阅读说明：本技术 一种塑料橡胶用空气中防变色的抗氧剂及其制备方法 (Anti-tarnishing antioxidant in air for plastic rubber and preparation method thereof ) 是由 姜友安 王耘 于 2020-06-28 设计创作，主要内容包括：本发明公开了一种塑料橡胶用空气中防变色的抗氧剂及其制备方法,属于抗氧剂技术领域,包括由主抗氧剂和终止剂型抗氧剂按重量比为1:0.25-0.7混合而成的混合物；所述的主抗氧剂中含有的受阻酚类抗氧剂和辅助抗氧剂,其中受阻酚类抗氧剂如下质量：2,6-三级丁基-4-甲基苯酚的含量为13-24％、双,5-三级丁基-4-羟基苯基硫醚的含量为12-21％。塑料橡胶表面附有一层抗氧剂形成的保护层,终止剂型抗氧剂活性高,能在比较低的浓度范围内表现出优良的抗氧效果,通过使用的抗氧剂,成品白度高,初期着色性优,长期耐热性优、耐候性良好、与环氧大豆油并用可完全互溶,抗氧化抗黄变,可提升塑料橡胶。(The invention discloses an antioxidant for preventing discoloration in air for plastic rubber and a preparation method thereof, belonging to the technical field of antioxidants, and comprising a mixture formed by mixing a main antioxidant and a terminating agent type antioxidant according to the weight ratio of 1: 0.25-0.7; the main antioxidant contains hindered phenol antioxidants and auxiliary antioxidants, wherein the hindered phenol antioxidants comprise the following components in mass: the content of the 2, 6-tertiary butyl-4-methylphenol is 13-24 percent, and the content of the bis, 5-tertiary butyl-4-hydroxyphenyl sulfide is 12-21 percent. The surface of the plastic rubber is attached with a protective layer formed by a layer of antioxidant, the activity of the terminating agent type antioxidant is high, the terminating agent type antioxidant can show excellent antioxidant effect in a relatively low concentration range, and the used antioxidant has the advantages of high whiteness of a finished product, excellent initial colorability, excellent long-term heat resistance and good weather resistance, can be completely dissolved with the epoxy soybean oil, resists oxidation and yellowing, and can improve the plastic rubber.)

1. An antioxidant for preventing discoloration in air for plastic rubber is characterized by comprising a mixture formed by mixing a main antioxidant and a terminating agent type antioxidant according to the weight ratio of 1: 0.25-0.7;

the main antioxidant contains hindered phenol antioxidants and auxiliary antioxidants, wherein the hindered phenol antioxidants comprise the following components in mass: the content of 2, 6-tertiary butyl-4-methylphenol is 13-24%, the content of bis, 5-tertiary butyl-4-hydroxyphenyl thioether is 12-21%, and the content of tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester is 5-20%;

the auxiliary antioxidant comprises the following components in parts by mass: the content of the didodecyl alcohol ester is 3-13%, the content of the dimyristyl alcohol ester is 3-13%, the content of the dioctadecyl alcohol ester is 12-15% and the content of the phosphite ester is 23-26%;

the terminating agent type antioxidant comprises the following components in percentage by mass: the content of 4, 4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine is 6-8% and the content of tris [2, 4-di-tert-butylphenyl ] phosphite is 2-6%.

2. The antioxidant for preventing discoloration in air for plastic rubber according to claim 1, wherein the hindered phenol antioxidant is one of the following: the content of 2, 6-tertiary butyl-4-methylphenol is 19%, the content of bis, 5-tertiary butyl-4-hydroxyphenyl sulfide is 17%, and the content of tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester is 15%;

the auxiliary antioxidant comprises the following components in parts by mass: the content of the didodecanol ester is 7%, the content of the dimyristyl alcohol ester is 7%, the content of the dioctadecyl alcohol ester is 13% and the content of the phosphite ester is 24%;

the terminating agent type antioxidant comprises the following components in percentage by mass: the content of 4, 4' -bis (. alpha.,. alpha. -dimethylbenzyl) diphenylamine and the content of tris [ 2.4-di-tert-butylphenyl ] phosphite were 7%.

3. The antioxidant for preventing discoloration in air for plastic rubber as claimed in claim 1, wherein the mesh number of hindered phenol-based antioxidant and secondary antioxidant in the primary antioxidant is 100-120 mesh, and the mesh number of terminating agent-type antioxidant is 50-100 mesh.

4. The method for preparing the antioxidant for preventing discoloration in air for plastic rubber according to claim 1, comprising the steps of:

s1: proportionally mixing hindered phenol antioxidant and auxiliary antioxidant, adding into a reaction kettle, adding 20-30L deionized water along the edge of the reaction kettle, heating to 70-90 deg.C, and keeping the temperature for 10 min;

s2: in the process of heat preservation in S1, completely dissolving phenolic antioxidants in the mixture to form a liquid organic phase component, adding the mixture into a high-speed shearing machine for stirring, adjusting the stirring speed to 2000r/min to form a homogeneous mixed solution, and heating to 70-140 ℃;

s3: heating to the reaction temperature of 135-165 ℃ at the constant reaction temperature in S2, carrying out heat preservation reaction, filtering to remove impurities to obtain an antioxidant, stirring under the protection of nitrogen, and heating to 100 ℃;

s4: adding the terminating agent type antioxidant into the mixed solution in a homogenized state by using an emulsion conversion point method, and continuously shearing and stirring at a high speed to obtain the antioxidant of the compound emulsion.

5. The method for preparing the antioxidant for preventing discoloration in air for plastic rubber as claimed in claim 4, wherein the antioxidant is emulsified in S4 by high speed shearing to obtain an aqueous emulsion with a particle size of 0.3-1.0 μm, and the emulsion is adjusted to a suitable concentration with water and has a solid content of 50-60%.

Technical Field

The invention relates to the technical field of antioxidants, and particularly relates to an antioxidant for preventing discoloration in air for plastic rubber and a preparation method thereof.

Background

The ABS resin, namely the terpolymer of butadiene, styrene and acrylonitrile, is the polybutadiene component which is most affected by thermal oxidation, and plays a decisive role in the aging of the whole material, and butadiene rubber particles are firstly degraded in the aging process and can react with oxygen in the air to age after being exposed in the air. In addition, ABS graft powder to pass drying process, powder particle have very large specific surface, dry and go on under 110 duC to 130 duC generally, increase the contact time with hot air, under this condition, powder particle appear the yellow phenomenon of partial oxidation easily, granulate through the high-temperature screw rod, because of the thermal aging reason, its physical and mechanical properties suffer the destruction of different degrees again, the anti-aging problem of ABS resin is more outstanding, ABS resin under ambient temperature under the condition of heat, light, oxygen, can turn yellow gradually, harden, become brittle, can cause coking to turn black under higher temperature, in order to inhibit or postpone its oxidation degradation that takes place in production, processing, use, need to add suitable antioxidant.

Disclosure of Invention

The invention aims to provide an antioxidant for preventing discoloration in air for plastic rubber and a preparation method thereof, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: an antioxidant for preventing discoloration in air for plastic rubber comprises a mixture of a main antioxidant and a terminating agent type antioxidant in a weight ratio of 1: 0.25-0.7;

the main antioxidant contains hindered phenol antioxidants and auxiliary antioxidants, wherein the hindered phenol antioxidants comprise the following components in mass: the content of 2, 6-tertiary butyl-4-methylphenol is 13-24%, the content of bis, 5-tertiary butyl-4-hydroxyphenyl thioether is 12-21%, and the content of tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester is 5-20%;

the auxiliary antioxidant comprises the following components in parts by mass: the content of the didodecyl alcohol ester is 3-13%, the content of the dimyristyl alcohol ester is 3-13%, the content of the dioctadecyl alcohol ester is 12-15% and the content of the phosphite ester is 23-26%;

the terminating agent type antioxidant comprises the following components in percentage by mass: the content of 4, 4' -bis (alpha, alpha-dimethylbenzyl) diphenylamine is 6-8% and the content of tris [2, 4-di-tert-butylphenyl ] phosphite is 2-6%.

Further, the hindered phenol antioxidant is as follows: the content of 2, 6-tertiary butyl-4-methylphenol is 19%, the content of bis, 5-tertiary butyl-4-hydroxyphenyl sulfide is 17%, and the content of tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester is 15%;

the auxiliary antioxidant comprises the following components in parts by mass: the content of the didodecanol ester is 7%, the content of the dimyristyl alcohol ester is 7%, the content of the dioctadecyl alcohol ester is 13% and the content of the phosphite ester is 24%;

the terminating agent type antioxidant comprises the following components in percentage by mass: the content of 4, 4' -bis (. alpha.,. alpha. -dimethylbenzyl) diphenylamine and the content of tris [ 2.4-di-tert-butylphenyl ] phosphite were 7%.

Furthermore, the mesh number of the hindered phenol antioxidant and the auxiliary antioxidant in the main antioxidant is 100-120 meshes, and the mesh number of the terminating agent type antioxidant is 50-100 meshes.

The invention provides another technical scheme, which comprises a preparation method of an antioxidant for preventing discoloration in air for plastic rubber, and the preparation method comprises the following steps:

s1: proportionally mixing hindered phenol antioxidant and auxiliary antioxidant, adding into a reaction kettle, adding 20-30L deionized water along the edge of the reaction kettle, heating to 70-90 deg.C, and keeping the temperature for 10 min;

s2: in the process of heat preservation in S1, completely dissolving phenolic antioxidants in the mixture to form a liquid organic phase component, adding the mixture into a high-speed shearing machine for stirring, adjusting the stirring speed to 2000r/min to form a homogeneous mixed solution, and heating to 70-140 ℃;

s3: heating to the reaction temperature of 135-165 ℃ at the constant reaction temperature in S2, carrying out heat preservation reaction, filtering to remove impurities to obtain an antioxidant, stirring under the protection of nitrogen, and heating to 100 ℃;

s4: adding the terminating agent type antioxidant into the mixed solution in a homogenized state by using an emulsion conversion point method, and continuously shearing and stirring at a high speed to obtain the antioxidant of the compound emulsion.

Further, in S4, high-speed shearing emulsification is carried out to obtain the antioxidant of the water emulsion with the particle size of 0.3-1.0 micron, the emulsion is adjusted to a proper concentration by water, and the solid content is proper to be 50-60%.

Compared with the prior art, the invention has the beneficial effects that: the invention provides an antioxidant for preventing discoloration in air for plastic rubber and a preparation method thereof, wherein a protective layer formed by a layer of antioxidant is attached to the surface of the plastic rubber, the activity of a terminating agent type antioxidant is high, the antioxidant has excellent antioxidant effect in a relatively low concentration range, and the discoloration phenomenon is caused when a polymer is contacted with gases such as NOx due to the avoidance of the existence of phenolic substances, so that the discoloration of ABS grafted powder is effectively prevented. The antioxidant used is low in smell, high in heat resistance, excellent in vulcanization resistance and plasticizer compatibility, high in finished product whiteness, excellent in initial colorability, excellent in long-term heat resistance and weather resistance, can be completely mutually soluble with epoxy soybean oil, resists oxidation and yellowing, and can improve plastic rubber.

Drawings

FIG. 1 is a process flow diagram of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.