阅读说明：本技术 环保浸胶液、制备方法及应用 (Environment-friendly gum dipping solution, preparation method and application ) 是由 王文才 张博 田明 张立群 宁南英 于 2020-12-29 设计创作，主要内容包括：本发明属于高分子材料加工领域,公开了一种环保浸胶液、制备方法及应用,该发明所提供的环保浸胶液是通过混合封闭型异氰酸酯、多元醇和橡胶胶乳等原料制备而成,用以完全替代间二苯酚和甲醛混合的RFL传统浸胶液,降低环境污染、提高生产安全性以及进一步增强有机纤维材料的机械性能。本发明适用于浸胶液的制备,尤其适用于环保浸胶液的制备,所得环保浸胶液作为二浴浸胶液,用于浸渍有机材料。(The invention belongs to the field of processing of high polymer materials, and discloses an environment-friendly dipping solution, a preparation method and application thereof. The invention is suitable for the preparation of the dipping solution, in particular to the preparation of the environment-friendly dipping solution, and the obtained environment-friendly dipping solution is used as a two-bath dipping solution for dipping organic materials.)

1. An environment-friendly dipping solution is characterized in that: the active ingredients of the medicine composition comprise the following raw materials in parts by weight: 100 parts of deionized water, 0.1-10 parts of polyhydric alcohol, 2-50 parts of a sealing agent, 1-20 parts of isocyanate, 0.1-1 part of a cross-linking agent and 50-130 parts of rubber latex.

2. The environment-friendly impregnation solution of claim 1, characterized in that: the polyalcohol is at least one of ethylene glycol, propylene glycol, butanediol, pentaerythritol, xylitol, sorbitol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol.

3. The environment-friendly dipping solution as set forth in claim 1 or 2, characterized in that: the blocking agent is at least one of phenol, caprolactam, methanol, ethyl mercaptan, acetylacetone, methyl ethyl ketoxime, malonic acid and sodium bisulfite.

4. The environment-friendly dipping solution as set forth in claim 1 or 2, characterized in that: the isocyanate is at least one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, p-xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and toluene diisocyanate.

5. The environment-friendly dipping solution as set forth in claim 1 or 2, characterized in that: the cross-linking agent is at least one of triethylamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, trimethylolpropane, pentaerythritol, glycerol, castor oil and diethylene glycol.

6. The environment-friendly dipping solution as set forth in claim 1 or 2, characterized in that: the rubber latex is at least one of vinylpyridine latex, styrene-butadiene latex, pyridine styrene-butadiene latex, carboxylic acrylonitrile-butadiene latex, chlorosulfonated polyethylene latex, chloroprene latex, acrylonitrile-butadiene latex and hydrogenated acrylonitrile-butadiene latex; the solid content of the rubber latex is 20-50%.

7. The environment-friendly dipping solution as set forth in claim 1 or 2, characterized in that: the solid content of the environment-friendly dipping solution is 10-30%.

8. A method for preparing the environment-friendly dipping solution as claimed in any one of claims 1 to 7, which is characterized in that: the environment-friendly gum dipping solution is obtained by fully and uniformly mixing all raw materials.

9. The method of claim 8, wherein: the temperature for uniformly mixing is 20-35 ℃.

10. An application of the environment-friendly dipping solution as defined in any one of claims 1 to 7, wherein: the prepared environment-friendly dipping solution is used as a two-bath dipping solution in a two-bath dipping method.

Technical Field

The invention belongs to the field of processing of high polymer materials, and relates to a gum dipping solution, in particular to an environment-friendly gum dipping solution, a preparation method and application.

Background

In the rubber industry, the most common treatment for adhesion between fibers of widely differing polarity and rigidity and a rubber matrix is the conventional dip treatment of resorcinol-formaldehyde-latex (RFL) on the fiber material. In the RFL dipping layer, functional groups on the RF resin can be combined with polar groups on the surface of the fiber, and simultaneously, a rubber latex component in the RF resin cross-linked network structure can be cross-linked with the rubber matrix through co-vulcanization, so that an adhesion transition layer is formed between the fiber and the rubber matrix; although RFL impregnation technology has been well established and has a low production cost, formaldehyde, which is a main raw material, was listed as one of leukemia-causing chemicals by the international cancer research center in 2009, and a large amount of toxic and harmful gas is also emitted during the production of RFL. Therefore, nowadays, more and more attention is paid to environmental protection and safe production, a novel environment-friendly dipping treatment technology for fiber is developed, and a resorcinol-formaldehyde-latex (RFL) dipping technology which is widely used in industry and is toxic and harmful is urgently replaced.

Disclosure of Invention

In order to solve the defects in the prior art, the invention aims to provide the environment-friendly dipping solution, the preparation method and the application thereof so as to achieve the aims of replacing a toxic and harmful RFL dipping technology, improving the production safety and reducing the environmental pollution.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

an environment-friendly dipping solution comprises the following raw materials of effective components in parts by weight: 100 parts of deionized water, 0.1-10 parts of polyol, 2-50 parts of sealant, 1-20 parts of isocyanate, 0.1-1 part of cross-linking agent and 50-130 parts of rubber latex;

the polyhydric alcohol is at least one of ethylene glycol, propylene glycol, butanediol, pentaerythritol, xylitol, sorbitol, polyethylene glycol, polypropylene glycol and polybutylene glycol;

as another limitation of the present invention, the blocking agent is at least one of phenol, caprolactam, methanol, ethyl mercaptan, acetylacetone, methyl ethyl ketone oxime, malonic acid, and sodium bisulfite;

as a third limitation of the present invention, the isocyanate is at least one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, p-xylylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and toluene diisocyanate;

as a fourth limitation of the present invention, the cross-linking agent is at least one of triethylamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, trimethylolpropane, pentaerythritol, glycerol, castor oil, and diethylene glycol;

as a fifth limitation of the present invention, the rubber latex is at least one of vinylpyridine latex, styrene-butadiene latex, pyridine styrene-butadiene latex, carboxylated nitrile-butadiene latex, chlorosulfonated polyethylene latex, polychloroprene latex, nitrile latex, and hydrogenated nitrile-butadiene latex; the solid content of the rubber latex is 20-50%;

as a sixth limitation of the invention, the solid content of the environment-friendly dipping solution is 10-30%;

the invention also provides a preparation method of the environment-friendly dipping solution, which is to fully mix all the raw materials to obtain the environment-friendly dipping solution;

as a seventh limitation of the present invention, the mixing temperature is 20 to 35 ℃;

the invention also provides an application of the environment-friendly dipping solution, and the prepared environment-friendly dipping solution is used for dipping the organic fiber material by using the two-bath dipping solution of the two-bath dipping method;

the organic fiber material can be various organic fiber materials such as cotton fiber, rayon, nylon 66 fiber, polyester PET fiber, polyester PEN fiber, aramid fiber or ultra-high molecular weight polyethylene fiber, and the like, the aramid fiber and the nylon are selected for explaining the using effect of the environment-friendly dipping solution provided by the invention, and the application of the environment-friendly dipping solution is not limited by using the environment-friendly dipping solution as a limiting condition.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the following beneficial effects:

(1) in the environment-friendly dipping solution provided by the invention, the added isocyanate group can react with the isocyanate group and the amide group, amino group or carboxyl group on the surface of the fiber to graft the isocyanate on the surface of the fiber, and the hydroxyl group in the polyol and the amino group in the isocyanate can form a hydrogen bond with the latex, so that the intermolecular force is improved, and the mechanical property of the organic fiber is enhanced; the cross-linked network structure is formed by mixing the polyalcohol, the blocking agent, the isocyanate and the cross-linking agent, and rubber latex particles in the network structure can participate in the co-vulcanization of a rubber matrix, so that the adhesive property between the impregnated fiber material and the rubber is improved;

(2) the environment-friendly dipping solution provided by the invention realizes the use without resorcinol and formaldehyde, not only greatly reduces the harm to the environment and human body, but also has simple preparation and fiber dipping processes, short reaction time and is beneficial to industrial production;

(3) the environmental-friendly dipping solution provided by the invention has the advantages that the viscosity of a dipping solution system is not greatly increased at room temperature, the long-term storage in the dipping production process of fiber materials is facilitated, and the cost of industrial production is saved.

In conclusion, the environment-friendly dipping solution, the preparation method and the application thereof provided by the invention realize zero use of resorcinol and formaldehyde, greatly reduce harm to the environment and human bodies, and have simple preparation and fiber dipping processes, shortened process time, long-term storage and saved production cost.

The invention is suitable for the preparation of the dipping solution, in particular to the preparation of the environment-friendly dipping solution, and the prepared dipping solution is suitable for the dipping of organic fiber materials.

Detailed Description

The invention will be further described with reference to preferred embodiments thereof. It should be understood that the description of the preferred embodiment is only for purposes of illustration and understanding, and is not intended to limit the invention.

Example 1 preparation method of environmental protection impregnation solution A1

The embodiment provides a preparation method of an environment-friendly dipping solution A1, which comprises the steps of weighing 2kg of phenol and 1kg of isophorone diisocyanate respectively to carry out a crosslinking reaction to obtain 3kg of phenol-blocked isophorone diisocyanate, adding the phenol-blocked isophorone diisocyanate, 2kg of ethylene glycol and 0.1kg of triethylamine into 30kg of deionized water, mixing and stirring for 1.5h at 20 ℃, adding 90kg of butadiene-styrene-pyridine latex with a solid content of 40% at the temperature, and continuously stirring for 2h to obtain the environment-friendly dipping solution A1 with the solid content of 25.6%.

Examples 2-9 preparation methods of environmentally friendly dipping solutions A2-A9

Examples 2 to 9 provide a method for preparing the environmental-friendly dip solutions a2 to a9 in a one-to-one correspondence manner, the preparation method is basically the same as that of example 1, and the differences are only in the used raw materials, the used amounts and some process parameters, and specific data are shown in table 1.

Table 1: data table of preparation methods of environment-friendly dipping solutions A2-A9

The other steps were the same as in example 1.

Example 10 application of Environment-friendly dipping solution and comparison of dipping effect

In this example, the dipping effects of the environment-friendly dipping solutions A1-A9 obtained in examples 1-9 and the conventional RFL dipping solution are compared by application.

Respectively cutting 10 aramid fibers (1670 dtex/2, 300T/m of initial twist) with length of 20m and 10 aramid/nylon blended fibers (1670 dtex/2, Chin Shao mountain horse cord fabric development Co., Ltd.) with length of 20m⁺The nylon 2100dtex has the initial and secondary twist degree of 280T/m);

selecting 9 sections from 10 sections of aramid fiber, and adopting a two-bath dipping method (dipping solutions used in one bath are respectively 92.4kg of deionized water, 3.2kg of closed isocyanate and 1.3kg of epoxy resin, the dipping solutions used in the two baths are respectively environment-friendly dipping solutions A1-A9 provided in embodiments 1-9), and treating the remaining section of aramid fiber by using a traditional RFL dipping solution to obtain test materials S1-S9 and a comparison material C1;

and respectively treating 10 sections of aramid/nylon blended fibers according to the method to obtain test materials T1-T9 and a comparison material C2.

The 20-stage sample materials are subjected to H extraction test according to the method in the national standard GB/T2942-2009. The rubber formula used for preparing the H pull test sample is 90kg of natural rubber (smoked sheet rubber), 10kg of styrene butadiene rubber (SBR 1500) carbon black N33035 kg, 8kg of indirect zinc oxide (first grade), 2.5kg of sulfur, 1.2kg of vulcanization accelerator DM (superior product), 2kg of stearic acid (200 type, first grade), 0.03kg of vulcanization accelerator TMTD (superior product), 0.8kg of adhesive A and 0.96kg of adhesive RS; the vulcanization temperature for preparing the H extraction sample is 150 ℃, the pressure is 5MPa, the time is 20min, and the H extraction force data of each sample material is shown in Table 2.

Table 2: h pull-out force test data parameter table

Group of	H extraction force (N)	Group of	H extraction force (N)
				Test Material S1	178	Test Material T1	236
Test Material S2	192	Test Material T2	220
				Test Material S3	183	Test Material T3	214
Test Material S4	181	Test Material T4	206
				Test Material S5	185	Test Material T5	212
Test Material S6	180	Test Material T6	204
				Test Material S7	190	Test Material T7	210
Test Material S8	195	Test Material T8	226
				Test Material S9	176	Test Material T9	230
Comparative material C1	175	Comparative material C2	200

The test data in table 2 show that, after the aramid fiber or the aramid fiber/nylon mixed fiber is subjected to the dipping treatment by the environment-friendly dipping solution a 1-a 9 provided by the invention, the H extraction force is stronger than that of the aramid fiber and the aramid fiber/nylon mixed fiber dipped and treated by the traditional RFL dipping solution, which is enough to indicate that the environment-friendly dipping solution provided by the invention can replace the traditional RFL dipping solution containing harmful substances such as m-diphenol, formaldehyde and the like.

Example 11 standing viscosity test of Environment-friendly dipping solutions A1-A9

Preparing environment-friendly impregnation liquids A1-A9 and the traditional RFL impregnation liquid according to the process parameters in the embodiments 1-9, measuring the initial viscosity of each environment-friendly impregnation liquid after the preparation is finished, then placing the environment-friendly impregnation liquids in a dry and cool place, standing for 28 days, and measuring and recording the viscosity data of each environment-friendly impregnation liquid every 7 days, which is shown in Table 3.

Table 3: placing viscosity data table of environment-friendly dipping solution A1-A9 (viscosity unit: cP)

As can be seen from Table 3, the environmental-friendly dipping solutions A1-A9 provided by the invention have slow system viscosity change after being placed for a long time compared with the traditional RFL dipping solution, which can show that the environmental-friendly dipping solutions A1-A9 provided by the invention can be stored for a long time, and the production cost is saved.

Although the present invention has been described in detail with reference to the above embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.