阅读说明：本技术 聚对苯二甲酸环己烷二甲醇酯的工业制备方法 (Industrial preparation method of polycyclohexanedimethanol terephthalate ) 是由 陈培龙 李振中 王园淦 胡唯一 胡松华 陈培旭 刘冰肖 李智 胡泽 王强 余拥 于 2019-09-11 设计创作，主要内容包括：本发明实施例公开了一种聚对苯二甲酸环己烷二甲醇酯的工业制备方法,其包括将对苯二甲酸、1,4-环己烷二甲醇和催化剂先进行预聚反应得到PCT预聚物,再将所述PCT预聚物经固相增黏得到聚对苯二甲酸环己烷二甲醇酯的过程。本发明实施例的一种聚对苯二甲酸环己烷二甲醇酯的工业制备方法,采用对苯二甲酸、1,4-环己烷二甲醇和催化剂为原料,形成工业化的生产线,使得其形成规模化生产。(The embodiment of the invention discloses an industrial preparation method of polycyclohexanedimethanol terephthalate, which comprises the steps of carrying out prepolymerization reaction on terephthalic acid, 1, 4-cyclohexanedimethanol and a catalyst to obtain a PCT prepolymer, and then carrying out solid-phase tackifying on the PCT prepolymer to obtain the polycyclohexanedimethanol terephthalate. According to the industrial preparation method of the polycyclohexanedimethanol terephthalate, disclosed by the embodiment of the invention, terephthalic acid, 1, 4-cyclohexanedimethanol and a catalyst are used as raw materials to form an industrial production line, so that large-scale production is formed.)

1. An industrial preparation method of polycyclohexanedimethanol terephthalate is characterized by comprising the steps of carrying out prepolymerization reaction on terephthalic acid, 1, 4-cyclohexanedimethanol and a catalyst to obtain a PCT prepolymer, and then carrying out solid-phase tackifying on the PCT prepolymer to obtain the polycyclohexanedimethanol terephthalate.

2. The industrial production method of polycyclohexanedimethanol terephthalate as claimed in claim 1, wherein,

the prepolymerization reaction comprises the steps of mixing and stirring terephthalic acid, 1, 4-cyclohexanedimethanol and a catalyst to obtain a reaction mixture;

heating the reaction mixture to 60-80 ℃ under the protection of inert gas, and keeping the constant temperature for 0.5-1 h;

then heating the reaction mixture to 160-220 ℃, and keeping the constant temperature for 0.5-2h, wherein the pressure is 0.8-1.5 Mpa;

maintaining the reaction temperature of the reaction mixture, exhausting for 0.5-1.5h, and reducing the pressure by 0.2 Mpa;

cooling the reaction mixture, and filling inert gas into the reaction mixture to obtain the PCT prepolymer.

3. The industrial production method of polycyclohexanedimethanol terephthalate as claimed in claim 2, wherein,

the inert gas is any one of nitrogen, carbon dioxide and helium.

4. The industrial production method of polycyclohexanedimethanol terephthalate as claimed in claim 2, wherein,

when the reaction mixture reacts, the pressure of the inert gas is 0.2-0.4 MPa.

5. The industrial production method of polycyclohexanedimethanol terephthalate as claimed in claim 2, wherein,

the pressure of the inert gas is 0.2-1.2MPa when the reaction mixture is cooled.

6. The industrial production method of polycyclohexanedimethanol terephthalate as claimed in claim 1, wherein,

the solid phase tackifying process comprises the steps of drying the PCT prepolymer for 3-6h, then heating to 250-270 ℃ in a vacuum environment, and keeping for 4-5 h;

cooling the PCT prepolymer to below 60 ℃ to obtain the polycyclohexanedimethanol terephthalate.

7. The industrial production method of polycyclohexanedimethanol terephthalate as claimed in claim 1, wherein,

the catalyst is NaHTi (OC)₄H₉)，Mn(OAc)₂，Co(OAc)₂And Ge (OAc)₂One or more ofAnd (4) seed preparation.

8. The industrial production method of polycyclohexanedimethanol terephthalate as claimed in claim 1, wherein,

50 parts of terephthalic acid, 80-100 parts of 1, 4-cyclohexanedimethanol and 0.1-0.3 part of catalyst.

Technical Field

The embodiment of the invention relates to the technical field of high polymer material synthesis, and particularly relates to an industrial preparation method of polycyclohexanedimethanol terephthalate.

Background

Polyethylene terephthalate (PET) of the formula [ COC₆H₄COOCH₂CH₂O]n, the dihydroxy ethyl terephthalate is synthesized by exchanging dimethyl terephthalate with glycol ester or esterifying terephthalic acid with ethylene glycol, and then the dihydroxy ethyl terephthalate is obtained by polycondensation. Belongs to crystalline saturated polyester, is milk white or light yellow and highly crystalline polymer, and has smooth and glossy surface. The high-temperature-resistant and high-frequency-resistant composite material has excellent physical and mechanical properties in a wider temperature range, the long-term use temperature can reach 120 ℃, the electrical insulation property is excellent, even under high temperature and high frequency, the electrical property is still good, but the corona resistance is poor, and the creep resistance, the fatigue resistance, the friction resistance and the dimensional stability are good.

Polybutylene terephthalate (PBT), a polyester made by the polycondensation of terephthalic acid and 1, 4-butanediol. The most important thermoplastic polyester, one of five major engineering plastics. PBT is a milky translucent to opaque, semi-crystalline thermoplastic polyester. Has high heat resistance, long-term work at 140 ℃, toughness, fatigue resistance, self-lubrication and low friction coefficient. It is not resistant to strong acid and alkali, and can resist organic solvent, and is flammable and can be decomposed at high temp. Because of these excellent properties, they are widely used in the fields of automobiles, mechanical equipment, precision instrument parts, electronic and electrical appliances, textiles, and the like.

Poly (cyclohexane dimethanol terephthalate) (PCT) is a linear polyester high-performance engineering plastic which appears in recent decades, has a melting point 60 ℃ higher than that of PBT and 30 ℃ higher than that of PET, and has the characteristics of excellent chemical resistance, hydrolysis resistance, dimensional stability, capability of being used in a high-temperature environment and the like. Polyester engineering plastics such as PET and PBT have great productivity, but a blank is still formed for PCT products, and the development of an industrial preparation method of polycyclohexanedimethanol terephthalate is urgently needed.

Disclosure of Invention

Therefore, the embodiment of the invention provides an industrial preparation method of polycyclohexanedimethanol terephthalate, which aims to solve the problem of the prior art of preparing polycyclohexanedimethanol terephthalate industrially by random modeling.

In order to achieve the above object, the embodiments of the present invention provide the following technical solutions:

an industrial preparation method of polycyclohexanedimethanol terephthalate comprises the steps of carrying out prepolymerization reaction on terephthalic acid, 1, 4-cyclohexanedimethanol and a catalyst to obtain a PCT prepolymer, and then carrying out solid-phase tackifying on the PCT prepolymer to obtain the polycyclohexanedimethanol terephthalate.

Preferably, the prepolymerization reaction comprises mixing and stirring terephthalic acid, 1, 4-cyclohexanedimethanol and 0.1-0.3 part of catalyst to obtain a reaction mixture;

heating the reaction mixture to 60-80 ℃ under the protection of inert gas, and keeping the constant temperature for 0.5-1 h;

then heating the reaction mixture to 160-220 ℃, and keeping the constant temperature for 0.5-2h, wherein the pressure is 0.8-1.5 Mpa;

maintaining the reaction temperature of the reaction mixture, exhausting for 0.5-1.5h, and reducing the pressure by 0.2 Mpa;

cooling the reaction mixture, and filling inert gas into the reaction mixture to obtain the PCT prepolymer.

Preferably, the inert gas is any one of nitrogen, carbon dioxide and helium.

Preferably, the pressure of the inert gas is 0.2 to 0.4MPa when the reaction mixture is reacted.

Preferably, the pressure of the inert gas is 0.2 to 1.2MPa when the reaction mixture is cooled.

Preferably, the solid phase tackifying process comprises drying the PCT prepolymer for 3-6h, then heating to 250-270 ℃ in a vacuum environment, and keeping for 4-5 h;

cooling the PCT prepolymer to below 60 ℃ to obtain the polycyclohexanedimethanol terephthalate.

Preferably, the catalyst is NaHTi (OC)₄H₉)，Mn(OAc)₂，Co(OAc)₂And Ge (OAc)₂One or more of them.

Preferably, the terephthalic acid is 50 parts, the 1, 4-cyclohexanedimethanol is 80-100 parts, and the catalyst is 0.1-0.3 part.

The embodiment of the invention has the following advantages:

according to the industrial preparation method of the polycyclohexanedimethanol terephthalate, disclosed by the embodiment of the invention, the terephthalic acid, the 1, 4-cyclohexanedimethanol and the catalyst are used as raw materials to form an industrial production line, so that the purpose of large-scale production is achieved. The preparation method provided by the embodiment of the invention is simpler, the production cost is reduced, and the energy consumption loss is small.

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 should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.

FIG. 1 is a process scheme for the synthesis of PCT prepolymer provided in the examples of the present invention;

FIG. 2 is a schematic diagram of a solid phase adhesion process of PCT prepolymer according to the present invention.

Detailed Description

The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.