CN113831516B - Self-repairing polyester and preparation method thereof - Google Patents
Self-repairing polyester and preparation method thereof Download PDFInfo
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- CN113831516B CN113831516B CN202010589420.3A CN202010589420A CN113831516B CN 113831516 B CN113831516 B CN 113831516B CN 202010589420 A CN202010589420 A CN 202010589420A CN 113831516 B CN113831516 B CN 113831516B
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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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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Abstract
The invention discloses self-repairing polyester and a preparation method thereof, wherein the Mn of the self-repairing polyester is 20000-30000, the Mw is 30000-40000, the Mw/Mn is 1.2-1.6, and the intrinsic viscosity of the self-repairing polyester is more than 0.7dL/g. The self-repairing polyester is prepared from 2-methyl-1, 3-propanediol monomer and dicarboxylic acid monomer through direct esterification and polycondensation reaction, has shape restorability, has good spinnability, can be used for preparing polyester fibers, has high wet heat shrinkage rate, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to self-repairing polyester and a preparation method thereof.
Background
2-methyl-1, 3-propanediol (MPO) is a colorless transparent liquid dihydric alcohol with low toxicity and low viscosity, and the methyl side group structure and solvent compatibility of the MPO are better than those of other dihydric alcohols, so that the molecular structure is unique, the performance is excellent, various dibasic acids can be selected to prepare polyester, and the development prospect is wide.
At present, the MPO is mainly used as a third monomer to prepare polyester with other dihydric alcohol and dibasic acid, the addition amount of the MPO is small, and the polyester prepared by directly reacting the MPO as the main monomer with the dibasic acid is not disclosed and reported.
Disclosure of Invention
In order to overcome the problems, the inventor has conducted intensive researches and researches on a self-repairing polyester and a preparation method thereof, wherein the self-repairing polyester is prepared from 2-methyl-1, 3-propanediol and a dicarboxylic acid monomer, the Mw/Mn of the self-repairing polyester is 1.2-1.6, the intrinsic viscosity is more than 0.7dL/g, the self-repairing polyester is an amorphous compound, has shape restorability (or called self-repairing property), good spinnability, and a polyester fiber prepared from the self-repairing polyester has high wet heat shrinkage rate and good application prospect, and the preparation method of the self-repairing polyester is simple, raw materials are easy to obtain and can be used for large-scale industrial production, so that the invention is completed.
An object of the present invention is to provide a self-repairing polyester having Mn of 20000 to 30000, mw of 30000 to 40000, mw/Mn of 1.2 to 1.6,
the intrinsic viscosity of the self-healing polyester is greater than 0.7dL/g.
The self-repairing polyester is prepared by polymerizing 2-methyl-1, 3-propanediol and a dicarboxylic acid monomer, and the molar ratio of the 2-methyl-1, 3-propanediol to the dicarboxylic acid monomer is (1.2-1.8): 1.
the self-repairing polyester is prepared by a method comprising the following steps:
Another aspect of the present invention is to provide a method for preparing a self-repairing polyester, the method comprising the steps of:
In the step 1, 2-methyl-1, 3-propanediol and a dicarboxylic acid monomer are subjected to a direct esterification method to obtain an esterification product,
the dicarboxylic acid monomer is selected from terephthalic acid or mixed acid of terephthalic acid and isophthalic acid;
the temperature of the esterification reaction is 200-260 ℃, and the pressure in the reaction vessel is controlled to be 200-330 kPa during the water drainage period.
After the esterification reaction is finished, a polycondensation catalyst is added before the polycondensation reaction, preferably, after the esterification reaction is finished, the reaction system is vacuumized for 10-60min before the polycondensation reaction, and then the polycondensation catalyst is added.
The polycondensation catalyst is a titanium catalyst, preferably one or more selected from tetrabutyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate or tetraisooctyl titanate.
The added mass of the polycondensation catalyst is 0.1-1% of the mass of the dicarboxylic acid monomer.
In the step 2, the temperature of the polycondensation reaction is 210-280 ℃, and the vacuum degree of the polycondensation reaction is 10-100 Pa.
An auxiliary agent is also added before the polycondensation reaction, the auxiliary agent comprises one or two of a heat stabilizer and an antioxidant,
the addition amount of the heat stabilizer is 0.1 to 0.5 percent of the mass of the dicarboxylic acid monomer,
the heat stabilizer is one or more of trimethyl phosphate, triphenyl phosphite, triphenyl phosphate and trimethyl phosphite.
The invention has the beneficial effects that:
(1) The invention provides self-repairing polyester which is prepared from 2-methyl-1, 3-propanediol and dicarboxylic acid monomer, wherein Mw/Mn of the self-repairing polyester is 1.2-1.6;
(2) The invention provides a preparation method of the self-repairing polyester, and explores a polycondensation catalyst and the dosage thereof, and the addition time and the addition mode of the polycondensation catalyst, which are suitable for preparing the self-repairing polyester, so that the catalysis effect is better, and the polycondensation reaction is stable and controllable;
(3) The self-repairing polyester is prepared by taking the 2-methyl-1, 3-propanediol as an alcohol monomer, fills the blank of preparing the self-repairing polyester by taking the 2-methyl-1, 3-propanediol as a main alcohol monomer, widens the application of the self-repairing polyester, and the self-repairing polyester has good shape restorability, and the bent self-repairing polyester has extremely high shape restorability above 55 ℃ and can reach above 99.3%;
(4) The self-repairing polyester has good spinnability, and the prepared polyester fiber has high wet heat shrinkage rate and good application prospect;
(5) The preparation method of the self-repairing polyester is simple and easy to realize, and can be used for large-scale industrial production.
Drawings
FIG. 1 shows an infrared spectrum obtained in experimental example 1 of the present invention;
FIG. 2 is a view showing GPC chromatograms and molecular weight distribution obtained in Experimental example 3 of the present invention;
FIG. 3 shows a one-time temperature rise DSC curve of the self-repairing polyester obtained in examples 1 to 7 in Experimental example 4 of the present invention;
FIG. 4 shows DSC temperature rise curves of 2 hours, 4 hours and 6 hours of annealing treatment at 100℃of the modified polyester obtained in examples 1 to 2 in Experimental example 4 of the present invention;
FIG. 5 shows TG curves of the self-repairing polyesters obtained in examples 1 to 7 of Experimental example 4 of the present invention;
FIG. 6 shows a partial enlarged view of FIG. 5;
FIG. 7 shows the relationship between the shear rate and the shear viscosity at 225 ℃, 230 ℃ and 235 ℃ of the self-repairing polyester obtained in example 10 in experimental example 5;
FIG. 8 shows the relationship between the shear rate and the shear viscosity at 225 ℃, 230 ℃ and 235 ℃ of the self-repairing polyester obtained in example 13 in experimental example 5;
FIG. 9 shows pictures of a self-repairing polyester spline of experimental example 6 of the present invention before and after deformation.
Detailed Description
The invention is described in further detail below with reference to the drawings and the preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
According to the present invention, there is provided a self-healing polyester prepared from 2-methyl-1, 3-propanediol (MPO) and a dicarboxylic acid monomer, preferably, an esterification reaction of 2-methyl-1, 3-propanediol and a dicarboxylic acid monomer is performed and an esterification product is obtained, and a polycondensation reaction of the esterification product is performed to prepare the self-healing polyester.
According to the invention, the dicarboxylic acid monomer is selected from terephthalic acid or a mixed acid of terephthalic acid and isophthalic acid, preferably Terephthalic Acid (PTA).
According to the invention, a self-healing polyester MPTT is prepared from MPO and PTA.
According to a preferred embodiment of the present invention, the esterification product has a structure as shown in formula (I):
according to the present invention, the self-repairing polyester has a structure represented by the following formula (II):
according to the preferred embodiment of the invention, the self-repairing polyester is obtained by directly esterifying and polycondensing 2-methyl-1, 3-propanediol serving as a diol monomer with terephthalic acid without adding other alcohol monomers. The inventors theorize that: compared with the PTT molecular structure, the existence of the methyl of the side chain on the MPTT breaks the integrity of the molecular structure, the dissymmetry of the macromolecular chain structure leads the polyester to be difficult to crystallize, when the temperature reaches the temperature capable of enabling the molecular chain segment to start to move, the molecular chain is easier to move due to the fact that the amorphous structure has smaller constraint on the molecular chain, meanwhile, the existence of the methyl increases the steric hindrance effect, the internal repulsive force is increased, the molecular chain tends to move towards the direction with smaller repulsive force, and the MPTT material can obtain self-repairing capability. Of course, the mechanism by which the polyesters of the invention have good self-healing capabilities is not limited at all by the above theory.
The self-repairing polyester has the intrinsic viscosity of more than 0.7dL/g, preferably more than 0.8dL/g and even more than 0.86dL/g, has better fiber processing performance, and can be used for preparing polyester fibers.
According to the present invention there is provided a process for the preparation of a self-healing polyester, preferably a process for the preparation of a self-healing polyester according to the first aspect of the invention, the process comprising:
According to the invention, in the step 1, the MPO and the dicarboxylic acid monomer are subjected to esterification reaction by adopting a direct esterification method to obtain an esterification product, preferably, an intermittent direct esterification method is adopted, so that the method is flexible and convenient, and is suitable for developing functional polyester.
The inventor discovers that in the esterification reaction process, the charging ratio of alkyd, namely the charging molar ratio of MPO and dicarboxylic acid monomer has a larger influence on the esterification reaction, the charging molar ratio of the alkyd is too large, so that two molecules are condensed to form an ether compound, the molar ratio is too small, the esterification is incomplete, the carboxyl content in an esterification product is too high, and the esterification rate is low, so that the requirement of the process regulation cannot be met. In actual production, the optimal alkyd feeding molar ratio is adjusted according to the viscosity of slurry (a liquid-solid mixture of MPO and dicarboxylic acid monomer), the structure of slurry preparation equipment, the structure of slurry conveying pipelines, conveying process and other possible requirements (such as whether the diol in the esterification process is refluxed or not).
According to the invention, the molar ratio of MPO to dicarboxylic acid monomer is (1.2 to 1.8): 1, preferably (1.2 to 1.6): 1, more preferably (1.2 to 1.3): 1.
the inventor discovers that the esterification temperature has important influence on the esterification reaction, and properly increasing the esterification reaction temperature is beneficial to increasing the esterification reaction speed, but also increases the side reaction speed, and the low esterification reaction temperature can cause the phenomena of low esterification reaction speed, incomplete esterification reaction, excessively high carboxyl end group content, substandard esterification rate, insufficient molecular weight of polycondensation and the like, thereby leading to the quality reduction and poor performance of the obtained polyester MPTT product.
According to the invention, the temperature of the esterification reaction is 200 to 260 ℃, preferably 205 to 250 ℃, more preferably 240 to 248 ℃.
According to a preferred embodiment of the present invention, the esterification reaction temperature is 205 to 245 ℃, preferably 240 to 246 ℃, in a 2L polymerization reactor;
in a 30L polymerization reactor, the esterification reaction temperature is 220-250 ℃, preferably 245-247 ℃.
The inventor discovers that the pressure and the temperature of the esterification reaction are mutually influenced, and as the boiling point of MPO is lower than the temperature of the esterification reaction, when the esterification reaction pressure is low, partial MPO and water generated by the system form an azeotrope which is repeatedly condensed and vaporized in a fractionating column, so that more energy is consumed, and the reaction rate is reduced; the top temperature of the esterification fractionating column is difficult to control, the content of MPO in the esterification water is high, and the most ideal state of the esterification reaction is that MPO exists in a liquid phase system as much as possible, so that the MPO can react with terephthalic acid as soon as possible, and the fewer formed azeotrope is, the more favorable for the rapid progress of the esterification reaction;
the azeotrope formed when the esterification reaction pressure is high is less, the temperature of the top of the column is easy to control, and the content of alcohol in the discharged esterification water is low; since the esterification pressure is generated by the azeotrope of the esterification water and the alcohol, if the esterification reaction pressure is too high, the esterification water is used for maintaining the pressure of the reaction system, which is not beneficial to the discharge of the esterification water, but delays the progress of the esterification reaction, and although the increase of the MPO concentration is beneficial to the generation of the esterified substances, the generation amount of the ether compound is increased, so that the selection of the pressure not only meets the requirement of the discharge of the water, but also ensures the quantity (mole) ratio of substances required by the esterification reaction and reduces the generation amount of the ether compound.
According to the present invention, the initial pressure of the esterification reaction is 80 to 120kPa, preferably 90 to 110kPa, more preferably 100kPa.
According to the invention, the pressure in the reaction vessel is controlled to be 200-330 kPa, preferably 200-300 kPa during the water discharge period, the water produced by the esterification reaction is favorably discharged under the pressure, and the influence on the temperature of the esterification system is minimal, namely, when the pressure fluctuation is large, the internal temperature of the kettle also generates large fluctuation, which is unfavorable for the stable progress of the reaction and the control of the process.
In the invention, the esterification reaction time comprises positive pressure reaction time and normal pressure reaction time, and the esterification reaction time is influenced by factors such as stirring speed, esterification reaction temperature, esterification reaction pressure, drainage rate and the like. The time from the start of the esterification reaction to the pressure drop to normal pressure is called positive pressure esterification reaction time, and is determined by the pressure of the reaction kettle and the temperature of the top of the column. In general, when the temperature of the reaction kettle is not lower than 230 ℃, the esterification reaction pressure is not increased (or is increased slowly), which means that the water generated by the esterification reaction is insufficient to generate the internal pressure of the kettle of 270kPa, at the moment, the esterification reaction pressure needs to be actively and gradually reduced until the pressure reaches normal pressure, the pressure reduction process needs to be about 30-50min, and the pressure reduction process needs to ensure that the temperature of the reaction kettle is not reduced and larger fluctuation is generated. The time from the reduction of the esterification reaction pressure to the end of the normal pressure esterification reaction at 1 atmosphere is referred to as normal pressure esterification reaction time. And when the water outlet of the esterified water is not used for discharging water, and the temperature of the column top is lower than 60 ℃, judging that the normal-pressure esterification reaction is finished.
According to the invention, the positive pressure reaction time of the esterification reaction is 60-250 min, and the normal pressure reaction time is 30-200 min.
According to a preferred embodiment of the present invention, the positive pressure reaction time of the esterification reaction is 60 to 150 minutes and the normal pressure reaction time is 30 to 70 minutes in a 2L polymerization reaction vessel.
According to a preferred embodiment of the present invention, the positive pressure reaction time of the esterification reaction is 120 to 250 minutes and the normal pressure reaction time is 40 to 200 minutes in a 2L polymerization reaction vessel.
According to a preferred embodiment of the invention, in a 2L polymerization reaction kettle, when the esterification temperature is 215-240 ℃ and the esterification pressure is 200-270 kPa, the positive pressure reaction time of the esterification reaction is 70-140 min, and the normal pressure reaction time is 40-60 min.
According to a preferred embodiment of the present invention, in a 30L polymerization reaction vessel, the esterification reaction is carried out at a temperature of 230 to 247℃and at an esterification pressure of 200 to 300kPa for a positive pressure reaction time of 140 to 240 minutes, preferably 150 to 180 minutes, and at a normal pressure reaction time of 40 to 180 minutes, preferably 150 to 180 minutes.
In the invention, the water output of the esterification reaction needs to reach more than 93% of the theoretical water output, and the increase of the esterification reaction pressure and the prolongation of the pressurization time are unfavorable for water drainage, thereby being not helpful for accelerating the esterification reaction. Too short a reaction time at normal pressure may result in incomplete esterification. The esterification reaction temperature, pressure, water outlet rate and water outlet amount are comprehensively considered to control the esterification reaction.
In the invention, an esterification catalyst is not added in the esterification reaction, and the inventor discovers that the esterification catalyst has no influence on the esterification reaction process basically.
According to the invention, in the step 1, an auxiliary agent is also added, wherein the auxiliary agent comprises one or more of a heat stabilizer, an antioxidant and the like, and the heat stabilizer and the antioxidant can prevent the thermal degradation and the oxygen degradation of the polyester.
According to the invention, the heat stabilizer is preferably one or more of trimethyl phosphate, triphenyl phosphite, triphenyl phosphate and trimethyl phosphite, and the antioxidant is an antioxidant 1010 or an antioxidant 168, preferably an antioxidant 1010.
In the present invention, the addition of a heat stabilizer such as triphenyl phosphite prior to polycondensation is advantageous for improving the hue of the polyester.
According to the invention, the heat stabilizer is added in an amount of 0.1 to 0.5% by mass, preferably 0.2 to 0.4% by mass, based on TPA.
According to the invention, the antioxidant is added in an amount of 0.1 to 0.5% by mass, preferably 0.2 to 0.4% by mass, based on TPA.
In the invention, the step 1 is used for obtaining an esterification product, and the esterification product is used for carrying out polycondensation reaction to obtain the self-repairing polyester.
In the present invention, a polycondensation catalyst is required to be added during the polycondensation reaction to catalyze the polycondensation reaction.
The inventors found that the antimony-based catalyst has no catalytic effect on the polycondensation reaction, whereas the titanium-based catalyst has an obvious catalytic effect, but the titanium-based catalyst such as tetrabutyl titanate has no catalytic effect when added simultaneously with MPO and dicarboxylic acid monomers before the addition, and it is possible that tetrabutyl titanate has been completely hydrolyzed at the time of the esterification reaction, and the hydrolysis product has no catalytic effect on the polycondensation reaction.
According to the present invention, the polycondensation catalyst is a titanium-based catalyst, preferably one or more selected from tetrabutyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, or tetraisooctyl titanate, more preferably tetrabutyl titanate (TBT).
The inventors also found that, due to the specificity of the equipment and the esterification equilibrium reaction, a small amount of water still exists in the reaction system or the fractionating column after no water is removed at the end of the esterification reaction, and a small amount of dicarboxylic acid monomer continues to be esterified to generate water when vacuumizing in the reaction system, and the water causes tetrabutyl titanate to hydrolyze and lose the catalytic effect.
According to the invention, after the esterification reaction is finished, the system is vacuumized for 10-60min, the moisture in the system is removed as much as possible, and then the polycondensation catalyst is added, so that the polycondensation reaction is easy to control, and the polycondensation reaction time is stable. It should be noted that in the industrial five-pot process (two esterification, two pre-polycondensation and one final polycondensation) to produce polyester, the polycondensation catalyst is also added to the second pre-polycondensation pot, which is substantially anhydrous, and this does not occur.
The inventors found that the addition amount of the polycondensation catalyst has a large influence on the polycondensation reaction rate, the hue of the polycondensation product, and the content of by-products of the product. The visual influence on the polycondensation reaction rate is reflected in the polycondensation time, when the addition amount of the polycondensation catalyst is large, the polymerization reaction rate is increased, and the polymerization time is shortened, but the yellowing of the product is possibly caused, the addition amount of the polycondensation catalyst is small, the polymerization reaction rate is low, and the polymerization time is long.
According to the invention, the polycondensation catalyst is added in an amount of 0.1 to 1% by mass, preferably 0.3 to 0.8% by mass, for example 0.3% by mass, based on TPA.
According to the invention, in the step 2, an auxiliary agent is added before polycondensation, wherein the auxiliary agent comprises one or more of a heat stabilizer, an antioxidant and the like, and the heat stabilizer and the antioxidant can prevent thermal degradation and oxygen degradation of the polyester.
According to the invention, the heat stabilizer is preferably one or more of trimethyl phosphate, triphenyl phosphite, triphenyl phosphate and trimethyl phosphite, and the antioxidant is an antioxidant 1010 or an antioxidant 168, preferably an antioxidant 1010.
In the present invention, the addition of a heat stabilizer such as triphenyl phosphite prior to polycondensation is advantageous for improving the hue of the self-healing polyester, but the addition of an antioxidant increases the yellowness of the resulting self-healing polyester. The inventors have found that the addition of nucleating agents such as nano-silica or nano-titania does not promote crystallization of the polyester.
According to the invention, the heat stabilizer is added in an amount of 0.1 to 0.5% by mass, preferably 0.2 to 0.4% by mass, based on TPA.
According to the invention, the antioxidant is added in an amount of 0.1 to 0.5% by mass, preferably 0.2 to 0.4% by mass, based on TPA.
The inventors found that the reaction rate is not significantly increased when the polycondensation reaction temperature is too high, but the side reaction products are increased, the color of the product is yellow, in addition, the polycondensation reaction temperature is related to the polycondensation catalyst, and the catalyst with high catalytic efficiency can properly reduce the polycondensation reaction temperature, otherwise, the byproduct is increased, the polycondensation reaction temperature is low, the polymer viscosity is slowly increased, namely, the polymerization reaction rate is slow, and the polymerization time is prolonged.
According to the invention, the polycondensation reaction temperature is from 210 to 280℃and preferably from 210 to 260 ℃.
According to a preferred embodiment of the invention, the polycondensation reaction temperature is 210 to 260℃and preferably 230 to 260℃in a 2L polymerization reactor.
According to a preferred embodiment of the invention, the polycondensation reaction temperature is 230 to 260℃and preferably 240 to 255℃in a 30L polymerization reactor.
In the invention, in the polycondensation reaction, the vacuum degree has influence on the polycondensation reaction speed, the polycondensation reaction temperature and byproducts, the polycondensation reaction of the polyester is a gas-phase reversible reaction, and the equilibrium constant is very small, so that the reaction equilibrium needs to be manually broken to obtain the product with the required molecular weight. In order to promote the polycondensation reaction, it is possible to reduce the concentration of the gas phase product in the product by vacuum pumping. The vacuum degree can influence the reaction speed, and the higher the vacuum degree is, the more favorable the removal of gas-phase products is, and the faster the polycondensation reaction speed is. In contrast, the removal of the gas-phase product is not favored, the polycondensation reaction rate is slowed, and even only oligomers are obtained, and polymers with sufficiently high molecular weights cannot be obtained. However, too high a vacuum leads to a broadened molecular weight distribution, which is detrimental to polymer processing and product properties.
According to the invention, in step 2, the degree of vacuum of the polycondensation reaction is 10 to 100Pa, preferably 10 to 80Pa, and more preferably 10 to 60Pa.
According to the invention, in the step 2, the time of the polycondensation reaction comprises the time when the viscosity of the reaction system is unchanged and the time when the viscosity starts to change, wherein the time when the viscosity of the reaction system is unchanged (torque is unchanged) is 10-60min, and the time when the viscosity starts to change (torque starts to change) to the discharging time is 20-180 min.
According to a preferred embodiment of the invention, in a 2L polymerization reactor, the reaction system viscosity is unchanged for 20 to 60 minutes and the viscosity is changed from 30 to 90 minutes.
According to a preferred embodiment of the present invention, in a 30L polymerization reactor, the reaction system viscosity is unchanged for 10 to 20 minutes and the viscosity is started to change for 100 to 180 minutes.
According to the invention, after the detected product reaches a certain viscosity, the polycondensation reaction is finished, and the self-repairing polyester is obtained after discharging and slicing.
According to the invention, the self-repairing polyester of the invention has an intrinsic viscosity of more than 0.7dL/g, preferably more than 0.8dL/g, and can be used for preparing polyester fibers.
According to the invention, the self-repairing polyester obtained has Mn of 20000 to 30000, a weight average molecular weight Mw of 30000 to 40000, a Z average molecular weight of 40000 to 50000, and Mw/Mn of 1.2 to 1.6, preferably 1.3 to 1.6.
According to the invention, the rheology of the resulting self-healing polyesters, which are shear-thinning non-newtonian fluids, were tested and at the same shear rate, the melt shear viscosity decreased with increasing temperature.
According to the present invention, the self-repairing polyester has a glass transition temperature of 40 to 60℃and no crystallization peak or melting peak, is an amorphous polymer, has an initial thermal decomposition temperature (temperature at 5% thermal weight loss) of 354 to 367℃and has a thermal decomposition residual rate of about 3 to 12%.
The self-repairing polyester has good shape recovery, after being bent at a certain angle, the self-repairing polyester is subjected to temperature treatment at a temperature of more than 55 ℃, after deformation is finished, the bending angle is reduced to 1-5 ℃, the recovery time is less than 50s, and the shape recovery rate is higher than 88%;
preferably, when the deformation is finished through the temperature treatment above 60 ℃, the bending angle is reduced to 1-3 degrees, the recovery time is less than 8s and even reaches 1.5-5.8 s, the shape recovery rate is higher than 96%, even more preferably 96.7-99.3%, the deformation recovery rate can reach 99.3%, and the deformation recovery rate is basically recovered to the shape before deformation.
According to the invention, the self-repairing polyester is processed at the temperature of more than 60 ℃ after being deformed, has good deformation recovery property, and has good transmittance after recovery, namely, the transparency is recovered.
The self-repairing polyester provided by the invention has good spinnability and can be used for preparing polyester fibers.
Examples
Example 1
The polymerization reaction is carried out in a 2L polymerization reaction kettle, 500g of terephthalic acid and 436g of 2-methyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled at 237 ℃, the esterification reaction pressure is controlled at 270kPa, the esterification reaction pressurization time is 120min, the normal pressure time is 40min, and when the water yield is 74ml, the esterification reaction is finished to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 20min, adding 0.5ml TBT, controlling the polycondensation reaction pressure to be 30Pa, controlling the polycondensation reaction temperature to be 260 ℃, and controlling the polycondensation reaction time to be 90min (including the time that the viscosity of a reaction system is unchanged for 47min and the time that the viscosity is increased to be discharged for 43 min), discharging and slicing after a certain viscosity is achieved, thereby obtaining the self-repairing polyester.
Example 2
The polymerization reaction is carried out in a 2L polymerization reaction kettle, 500g of terephthalic acid and 414g of 2-methyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled at 240 ℃, the esterification reaction pressure is controlled at 300kPa, the esterification reaction pressurization time is 130min, the normal pressure time is 60min, and when the water yield is 70ml, the esterification reaction is finished to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 30min, adding 0.7mL TBT, adding 1mL triphenyl phosphite, controlling the polycondensation reaction pressure at 60Pa, controlling the polycondensation reaction temperature at 260 ℃, and controlling the polycondensation reaction time at 150min (including the time when the viscosity of the reaction system is unchanged for 60min and the time when the viscosity is increased to be discharged for 90 min), discharging and slicing after a certain viscosity is achieved, thereby obtaining the self-repairing polyester.
Example 3
The polymerization reaction is carried out in a 2L polymerization reaction kettle, 500g of terephthalic acid and 379g of dimethyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled to 245 ℃, the esterification reaction pressure is controlled to 270kPa, the esterification reaction pressurization time is 140min, the normal pressure time is 40min, and when the water yield is 78ml, the esterification reaction is finished to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 20min, adding 1.0mL TBT, adding 1mL triphenyl phosphite, controlling the polycondensation reaction pressure to be 10Pa, controlling the polycondensation reaction temperature to be 260 ℃ and the polycondensation reaction time to be 80min (including the time that the viscosity of a reaction system is unchanged for 35min and the time that the viscosity is increased to be 45min when the viscosity is discharged), discharging and slicing after a certain viscosity is reached, so as to obtain the self-repairing polyester.
Example 4
The polymerization reaction is carried out in a 2L polymerization reaction kettle, 500g of terephthalic acid and 379g of 2-methyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled at 245 ℃, the esterification reaction pressure is controlled at 330kPa, the esterification reaction pressurization time is 70min, the normal pressure time is 50min, and when the water yield is 77ml, the esterification reaction is finished to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 25min, adding 1.5mL TBT, adding 1mL triphenyl phosphite, controlling the polycondensation reaction pressure to be 10Pa, controlling the polycondensation reaction temperature to be 260 ℃, and controlling the polycondensation reaction time to be 57min (including the time that the viscosity of a reaction system is unchanged for 22min and the time that the viscosity is increased to be discharged for 35 min), discharging and slicing after a certain viscosity is achieved, so as to obtain the self-repairing polyester.
Example 5
The polymerization reaction is carried out in a 2L polymerization reaction kettle, 500g of terephthalic acid and 352g of 2-methyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled at 246 ℃, the esterification reaction pressure is controlled at 300kPa, the esterification reaction pressurization time is 100min, the normal pressure time is 40min, and when the water yield is 72ml, the esterification reaction is finished to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 20min, adding 1.5mL of TBT, adding 1mL of triphenyl phosphite, adding 0.5g of antioxidant, controlling the polycondensation reaction pressure to be 10Pa, controlling the polycondensation reaction temperature to be 261 ℃, controlling the polycondensation reaction time to be 74min (including the time when the viscosity of a reaction system is unchanged for 29min and the time when the viscosity is increased to be 45min, and discharging and slicing after a certain viscosity is reached to obtain the self-repairing polyester.
Example 6
The polymerization reaction is carried out in a 2L polymerization reaction kettle, 500g of terephthalic acid and 325g of 2-methyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled at 240 ℃, the esterification reaction pressure is controlled at 300kPa, the esterification reaction pressurization time is 120min, the normal pressure time is 60min, and when the water yield is 67ml, the esterification reaction is finished to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 15min, adding 1.2mL of TBT, adding 1mL of triphenyl phosphite, adding 0.25g of antioxidant, controlling the polycondensation reaction pressure to be 10Pa, controlling the polycondensation reaction temperature to be 259 ℃, controlling the polycondensation reaction time to be 73min (including the time that the viscosity of a reaction system is unchanged for 28min and the time that the viscosity is increased to be 45min when the material is discharged), discharging and slicing after a certain viscosity is achieved, so as to obtain the self-repairing polyester.
Example 7
The polymerization reaction is carried out in a 2L polymerization reaction kettle, 500g of terephthalic acid and 325g of 2-methyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled at 240 ℃, the esterification reaction pressure is controlled at 300kPa, the esterification reaction pressurization time is 120min, the normal pressure time is 60min, and when the water yield is 67ml, the esterification reaction is finished to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 15min, adding 1.2mL of TBT, adding 1mL of triphenyl phosphite, adding 0.25g of antioxidant, controlling the polycondensation reaction pressure to be 10Pa, controlling the polycondensation reaction temperature to be 259 ℃, controlling the polycondensation reaction time to be 73min (including the time that the viscosity of a reaction system is unchanged for 28min and the time that the viscosity is increased to be discharged for 45 min), discharging and slicing after a certain viscosity is achieved, and taking discharged samples after intervals of 10min to obtain the self-repairing polyester.
Example 8
The polymerization reaction is carried out in a 30L polymerization reaction kettle, 3kg of terephthalic acid and 2.11kg of 2-methyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled at 242 ℃, the esterification reaction pressure is controlled at 300kPa, the esterification reaction pressurization time is 240min, the normal pressure time is 60min, and the esterification reaction is finished when the water yield is 76.9%, so as to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 60min, adding 270ppm TBT, adding 1.5mL of triphenyl phosphite, controlling the polycondensation reaction pressure to be 30Pa, controlling the polycondensation reaction temperature to be 255 ℃, and controlling the polycondensation reaction time to be 115min (including the time when the viscosity of a reaction system is unchanged for 10min and the time when the viscosity is increased to be discharged for 105 min), discharging and slicing after a certain viscosity is reached, thereby obtaining the self-repairing polyester.
Example 9
The polymerization reaction is carried out in a 30L polymerization reaction kettle, 3kg of terephthalic acid and 2.11kg of 2-methyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled at 239 ℃, the esterification reaction pressure is controlled at 300kPa, the esterification reaction pressurization time is 240min, the normal pressure time is 60min, and the esterification reaction is finished when the water yield is 69.2%, so as to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 45min, adding 270ppm TBT, adding 1.5mL of triphenyl phosphite, controlling the polycondensation reaction pressure to be 25Pa, controlling the polycondensation reaction temperature to be 248 ℃, and controlling the polycondensation reaction time to be 135min (including the time that the viscosity of a reaction system is unchanged for 15min and the time that the viscosity is increased to be 120min when the material is discharged), discharging and slicing after a certain viscosity is achieved, so as to obtain the self-repairing polyester.
Example 10
The polymerization reaction is carried out in a 30L polymerization reaction kettle, 3kg of terephthalic acid and 2.11kg of 2-methyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled at 247 ℃, the esterification reaction pressure is controlled at 300kPa, the esterification reaction pressurization time is 180min, the normal pressure time is 180min, and the esterification reaction is finished when the water yield is 94.1%, so as to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 20min, adding 390ppm TBT, controlling the polycondensation reaction pressure to be 30Pa, controlling the polycondensation reaction temperature to be 255 ℃, and controlling the polycondensation reaction time to be 195min (including the time that the viscosity of a reaction system is unchanged for 15min and the time that the viscosity is increased to be discharged for 180 min), and discharging and slicing after a certain viscosity is achieved to obtain the self-repairing polyester.
Example 11
The polymerization reaction is carried out in a 30L polymerization reaction kettle, 3kg of terephthalic acid and 2.11kg of 2-methyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled at 245 ℃, the esterification reaction pressure is controlled at 300kPa, the esterification reaction pressurization time is 140min, the normal pressure time is 180min, and the esterification reaction is finished when the water yield is 94.1%, so as to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 20min, adding 540ppm TBT, adding 1.5mL of triphenyl phosphite, controlling the polycondensation reaction pressure to be 30Pa, controlling the polycondensation reaction temperature to be 255 ℃, and controlling the polycondensation reaction time to be 135min (including the time when the viscosity of a reaction system is unchanged for 10min and the time when the viscosity is increased to be discharged for 125 min), discharging and slicing after a certain viscosity is reached, thereby obtaining the self-repairing polyester.
Example 12
The polymerization reaction is carried out in a 30L polymerization reaction kettle, 3kg of terephthalic acid, 2.11kg of 2-methyl-1, 3-propanediol and 15g of titanium dioxide are added into the reaction kettle, the esterification reaction temperature is controlled at 245 ℃, the esterification reaction pressure is controlled at 300kPa, the esterification reaction pressurization time is 180min, the normal pressure time is 140min, and the esterification reaction is finished when the water yield is 94.1%, so as to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 20min, adding 650ppm TBT, adding 1.5mL of triphenyl phosphite, controlling the polycondensation reaction pressure to be 30Pa, controlling the polycondensation reaction temperature to be 255 ℃, and controlling the polycondensation reaction time to be 130min (including the time that the viscosity of a reaction system is unchanged for 10min and the time that the viscosity is increased to be discharged for 120 min), discharging and slicing after a certain viscosity is reached, thereby obtaining the self-repairing polyester.
Example 13
The polymerization reaction is carried out in a 30L polymerization reaction kettle, 3kg of terephthalic acid and 3kg of 2-methyl-1, 3-propanediol are added into the reaction kettle, the esterification reaction temperature is controlled at 247 ℃, the esterification reaction pressure is controlled at 300kPa, the esterification reaction pressurization time is 150min, the normal pressure time is 150min, and the esterification reaction is finished when the water yield is 96.3%, so as to obtain an esterification product;
after the esterification reaction is finished, vacuumizing for 20min, adding 760ppm TBT, adding 1.5mL of triphenyl phosphite, controlling the polycondensation reaction pressure to be 30Pa, controlling the polycondensation reaction temperature to be 255 ℃, and controlling the polycondensation reaction time to be 190min (including the time that the viscosity of a reaction system is unchanged for 10min and the time that the viscosity is increased to be 180min when the viscosity is discharged), discharging and slicing after a certain viscosity is reached, so as to obtain the self-repairing polyester.
Experimental example
Experimental example 1
The self-healing polyesters obtained in examples 1,3, 5 and 7 were subjected to infrared tests, and the spectra obtained are shown in fig. 1, in which curve # 1 corresponds to example 1, curve # 3 corresponds to example 3, curve # 5 corresponds to example 5, and curve # 7 corresponds to example 7.
As can be seen from FIG. 1, the self-repairing polyester samples are all 1712cm in length -1 The typical stretching vibration peak (v) of carbonyl in ester group (-COO-) -C＝O ) Indicating that a typical esterification structure is formed and 1700cm is not present in the infrared spectrum -1 Typical peaks in the vicinity have a small amount of carboxyl end groups.
Experimental example 2
Intrinsic viscosity is one of the representative parameters of the relative molecular weight of a polymer, which is used to measure the magnitude of the relative molecular weight of the polymer, which determines the use of the polymer.
The intrinsic viscosities of the self-healing polyesters obtained in examples 8-13 were measured by the dilute solution viscosity method at 25℃with phenol-tetrachloroethane as solvent at a concentration of about 0.5g/100mL and a capillary viscometer (capillary diameter 0.8 mm).
The calculation was performed by the "one-point method", and the test results are shown in table 2 below.
TABLE 2
As can be seen from Table 2, the intrinsic viscosity of the self-healing polyesters obtained in examples 8-13 is greater than 0.7dL/g, and may even reach 0.847dL/g, and can be used to make fibers.
Experimental example 3
The MPTT samples obtained in examples 8-12 were tested for molecular weight and molecular weight distribution using a Shimadzu 15C high performance liquid chromatograph, a RID-10A differential refractive index detector, a CTO-20A column incubator, and a Shimadzu GPC chromatographic workstation.
Liquid chromatography conditions: mobile phase: tetrahydrofuran (THF), flow rate and flow rate: 1mL/min, column temperature, shodex GPC KF-803 (8X 300 mm): 40 ℃, sample injection volume: 20. Mu.L.
About 10mg of each of the 5 samples of examples 8-12 was dissolved in 8mL of tetrahydrofuran overnight. Shaking, and filtering with 0.22 μm polytetrafluoroethylene membrane.
GPC calibration curves were drawn with 2K, 5K, 10K, 20K, 40K PEG standard samples, and linear regression equations were: y= -0.009727X 3 +0.2582X 2 -2.6562X+13.4471。
The results of GPC test of the obtained examples are shown in Table 3, and GPC chromatograms and molecular weight distribution views of the self-repairing polyesters obtained in example 8 are shown in FIG. 2.
TABLE 3 Table 3
As can be seen from Table 3, the resulting modified polyesters have Mn in the range of 20000 to 30000, mw in the range of 30000 to 40000, mz in the range of 40000 to 50000, mw/Mn lower than 1.6, and in the range of 1.3 to 1.6.
Experimental example 4
Testing the thermal stability of a sample by adopting a Q2000 type differential scanning calorimeter (DSC, TA company of America), wherein the testing temperature is 0-280 ℃, and the heating rate is 10 ℃/min; test sample thermal degradation performance by using 209F1 type thermogravimetric analyzer (TG, german relaxation company) tester under the test condition of N 2 Atmosphere, temperature range 30-800 deg.C, heating rate 20 deg.C/min. To the realityThe self-healing polyesters obtained in examples 1-7 were subjected to DSC and TG tests, FIG. 3 is a one-time temperature rise DSC curve, FIG. 4 is a DSC temperature rise curve obtained by annealing the self-healing polyester samples obtained in examples 1 and 2 at 100℃for 2h, 4h and 6h, and FIG. 5 and 6 are TG curves, wherein FIG. 6 is a partial enlarged view of the TG curve in FIG. 5. In fig. 3 to 6, # 1-example 1, # 2-example 2, # 3-example 3, # 4-example 4, # 5-example 5, # 6-example 6, # 7-example 7.
As can be seen from FIG. 3, the sample DSC curve shows only glass transition temperature, and at about 50 ℃, no crystallization peak or melting peak appears, which means that the crystallinity of the polyester is poor, the polyester is hardly crystallized, and the polyester belongs to a polymer which cannot be crystallized, and is possibly related to a lateral methyl group in an MPO structure, and as can be seen from FIG. 4, the sample is heated at 100 ℃ for 2-6 hours, and the self-repairing polyester is hardly crystallized.
As can be seen from FIGS. 5 to 6, the thermal degradation weight loss processes of the self-repairing polyesters obtained in examples 1 to 7 are not different much, the char formation of the samples is poor, and the temperature at 5% weight loss is taken as the initial decomposition temperature (T 5wt％ ) The initial decomposition temperature of the self-repairing polyester sample is 354-367 deg.C respectively.
Experimental example 5
The rheological properties of the self-healing polyesters were studied to investigate the spinnability of the self-healing polyesters. The polyesters obtained in examples 10 and 13 were tested for rheological properties and for shear rate versus shear viscosity at various temperatures for self-healing polyesters.
The self-healing polyesters obtained in examples 10 and 13 were dried in a vacuum oven at 75℃for 12 hours, cooled to room temperature, and the self-healing polyesters were subjected to rheological tests at different temperatures using a Rosand RH10 capillary rheometer in England to obtain shear rate and shear viscosity data for the self-healing polyesters at different temperatures. The test results are shown in FIGS. 7-8. FIG. 7 is a plot of shear rate versus shear viscosity at 225 ℃, 230 ℃ and 235 ℃ for the self-healing polyester obtained in example 10. FIG. 8 is a plot of shear rate versus shear viscosity at 225℃at 230℃and at 235℃for the self-healing polyester obtained in example 13.
It can be seen from FIGS. 7-8 that the shear rate and shear viscosity of the self-healing polyesters of examples 10 and 13 are related to shear thinning non-Newtonian fluids, and that at the same shear rate, the melt shear viscosity decreases with increasing temperature.
As can be seen from FIGS. 7-8, the shear rate is 1200s -1 At 235℃the shear viscosity of the polyester is about 170 Pa.s, so that the spinnability test of the self-repairing polyester can be tested at 235℃and adjusted according to the spinning conditions.
Experimental example 6
Preparing a cylindrical self-repairing polyester spline with the diameter of 3mm by using the self-repairing polyester obtained in the embodiment 1, bending the self-repairing polyester spline at a certain angle thetai at normal temperature, then placing the bent self-repairing polyester spline into a constant-temperature water bath kettle with different temperatures (50 ℃, 55 ℃, 60 ℃, 80 ℃ and 100 ℃), recording recovery time after deformation recovery is finished, measuring the bending angle thetaf after deformation by using a protractor, calculating the shape recovery rate Rb by using the following formula (1),
in the formula (1), when rb=1, it is specified to have complete shape recovery; when rb=0, there is no shape recovery.
The test results are shown in tables 4 to 6, wherein table 4 shows the bending angle θf, the recovery time and the shape recovery rate of the self-repairing polyester spline with θi of 45 degrees at different water temperatures, table 5 shows the bending angle θf, the recovery time and the shape recovery rate of the self-repairing polyester spline with θi of 90 degrees at different water temperatures, and table 6 shows the bending angle θf, the recovery time and the shape recovery rate of the self-repairing polyester spline with θi of 135 degrees at different water temperatures.
TABLE 4 Table 4
TABLE 5
TABLE 6
As can be seen from tables 4 to 6, the self-repairing polyester sample bars have no shape restorability in water at 50℃and exhibit shape restorability when the water temperature is 55℃or higher, but the bending angle after the deformation restoration is larger, the required recovery time is longer, the recovery rate is lower, and the recovery time becomes longer as the bending angle is larger. Along with the rise of the water temperature, the self-repairing polyester has better shape recovery performance, shortens the recovery time, reaches the recovery rate of 99.3 percent at 100 ℃, and basically recovers to the shape before deformation.
Vertical self-repairing polyester sample bars with the diameter of 3mm are bent into English letters 'W', the English letters are used as sample bar states before deformation, then the sample bars are placed in a constant-temperature water bath kettle with the temperature of 60 ℃, and pictures before deformation and pictures after deformation are recorded by adopting a camera, and the pictures are shown in (a) and (b) in fig. 9 respectively.
As can be seen from fig. 9, (a) the self-repairing polyester spline becomes a photograph of english letter W after being bent, and stress whitening phenomenon is seen from the bent position, (b) the stress whitening phenomenon is disappeared for the photograph of the polyester spline recovered to the vertical state before deformation at 60 ℃, the self-repairing polyester spline recovers to be transparent, which means that the self-repairing polyester spline has good shape recovery property at 60 ℃ and also can recover good transmittance.
The invention has been described in detail with reference to preferred embodiments and illustrative examples. It should be noted, however, that these embodiments are merely illustrative of the present invention and do not limit the scope of the present invention in any way. Various improvements, equivalent substitutions or modifications can be made to the technical content of the present invention and its embodiments without departing from the spirit and scope of the present invention, which all fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (6)
1. A process for preparing self-repairing polyester, which is characterized in that the polyester is obtained by esterification polymerization of 2-methyl-1, 3-propanediol monomer and dicarboxylic acid monomer, wherein Mn is 20000-30000, mw is 30000-40000, mw/Mn is 1.2-1.6,
the intrinsic viscosity of the polyester is greater than 0.7dL/g;
the method comprises the following steps:
step 1, esterification reaction: adding 2-methyl-1, 3-propanediol and a dicarboxylic acid monomer into a reaction vessel for esterification reaction to obtain an esterification product; the dicarboxylic acid monomer is selected from terephthalic acid or mixed acid of terephthalic acid and isophthalic acid, and the molar ratio of MPO to the dicarboxylic acid monomer is (1.2-1.8): 1, the temperature of the esterification reaction is 240-248 ℃;
step 2, polycondensation reaction: polycondensing the esterified product to obtain self-repairing polyester; after the esterification reaction is finished and before the polycondensation reaction, vacuumizing the system, wherein the vacuum degree is 10-100 Pa, adding a titanium catalyst which is a polycondensation catalyst, and the temperature of the polycondensation reaction is 210-260 ℃;
after the self-repairing polyester is bent, the temperature is over 55 ℃, after the deformation is finished, the bending angle is reduced to 1-5 ℃, the recovery time is less than 50s, and the shape recovery rate is higher than 88%.
2. The method according to claim 1, wherein in the step 1, 2-methyl-1, 3-propanediol and a dicarboxylic acid monomer are directly esterified to obtain an esterified product;
the pressure in the reaction vessel is controlled to be 200-330 kPa during the esterification reaction and the drainage.
3. The method according to claim 1, wherein after the esterification reaction is completed and before the polycondensation reaction, the reaction system is evacuated for 10 to 60 minutes, and a polycondensation catalyst is further added.
4. The method according to claim 1, wherein the polycondensation catalyst is selected from one or more of tetrabutyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetra-isopropyl titanate, and tetra-isooctyl titanate.
5. The method according to claim 1, wherein the polycondensation catalyst is added in an amount of 0.1 to 1% by mass of the dicarboxylic acid monomer.
6. The method according to claim 1, wherein an auxiliary agent is further added before the polycondensation reaction, the auxiliary agent comprising one or both of a heat stabilizer and an antioxidant,
the addition amount of the heat stabilizer is 0.1 to 0.5 percent of the mass of the dicarboxylic acid monomer,
the heat stabilizer is one or more of trimethyl phosphate, triphenyl phosphite, triphenyl phosphate and trimethyl phosphite.
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| JP6324177B2 (en) * | 2013-04-09 | 2018-05-16 | キヤノン株式会社 | Resin for toner and toner |
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