阅读说明：本技术 一种耐寒氯丁橡胶及其制备方法 (Cold-resistant chloroprene rubber and preparation method thereof ) 是由 张淑娟 齐中华 刘日� 赵海军 杨海燕 于 2019-11-04 设计创作，主要内容包括：本发明属于氯丁橡胶制备技术领域,为了解决硫磺调节型氯丁橡胶在在温度-30℃就会发生硬化,因此在东北等严寒地带或其它低温环境下,氯丁橡胶的使用受到了限制等问题,提供了一种耐寒氯丁橡胶胶料及其制备方法,由氯丁橡胶,硫化剂,加工助剂,增塑剂,补强剂,防老剂按一定比例制备而成。该胶料使用了单一的氯丁橡胶,解决了橡胶并用存在的差异性,从而影响橡胶特性的问题。同时通过按照不同比例不同种类添加增塑剂措施,降低了其在低温下的结晶性能,能够在低温-42℃的条件下依然保持橡胶弹性而不发生脆化,极大程度地改善了氯丁橡胶耐低温性能,扩大了氯丁橡胶使用地域与范围。(The invention belongs to the technical field of chloroprene rubber preparation, and provides a cold-resistant chloroprene rubber sizing material and a preparation method thereof, aiming at solving the problems that sulfur-regulated chloroprene rubber is hardened at the temperature of-30 ℃, so that the use of the chloroprene rubber is limited in severe cold regions such as northeast and the like or other low-temperature environments, and the like. The rubber material uses single chloroprene rubber, and solves the problem that the rubber characteristics are influenced due to the difference of the rubber combination. Meanwhile, the measures of adding plasticizers in different types according to different proportions reduce the crystallization performance at low temperature, can still keep the elasticity of the chloroprene rubber without embrittlement at the low temperature of 42 ℃ below zero, greatly improve the low-temperature resistance of the chloroprene rubber and enlarge the use region and range of the chloroprene rubber.)

1. The cold-resistant chloroprene rubber sizing material is characterized in that: the basic formula of the chloroprene rubber comprises the following components in parts by weight: 100 parts of chloroprene, 4-6 parts of regulator sulfur, 36 parts of rosin, 110 parts of soft water, 8 parts of sodium hydroxide and 4-6 parts of dispersant, polymerizing at 40 ℃, and adding the following terminating agents when the experimental polymerization degree is reached, wherein the formula of the terminating agent comprises the following components in parts by weight: 0.01-2 parts of organic solvent, 0.01-2 parts of emulsifier, 0.0001-0.1 part of polymerization inhibitor, 0.01-10 parts of vulcanizing agent, 0.01-2 parts of antioxidant and 0.1-40 parts of plasticizer;

wherein: the organic solvent is any one of toluene, acetone and xylene;

the emulsifier is at least one of OP-10, peregal, dodecyl sodium sulfonate, sodium dodecyl sulfate, naphthalene sulfonic acid formaldehyde condensation sodium salt mixed emulsifier or rosin soap solution;

the polymerization inhibitor is any one of phenothiazine, amine polymerization inhibitor, nitroxide free radical compound and derivative polymerization inhibitor thereof;

the vulcanizing agent is at least one of sulfur, alkali metal oxide, thiourea accelerator, thiuram accelerator, thiazole accelerator, guanidine accelerator and amine accelerator;

the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 264 or antioxidant 168 and liquid antioxidant;

the plasticizer is at least one of phthalate, fatty dibasic acid ester, fatty acid ester, phosphate, polyester, epoxy and other synthetic plasticizers.

2. The cold-resistant neoprene compound of claim 1, wherein: the vulcanizing agent is at least one of alkali metal oxide magnesium oxide, zinc oxide, ethylene thiourea (NA-22), diethyl thiourea, tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide (TS), dibenzothiazyl Disulfide (DM) and di-o-tolylguanidine (DOTG).

3. The cold-resistant neoprene compound of claim 1, wherein: the plasticizer is as follows: dioctyl sebacate (DOS) among fatty dibasic acid esters, bis (butoxyethoxy) adipate (TP-95), dioctyl adipate, dibutyl phthalate (DBP) among phthalic acid esters, dioctyl phthalate; at least one of acetyl tri-n-butyl citrate in fatty acid esters, tri (butoxyethyl) phosphate in phosphate esters, polybutylene adipate in polyesters, epoxidized soybean oil in epoxies, and dibutyl methylene bisthioglycol ester (Plastikator88) in other synthetic plasticizers.

4. A method for preparing the cold-resistant chloroprene rubber terminator as recited in any one of claims 1 to 3, characterized in that: the method comprises the following specific steps:

(1) dissolving an oil-soluble polymerization inhibitor, a vulcanizing machine, an antioxidant and a plasticizer in an organic solvent, and uniformly stirring by using a magnetic stirrer at normal temperature to prepare an oil phase; (2) adding a water-soluble emulsifier into soft water, and uniformly stirring by using a magnetic stirrer at normal temperature to prepare a water phase; (3) mixing the prepared water phase and the oil phase for emulsification to prepare stable emulsion for later use.

Technical Field

The invention belongs to the technical field of chloroprene rubber preparation, and particularly relates to a cold-resistant chloroprene rubber sizing material and a preparation method thereof.

Background

Chloroprene Rubber (CR), which has excellent physical and mechanical properties and is resistant to oil, weather, ozone, heat, fire, flexure, chemicals and air. But also widely applied to manufacturing various wires, cables, rubber plates, waterproof cloth, capsules, air cushions, conveyer belts, driving belts, sealing parts, tent cloth, air ducts, lifeboats, oil-proof rubber tubes, oil-proof rubber boots, damping products and the like.

However, chloroprene rubber is poor in cold resistance, and particularly, it is easily hardened and embrittled at low temperatures to lose its specific elasticity, thereby limiting the use value of chloroprene rubber at low temperatures. The prior chloroprene rubber product can be hardened at the temperature of-30 ℃, so that the use of the chloroprene rubber is limited in severe cold areas such as northeast and the like and other low-temperature environments.

The application number is 201310511433.9, the invention is named as 'a cold-resistant oil-resistant modified chloroprene rubber cable material', the performance of the traditional chloroprene rubber in the cable material is improved, the cable material is realized by using the synthetic rubber in common and adding more auxiliaries, the process is complex, and the cold-resistant performance of the chloroprene rubber is not improved to a great extent.

The invention is a modified chloroprene rubber and a preparation method thereof with the application number of 201710722861.4, and the invention is realized by using natural rubber and chloroprene rubber together, and simultaneously needs to add a vulcanizing agent in the process, thereby increasing the production cost in practical application.

In the document, the research on cold-resistant chloroprene rubber (Feng Junshuang, synthetic rubber industry, 1992,15 vol.3, 139-141), the cold-resistant rubber can be obtained by adding other components in the early polymerization process for copolymerization, and at present, domestic manufacturers do not have such commodities.

Disclosure of Invention

The invention provides a cold-resistant chloroprene rubber sizing material and a preparation method thereof, aiming at solving the problems that sulfur-regulated chloroprene rubber is hardened at the temperature of-30 ℃, so that the use of the chloroprene rubber is limited in severe cold regions such as northeast and the like or other low-temperature environments. Meanwhile, only single chloroprene rubber is adopted, the cold-resistant effect can be achieved by less auxiliaries, the process operation is simple, and the production cost can be effectively reduced.

The invention is realized by the following technical scheme: the cold-resistant chloroprene rubber compound takes traditional medium-crystallinity chloroprene rubber as a basic formula, and the chloroprene rubber basic formula comprises the following components in parts by weight: 100 parts of chloroprene, 4-6 parts of regulator sulfur, 36 parts of rosin, 110 parts of soft water, 8 parts of sodium hydroxide and 4-6 parts of dispersant, polymerizing at 40 ℃, and adding the following terminating agents when the experimental polymerization degree is reached, wherein the formula of the terminating agent comprises the following components in parts by weight: 0.01-2 parts of organic solvent, 0.01-2 parts of emulsifier, 0.0001-0.1 part of polymerization inhibitor, 0.01-10 parts of vulcanizing agent, 0.01-2 parts of antioxidant and 0.1-40 parts of plasticizer;

wherein: the organic solvent is any one of toluene, acetone and xylene;

the emulsifier is at least one of OP-10, peregal, dodecyl sodium sulfonate, sodium dodecyl sulfate, naphthalene sulfonic acid formaldehyde condensation sodium salt mixed emulsifier or rosin soap solution;

the polymerization inhibitor is any one of phenothiazine, amine polymerization inhibitor, nitroxide free radical compound and derivative polymerization inhibitor thereof;

the vulcanizing agent is at least one of sulfur, alkali metal oxide, thiourea accelerator, thiuram accelerator, thiazole accelerator, guanidine accelerator and amine accelerator;

the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 264 or antioxidant 168 and liquid antioxidant;

the plasticizer is at least one of phthalate, fatty dibasic acid ester, fatty acid ester, phosphate, polyester, epoxy and other synthetic plasticizers.

The vulcanizing agent is at least one of alkali metal oxide magnesium oxide, zinc oxide, ethylene thiourea (NA-22), diethyl thiourea, tetramethylthiuram disulfide (TMTD), tetramethylthiuram monosulfide (TS), dibenzothiazyl Disulfide (DM) and di-o-tolylguanidine (DOTG).

The plasticizer is as follows: dioctyl sebacate (DOS) among fatty dibasic acid esters, bis (butoxyethoxy) adipate (TP-95), dioctyl adipate, dibutyl phthalate (DBP) among phthalic acid esters, dioctyl phthalate; at least one of acetyl tri-n-butyl citrate in fatty acid esters, tri (butoxyethyl) phosphate in phosphate esters, polybutylene adipate in polyesters, epoxidized soybean oil in epoxies, and dibutyl methylene bisthioglycol ester (Plastikator88) in other synthetic plasticizers.

The method for preparing the cold-resistant chloroprene rubber sizing material comprises the following specific steps:

(1) dissolving an oil-soluble polymerization inhibitor, a vulcanizing machine, an antioxidant and a plasticizer in an organic solvent, and uniformly stirring by using a magnetic stirrer at normal temperature to prepare an oil phase; (2) adding a water-soluble emulsifier into soft water, and uniformly stirring by using a magnetic stirrer at normal temperature to prepare a water phase; (3) mixing the prepared water phase and the oil phase for emulsification to prepare stable emulsion for later use.

The cold-resistant rubber is developed through two modes, wherein the cold resistance of the chloroprene rubber is improved through formula improvement in the polymerization process, and the cold-resistant effect is realized through adding less auxiliaries or through the mutual matching of the auxiliaries in the chloroprene rubber processing process. The two methods have the characteristics respectively, and meanwhile, the process operation is simple, so that the production cost can be effectively reduced. The chloroprene rubber cold resistance is improved through a polymerization formula, the operation is simple, the realization is easy, the cold resistance is improved, and the process cost is not increased.

Detailed Description

The invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.