阅读说明：本技术 一种用于聚酯合成的缩聚催化剂、其制备方法与应用 (Polycondensation catalyst for polyester synthesis, preparation method and application thereof ) 是由 刘小青 费璇 刘敬楷 江艳华 于 2021-08-18 设计创作，主要内容包括：本发明公开了一种用于聚酯合成的缩聚催化剂、其制备方法与应用。所述制备方法包括：将Ti-(3)C-(2)T-(x)Mxene材料与苯并噁嗪单体均相共混,获得共混物,之后加热进行固化处理,得到Ti-(3)C-(2)T-(x)MXene/苯并噁嗪树脂复合材料；最后以激光对其进行辐照,制得用于聚酯合成的缩聚催化剂。本发明制备的用于聚酯合成的缩聚催化剂具有高催化活性,可以在更短的时间内缩聚聚合得到分子量更高的聚酯,从而提高聚酯的拉伸模量、拉伸强度等力学性能。此外,更短的聚合时间可以抑制原料二酸脱羧等副反应与聚酯的热降解,使所得聚酯有更优的色相。并且,聚酯中的LIG可以增加聚酯的结晶速率,并增强其导电性,赋予聚酯产品抗静电性能。(The invention discloses a polycondensation catalyst for polyester synthesis, and a preparation method and application thereof. The preparation method comprises the following steps: mixing Ti 3 C 2 T x The Mxene material and the benzoxazine monomer are blended homogeneously to obtain a blend, and then the blend is heated to be cured to obtain Ti 3 C 2 T x MXene/benzoxazine resin composite material; finally, the polyester is irradiated by laser to prepare the polycondensation catalyst for polyester synthesis. Book (I)The polycondensation catalyst for polyester synthesis prepared by the invention has high catalytic activity, and can be used for polycondensation polymerization in a shorter time to obtain polyester with higher molecular weight, so that the mechanical properties of the polyester, such as tensile modulus, tensile strength and the like, are improved. In addition, the shorter polymerization time can inhibit side reactions such as decarboxylation of raw material diacid and thermal degradation of polyester, so that the obtained polyester has better color. And the LIG in the polyester can increase the crystallization rate of the polyester, enhance the conductivity of the polyester and endow the polyester product with antistatic performance.)

1. A method for preparing a polycondensation catalyst for polyester synthesis, characterized by comprising:

providing Ti₃C₂T_xA Mxene material;

adding the Ti₃C₂T_xThe Mxene material and the benzoxazine monomer are blended homogeneously to obtain a blend,

heating the blend for curing to obtain Ti₃C₂T_xMXene/benzoxazine resin composite material;

laser irradiation of the Ti₃C₂T_xAnd irradiating the MXene/benzoxazine resin composite material to obtain the titanium-loaded laser-induced graphene composite material, namely the polycondensation catalyst for polyester synthesis.

2. The production method according to claim 1, characterized by comprising: using strong acid to Ti_xAl_yC_zChemical etching is carried out on MAX phase material to obtain Ti₃C₂T_xA Mxene material; preferably, the concentration of the strong acid is 5-50%, and the chemical etching time is 24-48 h; preferably, the strong acid comprises hydrofluoric acid, or alternatively, a mixture of a fluoride salt and hydrochloric acid.

3. The preparation method according to claim 1, wherein the benzoxazine monomer has a structure as shown in any one or two or more of formula (I), formula (II) and formula (III):

in the formula (I), R₁And R₂Independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group or a phenyl group;

in the formula (II), R₂is-CH₂-，-SO₂-, - (O) -, -S-or any of the following, R₁And R₃Each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group and/or a phenyl group;

in the formula (III), R₂is-CH₂-、And any one of, R₁And R₃Are each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group, or a phenyl group.

4. The method of claim 1, wherein: the Ti₃C₂T_xThe mass ratio of the Mxene material to the benzoxazine monomer is (2-9) to 25; and/or, the preparation method comprises the following steps: adding the Ti₃C₂T_xMixing Mxene material with benzoxazine monomer, heating and stirring to realize Ti₃C₂T_xHomogeneous blending of the Mxene material and the benzoxazine monomer to obtain a blend; and/or the temperature of the blending is 120-150 ℃, the temperature of the curing treatment is 150-180 ℃, and the time of the curing treatment is 6-10 h;

and/or the laser comprises infrared laser with the wavelength of 10.6 μm and/or continuous wave laser; and/or the power of the laser is 3-50W, and the laser speed is 0.01-1.27 m/s.

5. A polycondensation catalyst for polyester synthesis prepared by the method of any one of claims 1 to 4, comprising titanium and carbon, preferably, the content of titanium in the polycondensation catalyst is 10 to 50 wt%.

6. Use of the polycondensation catalyst for polyester synthesis according to claim 5 in polyester synthesis.

7. A method for synthesizing polyester, which is characterized by comprising the following steps:

(1) providing a first component and a second component, wherein the first component comprises at least one of terephthalic acid, furan dicarboxylic acid, terephthalic acid ester and furan dicarboxylic acid ester, and the second component comprises at least one of aromatic diol and aliphatic diol;

(2) mixing the first component, the second component and an esterification catalyst, and reacting in an inert atmosphere or a nitrogen atmosphere to obtain a first intermediate product, wherein the molar ratio of the first component to the second component is 1: 1.1-2.0;

(3) subjecting the first intermediate product to polycondensation reaction under vacuum conditions in the presence of the polycondensation catalyst for polyester synthesis according to claim 5 to obtain a polyester.

8. The method of synthesis according to claim 7, characterized in that: in the step (1), the terephthalate includes at least one of dimethyl terephthalate, diethyl terephthalate and dibutyl terephthalate; and/or the furan dicarboxylate comprises at least one of furan dicarboxylic acid dimethyl ester, furan dicarboxylic acid diethyl ester and furan dicarboxylic acid dibutyl ester;

and/or the aliphatic diol comprises at least one of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, cyclohexanedimethanol, 2, 4, 4-tetramethyl-1, 3-cyclobutanediol, and neopentyl glycol; and/or the aromatic dihydric alcohol comprises at least one of 2- [4- (2-hydroxyethyl) phenoxy ] ethanol, 1, 3-bis (2-hydroxyethoxy) benzene, bisphenol A and bisphenol S.

9. The method of synthesis according to claim 7, characterized in that: in the step (2), the reaction temperature is 150-220 ℃, preferably 150-200 ℃, and the reaction time is 0.5-5.0 h, preferably 2.0-5.0 h; and/or the molar ratio of the esterification catalyst to the first component is 0.05-1: 100, preferably 0.1-0.5: 100;

and/or in the step (3), the molar ratio of the polycondensation catalyst to the first component is 0.05-0.5: 100;

and/or, the synthesis method further comprises: adding a stabilizer into the first intermediate product, wherein the molar ratio of the stabilizer to the first component is 0.05-0.5: 100;

and/or, the synthesis method further comprises: adding an antioxidant into the first intermediate product, wherein the molar ratio of the antioxidant to the first component is 0.05-0.5: 100;

and/or in the step (3), the vacuum degree of the polycondensation reaction is less than 200Pa, preferably 1.5Pa to 200Pa, the reaction temperature is 240-280 ℃, and the reaction time is 0.5-4 h.

10. A polyester synthesized by the method of any one of claims 7 to 9, having a tensile modulus of 2.1 to 2.7GPa, a tensile strength of 68 to 82MPa, and a surface resistivity of 10⁸～10⁹Ω。

Technical Field

The invention relates to the technical field of materials, in particular to a titanium-loaded LIG (laser-induced graphene) composite polycondensation catalyst for polyester synthesis, a preparation method thereof and application thereof in polyester synthesis.

Background

Polyester is an important engineering plastic and fiber raw material, and has the advantages of friction resistance, good dimensional stability, solvent resistance and excellent thermo-mechanical property. Catalysts have great influence in the production of polyester, so the research on the catalysts is always a hotspot in the polyester industry. At present, the antimony-based catalyst which is applied more causes heavy metal pollution, has adverse effect on human health, and is expected to be gradually eliminated by the market. The titanium catalyst has moderate price, high activity and good safety, and is a powerful competitor of the antimony catalyst. However, there are still problems to be solved, such as more side reactions and poorer color of the product. Therefore, the development of new efficient polyester catalysts is crucial to the widening of the market.

Since 2011, Mxene has attracted extensive attention due to its unique nanostructure and electrical conductivity, and is rapidly applied to the fields of filtration, electromagnetic shielding, electronic sensing, and the like. Ti₃C₂T_xA large number of-OH, -F, -O and other functional groups on the surface of MXene can generate strong interaction with benzoxazine, so that the interface binding force is improved, and the comprehensive performance of the composite material is enhanced. By utilizing the characteristics of high char forming rate and good flame retardance of benzoxazine, CO can be used₂And preparing the titanium-loaded benzoxazine-based graphene material LIG with few defects and good conductivity by using laser. The catalyst plays a role in polyester production, and the residual graphene particles can enhance the conductivity of polyester so as to obtain an antistatic polyester product, and can be used in the fields of electronics and the like.

Patent CN111234194A discloses a liquid phase titanium catalyst, a preparation method thereof and application of the catalyst in polyester synthesis. The catalyst has good effect, and the obtained polyester product has good color and low content of residual carboxyl end groups. However, the thermal, crystalline and electrical properties of polyester products have not been improved for specific applications.

Patent CN112759751A discloses an aluminum catalyst for polyester synthesis, a preparation method and application thereof, and a polyester product obtained by using the catalyst has the characteristics of humidity resistance, heat resistance and aging resistance. Similarly, for applications requiring certain antistatic properties, such as capacitor packaging materials, moisture and heat resistance are not sufficient.

In addition, at present, research and development personnel in the industry use antimony-based catalysts, but antimony remained in polyester products can cause heavy metal pollution, so that the application of the antimony in the food field is limited, and the recovery of waste polyester is not facilitated.

Disclosure of Invention

The main object of the present invention is to provide a polycondensation catalyst for efficiently synthesizing polyester and a preparation method thereof, thereby overcoming the disadvantages of the prior art.

Another object of the present invention is to provide the use of said polycondensation catalyst for polyester synthesis.

In order to achieve the purpose, the invention adopts the following technical scheme:

the embodiment of the invention provides a preparation method of a polycondensation catalyst for polyester synthesis, which comprises the following steps:

providing Ti₃C₂T_xA Mxene material;

adding the Ti₃C₂T_xThe Mxene material and the benzoxazine monomer are blended homogeneously to obtain a blend,

heating the blend for curing to obtain Ti₃C₂T_xMXene/benzoxazine resin composite material;

laser irradiation of the Ti₃C₂T_xIrradiating the MXene/benzoxazine resin composite material to prepare the titanium-loaded laser-induced graphene composite material, namely the titanium-loaded laser-induced graphene composite material for polymerizationPolycondensation catalyst for ester synthesis.

In some embodiments, the method of making comprises: using strong acid to Ti_xAl_yC_zChemical etching is carried out on MAX phase material to obtain Ti₃C₂T_xMxene material.

In some embodiments, the benzoxazine monomer has a structure as shown in any one of formula (I), formula (II), formula (III) or two or more thereof:

in formula (I), R1 and R2 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group and/or a phenyl group;

in the formula (II), R2 is-CH₂-，-SO₂Any one of-O-, -S-; r1 and R3 are each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group and/or a phenyl group;

in the formula (III), R2 is-CH₂-、Any one of the above; r1 and R3 are each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group and/or a phenyl group.

The embodiment of the invention also provides a polycondensation catalyst for polyester synthesis, which is prepared by the method and comprises a titanium element and a carbon element.

Further, the content of titanium element in the polycondensation catalyst is 10 wt% to 50 wt%.

The embodiment of the invention also provides application of the polycondensation catalyst for polyester synthesis in polyester synthesis.

The embodiment of the invention also provides a synthetic method of polyester, which comprises the following steps:

(1) providing a first component and a second component, wherein the first component comprises at least one of terephthalic acid, furan dicarboxylic acid, terephthalic acid ester and furan dicarboxylic acid ester, and the second component comprises at least one of aromatic diol and aliphatic diol;

(2) mixing the first component, the second component and an esterification catalyst, and reacting in an inert atmosphere or a nitrogen atmosphere to obtain a first intermediate product, wherein the molar ratio of the first component to the second component is 1: 1.1-2.0;

(3) and carrying out polycondensation reaction on the first intermediate product in the presence of the polycondensation catalyst for polyester synthesis under vacuum conditions to obtain the polyester.

Correspondingly, the embodiment of the invention also provides the polyester synthesized by the method, wherein the tensile modulus of the polyester is 2.1-2.7 GPa, the tensile strength is 68-82 MPa, and the surface resistivity is 10⁸～10⁹Ω。

Compared with the prior art, the invention has the following beneficial effects:

the titanium-loaded LIG polycondensation catalyst for polyester synthesis prepared by the invention has high catalytic activity, high catalytic efficiency and short polycondensation time, and can be used for polycondensation polymerization in a shorter time to obtain polyester with higher molecular weight, so that the mechanical properties of the polyester, such as tensile modulus, tensile strength and the like, are improved. In addition, the shorter polymerization time can inhibit side reactions such as decarboxylation of raw material diacid and thermal degradation of polyester, so that the obtained polyester product has better hue. And, the LIG remaining in the polyester product can increase the crystallization rate of the polyester and enhance the conductivity thereof, giving the polyester product antistatic properties.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 shows Ti obtained in example 1 of the present invention₃C₂T_xScanning Electron Microscope (SEM) images of Mxene;

FIG. 2 shows Ti obtained in example 1 of the present invention₃C₂T_xBET nitrogen adsorption desorption profile of Mxene;

FIG. 3 shows Ti obtained in example 1 of the present invention₃C₂T_xAn infrared spectrogram of Mxene;

FIG. 4 is an X-ray photoelectron spectroscopy (XPS) chart of a titanium-supported LIG polycondensation catalyst prepared in example 1 of the present invention;

FIG. 5a is a torque variation line graph of the polycondensation process in which the titanium supported LIG polycondensation catalyst prepared in examples 1, 4 and 5 of the present invention is applied to the synthesis of terephthalic acid polyester;

FIG. 5b is a torque variation line diagram of the polycondensation process of applying the titanium supported LIG polycondensation catalyst prepared in examples 2 and 3 of the present invention to the synthesis of furan dicarboxylic acid polyester;

FIG. 6 is a torque variation line of a polycondensation process in which the polycondensation catalysts prepared in comparative examples 1, 2 and 5 and example 1 of the present invention are applied to the synthesis of a terephthalic acid polyester;

FIG. 7 is a torque variation line diagram of a polycondensation process in which the polycondensation catalysts prepared in comparative examples 3 and 4 and example 2 of the present invention are applied to the synthesis of furan dicarboxylic acid polyester;

FIG. 8 is a line graph of the semicrystallization time for terephthalic acid polyesters made in inventive example 1 and comparative example 5 and furan dicarboxylic acid polyesters made in example 2 and comparative example 4;

FIG. 9 is a graph comparing the tensile modulus of terephthalic acid polyesters made in example 1 and comparative example 5 of the present invention and furan dicarboxylic acid polyesters made in example 2 and comparative example 4;

FIG. 10 is a graph comparing the tensile strength of the terephthalic acid polyesters of the invention obtained in example 1 and comparative example 5 and the furan dicarboxylic acid polyesters of example 2 and comparative example 4.

Detailed Description

As described above, in view of the defects of the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose a technical solution of the present invention. The design principle of the inventor possibly lies in that: the characteristics of the catalyst are utilized in two aspects to obtain the polyester with excellent performance. The first is the catalytic effect during polyester polycondensation, the titanium-loaded LIG composite polycondensation catalyst prepared by the invention has high catalytic activity, the polymerization time is effectively shortened, the thermal degradation of a reaction system is reduced, and the obtained polyester has good hue; secondly, LIG remained in the polyester product can effectively improve the conductivity and crystallization rate of the polyester, so that a novel polyester product with fast crystallization and static electricity resistance is obtained, and the novel polyester product can be applied to the fields of electronic packaging and the like, so that the safety of the product is greatly improved.

The titanium LIG composite polycondensation catalyst provided by the invention, the preparation method thereof and the application thereof in the production of polyester are further described below.

Specifically, as an aspect of the technical solution of the present invention, there is provided a method for preparing a polycondensation catalyst for polyester synthesis, comprising:

providing Ti₃C₂T_xA Mxene material;

adding the Ti₃C₂T_xThe Mxene material and the benzoxazine monomer are blended homogeneously to obtain a blend,

heating the blend for curing to obtain Ti₃C₂T_xMXene/benzoxazine resin composite material;

laser irradiation of the Ti₃C₂T_xAnd irradiating the MXene/benzoxazine resin composite material to obtain the titanium-loaded laser-induced graphene composite material, namely the polycondensation catalyst for polyester synthesis.

In some embodiments, the method of making comprises: using strong acid to Ti_xAl_yC_zChemical etching is carried out on MAX phase material to obtain Ti₃C₂T_xMxene material.

In some embodiments, the method of making comprises: adding the Ti₃C₂T_xMixing Mxene material with benzoxazine monomer, heating and stirring to realize Ti₃C₂T_xHomogeneous blending of the Mxene material and the benzoxazine monomer to obtain a blend.

In some preferred embodiments, the preparation method specifically comprises the following steps:

the method comprises the following steps: using strong acid to Ti_xAl_yC_z(MAX phase material) is chemically etched to obtain Ti₃C₂T_xA Mxene material;

step two: adding the Ti₃C₂T_xMixing Mxene material with benzoxazine monomer, heating and stirring to realize Ti₃C₂T_xHomogeneous blending of the Mxene material and the benzoxazine monomer to obtain a blend; heating and curing the blend to obtain Ti₃C₂T_xMXene/poly (PBz, i.e., benzoxazine) resin composite;

step three: to the Ti₃C₂T_xAnd irradiating the MXene/poly (PBz) resin composite material to prepare the titanium-loaded LIG (laser-induced graphene) composite material, thus obtaining the polycondensation catalyst for polyester synthesis.

Further, in the step one, the concentration of the strong acid is 5% -50%, and the chemical etching time is 24-48 h. Taking Ti into account₃C₂T_xThe multi-layer structure and the catalyst efficiency of the Mxene material are not expected to be excessively etched, so that the strong acid concentration is preferably 10% and the etching time is preferably 24 h.

Further, the strong acid may be hydrofluoric acid, or a mixture of a fluoride salt and hydrochloric acid.

In some embodiments, in step two, the benzoxazine monomer has a structure as shown in any one or two or more of formula (I), formula (II), formula (III):

in the formula (I), R₁And R₂Independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group and/or a phenyl group;

in the formula (II), R₂is-CH₂-，-SO₂Any one of-O-, -S-;R₁and R₃Each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group and/or a phenyl group;

in the formula (III), R₂is-CH₂-、Any one of the above; r₁And R₃Are each independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group and/or a phenyl group.

Considering the flexibility of the design of benzoxazine molecules, the benzoxazine monomer can be any one of the structures shown in formula (I), formula (II) and formula (III) or the combination of more than two monomers.

In some embodiments, the Ti₃C₂T_xThe mass ratio of the Mxene material to the benzoxazine monomer is (2-9) to 25.

In some embodiments, in the second step, the blending temperature is 120-150 ℃, the curing treatment temperature is 150-180 ℃, and the curing treatment time is 6-10 h.

In some embodiments, in step three, the laser comprises an infrared laser and/or a continuous wave laser having a wavelength of 10.6 μm; the power of the laser is 3-50W, and the laser speed is 0.01-1.27 m/s.

In the above preparation method, Ti₃C₂T_xThe interface bonding force of the Mxene material and benzoxazine is high due to a large number of functional groups such as-OH, -F, -O and the like on the surface of the Mxene material, and Ti₃C₂T_xThe dispersity of the Mxene material is good. LIG prepared from benzoxazine by laser has the advantages of less defects, good conductivity and Ti₃C₂T_xTi in the Mxene material has high catalytic activity on polyester, and LIG remained in a polyester product can further modify the polyester, enhance the conductivity of the polyester and enable the polyester to have antistatic performance.

In conclusion, the method for preparing the titanium-loaded LIG composite polycondensation catalyst provided by the invention has the advantages of clear flow, simple and convenient operation method, good controllability, easiness in implementation, suitability for large-scale industrial production and high economical efficiency.

As another aspect of the technical solution of the present invention, it relates to a polycondensation catalyst for polyester synthesis prepared by the aforementioned method, which comprises titanium element and carbon element, wherein the titanium element is uniformly distributed on LIG, has high catalytic activity for polyester, and can enhance the crystallization rate of polyester and impart antistatic property to polyester.

Further, the content of titanium element in the polycondensation catalyst is 10 wt% to 50 wt%.

In another aspect of embodiments of the present invention, there is also provided the use of a polycondensation catalyst as described above for polyester synthesis in polyester synthesis.

Accordingly, another aspect of the embodiments of the present invention also provides a method for synthesizing a polyester, including:

(1) providing a first component and a second component, wherein the first component comprises at least one of terephthalic acid, furan dicarboxylic acid, terephthalic acid ester and furan dicarboxylic acid ester, and the second component comprises at least one of aromatic diol and aliphatic diol;

(2) mixing the first component, the second component and an esterification catalyst, and reacting in an inert atmosphere or a nitrogen atmosphere to obtain a first intermediate product, wherein the molar ratio of the first component to the second component is 1: 1.1-2.0;

(3) and carrying out polycondensation reaction on the first intermediate product in the presence of the polycondensation catalyst for polyester synthesis under vacuum conditions to obtain a polyester product.

In some embodiments, in step (1), the terephthalate includes at least one of dimethyl terephthalate, diethyl terephthalate, dibutyl terephthalate, and the like, but is not limited thereto.

Further, the furan dicarboxylate includes at least one of furan dicarboxylate, furan dicarboxylate diethyl, furan dicarboxylate, and the like, but is not limited thereto. Wherein, furan dicarboxylic acid or furan dicarboxylic acid ester is derived from biomass raw material, and the biomass raw material comprises at least one of cellulose, fructose, glucose, furoic acid and the like.

In view of the better activity of dimethyl terephthalate and dimethyl furandicarboxylate, it is preferable that the first component is dimethyl terephthalate or dimethyl furandicarboxylate.

In some embodiments, in step (1), the aliphatic diol includes at least one of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, heptylene glycol, octylene glycol, nonylene glycol, decylene glycol, cyclohexanedimethanol, 2, 4, 4-tetramethyl-1, 3-cyclobutane diol, neopentyl glycol, and the like, but is not limited thereto.

Further, the aromatic diol includes at least one of 2- [4- (2-hydroxyethyl) phenoxy ] ethanol, 1, 3-bis (2-hydroxyethoxy) benzene, bisphenol a, bisphenol S, and the like, but is not limited thereto.

In some embodiments, in step (2), the esterification catalyst comprises at least one of anhydrous zinc acetate, anhydrous cobalt acetate, anhydrous manganese acetate, dibutyl tin oxide, and the like, but is not limited thereto.

Further, the molar ratio of the esterification catalyst to the first component is 0.05-1: 100, that is, in another aspect, the molar amount of the esterification catalyst is 0.05-1% of the molar amount of the first component. The molar amount of the esterification catalyst is 0.1 to 0.5% of the molar amount of the first component, in view of ensuring sufficient catalytic efficiency while the amount of the catalyst used is not excessively large.

In some embodiments, the reaction comprises an esterification reaction or a transesterification reaction, wherein the reaction temperature is 150 ℃ to 220 ℃ and the reaction time is 0.5h to 5.0 h. In consideration of the boiling points of the aliphatic diol and the aromatic diol used, it is preferable that the reaction temperature is 150 to 200 ℃ and the reaction time is 2.0 to 5.0 hours.

In some embodiments, in step (3), the molar ratio of the polycondensation catalyst to the first component is from 0.05 to 0.5: 100, that is, in other words, the molar amount of the polycondensation catalyst is from 0.05 to 0.5% of the molar amount of the first component.

Further, in the step (3), the synthesis method further comprises adding a stabilizer or an antioxidant, or a mixture of a stabilizer and an antioxidant to the first intermediate product.

Further, the molar ratio of the stabilizer or the antioxidant to the first component is 0.05-0.5: 100, that is, in another aspect, the molar amount of the stabilizer or the antioxidant is 0.05-0.5% of the molar amount of the first component.

Among them, the stabilizer can reduce the thermal decomposition of the polyester. The stabilizer includes at least one of phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium dihydrogen phosphate, etc., but is not limited thereto.

Wherein the antioxidant inhibits free radicals and consumes trace amounts of oxygen, thereby reducing thermal oxidative decomposition of the polyester. The antioxidant includes phenolic antioxidant, preferably at least one of antioxidant-1010, antioxidant-1076, antioxidant-168, etc., but is not limited thereto.

In some embodiments, in step (3), the degree of vacuum of the polycondensation reaction is 200Pa or less, preferably 1.5Pa to 200Pa, the reaction temperature is 240 ℃ to 280 ℃, and the reaction time is 0.5h to 4 h. Thus, the first intermediate product is subjected to polycondensation reaction under suitable conditions, and its molecular weight gradually increases to obtain a polyester product.

Accordingly, another aspect of an embodiment of the present invention also provides a polyester synthesized by the foregoing method.

Further, the polyester (with the number average molecular weight Mn of 32100-38400 g/mol) is fast in crystallization and has antistatic property, specifically, the polyester has the tensile modulus of 2.1-2.7 GPa, the tensile strength of 68-82 MPa and the surface resistivity of 10⁸～10⁹Ω。

In conclusion, the titanium-loaded LIG composite polycondensation catalyst provided by the invention has the characteristics of high catalytic activity and short polycondensation time, so that a polyester product with a good hue is obtained. Meanwhile, the residual LIG catalyst can increase the crystallization rate of the polyester product, effectively improve the conductivity of the polyester, endow the polyester product with a unique antistatic effect, better meet the application of the polyester product in the field of electronics and electricity, and greatly improve the safety of the product.

Hereinafter, the terephthalic acid polyester, the furan dicarboxylic acid polyester and the preparation method thereof will be further described by the following specific examples. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. It is to be noted that the following examples are intended to facilitate the understanding of the present invention, and do not set forth any limitation thereto. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.

Example 1

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging to collect bottom sediment, and vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 2: 25, blended, heated to 120 ℃, mixed uniformly, heated to 150 ℃, and cured for 6 hours at the temperature to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using a CW laser with a wavelength of 10.6 microns on Ti₃C₂T_xThe MXene/poly (PBz) composite material is subjected to laser irradiation, the size of a laser irradiation area is set to be 20mm multiplied by 10mm, and Ti is subjected to the photo-thermal action of laser₃C₂T_xDirect conversion of MXene/poly (PBz) composites to titanium-loaded LIG polycondensation catalyst, wherein the laser power is 3W and the laser speed is 0.1 m/s.

(3) Adding dimethyl terephthalate, ethylene glycol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1: 1.5: 0.0015, vacuumizing, filling nitrogen for three times for replacement, starting stirring, gradually heating to 180 ℃, and reacting for 5 hours. Then adding a titanium-loaded LIG polycondensation catalyst which is 0.15 percent of the molar weight of 2, 5-dimethyl terephthalate, 0.1 percent of triphenyl phosphate and 0.1 percent of antioxidant-1010 into a reaction kettle, slowly vacuumizing to 600 Pa-2000 Pa, gradually heating to 280 ℃, and continuously vacuumizing to below 200Pa for reaction for 3 hours to obtain a terephthalic acid polyester product containing LIG. The minimum semicrystallization time of the polyester was 0.41 min. The surface resistivity measured by the insulation high resistance instrument is 3 multiplied by 10⁹Ω。

The inventors also examined Ti produced in this example₃C₂T_xMxene powder was analyzed. FIG. 1 shows the Ti₃C₂T_xIn a Scanning Electron Microscope (SEM) image of Mxene, it can be observed that the surface is rough and the particle size is less than 50 μm. The BET nitrogen adsorption and desorption curve of the material is shown in figure 2, and the test result shows that Ti₃C₂T_xThe Mxene powder has a specific surface area of 5-10m²And/g, and shows a remarkable type III adsorption and desorption curve, namely, the adsorption quantity is gradually increased along with the increase of the relative pressure, and the unlimited multi-layer adsorption is carried out. The Ti₃C₂T_xThe infrared spectrum of Mxene is shown in FIG. 3, and 3450cm can be clearly seen^-1Characteristic peak of hydroxyl group of (2), 1640cm^-1The peak is the C ═ O oscillation peak of the carbonyl group. In the X-ray electron spectrum analysis, two obvious peaks of the Ti2p spectrum of FIG. 4 at 461.4eV and 455.4eV respectively correspond to Ti2p_1/2And Ti2p_2/3The fitting result to the Ti2p spectrum shows that the TiO₂The concentration of Ti (II) and Ti (III) is 22.7: 30.8: 35.7. Under otherwise unchanged conditions (equipment, charge amount, etc.), the change of torque is proportional to the change of molecular weight, i.e. the trend of molecular weight increase along with time is reflected. The inventors of the present application compared the catalytic effects of the examples. As can be seen from FIG. 5a, the use of a Ti-supported LIG polycondensation catalystThe molecular weight of the terephthalic acid polyester obtained by catalysis is increased faster, and the growth rate and the final torque are lower than those of the terephthalic acid polyester because the activity of furan dicarboxylic acid is lower than that of terephthalic acid. FIG. 6 shows the torque increase trend with time of terephthalic acid prepared by using Ti-supported LIG polycondensation catalyst of the present invention and terephthalic acid prepared by using MAX-phase LIG, titanium dioxide and antimony trioxide as catalysts, and the results show that the absolute torque of terephthalic acid prepared by using Ti-supported LIG polycondensation catalyst is the highest, i.e. the molecular weight is the highest, and the increase rate is the fastest, which is better than the catalytic effect of using antimony trioxide. The inventor preliminarily characterizes the performance of the obtained polyester. The line plot of the crystallization half time of fig. 8 shows that the polyester sample doped with LIG possesses a shorter crystallization half time, i.e., LIG accelerates the crystallization rate of the polyester. Mechanical tests show that the antimony trioxide-catalyzed polyester product and the LIG-doped polyester have excellent mechanical properties (as shown in FIGS. 9 and 10). The surface resistivity of the polyester product is tested by using an insulation high resistance instrument, and the result shows that the surface resistivity of the polyester catalyzed by the common antimony trioxide is 7 multiplied by 10¹⁷Omega, and the surface resistivity of the polyester doped with LIG is 3X 10⁹Omega, the antistatic performance is provided.

Example 2

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging to collect bottom sediment, and vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 4: 25, blended, heated to 120 ℃, mixed uniformly, heated to 150 ℃, and cured for 6 hours at the temperature to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using CO with a wavelength of 10.6 microns₂Laser pair Ti₃C₂T_xMXene/poly (PBz) composite material is irradiated by laser, and Ti is irradiated under the photo-thermal action of laser₃C₂T_xThe MXene/poly (PBz) composite material is directly converted into the titanium-supported LIG polycondensation catalyst, wherein the laser power is 50W, and the laser speed is 1.27 m/s.

(3) Adding dimethyl furandicarboxylate, glycerol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1: 1.8: 0.002, vacuumizing, filling nitrogen for three times for replacement, starting stirring, gradually heating to 180 ℃, and reacting for 5 hours. Then adding a titanium-loaded LIG polycondensation catalyst which is 0.2 percent of the molar weight of the dimethyl 2, 5-furandicarboxylate, 0.1 percent of triphenyl phosphate and 0.1 percent of antioxidant-1010 into a reaction kettle, slowly vacuumizing to 600 Pa-2000 Pa, gradually heating to 240 ℃, continuously vacuumizing to below 200Pa, and reacting for 1.5h to obtain the furan dicarboxylate polyester product containing LIG. The minimum semicrystallization time of the polyester was 0.88 min. The surface resistivity measured by the insulation high resistance instrument is 10⁹Ω。

Figure 7 compares the torque growth over time of furandicarboxylic acid prepared using the Ti-supported LIG polycondensation catalyst of the present invention with furandicarboxylic acid catalyzed with graphene, antimony trioxide. The result shows that the catalytic effect of the Ti-loaded LIG polycondensation catalyst is obviously superior to that of antimony trioxide, and graphene has no catalytic effect basically.

Example 3

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging to collect bottom sediment, and vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 5: 25, blended, heated to 120 ℃, mixed evenly, heated to 180 ℃, and cured for 10 hours at the temperature to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using CO with a wavelength of 10.6 microns₂Laser pair Ti₃C₂T_xMXene/poly (PBz) composite material is irradiated by laser, and Ti is irradiated under the photo-thermal action of laser₃C₂T_xMXene/poly (PBz) composite material is directly converted into a titanium-supported LIG polycondensation catalyst, wherein the laser power is 7.5W, and the laser speed is 0.19 m/s.

(3) Adding dimethyl furandicarboxylate, pentaerythritol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1: 1.8: 0.0015, vacuumizing, filling nitrogen for three times for replacement, starting stirring, gradually heating to 190 ℃, and reacting for 4 hours. Then adding a titanium-loaded LIG polycondensation catalyst which is 0.2 percent of the molar weight of the dimethyl 2, 5-furandicarboxylate, 0.15 percent of triphenyl phosphate and 0.15 percent of antioxidant-1010 into a reaction kettle, slowly vacuumizing to 600 Pa-2000 Pa, gradually heating to 250 ℃, continuously vacuumizing to below 200Pa, and reacting for 2 hours to obtain a furandicarboxylic acid polyester product containing LIG. The minimum semicrystallization time of the polyester was 0.84 min. The surface resistivity measured by the insulation high resistance instrument is 10⁹Ω。

Example 4

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging to collect bottom sediment, and vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 6: 25, blended, heated to 120 ℃, mixed uniformly, heated to 150 ℃, and cured for 8 hours at the temperature to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using CO with a wavelength of 10.6 microns₂Laser pair Ti₃C₂T_xMXene/poly (PBz) composite material is irradiated by laser, and the laser is irradiatedTi under heat₃C₂T_xMXene/poly (PBz) composite material is directly converted into a titanium-supported LIG polycondensation catalyst, wherein the laser power is 4.5W, and the laser speed is 0.19 m/s.

(3) Dimethyl terephthalate, pentaerythritol and anhydrous zinc acetate are added into a reaction kettle according to the molar ratio of 1: 1.6: 0.002, the reaction kettle is vacuumized, nitrogen is filled for three times for replacement, stirring is started, the temperature is gradually raised to 190 ℃, and the reaction is carried out for 5 hours. Then adding a titanium-loaded LIG polycondensation catalyst which is 0.5 percent of the molar weight of 2, 5-dimethyl terephthalate, 0.12 percent of triphenyl phosphate and 0.15 percent of antioxidant-168 into a reaction kettle, slowly vacuumizing to 300-1600 Pa, gradually heating to 275 ℃, and continuously vacuumizing to below 200Pa for reaction for 2.5 hours to obtain a terephthalic acid polyester product containing LIG. The minimum semicrystallization time of the polyester was 0.26 min. The surface resistivity measured by the insulation high-resistance instrument is 6 multiplied by 10⁸Ω。

Example 5

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging to collect bottom sediment, and vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 7: 25, blended, heated to 120 ℃, mixed uniformly, heated to 150 ℃, and cured for 8 hours at the temperature to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using CO with a wavelength of 10.6 microns₂Laser pair Ti₃C₂T_xMXene/poly (PBz) composite material is irradiated by laser, and Ti is irradiated under the photo-thermal action of laser₃C₂T_xMXene/poly (PBz) composite material is directly converted into a titanium-supported LIG polycondensation catalyst, wherein the laser power is 5.6W, and the laser speed is 0.19 m/s.

(3) Adding dimethyl terephthalate, glycerol and anhydrous manganese acetate into a reaction kettle according to the molar ratio of 1: 1.4: 0.0025, vacuumizing, filling nitrogen for replacing three times, starting stirring, gradually heating to 180 ℃, and reacting for 3.5 hours. Then adding a titanium-loaded LIG polycondensation catalyst which is 0.2 percent of the molar weight of the 2, 5-dimethyl terephthalate, 0.14 percent of dimethyl phosphate and 0.1 percent of antioxidant-168 into a reaction kettle, slowly vacuumizing to below 2000Pa, gradually heating to 270 ℃, and continuously vacuumizing to below 200Pa for reaction for 3.5 hours to obtain a terephthalic acid polyester product containing LIG. The minimum semicrystallization time of the polyester was 0.40 min. The surface resistivity measured by the insulation high-resistance instrument is 2 multiplied by 10⁹Ω。

Example 6

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging to collect bottom sediment, and vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 8: 25, blended, heated to 150 ℃, uniformly mixed, heated to 160 ℃, and cured for 6 hours at the temperature to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using CO with a wavelength of 10.6 microns₂Laser pair Ti₃C₂T_xMXene/poly (PBz) composite material is irradiated by laser, and Ti is irradiated under the photo-thermal action of laser₃C₂T_xMXene/poly (PBz) composite material is directly converted into a titanium-supported LIG polycondensation catalyst, wherein the laser power is 5.6W, and the laser speed is 0.19 m/s.

(3) Adding dimethyl furandicarboxylate, 1, 2, 3, 4-butanetetraol and anhydrous manganese acetate into a reaction kettle according to the mol ratio of 1: 2.0: 0.002, vacuumizing, filling nitrogen for three times for replacement, starting stirring, gradually heating to 190 DEG CAnd reacting for 3 hours. Then adding a titanium-loaded LIG polycondensation catalyst which is 0.15 percent of the molar weight of the dimethyl 2, 5-furandicarboxylate, 0.15 percent of diphenyl phosphite and 0.15 percent of antioxidant-1076 into a reaction kettle, slowly vacuumizing to 200 Pa-1500 Pa, gradually heating to 245 ℃, continuously vacuumizing to below 200Pa, and reacting for 4 hours to obtain the furan dicarboxylate polyester product containing LIG. The minimum semicrystallization time of the polyester was 0.89 min. The surface resistivity measured by the insulation high resistance instrument is 4 multiplied by 10⁹Ω。

Example 7

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging to collect bottom sediment, and vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 9: 25, blended, heated to 120 ℃, mixed evenly, heated to 150 ℃, and cured for 8 hours at the temperature to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using CO with a wavelength of 10.6 microns₂Laser pair Ti₃C₂T_xMXene/poly (PBz) composite material is irradiated by laser, and Ti is irradiated under the photo-thermal action of laser₃C₂T_xMXene/poly (PBz) composite material is directly converted into a titanium-supported LIG polycondensation catalyst, wherein the laser power is 7.5W, and the laser speed is 0.19 m/s.

(3) Adding dimethyl furandicarboxylate, dipentaerythritol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1: 1.1: 0.002, vacuumizing, filling nitrogen for three times for replacement, starting stirring, gradually heating to 185 ℃, and reacting for 4 hours. Then adding 0.12 percent of titanium-loaded LIG polycondensation catalyst, 0.5 percent of ammonium phosphite and 0.5 percent of antioxidant-1076 in the molar weight of dimethyl 2, 5-furandicarboxylate into a reaction kettle, and slowly vacuumizing to 200 Pa-1000Pa, gradually heating to 250 ℃, continuously vacuumizing to below 200Pa, and reacting for 2h to obtain a furan dicarboxylic acid polyester product containing LIG. The minimum semicrystallization time of the polyester was 0.88 min. The surface resistivity measured by the insulation high resistance instrument is 4 multiplied by 10⁹Ω。

Example 8

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging to collect bottom sediment, and vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 4: 25, blended, heated to 120 ℃, mixed evenly, heated to 160 ℃, and cured for 6 hours at the temperature to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using CO with a wavelength of 10.6 microns₂Laser pair Ti₃C₂T_xMXene/poly (PBz) composite material is irradiated by laser, and Ti is irradiated under the photo-thermal action of laser₃C₂T_xMXene/poly (PBz) composite material is directly converted into a titanium-supported LIG polycondensation catalyst, wherein the laser power is 7.5W, and the laser speed is 0.19 m/s.

(3) Adding dimethyl terephthalate, butanediol and dibutyltin oxide into a reaction kettle according to the mol ratio of 1: 1.7: 0.005, vacuumizing, filling nitrogen for three times for replacement, starting stirring, gradually heating to 150 ℃, and reacting for 5 hours. Then adding a titanium-loaded LIG polycondensation catalyst which is 0.4 percent of the molar weight of dimethyl terephthalate, 0.5 percent of ammonium dihydrogen phosphate and 0.05 percent of antioxidant-168 into a reaction kettle, slowly vacuumizing to 300-1200 Pa, gradually heating to 260 ℃, and continuously vacuumizing to below 200Pa for reaction for 4 hours to obtain a terephthalic acid polyester product containing LIG. The minimum semicrystallization time of the polyester was 0.31 min. The surface resistivity measured by the insulation high-resistance instrument is 8 multiplied by 10⁸Ω。

Example 9

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging to collect bottom sediment, and vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 5: 25, blended, heated to 120 ℃, mixed uniformly, heated to 150 ℃, and cured for 6 hours at the temperature to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using CO with a wavelength of 10.6 microns₂Laser pair Ti₃C₂T_xMXene/poly (PBz) composite material is irradiated by laser, and Ti is irradiated under the photo-thermal action of laser₃C₂T_xMXene/poly (PBz) composite material is directly converted into a titanium-supported LIG polycondensation catalyst, wherein the laser power is 3W, and the laser speed is 0.1 m/s.

(3) Adding dimethyl furandicarboxylate, butanediol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1: 1.3: 0.01, vacuumizing, filling nitrogen for three times for replacement, starting stirring, gradually heating to 185 ℃, and reacting for 4 hours. Then adding a titanium-loaded LIG polycondensation catalyst which is 0.18 percent of the molar weight of the dimethyl furanoate, 0.8 percent of ammonium dihydrogen phosphate and 0.15 percent of antioxidant-1010 into a reaction kettle, slowly vacuumizing to 200-1000 Pa, gradually heating to 260 ℃, and continuously vacuumizing to below 200Pa for reaction for 1h to obtain the polyester furandicarboxylate product containing LIG. The minimum semicrystallization time of the polyester was 0.81 min. The surface resistivity measured by the insulation high-resistance instrument is 2 multiplied by 10⁹Ω。

Example 10

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging, and collecting bottom sedimentAnd vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 6: 25, blended, heated to 120 ℃, mixed uniformly, heated to 150 ℃, and cured for 8 hours at the temperature to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using a CW laser with a wavelength of 10.6 microns on Ti₃C₂T_xMXene/poly (PBz) composite material is irradiated by laser, and Ti is irradiated under the photo-thermal action of laser₃C₂T_xMXene/poly (PBz) composite material is directly converted into a titanium-supported LIG polycondensation catalyst, wherein the laser power is 3W, and the laser speed is 0.01 m/s.

(3) Dimethyl terephthalate, dipentaerythritol and dibutyltin oxide are added into a reaction kettle according to the mol ratio of 1: 1.3: 0.006, the reaction kettle is vacuumized, nitrogen is filled for three times for replacement, stirring is started, the temperature is gradually raised to 160 ℃, and the reaction is carried out for 5 hours. Then adding a titanium-loaded LIG polycondensation catalyst which is 0.5 percent of the molar weight of dimethyl terephthalate, 0.05 percent of triphenyl phosphate and 0.5 percent of antioxidant-1010 into a reaction kettle, slowly vacuumizing to 200-1200 Pa, gradually heating to 270 ℃, and continuously vacuumizing to below 200Pa for reaction for 0.5h to obtain a terephthalic acid polyester product containing LIG. The minimum semicrystallization time of the polyester was 0.25 min. The surface resistivity measured by the insulation high resistance instrument is 5 multiplied by 10⁸Ω。

Example 11

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging to collect bottom sediment, and vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 7: 25, blended,heating to 120 deg.C, mixing, heating to 150 deg.C, and curing at the temperature for 10 hr to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using CO with a wavelength of 10.6 microns₂Laser pair Ti₃C₂T_xMXene/poly (PBz) composite material is irradiated by laser, and Ti is irradiated under the photo-thermal action of laser₃C₂T_xMXene/poly (PBz) composite material is directly converted into a titanium-supported LIG polycondensation catalyst, wherein the laser power is 5W, and the laser speed is 0.19 m/s.

(3) Adding dimethyl furandicarboxylate, ethylene glycol and dibutyltin oxide into a reaction kettle according to the mol ratio of 1: 1.5: 0.0005, vacuumizing, filling nitrogen for three times, starting stirring, gradually heating to 220 ℃, and reacting for 0.5 h. Then adding a titanium-loaded LIG polycondensation catalyst which is 0.4 percent of the molar weight of the dimethyl furandicarboxylate, 0.4 percent of triphenyl phosphate as a stabilizer and 0.1 percent of antioxidant-1010 into a reaction kettle, slowly vacuumizing to 200-1600 Pa, gradually heating to 245 ℃, and continuously vacuumizing to below 200Pa for reaction for 1.5h to obtain a furan dicarboxylic acid polyester product containing LIG. The minimum semicrystallization time of the polyester was 0.65 min. The surface resistivity measured by the insulation high-resistance instrument is 7 multiplied by 10⁸Ω。

Example 12

(1) Mixing Ti₃AlC₂Adding MAX phase powder into 10% HF solution at a mass ratio of 1: 10, stirring for 24h, centrifuging to collect bottom sediment, and vacuum drying to obtain Ti₃C₂T_xMxene powder. Subjecting the obtained Ti to₃C₂T_xMxene and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 8: 25, blended, heated to 120 ℃, mixed evenly, heated to 160 ℃, and cured for 6 hours at the temperature to obtain Ti₃C₂T_xMXene/poly (PBz) composite;

(2) using CO with a wavelength of 10.6 microns₂Laser pair Ti₃C₂T_xMXene/poly (PBz) composite material is irradiated by laser, and Ti is irradiated under the photo-thermal action of laser₃C₂T_xMXene/poly (PBz) composite material is directly converted into a titanium-supported LIG polycondensation catalyst, wherein the laser power is 7.5W, and the laser speed is 0.19 m/s.

(3) Adding dimethyl furandicarboxylate, pentanol and anhydrous cobalt acetate into a reaction kettle according to the mol ratio of 1: 1.8: 0.0015, vacuumizing, filling nitrogen for replacement three times, starting stirring, gradually heating to 200 ℃, and reacting for 5 hours. Then adding a titanium-loaded LIG polycondensation catalyst which is 0.05 percent of the molar weight of the dimethyl furanoate, 0.2 percent of triphenyl phosphate as a stabilizer and 0.5 percent of antioxidant-1010 into a reaction kettle, slowly vacuumizing to 200-1800 Pa, gradually heating to 250 ℃, and continuously vacuumizing to below 200Pa for reaction for 4 hours to obtain the LIG-containing furandicarboxylic acid polyester product. The minimum semicrystallization time of the polyester was 0.82 min. The surface resistivity measured by the insulation high resistance instrument is 10⁹Ω。

Comparative example 1

(1) Mixing Ti₃AlC₂MAX phase powder and benzoxazine monomer (monomer structure shown in the following figure) are weighed according to the mass ratio of 5: 25, blended, heated to 120 ℃, mixed evenly, heated to 150 ℃, and cured for 8 hours at the temperature to obtain Ti₃AlC₂MAX/poly (PBz) composites;

(2) using CO with a wavelength of 10.6 microns₂Laser pair Ti₃AlC₂MXene/poly (PBz) composite material is irradiated by laser, and Ti is irradiated under the photo-thermal action of laser₃AlC₂Direct conversion of MXene/poly (PBz) composites to titanium supportedLIG, wherein the laser power is 7.5W and the laser speed is 0.19 m/s.

(3) Adding dimethyl terephthalate, ethylene glycol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1: 2.0: 0.003, vacuumizing, filling nitrogen for replacing three times, starting stirring, gradually heating to 180 ℃, and reacting for 4 hours. Then adding titanium-loaded LIG with the molar weight of 0.1 percent of dimethyl terephthalate, trimethyl phosphate with the molar weight of 0.2 percent of stabilizer and antioxidant-168 with the molar weight of 0.5 percent into a reaction kettle, slowly vacuumizing to 400 Pa-1000 Pa, gradually heating to 275 ℃, and continuously vacuumizing to below 200Pa for reaction for 3 hours to obtain a terephthalic acid polyester product containing LIG. The minimum semicrystallization time of the polyester was 0.55 min. The surface resistivity measured by the insulation high resistance instrument is 4 multiplied by 10⁹Ω。

Comparative example 2

Adding dimethyl terephthalate, glycerol and anhydrous cobalt acetate into a reaction kettle according to the mol ratio of 1: 1.9: 0.0015, vacuumizing, filling nitrogen for three times for replacement, starting stirring, gradually heating to 175 ℃, and reacting for 5 hours. Then adding nano TiO with 0.2 percent of dimethyl terephthalate molar weight into a reaction kettle₂0.2 percent of stabilizer triphenyl phosphate and 0.5 percent of antioxidant-1010, slowly vacuumizing to 200 Pa-1800 Pa, gradually heating to 280 ℃, and continuously vacuumizing to below 200Pa for reaction for 1.5h to obtain the terephthalic acid polyester product. The minimum semicrystallization time of the polyester was 1.39 min. The surface resistivity measured by the insulation high-resistance instrument is 2 multiplied by 10¹⁸Ω。

Comparative example 3

Adding dimethyl furandicarboxylate, pentaerythritol and dibutyltin oxide into a reaction kettle according to the molar ratio of 1: 1.3: 0.005, vacuumizing, filling nitrogen for three times for replacement, starting stirring, gradually heating to 160 ℃, and reacting for 5 hours. Then adding 0.5% of graphene, 0.05% of triphenyl phosphate as a stabilizer and 0.5% of antioxidant-1010 in terms of the molar weight of dimethyl furandicarboxylate into a reaction kettle, slowly vacuumizing to 200-1000 Pa, gradually heating to 240 ℃, and continuously vacuumizing to below 200Pa for reaction for 1h to obtain a graphene-containing furan dicarboxylic acid polyester product. The shortest semicrystallization time of the obtained polyester is 0.73min, and the surface resistivity measured by an insulation high-resistance instrument is 2×10⁹Ω。

Comparative example 4

Adding dimethyl furandicarboxylate, ethylene glycol and anhydrous zinc acetate into a reaction kettle according to the molar ratio of 1: 1.6: 0.002, vacuumizing, filling nitrogen for three times for replacement, starting stirring, gradually heating to 180 ℃, and reacting for 4 hours. Then antimony trioxide with the molar weight of 0.4 percent of furan dicarboxylic acid dimethyl ester, triphenyl phosphate with the molar weight of 0.5 percent and antioxidant-168 with the molar weight of 0.1 percent are added into a reaction kettle, the mixture is slowly vacuumized to 400Pa to 1600Pa, the temperature is gradually raised to 245 ℃, the mixture is continuously vacuumized to below 200Pa, and the furan dicarboxylic acid polyester product is obtained after the reaction for 1 hour. The polyester obtained has a shortest semicrystallization time of 1.25min and a surface resistivity of 10 measured by an insulation high-resistance meter¹⁸Ω。

Comparative example 5

Adding dimethyl terephthalate, glycerol and dibutyltin oxide into a reaction kettle according to the mol ratio of 1: 1.3: 0.0025, vacuumizing, filling nitrogen for replacing three times, starting stirring, gradually heating to 190 ℃, and reacting for 5 hours. Then, antimony trioxide with the molar weight of 0.2 percent of dimethyl terephthalate, diphenyl phosphite with the molar weight of 0.5 percent and antioxidant-168 with the molar weight of 0.05 percent are added into a reaction kettle, the reaction kettle is slowly vacuumized to 300Pa to 1400Pa, the temperature is gradually raised to 270 ℃, the reaction kettle is continuously vacuumized to below 200Pa, and the reaction kettle is reacted for 2.5 hours, so that the terephthalic acid polyester product is obtained. The minimum semicrystallization time of the polyester was 0.55 min. The surface resistivity measured by the insulation high-resistance instrument is 7 multiplied by 10¹⁷Ω。

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.