CN113831700B

CN113831700B - PET polyester composite material and preparation method thereof

Info

Publication number: CN113831700B
Application number: CN202111300238.2A
Authority: CN
Inventors: 程勇
Original assignee: Shenzhen Zhi Cheng Jin Plastic Technology Co ltd
Current assignee: Shenzhen Zhi Cheng Jin Plastic Technology Co ltd
Priority date: 2021-11-04
Filing date: 2021-11-04
Publication date: 2022-07-01
Anticipated expiration: 2041-11-04
Also published as: CN113831700A

Abstract

The application relates to the field of processing and production of high polymer materials, and particularly discloses a PET polyester composite material and a preparation method thereof. A PET polyester composite material is prepared from the following raw materials: 50 parts of terephthalic acid; 60-70 parts of ethylene glycol; 2-10 parts of a nucleating agent; 0.4-6 parts of a dispersing agent; 0.2-0.6 part of a lubricant; 0.2-3 parts of an antioxidant; 0.05-0.15 part of catalyst; the nucleating agent comprises the following components in a weight ratio of 1: (3-7): (1-9) titanium dioxide, trimethylolethane, and methyl methacrylate. The method comprises the following steps: uniformly mixing the raw materials; heating to 220-230 ℃, adjusting the pressure to 0.3-0.5 MPa, reacting for 4-5 h, adjusting the vacuum degree to 0.01MPa, adjusting the temperature to 270-280 ℃, and reacting for 1-2 h; the product after the reaction was cooled. The method has the advantage of improving the crystallization rate of the PET in the process molding.

Description

PET polyester composite material and preparation method thereof

Technical Field

The application relates to the field of processing and production of high polymer materials, in particular to a PET polyester composite material and a preparation method thereof.

Background

Polyethylene terephthalate (PET) is prepared by synthesizing dihydroxy ethyl terephthalate from terephthalic acid and ethylene glycol, and then carrying out polycondensation reaction. PET has excellent physical and mechanical properties, excellent electrical insulation, excellent creep resistance, fatigue resistance, friction resistance and dimensional stability, and is widely applied to the fields of packaging bottles, films and engineering plastics.

However, the PET molecular chain contains a rigid conjugated structure, and the rigid conjugated structure can slow down the movement of the PET molecular chain, so that the problem of slow crystallization rate of PET in the process of processing and forming is caused, the forming period of PET is longer, further application of PET in the fields such as injection molding and the like with higher requirements on the forming speed is not facilitated, and the development of PET in the field of engineering plastics is limited.

Disclosure of Invention

In order to improve the crystallization rate of PET in processing and forming, the application provides a PET polyester composite material and a preparation method thereof.

The PET polyester composite material adopts the following technical scheme:

the PET polyester composite material is prepared from the following raw materials in parts by weight:

50 parts of terephthalic acid;

60-70 parts of ethylene glycol;

2-10 parts of a nucleating agent;

0.4-6 parts of a dispersing agent;

0.2-0.6 part of a lubricant;

0.2-3 parts of an antioxidant;

0.05-0.15 part of catalyst;

the nucleating agent comprises the following components in a weight ratio of 1: (3-7): (1-9) titanium dioxide, trimethylolethane, and methyl methacrylate.

By adopting the technical scheme, experiments prove that compared with similar products on the market, the PET polyester composite material has high crystallization rate, can reduce the forming time of the PET polyester composite material, accelerates the forming speed of the PET polyester composite material, and is favorable for further application of the PET polyester composite material in engineering plastics by rapid forming. Furthermore, the experimental results show that the above-mentioned increase in crystallization rate is associated with the interaction between titanium dioxide, trimethylolethane and methyl methacrylate.

Optionally, the nucleating agent comprises a component in a weight ratio of 1: (4-6): (3-7) titanium dioxide, trimethylolethane, and methyl methacrylate.

By adopting the technical scheme, experiments prove that the weight ratio of the titanium dioxide, the trimethylolethane and the methyl methacrylate is 1: (4-6): (3-7), the crystallization rate of the PET polyester composite material is higher, the forming time of the PET polyester composite material can be further reduced, and the forming speed of the PET polyester composite material is further accelerated.

Optionally, the dispersant comprises 1: (8-15): (3-9) vinyl bis stearamide, calcium stearate and glycerol tristearate.

Through adopting above-mentioned technical scheme, the mutual gathering between the dispersant can reduce the nucleating agent makes the reaction of dispersant in the raw materials more abundant to promote PET polyester composite's crystallization rate, and, the experiment proves, adopts the weight ratio to be 1: (8-15): and (3-9) the crystallization rate of the PET polyester composite material can be effectively improved by the vinyl bis-stearamide, the calcium stearate and the tristearin.

Optionally, the dispersant comprises 1: (10-13): (5-6) vinyl bis stearamide, calcium stearate and glycerol tristearate.

By adopting the technical scheme, experiments prove that the weight ratio of the vinyl bis stearamide to the calcium stearate to the tristearin is 1: (10-13): (5-6), the crystallization rate of the PET polyester composite material can be further improved, and the molding cycle of the PET polyester composite material is shortened.

Optionally, the lubricant is pentaerythritol stearate.

By adopting the technical scheme, the pentaerythritol stearate enables the raw materials to be smoothly taken out of the reaction container after reaction, thereby facilitating the demoulding of the PET polyester composite material.

Optionally, the antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite.

By adopting the technical scheme, the tri (2, 4-di-tert-butylphenyl) phosphite can improve the oxidation resistance of the PET polyester composite material, so that the durability of the PET polyester composite material is improved.

Optionally, the catalyst adopts ethylene glycol antimony.

By adopting the technical scheme, the ethylene glycol antimony can shorten the reaction time of the raw materials and improve the reaction efficiency between the raw materials, so that the processing time from the raw materials to the PET polyester composite material is reduced, and the production efficiency of the PET polyester composite material is improved.

The preparation method of the PET polyester composite material comprises the following steps:

uniformly mixing the raw materials;

heating to 220-230 ℃, adjusting the pressure to 0.3-0.5 MPa, and reacting for 4-5 h;

after the reaction, adjusting the vacuum degree to 0.01MPa, adjusting the temperature to 270-280 ℃, and reacting for 1-2 h;

the product after the reaction was cooled.

By adopting the technical scheme, the preparation steps of the PET polyester composite material are simple and convenient, the operation of operators is facilitated, and the production efficiency is improved.

In summary, the present application has the following beneficial effects:

1. compared with the similar products on the market at present, the PET polyester composite material has high crystallization speed, shortens the molding cycle of the PET polyester composite material, and is beneficial to further application of the PET polyester composite material in engineering plastics;

2. experimental data prove that the crystallization speed of the PET polyester composite material can be further improved and the molding period of the PET polyester composite material can be shortened by adopting the titanium dioxide, the trimethylolethane and the methyl methacrylate as nucleating agents, so that the titanium dioxide, the trimethylolethane and the methyl methacrylate are cooperatively matched to jointly improve the crystallization speed of the PET polyester composite material;

3. according to the method, the raw materials are uniformly mixed, the reaction conditions are controlled, the reaction process is controlled, and finally the PET polyester composite material is obtained. The method is simple in operation mode, and is convenient for operators to operate, so that the production efficiency of the PET polyester composite material is improved.

Detailed Description

The present application is described in further detail below.

Examples

Example 1

A PET polyester composite material is prepared from the following raw materials:

50kg of terephthalic acid;

60kg of ethylene glycol;

2kg of nucleating agent;

6kg of dispersing agent;

0.2kg of lubricant;

3kg of antioxidant;

0.05kg of catalyst;

the nucleating agent comprises 1: 3: 9 titanium dioxide, trimethylolethane, and methyl methacrylate; namely, the weight of titanium dioxide is 0.12kg, the weight of trimethylolethane is 0.46kg, and the weight of methyl methacrylate is 1.38 kg;

the dispersing agent adopts vinyl bis stearamide;

the lubricant is pentaerythritol stearate;

the antioxidant adopts tri (2, 4-di-tert-butylphenyl) phosphite;

ethylene glycol antimony is used as the catalyst.

uniformly mixing the raw materials;

heating to 220 ℃, adjusting the pressure to 0.5MPa, and reacting for 4 hours;

after the reaction, the vacuum degree is adjusted to 0.01MPa, the temperature is adjusted to 270 ℃, and the reaction is carried out for 1 h;

the product after the reaction was cooled.

Example 2

50kg of terephthalic acid;

70kg of ethylene glycol;

10kg of nucleating agent;

0.4kg of dispersing agent;

0.6kg of lubricant;

0.2kg of antioxidant;

0.15kg of catalyst;

the nucleating agent comprises 1: 7: 1 of titanium dioxide, trimethylolethane, and methyl methacrylate; namely, the weight of titanium dioxide is 1.11kg, the weight of trimethylolethane is 7.77kg, and the weight of methyl methacrylate is 1.11 kg;

the dispersing agent adopts vinyl bis stearamide;

the lubricant is pentaerythritol stearate;

the antioxidant adopts tri (2, 4-di-tert-butylphenyl) phosphite;

ethylene glycol antimony is used as the catalyst.

uniformly mixing the raw materials;

heating to 230 ℃, adjusting the pressure to 0.3MPa, and reacting for 5 hours;

after the reaction, the vacuum degree is adjusted to 0.01MPa, the temperature is adjusted to 280 ℃, and the reaction is carried out for 2 hours;

the product after the reaction was cooled.

Example 3

50kg of terephthalic acid;

65kg of ethylene glycol;

6kg of nucleating agent;

3.2kg of dispersing agent;

0.4kg of lubricant;

1.6kg of antioxidant;

0.1kg of catalyst;

the nucleating agent comprises 1: 7: 1 titanium dioxide, trimethylolethane, and methyl methacrylate; namely, the weight of titanium dioxide is 0.67kg, the weight of trimethylolethane is 4.67kg, and the weight of methyl methacrylate is 0.67 kg;

the dispersing agent adopts vinyl bis stearamide;

the lubricant is pentaerythritol stearate;

the antioxidant adopts tri (2, 4-di-tert-butylphenyl) phosphite;

ethylene glycol antimony is used as the catalyst.

uniformly mixing the raw materials;

heating to 225 ℃, adjusting the pressure to 0.4MPa, and reacting for 4 hours;

after the reaction, the vacuum degree is adjusted to 0.01MPa, the temperature is adjusted to 275 ℃, and the reaction is carried out for 1 h;

the product after the reaction was cooled.

Example 4

The difference from example 3 is that the nucleating agent comprises, in a weight ratio of 1: 4: 7 titanium dioxide, trimethylolethane, and methyl methacrylate; that is, the weight of titanium dioxide was 0.5kg, the weight of trimethylolethane was 2kg, and the weight of methyl methacrylate was 3.5 kg.

Example 5

The difference from example 3 is that the nucleating agent comprises, in a weight ratio of 1: 6: 3 titanium dioxide, trimethylolethane, and methyl methacrylate; that is, the weight of titanium dioxide was 0.6kg, the weight of trimethylolethane was 3.6kg, and the weight of methyl methacrylate was 1.8 kg.

Example 6

The difference from example 3 is that the nucleating agent comprises, in a weight ratio of 1: 5: 5 titanium dioxide, trimethylolethane, and methyl methacrylate; that is, the weight of titanium dioxide was 0.55kg, the weight of trimethylolethane was 2.73kg, and the weight of methyl methacrylate was 2.73 kg.

Example 7

The difference from example 3 is that calcium stearate is used as the dispersant, i.e., the weight of calcium stearate is 3.2 kg.

Example 8

The difference from example 3 is that glycerol tristearate was used as the dispersant, i.e., the weight of glycerol tristearate was 3.2 kg.

Example 9

The difference from example 3 is that the dispersant comprises, by weight, 1: 8: 9, namely the weight of the vinyl bis stearamide is 0.18kg, the weight of the calcium stearate is 1.42kg, and the weight of the tristearin is 1.6 kg.

Example 10

The difference from example 3 is that the dispersant comprises, by weight, 1: 15: 3, namely the weight of the vinyl bis stearamide is 0.17kg, the weight of the calcium stearate is 2.53kg, and the weight of the tristearin is 0.51 kg.

Example 11

The difference from example 3 is that the dispersant comprises, by weight, 1: 10: 6, namely the weight of the vinyl bis stearamide is 0.19kg, the weight of the calcium stearate is 1.9kg, and the weight of the tristearin is 1.13 kg.

Example 12

The difference from example 3 is that the dispersant comprises, by weight, 1: 13: 5, namely the weight of the vinyl bis stearamide is 0.17kg, the weight of the calcium stearate is 2.19kg, and the weight of the tristearin is 0.84 kg.

Example 13

The difference from example 3 is that the dispersant comprises the following components in a weight ratio of 1: 11.5: 5.5 weight parts of vinyl bis stearamide, calcium stearate and glycerol tristearate, namely, the weight parts of the vinyl bis stearamide is 0.18kg, the weight parts of the calcium stearate is 2.04kg, and the weight parts of the glycerol tristearate is 0.98 kg.

Comparative example

Comparative example 1

The difference from example 3 is that the nucleating agent comprises, in a weight ratio of 1: 2: 10 titanium dioxide, trimethylolethane, and methyl methacrylate; namely, the weight of titanium dioxide was 0.46kg, the weight of trimethylolethane was 0.92kg, and the weight of methyl methacrylate was 4.62 kg.

Comparative example 2

The difference from example 3 is that the nucleating agent comprises, in a weight ratio of 1: 8: 0.5 of titanium dioxide, trimethylolethane and methyl methacrylate; namely, the weight of titanium dioxide was 0.63kg, that of trimethylolethane was 5.05kg, and that of methyl methacrylate was 0.32 kg.

Comparative example 3

The difference from example 3 is that trimethylolethane and the like in the nucleating agent were replaced by titanium dioxide, and methyl methacrylate and the like were replaced by titanium dioxide; i.e. the titanium dioxide weighs 6 kg.

Comparative example 4

The difference from example 3 is that titanium dioxide and the like in the nucleating agent are replaced by trimethylolethane and methyl methacrylate and the like are replaced by trimethylolethane; i.e., 6kg of trimethylolethane.

Comparative example 5

The difference from example 3 is that the weight of titanium dioxide in the nucleating agent is replaced by methyl methacrylate, and the weight of trimethylolethane is replaced by methyl methacrylate; i.e., 6kg of methyl methacrylate.

Comparative example 6

The difference from example 3 is that the dispersant comprises the following components in a weight ratio of 1: 7: 10 of vinyl bis stearamide, calcium stearate and glycerol tristearate, namely the weight of the vinyl bis stearamide is 0.18kg, the weight of the calcium stearate is 1.24kg, and the weight of the glycerol tristearate is 1.78 kg.

Comparative example 7

The difference from example 3 is that the dispersant comprises, by weight, 1: 16: 2, namely the weight of the vinyl bis stearamide is 0.17kg, the weight of the calcium stearate is 2.69kg, and the weight of the tristearin is 0.34 kg.

Comparative example 8

The PET copolyester comprises the following raw materials in parts by mass:

70kg of terephthalic acid;

29kg of ethylene glycol;

0.1kg of sodium benzoate;

0.1kg of polytetrahydrofuran;

0.1kg of styrene-sodium methacrylate;

0.25kg of polyethylene glycol;

the preparation method of the PET resin comprises the following steps:

stirring and dissolving sodium benzoate and ethylene glycol at 80 ℃, and performing ultrasonic oscillation and dispersion to prepare a sodium benzoate-ethylene glycol solution;

mixing the sodium benzoate-ethylene glycol solution with the rest raw materials;

adjusting the pressure to 0.3MPa and the temperature to 235 ℃, and reacting for 4 hours;

after the reaction, the pressure is adjusted to be 0.04MPa, the temperature is adjusted to be 278 ℃, and the reaction is carried out for 1h, so as to obtain the sample.

Performance detection

The test data of the examples and comparative examples are shown in Table 1.

The isothermal crystallization test method comprises the following steps: selecting a plurality of temperature points to perform polyester isothermal crystallization test on a DSC tester, raising the temperature of polyester from 25 ℃ to 290 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 5min, and then performing isothermal crystallization from 290 ℃ to 180 ℃ at a cooling rate of 400 ℃/min.

The isothermal crystallization behavior of the polyester can be described by the Avrami equation:

where k is a crystallization rate constant related to crystallization temperature, diffusion, and nucleation rate; n is the Avrami index, which is related to the nucleation mechanism and the crystal growth mode. Using lg [ -ln (1-Xt)]And lgt, calculating the crystallization kinetic parameters n and k by performing linear fitting, wherein the slope of a fitted straight line is n, and the intercept is lgk.

The semi-crystallization rate can be described as:

the crystallization rates of examples 1 to 13 and comparative examples 1 to 6 calculated from the above formula are shown in Table 1.

TABLE 1

	Crystallization Rate min^-1
		Example 1	1.24
Example 2	1.18
		Example 3	1.17
Example 4	1.31
		Example 5	1.28
Example 6	1.52
		Example 7	1.16
Example 8	1.17
		Example 9	1.36
Example 10	1.38
		Example 11	1.40
Example 12	1.39
		Example 13	1.45
Comparative example 1	0.89
		Comparative example 2	0.86
Comparative example 3	0.81
		Comparative example 4	0.83
Comparative example 5	0.81
		Comparative example 6	1.21
Comparative example 7	1.24
		Comparative example 8	0.96

According to the data of examples 1 to 6 and comparative example 8 in table 1, the crystallization rate of the PET polyester composite material is high, the crystallization speed is high, and the molding cycle of the PET polyester composite material is short.

According to the data of the embodiment 3 and the comparative examples 3 to 5, for the formula system of the present application, when the other conditions are the same, compared with the case that any one of single titanium dioxide, trimethylolethane or methyl methacrylate is added, the simultaneous addition of titanium dioxide, trimethylolethane and methyl methacrylate can improve the crystallization rate of the PET polyester composite material of the present application, and thus, the titanium dioxide, trimethylolethane and methyl methacrylate play a synergistic role in the crystallization process of the PET polyester composite material of the present application, and the molding of the PET polyester composite material is promoted together.

According to the data of example 3 and comparative examples 1-2, the weight ratio of titanium dioxide, trimethylolethane, and methyl methacrylate is 1: (3-7): (1-9), the nucleating agent can further improve the crystallization rate of the PET polyester composite material and shorten the molding cycle of the PET polyester composite material.

According to the data of examples 3 to 6, the weight ratio of titanium dioxide, trimethylolethane and methyl methacrylate is 1: (4-6): (3-7), the nucleating agent has a better effect of improving the crystallization rate of the PET polyester composite material, so that the molding period of the PET polyester composite material is further shortened.

According to the data of the embodiments 3, 7 to 8 and 9 to 13, it can be seen that, for the formulation system of the present application, when the other conditions are the same, compared with the case where any one of the vinyldistearamide, the calcium stearate or the glycerin tristearate is added, the simultaneous addition of the vinyldistearamide, the calcium stearate and the glycerin tristearate can increase the crystallization rate of the PET polyester composite material of the present application, and thus, the vinyldistearamide, the calcium stearate and the glycerin tristearate can play a synergistic role in the crystallization process of the PET polyester composite material.

According to the data of examples 9 to 10 and comparative examples 6 to 7, the weight ratio of vinyl bis stearamide, calcium stearate and glycerol tristearate was 1: (8-15): (3-9), the crystallization rate of the PET polyester composite material can be further improved by the vinyl bis-stearamide, the calcium stearate and the tristearin.

According to the data of examples 9 to 13, the weight ratio of vinyl bis stearamide, calcium stearate and glycerol tristearate was 1: (10-13): (5-6), the effect of promoting the crystallization of the PET polyester composite material by the vinyl bis-stearamide, the calcium stearate and the tristearin is better.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims

1. The PET polyester composite material is characterized in that the PET polyester composite material is prepared from the following raw materials in parts by weight:

50 parts of terephthalic acid;

60-70 parts of ethylene glycol;

2-10 parts of a nucleating agent;

0.4-6 parts of a dispersing agent;

0.2-0.6 part of a lubricant;

0.2-3 parts of an antioxidant;

0.05-0.15 part of catalyst;

the nucleating agent comprises the following components in a weight ratio of 1: (3-7): (1-9) titanium dioxide, trimethylolethane and methyl methacrylate, wherein the dispersant comprises the following components in a weight ratio of 1: (8-15): (3-9) vinyl bis stearamide, calcium stearate and glycerol tristearate, wherein the lubricant is pentaerythritol stearate, the antioxidant is tris (2, 4-di-tert-butylphenyl) phosphite, and the catalyst is ethylene glycol antimony.

2. A PET polyester composite material according to claim 1, characterized in that: the nucleating agent comprises the following components in a weight ratio of 1: (4-6): (3-7) titanium dioxide, trimethylolethane, and methyl methacrylate.

3. A PET polyester composite material according to claim 1, characterized in that: the dispersant comprises the following components in percentage by weight of 1: (10-13): (5-6) vinyl bis stearamide, calcium stearate and glycerol tristearate.

4. A method for preparing the PET polyester composite material according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:

uniformly mixing the raw materials;

the product after the reaction was cooled.