阅读说明：本技术 一种轻质可降解鞋用橡胶复合材料及制备方法 (Light degradable rubber composite material for shoes and preparation method thereof ) 是由 程扬健 陈瑞杰 杨鹏 于 2021-10-13 设计创作，主要内容包括：本发明公开了一种轻质可降解鞋用橡胶复合材料,包括如下重量份材料：80-100份天然橡胶3L、50-70份纳米二氧化硅、30-50份环烷油4006、0.5-2份硬脂酸、4-6份氧化锌、5-8份聚乙二醇4000、2-5份聚异丁烯、1-3份促进剂、2-4份硫磺、10-40份天然酸碱调节剂、10-40份增容填充剂。该橡胶复合材料具有操作简便、硫速适中、比重轻、易降解、气味温和、原料廉价易得等现有橡胶材料不具备的优点。相较于轻钙等无机增容填充剂,天然植物填料含有丰富的糖类、蛋白质、脂质,易于被微生物降解,极大减缓了橡胶废弃物所带来的的环保压力。(The invention discloses a light degradable rubber composite material for shoes, which comprises the following materials in parts by weight: 80-100 parts of natural rubber 3L, 50-70 parts of nano silicon dioxide, 30-50 parts of naphthenic oil 4006, 0.5-2 parts of stearic acid, 4-6 parts of zinc oxide, 5-8 parts of polyethylene glycol 4000, 2-5 parts of polyisobutylene, 1-3 parts of an accelerator, 2-4 parts of sulfur, 10-40 parts of a natural acid-base regulator and 10-40 parts of a bulking filler. The rubber composite material has the advantages of simple and convenient operation, moderate sulfur speed, light specific gravity, easy degradation, mild smell, cheap and easily obtained raw materials and the like which are not possessed by the existing rubber materials. Compared with inorganic bulking fillers such as light calcium and the like, the natural plant filler contains abundant saccharides, proteins and lipids, is easily degraded by microorganisms, and greatly relieves the environmental protection pressure brought by rubber wastes.)

1. The light degradable rubber composite material for shoes is characterized by comprising the following raw materials in parts by weight: 80-100 parts of natural rubber 3L, 50-70 parts of nano silicon dioxide, 30-50 parts of plasticizer, 0.5-2 parts of stearic acid, 4-6 parts of zinc oxide, 5-8 parts of activating dispersant, 2-5 parts of anti-emetic emulsion, 1-3 parts of accelerator, 2-4 parts of vulcanizing agent, 10-40 parts of natural acid-base regulator and 10-40 parts of bulking filler.

2. The lightweight degradable rubber composite for shoes as claimed in claim 1, wherein said plasticizer is naphthenic oil 4006.

3. The light degradable shoe rubber composite of claim 1, wherein the activating dispersant is polyethylene glycol 4000.

4. The lightweight degradable rubber composite for shoes as claimed in claim 1, wherein said anti-emetic agent is polyisobutylene.

5. The lightweight and degradable rubber composite material for shoes as claimed in claim 1, wherein said accelerator is a thiazole accelerator or a mixed accelerator of a thiuram accelerator and a sulfonamide derivative accelerator.

6. The light-weight degradable rubber composite for shoes as claimed in claim 1, wherein the vulcanizing agent is sulfur.

7. The light degradable rubber composite material for shoes as claimed in claim 1, wherein the natural acid-base modifier is one of peanut shell powder, wild jujube shell powder and almond shell powder, the aqueous solution of which is weakly acidic.

8. The light degradable rubber composite for shoes as claimed in claim 1, wherein the compatibilizer filler is 100 mesh red wood flour or red wood chips which is weakly alkaline in aqueous solution.

9. A method for preparing the light degradable rubber composite for shoes as claimed in any one of claims 1 to 8, which comprises the following steps:

s1: weighing the following materials in parts by weight: 80-100 parts of natural rubber 3L, 50-70 parts of nano silicon dioxide, 30-50 parts of plasticizer, 0.5-2 parts of stearic acid, 4-6 parts of zinc oxide, 5-8 parts of activating dispersant, 2-5 parts of anti-emetic emulsion, 1-3 parts of accelerator, 2-4 parts of vulcanizing agent, 10-40 parts of natural acid-base regulator and 10-40 parts of bulking filler;

s2: adding natural rubber, nano silicon dioxide, a plasticizer, stearic acid, zinc oxide, an activating dispersant and an anti-blooming agent into an internal mixer for mixing for 10-15min at the temperature of 110-;

s3: naturally cooling the mixed material, wherein the temperature of the cooled material is less than 60 ℃;

s4: and adding an accelerant, a vulcanizing agent, a natural acid-base regulator and a bulking filler into the cooled material in sequence, carrying out open milling for 8-10min at the temperature of 60-80 ℃, uniformly mixing, then taking out the mixture, and then carrying out vulcanization molding by a flat plate vulcanizing machine at the vulcanization temperature of 160 +/-5 ℃ for 90 +/-10 seconds to obtain the light degradable shoe rubber material.

Technical Field

The invention relates to the field of rubber composite materials, in particular to a light degradable rubber composite material for shoes and a preparation method thereof.

Background

The commercially available rubber sole materials generally use natural minerals such as calcium carbonate or kaolin as fillers, for example, application publication No. CN201711022164.4 uses metakaolin and fly ash as fillers. On one hand, the filler can reduce the volume cost and effectively enhance the wear resistance of the compound rubber; on the other hand, the filler is high in price, is not suitable for large-scale application, has high mineral substance proportion, and reduces the comprehensive performance of the shoe material. The natural fillers such as rosewood are used as the filling agent, so that the filler has wide sources and lighter specific gravity and can be suitable for soles of children shoes. The composite material formed by vulcanizing the traditional filler and the rubber material is difficult to degrade and occupies a large space after being discarded at will. Since the plant filler contains natural high molecular substances such as saccharides and lipids, which are gradually decomposed by the combined action of ultraviolet rays, oxygen and microorganisms, the use of the natural plant filler as a filler can alleviate this phenomenon. The traditional rubber composite material contains a large amount of toxic and harmful substances such as aromatic hydrocarbon and the like in the rubber auxiliary agent, can volatilize in a large amount at high temperature, has strong burnt odor, stimulates the respiratory tract of a human body (especially infants), and aldehyde compounds in rosewood and peanut shells are non-toxic and harmless to the human body, so that the harm to the respiratory tract is avoided.

The green manufacturing becomes a strong division of the rubber industry in China. Therefore, a certain amount of degradable natural plant materials are added into the traditional natural rubber, so that the specific gravity of the rubber composite material can be reduced on the premise of ensuring higher strength and wear resistance of the rubber composite material, the rubber composite material has good degradability, and the environmental pollution is greatly reduced.

Disclosure of Invention

The invention aims to provide a light degradable rubber composite material for shoes and a preparation method thereof. The natural filler provided by the invention is natural plant fibers such as the red wood powder and the red wood chips, the molecular weight of the rubber material can be reduced, so that the rubber material is easy to degrade, the agricultural wastes are recycled, and the enterprise cost is greatly reduced.

The invention provides a rubber material for soles, which is light in weight and degradable. The invention also provides a preparation method of the rubber material for the sole.

In order to achieve the purpose, the invention can be realized by the following technical scheme: a light degradable rubber composite material for shoes and a preparation method thereof are disclosed, the raw materials are as follows by weight: 80-100 parts of natural rubber 3L, 50-70 parts of nano silicon dioxide, 30-50 parts of plasticizer, 0.5-2 parts of stearic acid, 4-6 parts of zinc oxide, 5-8 parts of activating dispersant, 2-5 parts of anti-emetic emulsion, 1-3 parts of accelerator, 2-4 parts of vulcanizing agent, 10-40 parts of natural acid-base regulator and 10-40 parts of bulking filler.

The combination mode and the structural characteristics among the components are as follows: 1. the nano silicon dioxide accounts for 50 to 70 weight percent of the main glue 2, the plasticizer accounts for 30 to 50 weight percent of the main glue 3, the stearic acid accounts for 0 to 2 weight percent of the main glue 4, the zinc oxide accounts for 4 to 6 weight percent of the main glue 5, the activating and dispersing agent accounts for 10 to 15 weight percent of the nano silicon dioxide 6, the natural acid-base regulator and the bulking agent account for 30 to 40 weight percent of the main glue (the proportion of the natural acid-base regulator and the bulking agent can be any one of 1:1, 2.5:1.5, 1.5:2.5, 3:1 and 1: 3)

The invention also provides a preparation method of the light degradable rubber composite material for shoes, which comprises the following steps:

step 1: weighing the following components in parts by weight: 80-100 parts of natural rubber 3L, 50-70 parts of nano silicon dioxide, 30-50 parts of naphthenic oil 4006, 0.5-2 parts of stearic acid, 4-6 parts of zinc oxide, 5-8 parts of polyethylene glycol 4000, 2-5 parts of polyisobutylene, 1-3 parts of an accelerator, 2-4 parts of sulfur, 10-40 parts of 100-mesh peanut shell powder, 10-40 parts of 100-mesh rosewood powder or 10-40 parts of rosewood chips.

Step 2: and (2) adding the natural rubber, the nano silicon dioxide, the naphthenic oil 4006, the stearic acid, the zinc oxide, the polyethylene glycol 4000 and the polyisobutylene in the step 1 into an internal mixer for mixing for 10-15 minutes at the temperature of 110-.

And step 3: and (3) taking out the materials mixed in the step (2) and cooling, wherein the temperature of the cooled materials is less than 60 ℃.

And 4, step 4: and (3) carrying out open milling on the cooled material in the step (3), the accelerator, the vulcanizing agent, the natural acid-base regulator and the compatibilizer for 8-10 minutes at 60-80 ℃, uniformly mixing, then taking out the sheet, and then carrying out vulcanization molding by a flat plate vulcanizing machine at the vulcanization temperature of 160 +/-5 ℃ and the sulfur change time of 90 +/-10 seconds to obtain a 2 mm test piece.

In the whole mixing process, the optimal mixing temperature and time (60-80 ℃ and 8-10 minutes) of the vulcanizing agent and the accelerant in the step 4 are far lower than the optimal mixing temperature and time (110 ℃ and 140 ℃ and 10-15 minutes) of other materials in the step 2, so the material prepared in the step 1 is mixed in two steps.

Detailed Description

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. This application is capable of many other similar forms of embodiment than those described herein and it will thus be appreciated that those skilled in the art will be able to devise various arrangements which, although not explicitly described or shown herein, embody the principles of the application and are thus not limited to the specific embodiments disclosed below.

The rubber material for shoes comprises the following steps:

step 1: weighing the following components in parts by weight: 80-100 parts of natural rubber 3L, 50-70 parts of nano silicon dioxide, 30-50 parts of naphthenic oil 4006, 0.5-2 parts of stearic acid, 4-6 parts of zinc oxide, 5-8 parts of polyethylene glycol 4000, 2-5 parts of polyisobutylene, 1-3 parts of an accelerator, 2-4 parts of sulfur, 10-40 parts of 100-mesh peanut shell powder, 10-40 parts of 100-mesh rosewood powder or 10-40 parts of rosewood chips.

Step 2: and (2) adding the natural rubber, the nano silicon dioxide, the naphthenic oil 4006, the stearic acid, the zinc oxide, the polyethylene glycol 4000 and the polyisobutylene in the step 1 into an internal mixer for mixing for 10-15 minutes at the temperature of 110-.

And step 3: and (3) taking out the materials mixed in the step (2) and cooling, wherein the temperature of the cooled materials is less than 60 ℃.

And 4, step 4: and (3) carrying out open milling on the cooled material in the step (3), the accelerator, the vulcanizing agent, the natural acid-base regulator and the compatibilizer for 8-10 minutes at 60-80 ℃, uniformly mixing, then taking out the sheet, and then carrying out vulcanization molding by a flat plate vulcanizing machine at the vulcanization temperature of 160 +/-5 ℃ and the sulfur change time of 90 +/-10 seconds to obtain a 2 mm test piece.

In the whole mixing process, the optimal mixing temperature and time (60-80 ℃ and 8-10 minutes) of the vulcanizing agent and the accelerant in the step 4 are far lower than the optimal mixing temperature and time (110 ℃ and 140 ℃ and 10-15 minutes) of other materials in the step 2, so the material prepared in the step 1 is mixed in two steps.

The practical effects of the present invention will be further illustrated by the detailed examples.

Example 1

The material is prepared by the step 1: 100 parts of 3L of natural rubber, 38 parts of a mixture of a natural acid-base regulator and a compatibilizer filler (peanut shell powder: red wood powder in a mass ratio of 2.5: 1.5), 50 parts of nano silica, 30 parts of naphthenic oil 4006, 2 parts of stearic acid, 5 parts of zinc oxide, 5 parts of polyethylene glycol 4000, 2 parts of polyisobutylene, 2 parts of an accelerator and 2 parts of a vulcanizing agent.

And 2, mixing the materials except the vulcanizing agent, the accelerator, the natural acid-base regulator and the bulking filler prepared in the step 1 in an internal mixer for 10 minutes at 110 ℃.

And 3, taking the mixed materials out of the internal mixer, and naturally cooling to 50 ℃.

And 4, putting the cooled rubber compound, sulfur, an accelerator, a natural acid-base regulator and a bulking filler into an open mill for mixing for 8 minutes at the temperature of 60 ℃, uniformly mixing, discharging the mixture, and vulcanizing and molding the mixture by a flat vulcanizing machine at the vulcanization temperature of 160 ℃ for 95 seconds to obtain a 2 mm test piece.

Example 2

The material is prepared by the step 1: 100 parts of 3L of natural rubber, 38 parts of a mixture of a natural acid-base regulator and a compatibilizer filler (peanut shell powder: red wood powder in a mass ratio of 3: 1), 50 parts of nano silicon dioxide, 30 parts of naphthenic oil 4006, 2 parts of stearic acid, 5 parts of zinc oxide, 5 parts of polyethylene glycol 4000, 2 parts of polyisobutylene, 2 parts of an accelerator and 2 parts of a vulcanizing agent.

And 2, mixing the materials except the vulcanizing agent, the accelerating agent, the natural acid-base regulator and the compatibilizer prepared in the step 1 in an internal mixer for 10 minutes at 110 ℃.

And 3, taking the mixed materials out of the internal mixer, and naturally cooling to 50 ℃.

And 4, putting the cooled rubber compound, sulfur, an accelerator, a natural acid-base regulator and a bulking filler into an open mill for mixing for 8 minutes at the temperature of 60 ℃, uniformly mixing, discharging the mixture, and vulcanizing and molding the mixture by a flat vulcanizing machine at the vulcanization temperature of 160 ℃ for 96 seconds to obtain a 2 mm test piece.

Example 3

By the step 1, 100 parts of natural rubber 3L, 38 parts of a mixture of a natural acid-base regulator and a compatibilizer filler (peanut shell powder: red wood powder in a mass ratio of 1: 1), 50 parts of nano silica, 30 parts of naphthenic oil 4006, 2 parts of stearic acid, 5 parts of zinc oxide, 5 parts of polyethylene glycol 4000, 2 parts of polyisobutylene, 2 parts of an accelerant and 2 parts of a vulcanizing agent are prepared.

And 2, mixing the materials except the vulcanizing agent, the accelerator, the natural acid-base regulator and the bulking filler prepared in the step 1 in an internal mixer for 10 minutes at 110 ℃.

And 3, taking the mixed materials out of the internal mixer, and naturally cooling to 50 ℃.

And 4, putting the cooled rubber compound, sulfur, an accelerator, a natural acid-base regulator and a bulking filler into an open mill for mixing for 8 minutes at the temperature of 60 ℃, uniformly mixing, discharging the mixture, and vulcanizing and molding the mixture by a flat vulcanizing machine at the vulcanization temperature of 160 ℃ for 93 seconds to obtain a 2 mm test piece.

Comparative example 1

This comparative example is identical in materials and procedure except that 38 parts of the natural pH adjusting agent and the compatibilizer mixture of example 2 was changed to 38 parts of the compatibilizer (100 mesh red wood flour).

Comparative example 2

This comparative example is identical in materials and procedure except that 38 parts of the natural pH adjusting agent and compatibilizer mixture of example 2 was changed to light calcium carbonate.

Comparative example 3

This comparative example is identical in materials and procedure except that 38 parts of the natural pH adjusting agent and compatibilizer mixture of example 2 was changed to 38 parts of the natural pH adjusting agent (100 mesh peanut shell powder).

Comparative example 4

This comparative example is identical in materials and procedure except that 38 parts of the natural pH adjusting agent and compatibilizer mixture of example 2 was not added.

The performance of the composite rubber materials for shoes prepared in the examples 1, 2 and 3 was tested and compared with the performance of the comparative examples 1, 2, 3 and 4, and the results are shown in the following table 1.

As described above, the rubber composite for shoes described in the examples is slightly inferior in tensile strength and abrasion resistance to those of comparative examples 2 and 4, and mainly the plant powder particles are too large to be easily peeled off during the stretching. In addition, the acid and alkali are not adjusted in the comparative example 1 and the comparative example 3, only a single plant filler is added, so that the tensile strength is reduced compared with the examples. The specific gravity of the rubber is greatly reduced due to the fact that the plant filler replaces light calcium for compatibilization, and therefore compared with comparative example 2, the specific gravity of the embodiment is reduced. The plant powder filler is used for replacing light calcium and kaolin as a bulking filler to shorten the sulfur change time, and because the active ingredients such as fatty acid, tartaric acid and the like contained in the plant powder are equivalent to an activator of a vulcanization system and generate a synergistic effect with an accelerator, the reaction rate of rubber macromolecules and sulfur is improved, and the normal vulcanization time is shortened. The pectin and the lipid have better fluidity and generate a synergistic effect with the plasticizer. Thereby improving the industrial production efficiency and reducing the production cost. The addition of the plant filler greatly reduces the molecular weight of the composite material, so that the composite material is easily degraded by microorganisms in a natural state, and the environmental protection pressure is reduced. In the case of either a meta-acid or a meta-base, during the high temperature vulcanization process, the rubber macromolecules generate a large amount of free radicals, which cause the carbon chains to be broken by the attack thereof, and the tensile strength becomes low. In the traditional processing technology, acid and alkali are accurately regulated and controlled by dropwise adding an acid solution or an alkali solution, but a large amount of waste liquid is generated by the method, and the production cost is increased. The invention adopts plant fiber to adjust acid and alkali, and is environment-friendly and convenient. The aqueous solution of the peanut shell powder is weakly acidic and can neutralize alkaline oxide zinc oxide in the system, the aqueous solution of the rosewood is weakly alkaline and can neutralize an acidic compound stearic acid in the system, so that the whole formula system tends to be neutral, and the aqueous solution and the rosewood have the effect of slowly releasing and regulating acid and alkali. In the high-temperature vulcanization process, due to volatilization of chemical additives such as aromatic hydrocarbon, the composite material can generate pungent smell, and aldehyde compounds of the plant filler have unique fragrance of rosewood and peanut milk, so that aromatic hydrocarbon gas is diluted, discomfort is relieved, and the health of consumers is guaranteed.

The above description is only a preferred embodiment of the present invention and is not intended to be exclusive. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention.