阅读说明：本技术 一种橡胶母粒及制备方法和其橡胶及制备方法 (rubber master batch and preparation method thereof, and rubber and preparation method thereof ) 是由 何泓材 熊伟强 何朝凌 尹晓雨 曾辉振 张德伟 南策文 杨帆 于 2019-10-24 设计创作，主要内容包括：本发明公开了一种橡胶母粒及制备方法和其橡胶及制备方法,所述橡胶母粒由改性凹土、天然乳胶、第一助剂、第二助剂和去离子水制成,所述改性凹土由凹土、具有亲水基团和疏水基团的改性剂、乙醇制成；所述橡胶母粒的制备方法包括将改性凹土、第一助剂与去离子水混合均匀,搅拌、切割、分散得浆料,所得浆料进行球磨,所得球磨液体与天然乳胶混合均匀,加入第二助剂混合得混合液体,水洗后烘干制得；所述橡胶由橡胶母粒和天然橡胶制成；所述橡胶的制备方法是将橡胶母粒与天然橡胶混合均匀热压成型制得。本发明的橡胶母粒加强了橡胶的韧性,提高了橡胶制品的使用寿命；制备方法简单,容易实现大规模生产。(The invention discloses rubber master batches, a preparation method and rubber thereof and a preparation method, wherein the rubber master batches are prepared from modified attapulgite, natural latex, th auxiliary agent, a second auxiliary agent and deionized water, the modified attapulgite is prepared from attapulgite, a modifier with a hydrophilic group and a hydrophobic group and ethanol, the preparation method of the rubber master batches comprises the steps of uniformly mixing the modified attapulgite, the th auxiliary agent and the deionized water, stirring, cutting and dispersing to obtain slurry, carrying out ball milling on the obtained slurry, uniformly mixing the obtained ball milling liquid and the natural latex, adding the second auxiliary agent to obtain mixed liquid, washing and drying, and the rubber is prepared from the rubber master batches and the natural rubber.)

The rubber master batches are characterized by being prepared from modified attapulgite, natural latex, a th auxiliary agent, a second auxiliary agent and deionized water, wherein the modified attapulgite is prepared from attapulgite, a modifier with a hydrophilic group and a hydrophobic group and ethanol, the th auxiliary agent comprises an antioxidant and a pH regulator, the second auxiliary agent is a refrigerant, the mass ratio of the modified attapulgite to the natural latex is 1: 0.25-1: 1, and the mass ratio of the modified attapulgite to the antioxidant to the pH regulator to the refrigerant is 1:0.05:0.0125: 0.0025-1: 0.5:0.05: 0.025.

2. The rubber masterbatches of claim 1, wherein the antioxidant is tea polyphenol, the pH regulator is or more selected from sodium hydroxide, potassium hydroxide and magnesium hydroxide, and the refrigerant is calcium chloride.

3, A method for preparing the rubber masterbatch of claim 1, comprising the steps of:

(1) mixing attapulgite, a modifier with a hydrophilic group and a hydrophobic group and ethanol for reaction to prepare modified attapulgite;

(2) uniformly mixing the modified attapulgite, the th auxiliary agent and deionized water, stirring, cutting and dispersing to obtain slurry with the pH value of 8-10;

(3) ball-milling the slurry obtained in the step (2) to obtain ball-milling liquid;

(4) uniformly mixing the ball-milling liquid obtained in the step (3) with natural latex, and adding a second auxiliary agent to obtain a mixed liquid;

(5) washing the mixed liquid obtained in the step (4) with water until the pH value is 7-8, so as to obtain a material;

(6) and (5) drying the material obtained in the step (5) to obtain the rubber master batch.

4. The preparation method of kinds of rubber masterbatch according to claim 3, wherein the mass ratio of the attapulgite in the step (1) to the modifier having a hydrophilic group and a hydrophobic group is 1: 0.005-1: 0.015.

5. The preparation method of kinds of rubber master batches according to claim 3, wherein the attapulgite clay in the step (1) has a purity of 97% or more and is composed of attapulgite crystals, the attapulgite crystals have a rod crystal length of 1-2 μm, a diameter of 40-60 nm and a specific surface area of 150-200 m²/g。

6. The preparation method of kinds of rubber master batches according to claim 3, wherein the stirring speed in the step (2) is 20-60 RPM, the cutting speed is 500-2000 RPM, and the dispersion time is 1-2 hours, so that slurry with the solid content of 10-20% is obtained.

7. The preparation method of kinds of rubber master batches according to claim 3, wherein the ratio of the ball-milled particles to the slurry in the step (3) is 3: 1-7: 1, the ball-milling speed is 100-400 RPM, and the ball-milling time is 24-48 h.

8. The method for preparing kinds of rubber masterbatch according to claim 3, wherein the natural latex in the step (4) has a mesh size of 80-120 meshes, an average particle size of 110-170 μm, and a bulk density of 200-300 kg/m³。

9, rubber prepared by using the rubber masterbatch of any of claims 1-8, wherein the rubber comprises the following raw materials, by weight, 20-40 parts of the rubber masterbatch and 60-80 parts of natural rubber.

10, the method for preparing the rubber of claim 9, wherein the rubber masterbatch is mixed with natural rubber uniformly, and hot-pressed at 50-100 ℃.

Technical Field

The invention relates to rubber master batches, a preparation method thereof, rubber thereof and a preparation method thereof, in particular to rubber master batches for enhancing the toughness of the rubber by using attapulgite, a preparation method thereof, the rubber thereof and a preparation method thereof.

Background

With the increasing application of rubber products in life and industry, many problems such as the service life of rubber products, in which the tensile strength is which is important indicators of rubber products, are met, and the service life of many rubber products is directly related to the tensile strength, such as the cover rubber of conveyer belts and the durability of rubber shock absorbers are improved along with the increase of the tensile strength.

In consideration of the fact that carbon black and the like are expensive, inorganic fillers are gradually developed to replace carbon black, such as layered silicate, wherein the inorganic fillers need larger length-diameter ratio and nano-scale size, and attapulgite is a layered structure, and natural silicon-containing minerals with large length-diameter ratio and nano-scale size are adopted, but the compatibility of the attapulgite in rubber emulsion is poor and the distribution is not easy to be uniform.

Disclosure of Invention

The invention aims to provide rubber master batches for enhancing the toughness of rubber by using attapulgite, which can improve the toughness and prolong the service life of rubber products, the second aim of the invention is to provide preparation methods based on the rubber master batches, the third aim of the invention is to provide rubber prepared by using the rubber master batches, and the fourth aim of the invention is to provide methods for preparing rubber by using the rubber master batches.

The rubber master batch is prepared from modified attapulgite, natural latex, th auxiliary agent, a second auxiliary agent and deionized water, wherein the modified attapulgite is prepared from attapulgite, a modifier with a hydrophilic group and a hydrophobic group and ethanol, the th auxiliary agent comprises an antioxidant and a pH regulator, the second auxiliary agent is a refrigerant, the mass ratio of the modified attapulgite to the natural latex is 1: 0.25-1: 1, and the mass ratio of the modified attapulgite to the antioxidant to the pH regulator to the refrigerant is 1:0.05:0.0125: 0.0025-1: 0.5:0.05: 0.025.

The th auxiliary agent and the second auxiliary agent do not react with the modified attapulgite and the natural latex to provide a material preparation environment, the natural latex in the prepared rubber master batch wraps the modified attapulgite particles, and natural latex molecules are filled in pore channels of the modified attapulgite particles.

Preferably, the antioxidant is tea polyphenol, the pH regulator is or more selected from sodium hydroxide, potassium hydroxide and magnesium hydroxide, and the refrigerant is calcium chloride.

The antioxidant is used for preventing latex components in the mixed liquid from being oxidized to influence the service life of the rubber containing the rubber master batch; the PH regulator enables the PH of the mixed solution to be kept at 8-10, and the mixture is easy to keep a good dispersion state in the environment; the refrigerant enables the prepared mixed solution to maintain the current state for a long time, and prevents slurry from agglomerating and denaturing.

The preparation method of the rubber master batch comprises the following steps of (1) mixing attapulgite, a modifier with a hydrophilic group and a hydrophobic group and ethanol for reaction to obtain modified attapulgite, (2) uniformly mixing the modified attapulgite, an th auxiliary agent and deionized water, stirring, cutting and dispersing to obtain slurry with the pH value of 8-10, (3) ball-milling the slurry obtained in the step (2) to obtain ball-milled liquid, (4) uniformly mixing the ball-milled liquid obtained in the step (3) with natural latex, adding a second auxiliary agent to obtain mixed liquid, (5) washing the mixed liquid obtained in the step (4) with water until the pH value is 7-8 to obtain a material, and (6) drying the material obtained in the step (5) to obtain the rubber master batch.

Wherein, the step (1) is that the attapulgite: the mass ratio of the modifier having a hydrophilic group and a hydrophobic group is 1: 0.005-1: 0.015; preferably, the ratio of attapulgite: the mass ratio of the modifier having a hydrophilic group and a hydrophobic group is 1: 0.005-1: 0.010.

the used attapulgite has the purity of more than or equal to 97 percent and consists of attapulgite crystals; the attapulgite crystal has a rod crystal length of 1-2 μm, a diameter of 40-60 nm, and a specific surface area of 150-200 m²/g。

The solvent ethanol for sufficiently mixing and reacting the attapulgite and the modifier is not limited to a fixed amount, and may be added in an amount of 10 times the mass of the attapulgite, so that the attapulgite and the modifier can be uniformly mixed.

Preferably, the hydrophilic group is a siloxy group or a hydroxyl group, and the hydrophobic group is an alkyl group; more preferably, the modifier having a hydrophilic group and a hydrophobic group is selected from 3- (2, 3-glycidoxy) propyltrimethoxysilane or KH 550.

And combining the hydrophilic groups on the surface of the modifier with the hydroxyl groups of the attapulgite to obtain the modified attapulgite with hydrophobic groups.

And (3) stirring in the step (2) at the rotating speed of 20-60 RPM, cutting at the rotating speed of 500-2000 RPM, and dispersing for 1-2 h to obtain slurry with the solid content of 10-20%.

Wherein, the proportion of the ball-milled particles and the slurry in the step (3) is 3: 1-7: 1, ball milling speed is 100-400 RPM, and ball milling time is 24-48 h; preferably, the diameter of the ball-milled particles is 10-35 mm.

The average particle size of the attapulgite clay particles in the ball-milling liquid is 10-15 um, the selection of the particle size has great influence on the rubber performance, because the particle size is too small, the attapulgite clay particles are easy to self-aggregate and difficult to disperse, and the particle size is too large, the mechanical performance of the rubber prepared from the attapulgite clay particles can be influenced.

The ball-milling liquid is magnetically stirred for 5-15 min at the temperature of 30-60 ℃, then is uniformly mixed with the natural latex, and is added into a second auxiliary agent solution for mixing to obtain a mixed liquid, wherein the second auxiliary agent is a refrigerant, when the mass fraction of the refrigerant solution reaches , the freezing point of the refrigerant solution can reach-55 ℃, the refrigerant solution is added into the system to reduce the freezing point, and in the step , the refrigerant is a calcium chloride solution.

The natural latex has a mesh size of 80 to 120 meshes, an average particle diameter of 110 to 170 μm, and a bulk density of 200 to 300kg/m³。

And (3) washing the mixed solution to a pH value of 7-8 in the step (5), so as to wash off the th aid and the second aid in the mixed solution, and avoid excessive cations in the mixed solution from reducing the mechanical property of the rubber.

The rubber prepared by using the rubber master batch comprises the following raw materials in parts by weight: 20-40 parts of rubber master batch and 60-80 parts of natural rubber emulsion.

According to the method for preparing the rubber by using the rubber master batch, the rubber master batch and the natural rubber are uniformly mixed and are subjected to hot press molding at 50-100 ℃.

The attapulgite is natural minerals containing water and magnesium-rich aluminum silicate with fiber structures, the structure of the attapulgite has an inverted tetrahedral configuration and a pore channel structure formed by discontinuous octahedral layers, the unique pure natural fiber structure can well enhance the toughness of rubber and increase the tensile strength of the rubber so as to achieve the purpose of prolonging the service life of rubber products.

Has the advantages that: the invention has the following advantages: (1) the rubber master batch prepared by utilizing the special fiber structure of the attapulgite enhances the toughness of rubber and prolongs the service life of rubber products; (2) the attapulgite is rich in resources and low in cost; (3) the resource waste and environmental protection problems of the waste rubber are reduced; (4) the preparation method has simple process and is easy to realize large-scale production.

Drawings

FIG. 1 is a flow chart of the production of the rubber masterbatch of the present invention.

Detailed Description

The technical solution of the present invention is further illustrated in step with reference to the accompanying drawings and examples.

As shown in figure 1, the rubber master batch preparation flow chart comprises the steps of firstly carrying out mixing reaction on attapulgite, a modifier with hydrophilic groups and hydrophobic groups and ethanol, carrying out modification treatment on the attapulgite to obtain modified attapulgite, secondly stirring, cutting and dispersing the modified attapulgite and an th auxiliary agent with deionized water to obtain slurry, then carrying out ball milling, finally uniformly mixing the slurry with natural latex, adding the mixture into a second auxiliary agent solution, uniformly mixing, washing with water until the pH value is 7-8 to obtain a material, drying to obtain the rubber master batch, and carrying out freeze preservation for later use.

In the following examples of the invention, for convenience of configuration and use, a pH regulator is selected to be a regulator solution with a mass fraction of 5%, a refrigerant is a calcium chloride solution with a mass fraction of 5%, and modified attapulgite in the examples is obtained according to the content of the specification: antioxidant: PH adjuster solution: the mass ratio of the refrigerant solution is 1:0.05:0.25: 0.05-1: 0.5:1: 0.5. The attapulgite used in the embodiment has the purity of more than or equal to 97 percent and consists of attapulgite crystals, the rod crystal length of the attapulgite crystals is 1-2 mu m, the diameter is 40-60 nm, and the specific surface area is 150-200 m²/g。