Ionic liquid-loaded zeolite rubber reinforcing agent and preparation method thereof

文档序号：401157 发布日期：2021-12-17 浏览：2次中文

阅读说明：本技术 一种离子液体负载沸石的橡胶补强剂及其制备方法 (Ionic liquid-loaded zeolite rubber reinforcing agent and preparation method thereof ) 是由郭书利付琬璐郭万元于帅刘国为徐秀志刘国惠于 2021-09-23 设计创作，主要内容包括：本发明属于橡胶助剂的技术领域,尤其涉及一种离子液体负载沸石的橡胶补强剂及其制备方法。将离子液体负载到天然沸石表面代替全部或部分炭黑,起到对天然橡胶的补强作用。一方面为攻克天然沸石资源利用率低,损失浪费严重及加工程度低等关键共性问题,发挥天然沸石的独特作用,实现天然沸石的综合利用；另一方面通过对天然沸石进行表面改性,改善橡胶基体与补强剂(沸石)相容性问题,实现替代或减少传统补强剂炭黑等高环境负担物质。(The invention belongs to the technical field of rubber additives, and particularly relates to an ionic liquid zeolite-loaded rubber reinforcing agent and a preparation method thereof. The ionic liquid is loaded on the surface of the natural zeolite to replace all or part of carbon black, so that the reinforcing effect on the natural rubber is achieved. On one hand, the method solves the key common problems of low utilization rate of natural zeolite resources, serious loss and waste, low processing degree and the like, plays the unique role of the natural zeolite and realizes the comprehensive utilization of the natural zeolite; on the other hand, the compatibility problem of the rubber matrix and the reinforcing agent (zeolite) is improved by carrying out surface modification on the natural zeolite, and high environmental burden substances such as the traditional reinforcing agent carbon black are replaced or reduced.)

1. The ionic liquid loaded zeolite rubber reinforcing agent is characterized by comprising the following raw materials: 1-2ml of 3mol/L methanesulfonic acid solution, 7-10 g of glycine betaine, 10-15ml of 2mol/L primary alcohol, 15-25g of sodium salt and 5-20g of natural zeolite.

2. The preparation method of the ionic liquid loaded zeolite rubber reinforcing agent is characterized by comprising the following steps:

step 1, adding 7-10 g of glycine betaine and 10-15ml of 2mol/L primary alcohol into 1-2ml of 3mol/L methanesulfonic acid solution, gradually heating to 130 ℃ and 140 ℃ under a reduced pressure condition, reacting for 0.5-1h to make the reaction mixture uniform, cooling the brown mixture to room temperature after 7-10 h, washing with diethyl ether to remove redundant primary alcohol, and crystallizing and purifying in a mixed solution of ethyl acetate and diethyl ether to obtain a betaine type ionic liquid intermediate;

step 2, performing ion exchange on the obtained betaine type ionic liquid intermediate and sodium salt in acetone, performing vacuum filtration, removing the acetone in a reduced pressure distillation mode, performing Soxhlet extraction for 24 hours by using dichloromethane, washing by deionized water, performing reduced pressure distillation to remove the dichloromethane, and drying to obtain the betaine type amphoteric ionic liquid;

and 3, adding 250ml of 200-plus deionized water and 5-20g of ionic liquid into a beaker, heating in a water bath for 30-60min, adding 5-20 natural zeolite, heating to 70-80 ℃, stirring at a constant speed of 300-plus water/min for 4-5h, after the liquid mixture is pasty, finishing the reaction, pouring the reaction product into a tray for uniform dispersion, and drying in a forced air drying oven at 80 ℃ for 12-24 h to obtain the ionic liquid loaded natural zeolite.

3. The method of claim 2 wherein the primary alcohol is one of n-hexanol, n-dodecanol, n-tetradecanol, n-hexadecanol, and n-docosanol.

4. The method of claim 2, wherein the reduced pressure in step 1 is 5KPa to 10 KPa, and the mass ratio of the mixed solution of ethyl acetate and ethyl ether is 1: 1.

5. the method for preparing ionic liquid supported zeolite rubber reinforcing agent as claimed in claim 2, wherein vacuum degree of vacuum filtration in step 2 is in the range of 0.85-0.95 MPa.

6. The method of claim 2 wherein said sodium salt in step 2 is sodium chlorate or sodium tetrafluoroborate.

7. The method for preparing ionic liquid supported zeolite rubber reinforcing agent as claimed in claim 2, wherein the adding mass ratio of betaine type ionic liquid intermediate and sodium salt obtained in step 2 is 1: (1-5).

8. A method for preparing natural rubber incorporating the ionic liquid-supported zeolite reinforcement of claim 1, comprising the steps of:

step 1, plasticating natural rubber on an open mill, and sequentially adding 80-100g of natural rubber, 3.2-4g of stearic acid, 4-5g of zinc oxide, 0.28-0.8g of accelerator, 0.8-1g of anti-aging agent, 20-40g of carbon black, 5-20g of zeolite reinforcing agent, 0.8-1g of liquid paraffin and 1.6-2g of sulfur after coating a roller;

and 2, uniformly mixing, packaging in a triangular bag, discharging, and vulcanizing the mixed rubber by using a flat vulcanizing machine.

9. The method for preparing natural rubber with an ionic liquid supported zeolite reinforcement as claimed in claim 8, wherein the accelerator in step 1 is at least one of accelerators CZ and TMTD; the anti-aging agent is anti-aging agent 4010.

10. The method for preparing natural rubber with added ionic liquid zeolite as reinforcing agent in claim 8, wherein the vulcanization condition of natural rubber in step 2 is 130-160 ℃ and 10-18 MPa.

Technical Field

The invention belongs to the technical field of rubber additives, and particularly relates to an ionic liquid zeolite-loaded rubber reinforcing agent and a preparation method thereof.

Background

At present, a reinforcing agent commonly used in the rubber industry is mainly carbon black type filler, but carbon black causes serious damage to the surrounding environment in the production process, and carbon black dust enters the lung of a worker through breathing, so that the body and mind of an operator are seriously influenced. The energy crisis has caused the sales price of coal tar, the main raw material for carbon black production, to rise all the time, leading to the rise of the cost of the rubber industry.

The diversity and adjustable characteristics of ionic liquids greatly expand the application fields thereof. The ionic liquid has the advantages of low viscosity, low toxicity, nonflammability, difficult volatilization, high chemical stability, good thermal stability, high ionic conductivity and the like, is called as a green solvent, namely, the ionic liquid with special physical and chemical properties can be customized according to the structures of anions and cations, so that the ionic liquid for specific application is purposefully designed. Due to the particularity of the zwitterionic structure, dipole-dipole interaction exists between the zwitterionic groups on the polymer skeleton, and ion-dipole interaction also exists between the zwitterionic groups and the bulk ionic liquid, so that the bi-component ions show excellent mechanical strength without adding any cross-linking agent, and the strength of the bi-component ions can be compared with that of a chemically cross-linked system. Glycine betaine is a natural and cost-effective substance with quaternary trimethyl alkyl amino moieties and carboxylate functions, obtained after extraction of sucrose, is an abundant raw material, accounting for 27% of beet molasses. It is one of the most effective osmoprotectants to date and has been widely used in the study of this particular osmoprotectant.

The natural zeolite is a valuable natural resource, compared with the synthetic zeolite, the natural zeolite has rich resources and low cost, and the cost of extracting the industrial material from the natural zeolite rich ore is only 1 to 5 percent of that of the synthetic zeolite. The natural zeolite resources in China are large in quantity and wide in distribution, the discovered mining sites exceed 400, the annual production capacity reaches 800 ten thousand tons, and the reserves are listed in the top in the world. The natural zeolite has larger structural openness, a plurality of holes and channels with uniform size are arranged in the crystal, and the natural zeolite has larger specific surface area and unique crystal structure; meanwhile, the natural zeolite is a good filling agent, and the production cost can be reduced by partially replacing carbon black.

At present, the application of the ionic liquid loaded natural zeolite in the rubber reinforcing agent is not purposefully developed in the prior art.

Disclosure of Invention

Aiming at the problems, the invention provides the ionic liquid loaded zeolite rubber reinforcing agent and the preparation method thereof, and the ionic liquid is loaded on the surface of the natural zeolite to replace all or part of carbon black, so that the reinforcing effect on the natural rubber is achieved. On one hand, the method solves the key common problems of low utilization rate of natural zeolite resources, serious loss and waste, low processing degree and the like, plays the unique role of the natural zeolite and realizes the comprehensive utilization of the natural zeolite; on the other hand, the compatibility problem of the rubber matrix and the reinforcing agent (zeolite) is improved by carrying out surface modification on the natural zeolite, and high environmental burden substances such as the traditional reinforcing agent carbon black are replaced or reduced.

In order to achieve the purpose, the invention adopts the following technical scheme.

The ionic liquid loaded zeolite rubber reinforcing agent is prepared from the following raw materials: 1-2ml of 3mol/L methanesulfonic acid solution, 7-10 g of glycine betaine, 10-15ml of 2mol/L primary alcohol, 15-25g of sodium salt and 5-20g of natural zeolite.

A preparation method of an ionic liquid loaded zeolite rubber reinforcing agent comprises the following steps:

step 1, adding 7-10 g of glycine betaine and 10-15ml of 2mol/L primary alcohol into 1-2ml of 3mol/L methanesulfonic acid solution, gradually heating to 140 ℃ under the condition of reduced pressure, reacting for 0.5-1h, enabling the reaction mixture to be uniform, and cooling the brown mixture to room temperature after 7-10 h. Washing with diethyl ether to remove excessive primary alcohol, and crystallizing and purifying in the mixed solution of ethyl acetate and diethyl ether to obtain the betaine type ionic liquid intermediate.

And 2, performing ion exchange on the obtained betaine type ionic liquid intermediate and sodium salt in acetone, performing vacuum filtration, removing the acetone in a reduced pressure distillation mode, performing Soxhlet extraction for 24 hours by using dichloromethane, washing by deionized water, performing reduced pressure distillation to remove the dichloromethane, and drying to obtain the betaine type amphoteric ionic liquid.

And 3, adding 250ml of 200-plus deionized water and 5-20g of ionic liquid into a beaker, heating in a water bath for 30-60min, adding 5-20 natural zeolite, heating to 70-80 ℃, stirring at a constant speed of 300-plus water/min for 4-5h, after the liquid mixture is pasty, finishing the reaction, pouring the reaction product into a tray for uniform dispersion, and drying in a forced air drying oven at 80 ℃ for 12-24 h to obtain the ionic liquid loaded natural zeolite.

Further, the primary alcohol is one of n-hexanol, n-dodecanol, n-tetradecanol, n-hexadecanol and n-docosanol.

Further, the condition of the decompression in the step 1 is 5KPa to 10 KPa.

Further, the mass ratio of the mixed solution of ethyl acetate and diethyl ether in the step 1 is 1: 1.

further, the vacuum degree range of the vacuum filtration in the step 2 is 0.85-0.95 MPa.

Further, the sodium salt in the step 2 is sodium chlorate or sodium tetrafluoroborate.

Further, the adding mass ratio of the betaine type ionic liquid intermediate obtained in the step 2 to the sodium salt is 1: (1-5).

The preparation method of the natural rubber added with the ionic liquid loaded zeolite reinforcing agent comprises the following steps:

And 2, uniformly mixing, packaging in a triangular bag, discharging, and vulcanizing the mixed rubber by using a flat vulcanizing machine.

Further, the promoter in the step 1 is at least one of promoters CZ and TMTD.

Further, the anti-aging agent in the step 1 is an anti-aging agent 4010.

Further, the natural rubber vulcanization condition in the step 2 is 130-160 ℃ and 10-18 MPa.

Compared with the prior art, the invention has the beneficial effect that.

(1) The invention discloses a betaine type amphoteric ionic liquid, which is prepared by using methanesulfonic acid as a catalyst, esterifying glycine betaine and primary alcohol to synthesize mesylate of glycine betaine cationic ester, and performing ion exchange with sodium salt.

(2) The rubber reinforcing agent prepared by the invention loads the ionic liquid on the surface of the natural zeolite, so that the surface polarity of the natural zeolite is reduced, the compatibility of the natural zeolite and a rubber matrix is further improved, and the added ionic liquid assists the natural zeolite to be better dispersed in the natural rubber, so that a uniform filler network is formed.

(3) The invention provides a preparation method of a rubber reinforcing agent by using natural zeolite rich in mineral resources as a raw material, which can partially replace carbon black to obtain a reinforcing effect similar to that of the carbon black and reduce the use of petrochemical resources.

(4) The invention relates to a preparation process of rubber reinforcing agent reinforced natural rubber, which adopts the traditional rubber processing technology, has simple operation and better economic and social benefits.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

An ionic liquid loaded zeolite rubber reinforcing agent is prepared from the following raw materials: 7-10 g glycine betaine, 10-15ml 2mol/L primary alcohol, 15-25g sodium salt and 5-20g natural zeolite.

A preparation method of an ionic liquid loaded zeolite rubber reinforcing agent comprises the following steps:

step 1, adding 7-10 g of glycine betaine and 10-15ml of 2mol/L primary alcohol into 1-2ml of 3mol/L methanesulfonic acid solution, gradually heating to 140 ℃ under the condition of reduced pressure, reacting for 0.5-1h, enabling the reaction mixture to be uniform, and cooling the brown mixture to room temperature for 7-10 h. Washing with diethyl ether to remove excessive primary alcohol, and crystallizing and purifying in the mixed solution of ethyl acetate and diethyl ether to obtain the betaine type ionic liquid intermediate.

And 3, adding 250ml of ion water and 5-20g of ion liquid into a beaker, heating in a water bath for 30-60min, adding 5-20g of natural zeolite, heating to 70-80 ℃, stirring at a constant speed of 300r/min for 4-5h, after the liquid mixture is pasty, finishing the reaction, pouring the reaction product into a tray for uniform dispersion, and drying in a forced air drying box at 80 ℃ for 12-24 h to obtain the ion liquid loaded natural zeolite.