阅读说明：本技术 一种有色聚丁二烯材料及其制备方法 (Colored polybutadiene material and preparation method thereof ) 是由 吴超群 于 2021-01-22 设计创作，主要内容包括：本发明公开一种有色聚丁二烯材料及其制备方法；有色聚丁二烯材料由下述组分组成：60～100质量份聚丁二烯接枝着色剂,5～20质量份抗滴落剂,1～3质量份抗氧剂,2～5质量份其他助剂；本发明通过在聚丁二烯分子链上接枝着色剂,使聚丁二烯分子具有颜色,解决了胶料需要在高温高压等复杂条件下混炼上色的问题,通过在聚丁二烯分子链上接枝着色剂,着色剂分子上的大量的氰基和羧基与抗氧剂上的羟基或酯基相互作用,两者具有协同增效的作用,使聚丁二烯材料的着色效果和抗氧化效果更佳。(The invention discloses a colored polybutadiene material and a preparation method thereof; the colored polybutadiene material consists of the following components: 60-100 parts by mass of polybutadiene grafted coloring agent, 5-20 parts by mass of anti-dripping agent, 1-3 parts by mass of antioxidant and 2-5 parts by mass of other auxiliary agents; according to the invention, the polybutadiene molecules have colors by grafting the coloring agent on the polybutadiene molecular chain, the problem that rubber materials need to be mixed and colored under complex conditions such as high temperature and high pressure is solved, and a large amount of cyano groups and carboxyl groups on the coloring agent molecules interact with hydroxyl groups or ester groups on the antioxidant by grafting the coloring agent on the polybutadiene molecular chain, so that the cyano groups and the carboxyl groups have a synergistic effect, and the coloring effect and the antioxidant effect of the polybutadiene material are better.)

1. The colored polybutadiene material is characterized by comprising the following components in parts by weight: 60-100 parts by mass of a polybutadiene grafted coloring agent, 5-20 parts by mass of an anti-dripping agent, 1-3 parts by mass of an antioxidant and 2-5 parts by mass of other auxiliaries, wherein the polybutadiene grafted coloring agent has a structure shown in a formula (I):

the value of n is 15-50.

2. The colored polybutadiene material of claim 1, wherein the polybutadiene graft colorant is prepared by a method comprising the steps of:

adding a coloring agent into a flask with a branch mouth, adding tetrahydrofuran for dissolving, heating to 70-80 ℃, and dropwise adding SOCl₂Carrying out acyl chlorination reaction; n is a radical of₂Under protection, pyridine is used as an acid-binding agent, toluene is used as a solvent, and hydroxyl-terminated polybutadiene and the polybutadiene are subjected to esterification reaction to obtain the polybutadiene grafting colorant.

3. The colored polybutadiene material of claim 2, wherein the polybutadiene graft-linking colorant is prepared by a method comprising adding the colorant, SOCl₂The molar ratio to hydroxyl-terminated polybutadiene is 1:1: 10.

4. The colored polybutadiene material of claim 2, wherein the polybutadiene graft colorant is prepared by a method comprising the following steps:

5. the colored polybutadiene material of claim 1, wherein the anti-dripping agent is a fluoropolymer.

6. The colored polybutadiene material of claim 1, wherein the antioxidant is one or more selected from hindered phenols and phosphites.

7. The colored polybutadiene material of claim 1, wherein said other additives are hollow glass microspheres or solid glass microspheres.

8. The method for preparing colored polybutadiene material according to claim 1, wherein the method comprises the following steps:

60-100 parts by mass of polybutadiene grafted coloring agent, 5-20 parts by mass of anti-dripping agent, 1-3 parts by mass of antioxidant and 2-5 parts by mass of other additives are mixed in a mixer at the rotating speed of 400-800 revolutions per minute at the temperature of 20-35 ℃ for 10-30 minutes, and the mixed material is extruded, cooled, dried and granulated at the temperature of 220-230 ℃ through an extruder to obtain the colored polybutadiene material.

Technical Field

The invention belongs to the field of polymer chemical synthesis, and particularly relates to a colored polybutadiene material and a preparation method thereof.

Background

In the past, most of rubber products produced by people are mainly black, gray or white, but with the increasing use requirements and color requirements of people on the rubber products, colorful rubber products are often needed, and the requirement that the rubber is colored by a mixture of various colors is required; the rubber compound is usually mixed and colored under complex conditions of high temperature, high pressure and the like, and the cost and the performance of pigments, products and the like are considered, for example, the prepared colored rubber product also has the general performance of common rubber, such as: adaptability, fatigue resistance, environmental protection, no toxicity, safety and the like, which have higher technical requirements on rubber dyeing; based on the above, the invention provides a colored polybutadiene material and a preparation method thereof, and solves the problem that rubber materials need to be mixed and colored under complex conditions such as high temperature and high pressure by using a polybutadiene molecular weight upper block colorant.

Disclosure of Invention

In order to solve the defects of the prior art, the invention provides a colored polybutadiene material and a preparation method thereof, wherein a colorant is grafted on a polybutadiene molecular chain, a large amount of cyano groups and carboxyl groups on colorant molecules interact with hydroxyl groups or ester groups on an antioxidant, and the cyano groups and the carboxyl groups and the hydroxyl groups or the ester groups have a synergistic effect, so that the coloring effect and the antioxidant effect of the polybutadiene material are better.

The invention aims to provide a colored polybutadiene material.

The invention also aims to provide a preparation method of the colored polybutadiene material.

The above purpose of the invention is realized by the following technical scheme:

the preparation method of the colored polybutadiene material comprises the following steps:

the components by weight portion are as follows: 60-100 parts by mass of polybutadiene grafted coloring agent, 5-20 parts by mass of anti-dripping agent, 1-3 parts by mass of antioxidant and 2-5 parts by mass of other additives are mixed in a mixer at the temperature of 20-35 ℃ and the rotating speed of 400-800 revolutions per minute for 10-30 minutes, and the mixed material is extruded, cooled, dried and granulated by an extruder at the temperature of 220-230 ℃ to obtain the colored polybutadiene material.

The polybutadiene grafted colorant has a structural formula shown as the following formula (I):

the value of n is 15-50.

The preparation method of the polybutadiene grafted colorant comprises the following steps:

adding a coloring agent into a flask with a branch mouth, adding tetrahydrofuran for dissolving, heating to 70-80 ℃, and dropwise adding SOCl₂Carrying out acyl chlorination reaction; n is a radical of₂Under protection, pyridine is used as an acid-binding agent, toluene is used as a solvent, and hydroxyl-terminated polybutadiene and the polybutadiene are subjected to esterification reaction to obtain the polybutadiene grafting colorant.

The colorant has the structure shown below:

the colorant, SOCl₂The molar ratio to hydroxyl-terminated polybutadiene is 1:1: 10.

The anti-dripping agent is fluorine-containing polymer.

The antioxidant is one or more selected from hindered phenols or phosphites.

The other auxiliary agents are hollow glass microspheres or solid glass microspheres.

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

(1) the invention provides a colored polybutadiene material, which enables polybutadiene molecules to have colors by grafting a colorant on a polybutadiene molecular chain, solves the problem that rubber materials need to be mixed and colored under complex conditions of high temperature, high pressure and the like, and enables a large amount of cyano groups and carboxyl groups on the colorant molecules to interact with hydroxyl groups or ester groups on an antioxidant by grafting the colorant on the polybutadiene molecular chain, so that the cyano groups and the carboxyl groups have a synergistic effect, and the coloring effect and the antioxidant effect of the polybutadiene material are better.

(2) The invention provides a colored polybutadiene material, wherein colorant molecules and covalent bonds are combined with polybutadiene, the problems that the colorant is added into a polybutadiene base material by a physical mixing method, the compatibility of the colorant and a polymer is poor, and a flame retardant is easy to run off are solved, and the obtained polymer material has a durable color.

Drawings

FIG. 1 is a nuclear magnetic hydrogen spectrum of a polybutadiene grafted colorant.

Detailed Description

The present invention will be further described in detail with reference to the following specific examples, which are not intended to limit the invention in any manner; reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.

Example 1

The colorant (5.0mmol) and 20ml of anhydrous tetrahydrofuran THF were added to the reactor, and after the reaction temperature rose to 70 deg.C, SOCl was slowly added dropwise₂(5.0mmol) and after the dropwise addition reaction for 2 hours, the reaction was terminated and then SOCl was removed by distillation under reduced pressure₂And THF to give the colorant acylchlorinated product.

Hydroxyl-terminated polybutadiene (50.0mmol) was charged into a 50ml Schlenk flask, and after purging nitrogen three times, N₂Under protection, 30ml of anhydrous toluene is added into a disposable syringe, the temperature is raised to 70 ℃, 1ml of pyridine is injected after hydroxyl-terminated polybutadiene is completely dissolved, the mixture is stirred for 30min, the coloring agent acyl chloride product dissolved in the toluene is dropwise added, the temperature is raised to 80 ℃, the reaction is continued for 3h, the product is cooled to room temperature, the product is continuously dissolved/precipitated by toluene/methanol for twice, and the product is dried under vacuum at 45 ℃ to constant weight, so that the polybutadiene grafted coloring agent is obtained, and the yield is 75.2%.

Example 2

100 parts by mass of polybutadiene grafted coloring agent, 10 parts by mass of anti-dripping agent, 2 parts by mass of composite antioxidant and 3 parts by mass of other additives are mixed in a mixer at 25 ℃ for 20 minutes at a rotating speed of 600 revolutions per minute, and the mixed material is extruded, cooled, dried and granulated by an extruder at 230 ℃ to obtain the colored polybutadiene material.

Example 3

Mixing 80 parts by mass of polybutadiene grafted coloring agent, 10 parts by mass of anti-dripping agent, 2 parts by mass of composite antioxidant and 3 parts by mass of other additives in a mixer at 25 ℃ for 20 minutes at a rotating speed of 600 revolutions per minute, and extruding, cooling, drying and granulating the mixed material at 230 ℃ through an extruder to obtain the colored polybutadiene material.

Example 4

60 parts by mass of polybutadiene grafted coloring agent, 10 parts by mass of anti-dripping agent, 2 parts by mass of composite antioxidant and 3 parts by mass of other additives are mixed in a mixer at 25 ℃ for 20 minutes at a rotating speed of 600 revolutions per minute, and the mixed material is extruded, cooled, dried and granulated by an extruder at 230 ℃ to obtain the colored polybutadiene material.

Comparative example 1

Mixing 100 parts by mass of polybutadiene, 10 parts by mass of an anti-dripping agent, 2 parts by mass of a composite antioxidant and 3 parts by mass of other additives in a mixer at 25 ℃ for 20 minutes at a rotating speed of 600 revolutions per minute, and extruding, cooling, drying and granulating the mixed material at 230 ℃ through an extruder to obtain the polybutadiene material.

Comparative example 2

Mixing 80 parts by mass of polybutadiene, 10 parts by mass of an anti-dripping agent, 2 parts by mass of a composite antioxidant and 3 parts by mass of other additives in a mixer at 25 ℃ for 20 minutes at a rotating speed of 600 revolutions per minute, and extruding, cooling, drying and granulating the mixed material at 230 ℃ through an extruder to obtain the polybutadiene material.

Comparative example 3

Mixing 60 parts by mass of polybutadiene, 10 parts by mass of an anti-dripping agent, 2 parts by mass of a composite antioxidant and 3 parts by mass of other additives in a mixer at 25 ℃ for 20 minutes at a rotating speed of 600 revolutions per minute, and extruding, cooling, drying and granulating the mixed material at 230 ℃ through an extruder to obtain the polybutadiene material.

And (3) antioxidant test: the test was carried out using a DSC-Q10 type differential scanning calorimeter, dynamic DSC test conditions: the nitrogen flow is 30mL/min, the oxygen flow is 20mL/min, the heating rate is 20 ℃/min, and the data of 100 ℃ and 400 ℃ are recorded. When the test is started, nitrogen is firstly introduced, when the temperature reaches the set temperature of 100 ℃, the system automatically converts into oxygen, and the relation between the heat and the temperature is recorded when the temperature reaches 100-.

And (3) testing the coloring performance: QUV UV testing according to ASTM G154.

Thermal oxidative aging color test: the aged panels were compared to the unaged panels using the specifications of GB/T11186.2-11186.3.

Table 1 shows the results of the colorability tests of polybutadiene.

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.