction system is in a negative pressure state because the polycondensation reaction stage is adopted, and the dihydric alcohol II with small molecular weight is easily extracted, which causes adverse effect on the stability of polymerization and waste of the raw material of the dihydric alcohol II. The branched structure acid or anhydride and the dihydric alcohol II are subjected to chemical reaction at first, and then are introduced in the polyester polycondensation stage, and are connected into a polyester molecular chain, so that the problems are effectively solved, the branched structure acid or anhydride promotes the flow property of the master batch matrix material, the introduction of the dihydric alcohol II improves the activity of the prepared high-fluidity branched structure modifier participating in ester exchange reaction, the introduction of the branched structure acid or anhydride improves the molecular weight of the dihydric alcohol II, so that the dihydric alcohol II is not easy to extract, meanwhile, the fluidity of the master batch matrix material can be further enhanced, the dihydric alcohol II and the branched structure acid or anhydride have synergistic effect, the effective connection of the high-fluidity branched structure modifier in the polyester molecular chain is ensured, and the flow property of the polyester master batch matrix material is further improved.
Has the advantages that:
(1) the preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material has simple process, prepares the polyester master batch matrix material with excellent fluidity by introducing the high-fluidity branched structure modifier, has low cost and has wide application prospect;
(2) the copolymerization type high-fluidity cationic polyester master batch matrix material disclosed by the invention is excellent in fluidity, functional inorganic powder materials can be introduced to prepare functional master batches, and meanwhile, the matrix material contains high-fluidity components with high content, and the components are rich in functional groups such as ether bonds and ester bonds, and can also be directly used as polyester blending modified master batches, so that the hand feeling and the dyeing property of polyester fibers are effectively improved, and the application prospect is good.
Drawings
FIG. 1 shows the NMR spectrum of the matrix material of the copolymer type high-fluidity cationic polyester masterbatch prepared in example 1 (i.e. the NMR spectrum1H-NMR spectrum).
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
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping phthalic acid, 5-sodium sulfoisophthalate, ethylene glycol and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is prepared by compounding silicon dioxide loaded tetrabutyl titanate with cobalt acetate, the mixing and pulping stirring speed is 10rpm, the time is 0.8h, and the molar ratio of the phthalic acid to the 5-sodium sulfoisophthalate is 1: 4; the ratio of the sum of the molar weight of the phthalic acid and the isophthalic acid-5-sodium sulfonate to the molar weight of the ethylene glycol is 1:1.1, the adding amount of the titanium composite catalyst is 100ppm of the sum of the mass of the phthalic acid and the isophthalic acid-5-sodium sulfonate, and the molar ratio of tetrabutyl titanate, silicon dioxide and cobalt acetate in the titanium composite catalyst is 1:0.8: 3;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 200 ℃, the pressure is 40KPa, the time is 2h, the stirring speed is 13rpm, and the intrinsic viscosity of the esterification reaction product is 0.15 dL/g;
(3) preparation of high-fluidity branched structure modifier
The preparation method comprises the following steps of reacting pyromellitic dianhydride with ethylene glycol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an esterified substance capped by hydroxyl, the reaction temperature is 180 ℃, the pressure is normal pressure, the reaction time is 2.5 hours, the molar ratio of the pyromellitic dianhydride to the ethylene glycol is 1:1.8, a catalyst is p-toluenesulfonic acid, and the addition amount of the toluenesulfonic acid is 120ppm of the mass of the pyromellitic dianhydride;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, trimethyl phosphate and an antioxidant 1010 into an esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain the copolymer type high-fluidity cationic polyester master batch base material, wherein the addition amount of the high-fluidity branched structure modifier is 7% of the mole fraction of isophthalic acid-5-sodium sulfonate in the slurry, the temperature of the pre-polycondensation reaction is 230 ℃, the pressure is 0.6KPa, the time is 0.5h, the stirring speed is 11rpm, the temperature of the final polycondensation reaction is 240 ℃, the pressure is 130Pa, the time is 1.0h, the stirring speed is 6rpm, the addition amount of the trimethyl phosphate is 0.005% of the mass sum of the phthalic acid and the isophthalic acid-5-sodium sulfonate, and the addition amount of the antioxidant 1010 is 0.015% of the mass sum of the phthalic acid and the isophthalic acid-5-sodium sulfonate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a phthalic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, an ethylene glycol chain segment and a pyromellitic dianhydride chain segment, and the pyromellitic dianhydride chain segment is connected with the ethylene glycol chain segment to form a high-fluidity branched structure modifier chain segment. Copolymerization type high-fluidity cationic polyester master batch matrix material1The H-NMR spectrum is shown in figure 1, the hydrogen atom of pyromellitic acid in the introduced high-fluidity branched structure modifier is at chemical shift delta a, and the chemical shifts of ethylene glycol are at delta c and delta d, which shows that the high-fluidity branched structure modifier is grafted into the polyester molecular chain, and can be used for preparing the polyesterSo as to realize the improvement of the flow performance of the master batch matrix material.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 10g/10min, and the viscosity is reduced to 0.015dL/g in the melt processing process.
The copolymerization type high-fluidity cation polyester master batch matrix material has the number average molecular weight of 14000g/mol and the intrinsic viscosity of 0.6 dL/g.
Example 2
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping isophthalic acid, isophthalic acid-5-sodium sulfonate, propylene glycol and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is prepared by compounding silicon dioxide loaded metatitanic acid with cobalt acetate, the mixing and pulping stirring speed is 18rpm, the time is 0.8h, and the molar ratio of the isophthalic acid to the isophthalic acid-5-sodium sulfonate is 1: 3; the ratio of the sum of the molar weight of isophthalic acid and isophthalic acid-5-sodium sulfonate to the molar weight of propylene glycol is 1:1.5, the addition amount of the titanium composite catalyst is 50ppm of the sum of the mass of isophthalic acid and isophthalic acid-5-sodium sulfonate, and the molar ratio of metatitanic acid, silicon dioxide and cobalt acetate in the titanium composite catalyst is 1:1: 8;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 210 ℃, the pressure is 60KPa, the time is 4h, the stirring speed is 5rpm, and the intrinsic viscosity of the esterification reaction product is 0.10 dL/g;
(3) preparation of high-fluidity branched structure modifier
Reacting cyclopentane tetracarboxylic dianhydride and propylene glycol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an ester capped by hydroxyl, the reaction temperature is 190 ℃, the pressure is normal pressure, the time is 2.5h, the molar ratio of the cyclopentane tetracarboxylic dianhydride to the propylene glycol is 1:1.6, the catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 150ppm of the weight of the cyclopentane tetracarboxylic dianhydride;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, trimethyl phosphate and an antioxidant 168 into an esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain the copolymer type high-fluidity cationic polyester master batch base material, wherein the addition amount of the high-fluidity branched structure modifier is 4% of the mole fraction of isophthalic acid-5-sodium sulfonate in the slurry, the temperature of the pre-polycondensation reaction is 270 ℃, the pressure is 0.5KPa, the time is 1h, the stirring rate is 13rpm, the temperature of the final polycondensation reaction is 220 ℃, the pressure is 80Pa, the time is 1.0h, the stirring rate is 5rpm, the addition amount of the trimethyl phosphate is 0.009% of the mass sum of the isophthalic acid and the isophthalic acid-5-sodium sulfonate, and the addition amount of the antioxidant 168 is 0.02% of the mass sum of the isophthalic acid and the isophthalic acid-5-sodium sulfonate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises an isophthalic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, a propylene glycol chain segment and a cyclopentane tetracarboxylic dianhydride chain segment, and the cyclopentane tetracarboxylic dianhydride chain segment is connected with the propylene glycol chain segment to form a high-fluidity branched structure modifier chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 9g/10min, and the viscosity is reduced to 0.01dL/g in the melt processing process.
The number average molecular weight of the copolymerization type high-fluidity cation polyester master batch matrix material is 15000g/mol, and the intrinsic viscosity is 0.55 dL/g.
Example 3
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping furan dicarboxylic acid, isophthalic acid-5-sodium sulfonate, butanediol and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is prepared by compounding a silicon dioxide-loaded tetrabutyl titanate titanium-silicon composite catalyst and cobalt acetate, the mixing and pulping speed is 22rpm, the time is 0.5h, and the molar ratio of furan dicarboxylic acid to isophthalic acid-5-sodium sulfonate is 1: 2; the ratio of the sum of the molar weight of the furandicarboxylic acid and the isophthalic acid-5-sodium sulfonate to the molar weight of the butanediol is 1:1.8, the adding amount of the titanium composite catalyst is 90ppm of the sum of the mass of the furandicarboxylic acid and the isophthalic acid-5-sodium sulfonate, and the molar ratio of tetrabutyl titanate, silicon dioxide and cobalt acetate in the titanium composite catalyst is 1:0.1: 4.5;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 220 ℃, the pressure is 75KPa, the time is 4h, the stirring speed is 10rpm, and the intrinsic viscosity of the esterification reaction product is 0.18 dL/g;
(3) preparation of high-fluidity branched structure modifier
Reacting benzophenone tetracarboxylic dianhydride with ethylene glycol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an esterified substance capped with hydroxyl, the reaction temperature is 190 ℃, the pressure is normal pressure, the time is 3 hours, the molar ratio of the benzophenone tetracarboxylic dianhydride to the ethylene glycol is 1:1.9, a catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 100ppm of the mass of the benzophenone tetracarboxylic dianhydride;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, diethyl dodecyl phosphonate and an antioxidant 616 into an esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain a copolymerization type high-fluidity cationic polyester master batch base material, wherein the addition amount of the high-fluidity branched structure modifier is 15% of the mole fraction of isophthalic acid-5-sodium sulfonate in slurry, the temperature of the pre-polycondensation reaction is 250 ℃, the pressure is 0.8KPa, the time is 1h, the stirring speed is 10rpm, the temperature of the final polycondensation reaction is 220 ℃, the pressure is 100Pa, the time is 1.5h, and the stirring speed is 10 rpm; the addition amount of diethyl dodecyl phosphonate is 0.015 percent of the mass sum of the furandicarboxylic acid and the isophthalic acid-5-sodium sulfonate, and the addition amount of the antioxidant 616 is 0.02 percent of the mass sum of the furandicarboxylic acid and the isophthalic acid-5-sodium sulfonate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a furan dicarboxylic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, a butanediol chain segment, an ethylene glycol chain segment and a benzophenone tetracarboxylic dianhydride chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 13g/10min, and the viscosity is reduced to 0.015dL/g in the melt processing process.
The copolymerization type high-fluidity cation polyester master batch matrix material has the number average molecular weight of 16000g/mol and the intrinsic viscosity of 0.55 dL/g.
Example 4
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping a mixture of phthalic acid and isophthalic acid (the mass ratio is 1:1), isophthalic acid-5-sodium sulfonate, pentanediol and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is obtained by compounding silicon dioxide-loaded metatitanic acid and cobalt acetate, the mixing and pulping stirring speed is 8rpm, the time is 0.8h, and the molar ratio of the mixture of phthalic acid and isophthalic acid to isophthalic acid-5-sodium sulfonate is 1: 1; the ratio of the sum of the molar weight of the mixture of the phthalic acid and the isophthalic acid-5-sodium sulfonate to the molar weight of the pentanediol is 1:1.2, the addition amount of the titanium composite catalyst is 130ppm of the sum of the mass of the mixture of the phthalic acid and the isophthalic acid-5-sodium sulfonate, and the molar ratio of the metatitanic acid, the silicon dioxide and the cobalt acetate in the titanium composite catalyst is 1:5: 10;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 200 ℃, the pressure is 35KPa, the time is 2h, the stirring speed is 20rpm, and the intrinsic viscosity of the esterification reaction product is 0.10 dL/g;
(3) preparation of high-fluidity branched structure modifier
Reacting trimellitic anhydride and propylene glycol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an esterified product terminated by hydroxyl, the reaction temperature is 185 ℃, the pressure is normal pressure, the time is 4.0h, the molar ratio of the trimellitic anhydride to the propylene glycol is 1:1.7, a catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 100ppm of the mass of the trimellitic anhydride;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, tris (nonylphenyl) phosphite and a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 1:1 into an esterification reaction product, and then carrying out a pre-polycondensation reaction and a final polycondensation reaction to obtain a copolymer type high-fluidity cationic polyester master batch matrix material, wherein the addition amount of the high-fluidity branched structure modifier is 7.5% of the mole fraction of isophthalic acid-5-sodium sulfonate in the slurry, the temperature of the pre-polycondensation reaction is 240 ℃, the pressure is 0.9KPa, the time is 2.5h, the stirring rate is 5rpm, the temperature of the final polycondensation reaction is 230 ℃, the pressure is 90Pa, the time is 2.0h, and the stirring rate is 8 rpm; the amount of tris (nonylphenyl) phosphite added was 0.02% of the sum of the masses of the mixture of phthalic acid and isophthalic acid and sodium 5-sulfonate isophthalate, and the amount of the mixture of antioxidant 1010 and antioxidant 168 was 0.022% of the sum of the masses of the mixture of phthalic acid and isophthalic acid and sodium 5-sulfonate isophthalate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a phthalic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, a pentanediol chain segment, a propylene glycol chain segment and a trimellitic anhydride chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 10g/10min, and the viscosity is reduced to 0.018dL/g in the melt processing process.
The copolymerization type high-fluidity cation polyester master batch matrix material has the number average molecular weight of 18000g/mol and the intrinsic viscosity of 0.58 dL/g.
Example 5
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping a mixture of phthalic acid and furandicarboxylic acid (the mass ratio is 2:1), isophthalic acid-5-sodium sulfonate, hexanediol and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is obtained by compounding silicon dioxide loaded tetrabutyl titanate and cobalt acetate, the mixing and pulping stirring speed is 5rpm, the time is 0.6h, and the molar ratio of the mixture of the phthalic acid and the furandicarboxylic acid to the isophthalic acid-5-sodium sulfonate is 1: 2; the ratio of the sum of the molar weight of the mixture of the phthalic acid and the furandicarboxylic acid and the isophthalic acid-5-sodium sulfonate to the molar weight of the hexanediol is 1:1.8, the addition amount of the titanium composite catalyst is 180ppm of the sum of the mass of the mixture of the phthalic acid and the furandicarboxylic acid and the isophthalic acid-5-sodium sulfonate, and the molar ratio of tetrabutyl titanate, silicon dioxide and cobalt acetate in the titanium composite catalyst is 1:10: 0.1;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 250 ℃, the pressure is 20KPa, the time is 2.5h, the stirring speed is 15rpm, and the intrinsic viscosity of the esterification reaction product is 0.25 dL/g;
(3) preparation of high-fluidity branched structure modifier
Reacting pyromellitic dianhydride and butanediol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an ester capped by hydroxyl, the reaction temperature is 195 ℃, the pressure is normal pressure, the time is 4.0h, the molar ratio of the pyromellitic dianhydride to the butanediol is 1:2.0, the catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 180ppm of the mass of the pyromellitic dianhydride;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, a mixture of trimethyl phosphate and diethyl dodecyl phosphonate in a mass ratio of 2:1 and an antioxidant 168 into an esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain a copolymer type high-fluidity cationic polyester master batch base material, wherein the addition amount of the high-fluidity branched structure modifier is 1% of the mole fraction of isophthalic acid-5-sodium sulfonate in the slurry, the temperature of the pre-polycondensation reaction is 235 ℃, the pressure is 0.5KPa, the time is 1.5h, the stirring speed is 8rpm, the temperature of the final polycondensation reaction is 270 ℃, the pressure is 150Pa, the time is 2.5h, and the stirring speed is 8 rpm; the amount of the mixture of trimethyl phosphate and diethyl dodecylphosphonate added was 0.001% by mass of the sum of the mass of the mixture of phthalic acid and furandicarboxylic acid and sodium 5-sulfonate of isophthalic acid, and the amount of the antioxidant 168 was 0.028% by mass of the sum of the mass of the mixture of phthalic acid and furandicarboxylic acid and sodium 5-sulfonate of isophthalic acid.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a phthalic acid chain segment, a furan dicarboxylic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, a hexanediol chain segment, a butanediol chain segment and a pyromellitic dianhydride chain segment, and the pyromellitic dianhydride chain segment is connected with the butanediol chain segment to form a high-fluidity branched structure modifier chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 8g/10min, and the viscosity is reduced to 0.009dL/g in the melt processing process.
The copolymerization type high-fluidity cation polyester master batch matrix material has the number average molecular weight of 19000g/mol and the intrinsic viscosity of 0.59 dL/g.
Example 6
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping a mixture of phthalic acid, isophthalic acid and furandicarboxylic acid (the mass ratio is 1:1:1), 5-sodium sulfoisophthalate, heptanediol and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is obtained by compounding silicon dioxide loaded metatitanic acid and cobalt acetate, the mixing and pulping stirring speed is 23rpm and the time is 1.0h, and the molar ratio of the mixture of the phthalic acid, the isophthalic acid and the furandicarboxylic acid to the 5-sodium sulfoisophthalate is 1: 1; the ratio of the sum of the molar weight of the mixture of the phthalic acid, the isophthalic acid and the furandicarboxylic acid and the 5-sodium sulfoisophthalate to the molar weight of the heptanediol is 1:2.0, the adding amount of the titanium composite catalyst is 200ppm of the sum of the mass of the mixture of the phthalic acid, the isophthalic acid and the furandicarboxylic acid and the 5-sodium sulfoisophthalate, and the molar ratio of the metatitanic acid, the silicon dioxide and the cobalt acetate in the titanium composite catalyst is 1:10: 7.5;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 240 ℃, the pressure is 80KPa, the time is 3h, the stirring speed is 18rpm, and the intrinsic viscosity of the esterification reaction product is 0.20 dL/g;
(3) preparation of high-fluidity branched structure modifier
Reacting a mixture (mass ratio is 2:1) of pyromellitic anhydride and cyclopentanetetraic dianhydride with pentanediol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an esterified product terminated by hydroxyl, the reaction temperature is 200 ℃, the pressure is normal pressure, the time is 3.5h, the molar ratio of the mixture of pyromellitic anhydride and cyclopentanetetraic dianhydride to pentanediol is 1:1.9, the catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 200ppm of the mass of the mixture of pyromellitic anhydride and cyclopentanetetraic dianhydride;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, trimethyl phosphate and an antioxidant 616 into the esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain the copolymerization type high-fluidity cationic polyester master batch matrix material. Wherein the addition amount of the high-fluidity branched structure modifier is 5% of the mole fraction of the isophthalic acid-5-sodium sulfonate in the slurry, the temperature of the pre-polycondensation reaction is 220 ℃, the pressure is 1.0KPa, the time is 1.5h, the stirring speed is 5rpm, the temperature of the final polycondensation reaction is 250 ℃, the pressure is 130Pa, the time is 1.5h, and the stirring speed is 5 rpm; the addition amount of trimethyl phosphate was 0.014% of the sum of the masses of phthalic acid, a mixture of isophthalic acid and furandicarboxylic acid and sodium 5-sulfoisophthalic acid, and the addition amount of the antioxidant 616 was 0.021% of the sum of the masses of phthalic acid, a mixture of isophthalic acid and furandicarboxylic acid and sodium 5-sulfoisophthalic acid.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a phthalic acid chain segment, an isophthalic acid chain segment, a furandicarboxylic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, a heptanediol chain segment, a pentanediol chain segment, a pyromellitic dianhydride chain segment and a cyclopentanetetracarboxylic dianhydride chain segment, and the pyromellitic dianhydride chain segment and the cyclopentanetetracarboxylic dianhydride chain segment are connected with the pentanediol chain segment to form a high-fluidity branched structure modifier chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 9g/10min, and the viscosity is reduced to 0.02dL/g in the melt processing process.
The number average molecular weight of the copolymerization type high-fluidity cation polyester master batch matrix material is 20000g/mol, and the intrinsic viscosity is 0.63 dL/g.
Example 7
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping phthalic acid, 5-sodium sulfoisophthalate, octanediol and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is obtained by compounding silicon dioxide loaded tetrabutyl titanate with cobalt acetate, the mixing and pulping stirring speed is 14rpm, the time is 0.9h, and the molar ratio of the phthalic acid to the 5-sodium sulfoisophthalate is 3: 2; the ratio of the sum of the molar weight of phthalic acid and isophthalic acid-5-sodium sulfonate to the molar weight of octanediol is 1:1.3, the addition amount of the titanium-based composite catalyst is 20ppm of the sum of the mass of phthalic acid and isophthalic acid-5-sodium sulfonate, and the molar ratio of tetrabutyl titanate, silicon dioxide and cobalt acetate in the titanium-based composite catalyst is 1:0.8: 3.3;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 260 ℃, the pressure is 65KPa, the time is 4h, the stirring speed is 6rpm, and the intrinsic viscosity of the esterification reaction product is 0.22 dL/g;
(3) preparation of high-fluidity branched structure modifier
Reacting pyromellitic anhydride, a mixture of cyclopentanetetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride (the mass ratio is 1:1:2) with hexanediol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an esterified product capped by hydroxyl, the reaction temperature is 205 ℃, the pressure is normal pressure, the reaction time is 2.5h, the molar ratio of the mixture of pyromellitic anhydride, cyclopentanetetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride to hexanediol is 1:1.8, the catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 250ppm of the mass of the mixture of pyromellitic anhydride, cyclopentanetetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, tris (nonylphenyl) phosphite and a mixture of an antioxidant 1010 and an antioxidant 168 in a mass ratio of 3:1 into an esterification reaction product, and then carrying out a pre-polycondensation reaction and a final polycondensation reaction to obtain a copolymer type high-fluidity cationic polyester master batch base material, wherein the addition amount of the high-fluidity branched structure modifier is 18% of the mole fraction of isophthalic acid-5-sodium sulfonate in the slurry, the temperature of the pre-polycondensation reaction is 270 ℃, the pressure is 0.9KPa, the time is 2.5h, the stirring speed is 14rpm, the temperature of the final polycondensation reaction is 260 ℃, the pressure is 200Pa, the time is 3.0h, and the stirring speed is 6 rpm; the addition amount of tris (nonylphenyl) phosphite is 0.017 percent of the mass sum of the phthalic acid and the isophthalic acid-5-sodium sulfonate, and the addition amount of the mixture of the antioxidant 1010 and the antioxidant 168 is 0.001 percent of the mass sum of the phthalic acid and the isophthalic acid-5-sodium sulfonate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a phthalic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, an octanediol chain segment, a hexanediol chain segment, a pyromellitic anhydride chain segment, a cyclopentane tetracarboxylic dianhydride chain segment and a benzophenone tetracarboxylic dianhydride chain segment, and the pyromellitic anhydride chain segment, the cyclopentane tetracarboxylic dianhydride chain segment and the benzophenone tetracarboxylic dianhydride chain segment are connected with the hexanediol chain segment to form a high-fluidity branched structure modifier chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 14g/10min, and the viscosity is reduced to 0.012dL/g in the melt processing process.
The number average molecular weight of the copolymerization type high-fluidity cation polyester master batch matrix material is 15000g/mol, and the intrinsic viscosity is 0.57 dL/g.
Example 8
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping isophthalic acid, isophthalic acid-5-sodium sulfonate, nonanediol and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is prepared by compounding silicon dioxide loaded metatitanic acid with cobalt acetate, the mixing and pulping are carried out at a stirring speed of 20rpm for 0.6h, and the molar ratio of the isophthalic acid to the isophthalic acid-5-sodium sulfonate is 1: 4; the ratio of the sum of the molar weight of isophthalic acid and isophthalic acid-5-sodium sulfonate to the molar weight of nonanediol is 1:1.9, the addition amount of the titanium composite catalyst is 20ppm of the sum of the mass of isophthalic acid and isophthalic acid-5-sodium sulfonate, and the molar ratio of metatitanic acid, silicon dioxide and cobalt acetate in the titanium composite catalyst is 1:0.1: 0.1;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 230 ℃, the pressure is 60KPa, the time is 3.5h, the stirring speed is 14rpm, and the intrinsic viscosity of the esterification reaction product is 0.15 dL/g;
(3) preparation of high-fluidity branched structure modifier
The high-fluidity branched structure modifier is prepared by reacting pyromellitic acid and heptanediol, wherein the high-fluidity branched structure modifier is an esterified product terminated by hydroxyl, the reaction temperature is 210 ℃, the pressure is normal pressure, the time is 2.5 hours, the molar ratio of the pyromellitic acid to the heptanediol is 1:1.7, the catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 250ppm of the mass of the pyromellitic acid;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, a mixture of trimethyl phosphate, diethyl dodecyl phosphonate and tris (nonylphenyl) phosphite and an antioxidant 1010 in a mass ratio of 1:1:2 into an esterification reaction product, and then carrying out a pre-polycondensation reaction and a final polycondensation reaction to obtain a copolymer type high-fluidity cationic polyester master batch matrix material, wherein the addition amount of the high-fluidity branched structure modifier is 20% of the mole fraction of 5-sodium sulfoisophthalate in slurry, the temperature of the pre-polycondensation reaction is 230 ℃, the pressure is 0.7KPa, the time is 2.0h, the stirring speed is 11rpm, the temperature of the final polycondensation reaction is 220 ℃, the pressure is 180Pa, the time is 2.5h, and the stirring speed is 9 rpm; the amount of the mixture of trimethyl phosphate, diethyl dodecylphosphonate and tris (nonylphenyl) phosphite added was 0.015% by mass of the sum of the masses of isophthalic acid and 5-sodium sulfoisophthalate, and the amount of the antioxidant 1010 was 0.008% by mass of the sum of the masses of isophthalic acid and 5-sodium sulfoisophthalate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises an isophthalic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, a nonanediol chain segment, a heptanediol chain segment and a pyromellitic acid chain segment, and the pyromellitic acid chain segment is connected with the heptanediol chain segment to form a high-fluidity branched structure modifier chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 15g/10min, and the viscosity is reduced to 0.01dL/g in the melt processing process.
The copolymerization type high-fluidity cation polyester master batch matrix material has the number average molecular weight of 16000g/mol and the intrinsic viscosity of 0.60 dL/g.
Example 9
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping isophthalic acid, isophthalic acid-5-sodium sulfonate, decanediol and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is prepared by compounding silicon dioxide loaded metatitanic acid and cobalt acetate, the mixing and pulping stirring speed is 25rpm, the time is 1.0h, and the molar ratio of the isophthalic acid to the isophthalic acid-5-sodium sulfonate is 1: 3; the ratio of the sum of the molar weight of isophthalic acid and isophthalic acid-5-sodium sulfonate to the molar weight of decanediol is 1:1.5, the addition amount of the titanium-based composite catalyst is 40ppm of the sum of the mass of isophthalic acid and isophthalic acid-5-sodium sulfonate, and the molar ratio of metatitanic acid, silicon dioxide and cobalt acetate in the titanium-based composite catalyst is 1:2.5: 8;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 200 ℃, the pressure is 50KPa, the time is 3h, the stirring speed is 18rpm, and the intrinsic viscosity of the esterification reaction product is 0.18 dL/g;
(3) preparation of high-fluidity branched structure modifier
Reacting cyclopentane tetracarboxylic acid and octanediol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an ester terminated by hydroxyl, the reaction temperature is 215 ℃, the pressure is normal pressure, the time is 4.0h, the molar ratio of the cyclopentane tetracarboxylic acid to the octanediol is 1:1.6, the catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 230ppm of the mass of the cyclopentane tetracarboxylic acid;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, diethyl dodecyl phosphonate and a mixture of an antioxidant 1010, an antioxidant 168 and an antioxidant 616 in a mass ratio of 3:1:1 into an esterification reaction product, and then carrying out a pre-polycondensation reaction and a final polycondensation reaction to obtain a copolymer type high-fluidity cationic polyester master batch matrix material, wherein the addition amount of the high-fluidity branched structure modifier is 8% of the mole fraction of isophthalic acid-5-sodium sulfonate in the slurry, the temperature of the pre-polycondensation reaction is 250 ℃, the pressure is 0.5KPa, the time is 1.0h, the stirring rate is 10rpm, the temperature of the final polycondensation reaction is 240 ℃, the pressure is 200Pa, the time is 2.0h, and the stirring rate is 7 rpm; diethyl dodecylphosphonate is added in an amount of 0.01% by mass of the sum of the masses of isophthalic acid and isophthalic acid-5-sulfonate and the mixture of antioxidant 1010, antioxidant 168 and antioxidant 616 is added in an amount of 0.02% by mass of the sum of isophthalic acid and isophthalic acid-5-sulfonate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises an isophthalic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, a decanediol chain segment and a cyclopentane tetracarboxylic acid chain segment, and the cyclopentane tetracarboxylic acid chain segment is connected with an octanediol chain segment to form a high-fluidity branched structure modifier chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 10g/10min, and the viscosity is reduced to 0.014dL/g in the melt processing process.
The copolymerization type high-fluidity cation polyester master batch matrix material has the number average molecular weight of 19000g/mol and the intrinsic viscosity of 0.64 dL/g.
Example 10
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping a mixture of ethylene glycol and propylene glycol (the mass ratio is 2:3), phthalic acid, isophthalic acid-5-sodium sulfonate and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is obtained by compounding silicon dioxide loaded tetrabutyl titanate and cobalt acetate, the mixing and pulping stirring speed is 8rpm, the time is 0.5h, and the molar ratio of the phthalic acid to the isophthalic acid-5-sodium sulfonate is 1: 2; the ratio of the sum of the molar weight of the phthalic acid and the isophthalic acid-5-sodium sulfonate to the molar weight of the mixture of the ethylene glycol and the propylene glycol is 1:1.7, the addition amount of the titanium composite catalyst is 90ppm of the sum of the mass of the phthalic acid and the isophthalic acid-5-sodium sulfonate, and the molar ratio of tetrabutyl titanate, silicon dioxide and cobalt acetate in the titanium composite catalyst is 1:4: 4;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 210 ℃, the pressure is 20KPa, the time is 2.5h, the stirring speed is 15rpm, and the intrinsic viscosity of the esterification reaction product is 0.10 dL/g;
(3) preparation of high-fluidity branched structure modifier
Reacting benzophenone tetracarboxylic acid with a mixture (mass ratio is 2:3) of ethylene glycol and propylene glycol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an esterified product capped by hydroxyl, the reaction temperature is 220 ℃, the pressure is normal pressure, the time is 4.0h, the molar ratio of the benzophenone tetracarboxylic acid to the mixture of the ethylene glycol and the propylene glycol is 1:1.8, a catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 280ppm of the mass of the benzophenone tetracarboxylic acid;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, trimethyl phosphate and a mixture of an antioxidant 1010 and an antioxidant 616 in a mass ratio of 2:1 into an esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain a copolymer type high-fluidity cationic polyester master batch base material, wherein the addition amount of the high-fluidity branched structure modifier is 2% of the mole fraction of isophthalic acid-5-sodium sulfonate in slurry, the pre-polycondensation reaction temperature is 260 ℃, the pressure is 1.0KPa, the time is 0.5h, the stirring speed is 15rpm, the final polycondensation reaction temperature is 230 ℃, the pressure is 0Pa, the time is 1.5h, and the stirring speed is 7 rpm; the addition amount of trimethyl phosphate was 0.02% of the sum of the masses of phthalic acid and isophthalic acid-5-sodium sulfonate, and the addition amount of the mixture of antioxidant 1010 and antioxidant 616 was 0.03% of the sum of the masses of phthalic acid and isophthalic acid-5-sodium sulfonate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a phthalic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, an ethylene glycol chain segment, a propylene glycol chain segment and a benzophenone tetracarboxylic acid chain segment, and the benzophenone tetracarboxylic acid chain segment is connected with the ethylene glycol chain segment and the propylene glycol chain segment to form a high-fluidity branched structure modifier chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 8g/10min, and the viscosity is reduced to 0.01dL/g in the melt processing process.
The copolymerization type high-fluidity cation polyester master batch matrix material has the number average molecular weight of 14000g/mol and the intrinsic viscosity of 0.56 dL/g.
Example 11
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping a mixture of butanediol and pentanediol (the mass ratio is 3:1), phthalic acid, isophthalic acid-5-sodium sulfonate and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is prepared by compounding silicon dioxide loaded metatitanic acid and cobalt acetate, the mixing and pulping speed is 11rpm, the mixing and pulping time is 0.5h, and the molar ratio of the phthalic acid to the isophthalic acid-5-sodium sulfonate is 3: 2; the ratio of the sum of the molar weight of the phthalic acid and the isophthalic acid-5-sodium sulfonate to the molar weight of the mixture of the butanediol and the pentanediol is 1:1.7, the adding amount of the titanium composite catalyst is 170ppm of the sum of the mass of the phthalic acid and the isophthalic acid-5-sodium sulfonate, and the molar ratio of the metatitanic acid, the silicon dioxide and the cobalt acetate in the titanium composite catalyst is 1:6.5: 10;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 200 ℃, the pressure is 25KPa, the time is 2h, the stirring speed is 14rpm, and the intrinsic viscosity of the esterification reaction product is 0.25 dL/g;
(3) preparation of high-fluidity branched structure modifier
Reacting trimellitic acid and nonane diol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an ester terminated by hydroxyl, the reaction temperature is 225 ℃, the pressure is normal pressure, the time is 3.0h, the molar ratio of the trimellitic acid to the nonane diol is 1:1.6, a catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 300ppm of the mass of the trimellitic acid;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, tris (nonylphenyl) phosphite and an antioxidant 168 into an esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain a copolymer type high-fluidity cationic polyester master batch matrix material, wherein the addition amount of the high-fluidity branched structure modifier is 14% of the mole fraction of isophthalic acid-5-sodium sulfonate in the slurry, the temperature of the pre-polycondensation reaction is 220 ℃, the pressure is 0.5KPa, the time is 2.0h, the stirring speed is 7rpm, the temperature of the final polycondensation reaction is 270 ℃, the pressure is 120Pa, the time is 2.5h, and the stirring speed is 10 rpm; the amount of tris (nonylphenyl) phosphite added was 0.013% by mass of the sum of the masses of phthalic acid and isophthalic acid-5-sulfonate and the amount of antioxidant 168 was 0.03% by mass of the sum of the masses of phthalic acid and isophthalic acid-5-sulfonate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a phthalic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, a butanediol chain segment, a pentanediol chain segment, a nonanediol chain segment and a trimellitic acid chain segment, and the trimellitic acid chain segment is connected with the nonanediol chain segment to form a high-fluidity branched structure modifier chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 13g/10min, and the viscosity is reduced to 0.018dL/g in the melt processing process.
The copolymerization type high-fluidity cation polyester master batch matrix material has the number average molecular weight of 14000g/mol and the intrinsic viscosity of 0.62 dL/g.
Example 12
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping a mixture (mass ratio is 2:1:1) of ethylene glycol, propylene glycol and butanediol, furan dicarboxylic acid, isophthalic acid-5-sodium sulfonate and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is prepared by compounding silicon dioxide loaded metatitanic acid and cobalt acetate, the mixing and pulping stirring speed is 16rpm, the time is 0.5h, and the molar ratio of furan dicarboxylic acid to isophthalic acid-5-sodium sulfonate is 1: 4; the ratio of the sum of the molar weight of furan dicarboxylic acid and 5-sodium sulfoisophthalate to the molar weight of the mixture of ethylene glycol, propylene glycol and butanediol is 1:2.0, the addition amount of the titanium composite catalyst is 200ppm of the sum of the mass of furan dicarboxylic acid and 5-sodium sulfoisophthalate, and the molar ratio of metatitanic acid, silicon dioxide and cobalt acetate in the titanium composite catalyst is 1:3: 6;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 260 ℃, the pressure is 60KPa, the time is 3h, the stirring speed is 10rpm, and the intrinsic viscosity of the esterification reaction product is 0.25 dL/g;
(3) preparation of high-fluidity branched structure modifier
Reacting pyromellitic acid and decanediol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an ester capped by hydroxyl, the reaction temperature is 230 ℃, the pressure is normal pressure, the time is 3.0h, the molar ratio of the pyromellitic acid to the decanediol is 1:2.0, the catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 110pm of the weight of the pyromellitic acid;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, diethyl dodecyl phosphonate and an antioxidant 168 into an esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain a copolymerization type high-fluidity cationic polyester master batch base material, wherein the addition amount of the high-fluidity branched structure modifier is 18% of the mole fraction of slurry isophthalic acid-5-sodium sulfonate, the temperature of the pre-polycondensation reaction is 270 ℃, the pressure is 0.5KPa, the time is 0.8h, the stirring speed is 5rpm, the temperature of the final polycondensation reaction is 260 ℃, the pressure is 140Pa, the time is 1.5h, and the stirring speed is 6 rpm; the diethyl dodecylphosphonate was added in an amount of 0.001% by mass of the sum of the masses of furandicarboxylic acid and sodium 5-sulfoisophthalate, and the antioxidant 168 was added in an amount of 0.028% by mass of the sum of the masses of furandicarboxylic acid and sodium 5-sulfoisophthalate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a furan dicarboxylic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, an ethylene glycol chain segment, a propylene glycol chain segment, a butanediol chain segment, a decanediol chain segment and a trimellitic acid chain segment, and the trimellitic acid chain segment is connected with the decanediol chain segment to form a high-fluidity branched structure modifier chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 14g/10min, and the viscosity is reduced to 0.02dL/g in the melt processing process.
The copolymerization type high-fluidity cation polyester master batch matrix material has the number average molecular weight of 14000g/mol and the intrinsic viscosity of 0.61 dL/g.
Example 13
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping furan dicarboxylic acid, isophthalic acid-5-sodium sulfonate, ethylene glycol and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is prepared by compounding a silicon dioxide-loaded tetrabutyl titanate titanium-silicon composite catalyst and cobalt acetate, the mixing and pulping speed is 5rpm, the time is 0.6h, and the molar ratio of furan dicarboxylic acid to isophthalic acid-5-sodium sulfonate is 1: 2; the ratio of the sum of the molar weight of furan dicarboxylic acid and isophthalic acid-5-sodium sulfonate to the molar weight of ethylene glycol is 1:1.6, the adding amount of the titanium composite catalyst is 100ppm of the sum of the mass of furan dicarboxylic acid and isophthalic acid-5-sodium sulfonate, and the molar ratio of tetrabutyl titanate, silicon dioxide and cobalt acetate in the titanium composite catalyst is 1:7: 0.5;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 250 ℃, the pressure is 80KPa, the time is 2h, the stirring speed is 5rpm, and the intrinsic viscosity of the esterification reaction product is 0.15 dL/g;
(3) preparation of high-fluidity branched structure modifier
Reacting a mixture of cyclopentanetetracarboxylic acid and benzophenone tetracarboxylic acid (the mass ratio is 3:2) and a mixture of propylene glycol and hexanediol (the mass ratio is 2:1) to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an ester capped by hydroxyl, the reaction temperature is 240 ℃, the pressure is normal pressure, the reaction time is 2.5h, the molar ratio of the mixture of cyclopentanetetracarboxylic acid and benzophenone tetracarboxylic acid to the mixture of propylene glycol and hexanediol is 1:2.0, the catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 120ppm of the mass of the mixture of cyclopentanetetracarboxylic acid and benzophenone tetracarboxylic acid;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, trimethyl phosphate and an antioxidant 616 into an esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain a copolymerization type high-fluidity cationic polyester master batch base material, wherein the addition amount of the high-fluidity branched structure modifier is 11% of the mole fraction of isophthalic acid-5-sodium sulfonate in the slurry, the temperature of the pre-polycondensation reaction is 220 ℃, the pressure is 0.5KPa, the time is 0.5h, the stirring speed is 15rpm, the temperature of the final polycondensation reaction is 270 ℃, the pressure is 30Pa, the time is 1.0h, and the stirring speed is 10 rpm; the addition amount of trimethyl phosphate is 0.02 percent of the mass sum of the furandicarboxylic acid and the isophthalic acid-5-sodium sulfonate, and the addition amount of the antioxidant 616 is 0.025 percent of the mass sum of the furandicarboxylic acid and the isophthalic acid-5-sodium sulfonate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a furan dicarboxylic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, an ethylene glycol chain segment, a propylene glycol chain segment, a hexanediol chain segment, a cyclopentane tetracarboxylic acid chain segment and a benzophenone tetracarboxylic acid chain segment, and the cyclopentane tetracarboxylic acid chain segment and the benzophenone tetracarboxylic acid chain segment are connected with the propylene glycol chain segment and the hexanediol chain segment to form a high-fluidity branched structure modifier chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 11g/10min, and the viscosity is reduced to 0.02dL/g in the melt processing process.
The number average molecular weight of the copolymerization type high-fluidity cation polyester master batch matrix material is 16000g/mol, and the intrinsic viscosity is 0.65 dL/g.
Example 14
The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material comprises the following specific steps:
(1) prepared slurry
Mixing and pulping a mixture of phthalic acid and furandicarboxylic acid (the mass ratio is 2:3), isophthalic acid-5-sodium sulfonate, propylene glycol and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is obtained by compounding silicon dioxide-loaded metatitanic acid and cobalt acetate, the mixing and pulping stirring speed is 13rpm, the time is 0.7h, and the molar ratio of the mixture of phthalic acid and furandicarboxylic acid to isophthalic acid-5-sodium sulfonate is 1: 2; the ratio of the sum of the molar weight of the mixture of the phthalic acid and the furandicarboxylic acid and the isophthalic acid-5-sodium sulfonate to the molar weight of the propylene glycol is 1:1.1, the adding amount of the titanium composite catalyst is 30ppm of the sum of the mass of the mixture of the phthalic acid and the furandicarboxylic acid and the isophthalic acid-5-sodium sulfonate, and the molar ratio of the metatitanic acid, the silicon dioxide and the cobalt acetate in the titanium composite catalyst is 1:1: 8;
(2) esterification reaction
Carrying out esterification reaction on the slurry, wherein the temperature of the esterification reaction is 260 ℃, the pressure is 50KPa, the time is 2h, and the stirring speed is 10 rpm; the intrinsic viscosity of the esterification reaction product is 0.10 dL/g;
(3) preparation of high-fluidity branched structure modifier
The preparation method comprises the following steps of reacting pyromellitic dianhydride and decanediol to prepare a high-fluidity branched structure modifier, wherein the high-fluidity branched structure modifier is an esterified substance capped by hydroxyl, the reaction temperature is 230 ℃, the pressure is normal pressure, the reaction time is 4.0h, the molar ratio of the pyromellitic dianhydride to the decanediol is 1:1.6, a catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 120ppm of the mass of the pyromellitic dianhydride;
(4) polycondensation reaction
Adding a high-fluidity branched structure modifier, trimethyl phosphate and an antioxidant 168 into an esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain a copolymerization type high-fluidity cationic polyester master batch base material, wherein the addition amount of the high-fluidity branched structure modifier is 19.5% of the mole fraction of slurry isophthalic acid-5-sodium sulfonate, the temperature of the pre-polycondensation reaction is 220 ℃, the pressure is 0.6KPa, the time is 1.2h, the stirring speed is 11rpm, the temperature of the final polycondensation reaction is 270 ℃, the pressure is 0Pa, the time is 2.0h, and the stirring speed is 5 rpm; the addition amount of trimethyl phosphate was 0.001% of the sum of the mass of the mixture of phthalic acid and furandicarboxylic acid and sodium 5-sulfoisophthalate, and the addition amount of antioxidant 168 was 0.001% of the sum of the mass of the mixture of phthalic acid and furandicarboxylic acid and sodium 5-sulfoisophthalate.
The molecular chain of the finally prepared copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a phthalic acid chain segment, a furan dicarboxylic acid chain segment, an isophthalic acid-5-sodium sulfonate chain segment, a propylene glycol chain segment, a decanediol chain segment and a pyromellitic dianhydride chain segment, and the pyromellitic dianhydride chain segment is connected with the decanediol chain segment to form a high-fluidity branched structure modifier chain segment.
The melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 15g/10min, and the viscosity is reduced to 0.02dL/g in the melt processing process.
The copolymerization type high-fluidity cation polyester master batch matrix material has the number average molecular weight of 17000g/mol and the intrinsic viscosity of 0.61 dL/g.

Claims (9)

1. The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material is characterized by comprising the following steps of: uniformly mixing dibasic acid I, dibasic acid II and dihydric alcohol I, then carrying out esterification reaction, introducing a high-fluidity branched structure modifier after the esterification reaction is finished, and carrying out pre-polycondensation reaction and final polycondensation reaction to obtain a copolymerization type high-fluidity cationic polyester master batch matrix material;
the dibasic acid I is more than one of dibasic acids used for synthesizing polyester except for isophthalic acid-5-sodium sulfonate;
the dibasic acid II is isophthalic acid-5-sodium sulfonate;
the high-fluidity branched structure modifier is an ester which is prepared by the reaction of a branched structure acid or anhydride and dihydric alcohol II and is terminated by hydroxyl;
the branched structure acid or anhydride is more than one of pyromellitic anhydride, cyclopentane tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, trimellitic anhydride, trimellitic dianhydride, pyromellitic acid, cyclopentane tetracarboxylic acid, benzophenone tetracarboxylic acid, trimellitic acid and trimellitic acid;
the dihydric alcohol II is more than one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol and decanediol;
the dihydric alcohol I is the same as the dihydric alcohol II or is more than one of dihydric alcohols used for synthesizing polyester except the dihydric alcohol II.
2. The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material according to claim 1, wherein the preparation conditions of the high-fluidity branched structure modifier are as follows: the temperature is 180-240 ℃, the pressure is normal pressure, the time is 2.5-4.0 h, the molar ratio of the branched structure acid or anhydride to the dihydric alcohol II is 1: 1.6-2.0, the catalyst is p-toluenesulfonic acid, and the addition amount of the catalyst is 100-300 ppm of the mass of the branched structure acid or anhydride.
3. The preparation method of the copolymerization type high-fluidity cationic polyester master batch matrix material according to claim 1, which is characterized by comprising the following specific steps:
(1) prepared slurry
Mixing and pulping dibasic acid I, dibasic acid II, dihydric alcohol I and a titanium composite catalyst to prepare slurry, wherein the titanium composite catalyst is prepared by compounding a titanium-silicon composite catalyst and a cobalt catalyst, and the titanium-silicon composite catalyst is prepared by loading a titanium catalyst on a silicon catalyst;
(2) esterification reaction
Carrying out esterification reaction on the slurry;
(3) polycondensation reaction
Adding a high-fluidity branched structure modifier, a heat stabilizer and an antioxidant into the esterification reaction product, and then carrying out pre-polycondensation reaction and final polycondensation reaction to obtain the copolymerization type high-fluidity cationic polyester master batch matrix material.
4. The method for preparing a matrix material of a copolymerized high-fluidity cationic polyester masterbatch according to claim 3, wherein the dibasic acid I is one or more of terephthalic acid, isophthalic acid and furandicarboxylic acid, the dibasic alcohol I is one or more of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol and decylene glycol, the titanium-based catalyst is tetrabutyl titanate or metatitanic acid, the silicon-based catalyst is silicon dioxide, the cobalt-based catalyst is cobalt acetate, the heat stabilizer is one or more of trimethyl phosphate, alkyl diester phosphate and tris (nonylphenyl) phosphite, and the antioxidant is one or more of antioxidant 1010, antioxidant 168 and antioxidant 616.
5. The preparation method of the copolymer type high-fluidity cationic polyester master batch matrix material according to claim 3, wherein in the step (1), the stirring speed of mixing and beating is 5-25 rpm, and the time is 0.5-1.0 h;
the molar ratio of the dibasic acid I to the dibasic acid II is 1: 4-3: 2; the ratio of the sum of the molar weight of the dibasic acid I and the molar weight of the dibasic acid II to the molar weight of the dibasic alcohol I is 1: 1.1-2.0, the addition amount of the titanium-based composite catalyst is 20-200 ppm of the sum of the mass of the dibasic acid I and the mass of the dibasic acid II, and the molar ratio of the titanium-based catalyst, the silicon-based catalyst and the cobalt-based catalyst in the titanium-based composite catalyst is 1: 0.1-10.
6. The preparation method of the copolymer type high-fluidity cationic polyester masterbatch base material according to claim 5, wherein in the step (2), the temperature of the esterification reaction is 200-260 ℃, the pressure is 20-80 KPa, the time is 2-4 h, and the stirring speed is 5-20 rpm; the intrinsic viscosity of the esterification reaction product is 0.10-0.25 dL/g.
7. The method according to claim 6, wherein in the step (3), the temperature of the pre-polycondensation reaction is 220-270 ℃, the pressure is 0.5-1.0 KPa, the time is 0.5-2.5 h, the stirring speed is 5-15 rpm, the temperature of the final polycondensation reaction is 220-270 ℃, the pressure is 0-200 Pa, the time is 1.0-3.0 h, and the stirring speed is 5-10 rpm;
the addition amount of the high-fluidity branched structure modifier is 1-20% of the mole fraction of the dibasic acid II in the slurry, the addition amount of the heat stabilizer is 0.001-0.02% of the mass sum of the dibasic acid I and the dibasic acid II, and the addition amount of the antioxidant is 0.001-0.03% of the mass sum of the dibasic acid I and the dibasic acid II.
8. The preparation method of the copolymerization type high-fluidity cationic polyester masterbatch matrix material according to claim 1, characterized in that: the molecular chain of the copolymerization type high-fluidity cationic polyester master batch matrix material mainly comprises a dibasic acid I chain segment, a dibasic acid II chain segment, a dihydric alcohol I chain segment, a dihydric alcohol II chain segment and an M chain segment;
the dibasic acid I chain segment is more than one of dibasic acid chain segments used for synthesizing polyester except for isophthalic acid-5-sodium sulfonate;
the dibasic acid II chain segment is an isophthalic acid-5-sodium sulfonate chain segment;
the dihydric alcohol II chain segment is more than one of ethylene glycol chain segment, propylene glycol chain segment, butanediol chain segment, pentanediol chain segment, hexanediol chain segment, heptanediol chain segment, octanediol chain segment, nonanediol chain segment and decanediol chain segment;
the diol I chain segment is the same as the diol II chain segment or is more than one of the diol chain segments for synthesizing the polyester except the diol II;
the M chain segment is more than one of a pyromellitic acid chain segment, a cyclopentane tetracarboxylic acid chain segment, a benzophenone tetracarboxylic acid chain segment, a trimellitic acid chain segment and a trimellitic acid chain segment;
the melt index of the copolymerization type high-fluidity cationic polyester master batch matrix material is 8-15 g/10min, and the viscosity is reduced by less than or equal to 0.02dL/g in the melt processing process.
9. The preparation method of the copolymer type high-fluidity cationic polyester masterbatch matrix material according to claim 8, wherein the number average molecular weight of the copolymer type high-fluidity cationic polyester masterbatch matrix material is 14000-20000 g/mol, and the intrinsic viscosity is 0.55-0.65 dL/g;
the dibasic acid I is more than one of terephthalic acid, isophthalic acid and furandicarboxylic acid, and the dihydric alcohol I is more than one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol and decanediol.
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