阅读说明：本技术 一种高冲击强度仿陶瓷pet及其制备方法 (high-impact-strength ceramic-like PET and preparation method thereof ) 是由 万锋 杨杰 戴李宗 全敦华 王伟 陈明进 袁丛辉 孙玉璞 申应军 吴腾达 刁雪峰 于 2019-10-11 设计创作，主要内容包括：本发明公开了一种高冲击强度仿陶瓷PET及其制备方法,由如下质量百分比的组分制成：PET树脂25-40％、填充物50-70％、增韧剂3-10％、成核剂0.2-1％、结晶促进剂0.2-0.5％、偶联剂0.2-1％、抗氧剂0.2-0.5％、和润滑剂0.2-1％。本发明氧化锌作为仿陶瓷塑料的填充物,其自身比重大,且与塑料共混改性时易分散,比相同份数的硫酸钡在熔融挤出时更易加工,其制品耐冲击性能极佳,有望替代陶瓷材料。(The invention discloses high-impact-strength ceramic-like PET (polyethylene terephthalate) and a preparation method thereof, wherein the ceramic-like PET is prepared from 25-40% by mass of PET resin, 50-70% by mass of filler, 3-10% by mass of toughening agent, 0.2-1% by mass of nucleating agent, 0.2-0.5% by mass of crystallization promoter, 0.2-1% by mass of coupling agent, 0.2-0.5% by mass of antioxidant and 0.2-1% by mass of lubricant.)

1, kinds of high impact strength imitation ceramic PET, which is characterized in that the high impact strength imitation ceramic PET is prepared from the following components by mass percent:

the PET resin has an intrinsic viscosity of 0.8 to 1.0dl/g, the filler is ZnO, the nucleating agent is composed of a modified compound nucleating agent NA-95 and a sodium ion type E/MMA copolymer 8920, and the crystallization accelerator is tribenzylidene propyl ether diester hexanol PX-520.

2. The kinds of high-impact ceramic-like PET of claim 1, wherein the toughening agent is ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, ethylene-vinyl acetate, ethylene-methyl acrylate, ethylene-ethyl acrylate, ethylene-butyl acrylate or low-density polyethylene.

3. The kinds of high-impact ceramic-like PET of claim 1, wherein the coupling agent is Y-aminopropyltriethoxysilane KH-550 or Y- (2, 3-glycidoxy) propyltrimethoxysilane KH-560.

4. The kinds of high-impact-strength ceramic-like PET of claim 1, wherein the antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester 1010 or tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenyl) diphosphonite HostanoxP-EPQ, the secondary antioxidant is 9228, and the mass ratio of the primary antioxidant to the secondary antioxidant is 1-3: 1.

5. The high impact ceramic-like PET of claim 1, wherein the lubricant is pentaerythritol tetrastearate GLYCOLUBE PETS, ethylene bis stearamide EBS, polydimethylsiloxane, or zinc stearate.

6. The high impact strength ceramic-like PET as claimed in claim 1, wherein the toughening agent is ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, ethylene-vinyl acetate, ethylene-methyl acrylate, ethylene-ethyl acrylate, ethylene-butyl acrylate or low density polyethylene, the coupling agent is Y-aminopropyl triethoxysilane KH-550 or Y- (2, 3-epoxypropoxy) propyl trimethoxysilane KH-560, and the antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester 1010 or tetrakis (2, 4-di-tert-butylphenyl-4, 4' biphenyl) diphosphonite HostanoxP-EPQ, the secondary antioxidant is antioxidant 9228, the mass ratio of the primary antioxidant to the secondary antioxidant is 1-3: 1, and the lubricant is pentaerythritol tetrastearate GLOLUBYCEPS, ethylene bis stearamide EBS, polydimethylsiloxane or zinc stearate.

7. The method of preparing kinds of high impact strength ceramic-like PET as claimed in any of claims 1-6, which comprises the following steps:

(1) weighing the components according to the mass percentage;

(2) drying the PET resin and the filler in a forced air drying oven at 100 ℃, and detecting that the moisture content is less than 500 PPM;

(3) putting the PET resin treated in the step (2), the filler, the toughening agent, the nucleating agent, the crystallization accelerator, the coupling agent, the antioxidant and the lubricant into a low-speed mixer, and uniformly mixing to obtain a premix;

(4) and (4) adding the premix obtained in the step (3) into a main feeding hopper of a double-screw extruder, and performing melt blending extrusion through the double-screw extruder, wherein the extrusion temperature is 240-250 ℃, and the screw rotation speed is 300-400 r/min.

Technical Field

The invention belongs to the technical field of PET (polyethylene terephthalate) preparation, and particularly relates to high-impact-strength ceramic-like PET and a preparation method thereof.

Background

The ceramic is a material and various products prepared by crushing, mixing, molding and calcining clay serving as a main raw material and various natural minerals. The ceramic product has the features of being natural, beautiful, durable, low in cost, high in hardness, high in wear resistance, high in solvent resistance and high in weather resistance, and may be used in tableware and decoration. However, the ceramic also has the defects of high firing energy consumption, poor toughness, poor impact resistance, brittleness and the like. Accordingly, much research has been conducted on plastic products instead of ceramic products.

The plastic product has the advantages of light specific weight, good impact resistance, easy preparation, easy recycling and the like, is widely applied to the aspects of life, but the plastic product has many defects, such as low surface hardness, easy scratching, poor solvent resistance, poor ultraviolet light aging resistance and easy combustion, therefore, the plastic product has great difficulty in replacing ceramic materials with plastics.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides high-impact-strength ceramic-like PET and a preparation method thereof.

The technical scheme of the invention is as follows:

kinds of high impact strength ceramic-like PET, which is prepared from the following components in percentage by mass:

the PET resin (Dongguan city brocade plastic material Co., Ltd.) has a characteristic viscosity of 0.8 to 1.0dl/g, the filler is ZnO (Jinan century Tongda chemical Co., Ltd.), the nucleating agent is composed of a modified double nucleating agent NA-95 (Shanghai Liangdian chemical Co., Ltd.) and a sodium ion type E/MMA copolymer 8920 (DuPont, USA), and the crystallization accelerator is tribenzylidesopropyl ether diester hexanol PX-520 (Dongguan Sanhe chemical Co., Ltd.).

In preferred embodiments of the present invention, the toughening agent is of ethylene-methyl acrylate-glycidyl methacrylate random terpolymer (acaoma, france), ethylene-vinyl acetate (dupont, usa), ethylene-methyl acrylate (dupont, usa), ethylene-ethyl acrylate (dow, usa), ethylene-butyl acrylate (acaoma, france), or low density polyethylene (metallocene).

In preferred embodiments of the invention, the coupling agent is Y-aminopropyltriethoxysilane KH-550 (Nanjing eosin chemical group, Inc.) or Y- (2, 3-glycidoxy) propyltrimethoxysilane KH-560 (Nanjing eosin chemical group, Inc.).

In preferred embodiments of the present invention, the antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester 1010(BASF) or tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenyl) diphosphonite HostanoxP-EPQ, the secondary antioxidant is antioxidant 9228 (U.S. Dover chemical), and the mass ratio of the primary antioxidant to the secondary antioxidant is 1-3: 1.

In preferred embodiments of the present invention, the lubricant is pentaerythritol tetrastearate GLYCOLUBEPETS (LONGSHA USA), ethylene bis stearamide EBS (south Korean Malaysia), polydimethylsiloxane (Maya reagent, Inc.) or zinc stearate (hundred million peaking Industrial technologies, ).

In preferred embodiments of the present invention, the toughening agent is ethylene-methyl acrylate-glycidyl methacrylate random terpolymer, ethylene-vinyl acetate, ethylene-methyl acrylate, ethylene-ethyl acrylate, ethylene-butyl acrylate or low density polyethylene, the coupling agent is Y-aminopropyltriethoxysilane KH-550 or Y- (2, 3-epoxypropoxy) propyltrimethoxysilane KH-560, and the antioxidant comprises a primary antioxidant and a secondary antioxidant, wherein the primary antioxidant is tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester 1010 or tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenyl) diphosphonite HostanoxP-EPQ, the secondary antioxidant is antioxidant 9228, the mass ratio of the primary antioxidant to the secondary antioxidant is 1-3: 1, and the lubricant is pentaerythritol tetrastearate GLOLUBE PETS, ethylene bis stearamide EBS, polydimethylsiloxane or zinc stearate.

The preparation method of the ceramic-like PET with high impact strength comprises the following steps:

(1) weighing the components according to the mass percentage;

(2) drying the PET resin and the filler in a forced air drying oven at 100 ℃, and detecting that the moisture content is less than 500 PPM;

(3) putting the PET resin treated in the step (2), the filler, the toughening agent, the nucleating agent, the crystallization accelerator, the coupling agent, the antioxidant and the lubricant into a low-speed mixer, and uniformly mixing to obtain a premix;

(4) and (4) adding the premix obtained in the step (3) into a main feeding hopper of a double-screw extruder, and performing melt blending extrusion through the double-screw extruder, wherein the extrusion temperature is 240-250 ℃, and the screw rotation speed is 300-400 r/min.

The invention has the beneficial effects that:

1. the PET is used as a matrix, the zinc oxide is used as a filler of the ceramic-like plastic, the zinc oxide has high specific gravity, is easy to disperse when being blended and modified with the PET, is easier to process than the same parts of barium sulfate during melt extrusion, has excellent impact resistance, and is expected to replace ceramic materials.

2. The invention adds the compound nucleating agent NA-95 and the sodium ion type E/MMA copolymer 8920 as the nucleating agent, integrates the advantages of the two, avoids the disadvantages of the single nucleating agent, and considers the crystallization effect of the PET at each crystallization temperature section, so that the prepared PET is improved in each performance aspect

3. The raw materials of the invention are easy to purchase, the price is cheap, and the overall cost is reduced.

Detailed Description

The technical solution of the present invention is illustrated and described in step by the following detailed description.

The following comparative examples and examples include the following steps:

(1) weighing the components according to the mass percentage;

(2) drying the PET resin and the filler in a forced air drying oven at 100 ℃, and detecting that the moisture content is less than 500 PPM;

(3) putting the PET resin treated in the step (2), the filler, the toughening agent, the nucleating agent, the crystallization accelerator, the coupling agent, the antioxidant and the lubricant into a low-speed mixer, and uniformly mixing to obtain a premix;

(4) and (4) adding the premix obtained in the step (3) into a main feeding hopper of a double-screw extruder, and performing melt blending extrusion through the double-screw extruder, wherein the extrusion temperature is 240-250 ℃, and the screw rotation speed is 300-400 r/min.

The PET resin has the characteristic viscosity of 0.8-1.0 d1/g, the nucleating agent consists of a modified compound nucleating agent NA-95 and a sodium ion type E/MMA copolymer 8920 in a mass ratio of 1: 1, and the crystallization accelerator is tribenzylidene propyl ether diester hexanol PX-520.

The amounts of each component added in each comparative example and example are shown in table 1 below:

TABLE 1

Name of raw materials	Comparative example 1	Example 1	Comparative example 2	Comparative example 3
					PET resin	43.3	33.3	23.3	33.3
Filler (ZnO)	50	60	70	0
					Filler (BaSO)4)	0	0	0	60
Toughening agent (AX8900)	5	5	5	5
					Nucleating agent (NA-95)	0.1	0.1	0.1	0.1
Nucleating agent (8920)	0.1	0.1	0.1	0.1
					Crystallization accelerator (PX-520)	0.1	0.1	0.1	0.1
Silane coupling agent (KH-550)	0.5	0.5	0.5	0.5
					Antioxidant (HostanoxP-EPQ)	0.3	0.3	0.3	0.3
Auxiliary antioxidant (9228)	0.1	0.1	0.1	0.1
					Lubricant (GLYCOLUBE PETS)	0.5	0.5	0.5	0.5

The technical effects obtained for the respective proportions are shown in table 2 below:

TABLE 2

As shown by table 2:

as can be seen from the comparison of the data of comparative example 1, comparative example 2 and comparative example 3, the impact properties of the ceramic-like PET prepared by using barium sulfate as filler are very poor, the density does not meet the requirements, which is related to the characteristics of barium sulfate itself, the dispersibility of low-mesh barium sulfate is poor, the phenomenon of kettle explosion caused by the dispersion unevenness during blending and extrusion of PET is caused, and the prepared sample bar also presents very poor force due to the dispersion unevennessThe chemical property can not achieve the purpose of imitating ceramics; the zinc oxide is easy to disperse, has high specific gravity, is easy to blend and extrude with PET, has ideal impact performance and can achieve the aim of imitating ceramics. Comparing the test data of comparative example 1, example 1 and comparative example 2, it can be seen that the impact performance of comparative example 1 is comparable to that of example 1, while the impact performance of comparative example 2 is inferior, which indicates that the higher the zinc oxide composition, the lower the impact performance and the greater the processing difficulty. Example 1 has moderate density which is 2.2-2.7 g.cm^-3) Close to each other, and the impact property is far better than that of ceramics, thus being an ideal material for imitating ceramics.

The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.