阅读说明：本技术 一种单组份橡胶处理剂及其制备方法 (Single-component rubber treating agent and preparation method thereof ) 是由 郑李华 梁建桁 梁建锋 于 2019-09-18 设计创作，主要内容包括：本发明公开了一种单组份橡胶处理剂,其以重量份计的原料包括：SBR橡胶13-15份、碳酸二甲酯28-36份、丁酮8-16份、醋酸乙酯18-22份、改性EVM橡胶2.3-4.7份、甲基环己烷8-16份、HEMA 0.5-1.5份、MMA 9-10份、氯化聚烯烃1-2份、BPO 0.3-1.0份和防结皮剂1-3份。相应的,本发明还公开了上述单组份橡胶处理剂的制备方法。本发明的单组份橡胶处理剂专用于非极性橡胶材料的表面预处理,能有效改善橡胶材质的表面极性,大大提高其表面附着力,在使用本处理剂预处理的橡胶上喷漆、丝网印刷有良好效果,无吸水泛白现象。(The invention discloses a single-component rubber treating agent which comprises the following raw materials in parts by weight: 13-15 parts of SBR rubber, 28-36 parts of dimethyl carbonate, 8-16 parts of butanone, 18-22 parts of ethyl acetate, 2.3-4.7 parts of modified EVM rubber, 8-16 parts of methylcyclohexane, 0.5-1.5 parts of HEMA, 9-10 parts of MMA, 1-2 parts of chlorinated polyolefin, 0.3-1.0 part of BPO and 1-3 parts of anti-skinning agent. Correspondingly, the invention also discloses a preparation method of the single-component rubber treating agent. The single-component rubber treating agent is specially used for surface pretreatment of nonpolar rubber materials, can effectively improve the surface polarity of the rubber materials, greatly improves the surface adhesive force of the rubber materials, has good effects on paint spraying and screen printing of the rubber pretreated by the treating agent, and has no phenomenon of water absorption and whitening.)

1. The single-component rubber treating agent is characterized by comprising the following raw materials in parts by weight: 13-15 parts of SBR rubber, 28-36 parts of dimethyl carbonate, 8-16 parts of butanone, 18-22 parts of ethyl acetate, 2.3-4.7 parts of modified EVM rubber, 8-16 parts of methylcyclohexane, 0.5-1.5 parts of HEMA, 9-10 parts of MMA, 1-2 parts of chlorinated polyolefin, 0.3-1.0 part of BPO and 1-3 parts of anti-skinning agent.

2. The one-component rubber treatment agent according to claim 1, wherein the SBR rubber is selected from one or more of Keteng 1105, Yuetization 792 and the like; the analogs are thermoplastic elastomers with styrene and butadiene contents, and polymer molecular structures similar to kraton 1105 or yuenation 792.

3. The single-component rubber treatment agent according to claim 1, wherein the modified EVM rubber is an ethylene-vinyl acetate copolymer rubber modified by organic silicon, and the mass ratio of ethylene to vinyl acetate of the modified EVM rubber is 6: (3-5).

4. The single-component rubber treatment agent according to claim 1, wherein the mass ratio of the modified EVM rubber to the chlorinated polyolefin in the raw material formula of the single-component rubber treatment agent is 7 (2-4).

5. The one-component rubber treatment agent according to claim 1, wherein the chlorinated polyolefin is one or two selected from chlorinated polypropylene and chlorinated polyethylene; the anti-skinning agent is selected from one or more of mercapto compounds and oxime compounds.

6. The one-component rubber treatment agent according to claim 1, wherein the one-component rubber treatment agent is used for pre-treatment of rubber before printing ink.

7. The method for preparing the single-component rubber treating agent of claims 1 to 6, characterized by comprising the steps of:

(1) adding dimethyl carbonate, methylcyclohexane, SBR rubber and ethyl acetate with the formula amount of 10-15% into a reaction kettle according to the formula amount, heating to 80-90 ℃, and stirring for 0.5-1.5 hours;

(2) adjusting the temperature in the reaction kettle to 70-80 ℃, adding MMA according to the formula amount, and reacting for 20-40 minutes;

(3) adjusting the temperature in the reaction kettle to 80-90 ℃, adding BPO with the formula amount of 50%, and stirring for reaction for 1-1.5 hours;

(4) adding HEMA and BPO with the formula amount of 50% to continue the reaction, and closing the heater when the materials are in a conglobation state;

(5) and transferring the materials in the reaction kettle into a high-speed dispersing machine while the materials are hot, sequentially adding chlorinated polyolefin, modified EVM rubber, an anti-skinning agent, ethyl acetate and butanone according to the formula amount, performing high-speed dispersion, and filtering and packaging to obtain a finished product, wherein the addition amount of the ethyl acetate is the formula residual amount.

8. The production method according to claim 7, wherein in the step (1), the rotation speed of the stirring is 80 to 120 rpm; in the step (3), the stirring speed is 40-80 rpm.

9. The method as claimed in claim 7, wherein in the step (4), the reaction is carried out for 1.5 to 2.5 hours, and the heater is turned off when the materials are agglomerated and the measured viscosity is in the range of 13 to 18 ten thousand CPS/25 ℃.

10. The method as claimed in claim 7, wherein the rotation speed of the high speed dispersion in step (5) is 800-1000 rpm for 0.5-1.5 hours.

Technical Field

The invention relates to the technical field of surface treating agents, in particular to a single-component rubber treating agent and a preparation method thereof.

Background

The two-component A + B rubber treating agent in the market at present contains a strong chlorine compound, and the B powder dissolved in the polar A component solvent releases active chlorine to change the material from low polarity to high polarity, so that strong adhesive force is generated, but the later stage is easy to yellow, and the addition amount of the B powder cannot exceed 1% for the material with high yellow resistance, so that the pretreatment effect on the light-colored rubber material is influenced. The single-component rubber treating agent in the market has good treatment effect on the rubber bottom sheet and few products with strong ink adsorption capacity.

Disclosure of Invention

The invention aims to provide a single-component rubber treating agent and a preparation method thereof, wherein the single-component rubber treating agent can improve the adhesive force of ink and has no phenomenon of water absorption and whitening.

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

a single-component rubber treating agent comprises the following raw materials in parts by weight: 13-15 parts of SBR rubber, 28-36 parts of dimethyl carbonate, 8-16 parts of butanone, 18-22 parts of ethyl acetate, 2.3-4.7 parts of modified EVM rubber, 8-16 parts of methylcyclohexane, 0.5-1.5 parts of HEMA, 9-10 parts of MMA, 1-2 parts of chlorinated polyolefin, 0.3-1.0 part of BPO and 1-3 parts of anti-skinning agent.

Further, the SBR rubber is selected from one or more of kraton 1105, yuanization 792 and the like; the analogs are thermoplastic elastomers with styrene and butadiene contents, and polymer molecular structures similar to kraton 1105 or yuenation 792.

Further, the modified EVM rubber is an ethylene-vinyl acetate copolymer rubber modified by organic silicon, and the mass ratio of ethylene to vinyl acetate of the modified EVM rubber is 6: (3-5).

Furthermore, in the raw material formula of the single-component rubber treating agent, the mass ratio of the modified EVM rubber to the chlorinated polyolefin is 7 (2-4).

Further, the chlorinated polyolefin is selected from one or two of chlorinated polypropylene and chlorinated polyethylene; the anti-skinning agent is selected from one or more of mercapto compounds and oxime compounds.

Further, the single-component rubber treating agent is used for the pretreatment of printing ink of rubber.

The preparation method of the single-component rubber treating agent comprises the following steps:

(1) adding dimethyl carbonate, methylcyclohexane, SBR rubber and ethyl acetate with the formula amount of 10-15% into a reaction kettle according to the formula amount, heating to 80-90 ℃, and stirring for 0.5-1.5 hours;

(2) adjusting the temperature in the reaction kettle to 70-80 ℃, adding MMA according to the formula amount, and reacting for 20-40 minutes;

(3) adjusting the temperature in the reaction kettle to 80-90 ℃, adding BPO with the formula amount of 50%, and stirring for reaction for 1-1.5 hours;

(4) adding HEMA and BPO with the formula amount of 50% to continue the reaction, and closing the heater when the materials are in a conglobation state;

(5) and transferring the materials in the reaction kettle into a high-speed dispersing machine while the materials are hot, sequentially adding chlorinated polyolefin, modified EVM rubber, an anti-skinning agent, ethyl acetate and butanone according to the formula amount, performing high-speed dispersion and tail-end reaction, filtering and packaging to obtain a finished product, wherein the addition amount of the ethyl acetate is the formula residual amount.

Further, in the step (1), the stirring speed is 80-120 r/min; in the step (3), the stirring speed is 40-80 rpm.

Further, in the step (4), the reaction is carried out for 1.5 to 2.5 hours, when the materials are agglomerated and the viscosity is measured to be 13 to 18 ten thousand CPS/25 ℃, the heater is closed.

Further, in the step (5), the rotation speed of the high-speed dispersion is 800-.

The invention has the beneficial effects that:

the single-component rubber treating agent is specially used for surface pretreatment of nonpolar rubber materials, can effectively improve the surface polarity of the rubber materials, greatly improves the surface adhesive force of the rubber materials, has good effects on paint spraying and screen printing of the rubber pretreated by the treating agent, and has no phenomenon of water absorption and whitening.

In the preparation method, ethyl acetate is used as a solvent to obtain SBR dissolved solution with a certain concentration in the first half of reaction, and the SBR dissolved solution and BPO are matched to achieve the optimal reaction rate; the ethyl acetate can be matched with butanone by adding the ethyl acetate in the later section of the reaction, the solubility parameter of the reaction liquid is adjusted, and the viscosity of the product is adjusted, so that the brushing performance of the rubber treating agent is better. The addition of excessive butanone can make the rubber treating agent easily absorb water and whiten, so that the use of ethyl acetate and butanone can control and reduce the consumption of ketone solvent.

In the preparation process, MMA is added into a reaction liquid of dimethyl carbonate, methylcyclohexane, SBR rubber and ethyl acetate at a stable temperature for reaction, HEMA and BPO with the formula amount of 50% are added for reaction, and a grafting product with a better ternary grafting structure can be obtained by limiting the adding sequence of MMA and HEMA, so that the rubber surface dyne value can be effectively improved, the treated rubber surface dyne value can be closer to ink, and the ink has better adhesive force. The BPO is added twice to control the reaction speed and the chain segment structure, and the rubber treating agent can further improve the surface tension of the rubber.

Detailed Description

The technical solution of the present invention will be further described with reference to the accompanying embodiments.

The invention provides a single-component rubber treating agent which comprises the following raw materials in parts by weight: 13-15 parts of SBR rubber, 28-36 parts of dimethyl carbonate, 8-16 parts of butanone, 18-22 parts of ethyl acetate, 2.3-4.7 parts of modified EVM rubber, 8-16 parts of methylcyclohexane, 0.5-1.5 parts of HEMA, 9-10 parts of MMA, 1-2 parts of chlorinated polyolefin, 0.3-1.0 part of BPO and 1-3 parts of anti-skinning agent.

MMA, HEMA and SBR rubber form a ternary grafting system. SBR rubber, namely styrene butadiene rubber and modified EVM rubber are graftable raw materials, the modified EVM rubber can be cross-linked and wound with the SBR graft copolymer, oil substances such as softening agents, plasticizers and the like which are emitted from the rubber can be adsorbed and locked, and the dyne value of the surface of the treated rubber material is improved. HEMA (hydroxyethyl methacrylate) is crosslinked with SBR rubber and modified EVM rubber, and can improve the adhesive force of rubber materials to printing ink or adhesives. MMA, i.e., methyl methacrylate, is the grafting monomer. BPO, benzoyl peroxide, is the initiator. The butanone is used for adjusting the viscosity, so that the rubber treating agent can be conveniently and uniformly coated on the surface of the rubber. The introduction of the chlorinated polyolefin enables the rubber treating agent to moderately halogenate the surface of the rubber material and improve the surface polarity of the rubber material. The adhesion force between the ink and the rubber material is obviously reduced after the surface of the ink is skinned, and the anti-skinning agent can further delay the surface skinning speed of the ink on the contact surface and can also inhibit the phenomenon of water absorption and whitening.

The surface dyne value of rubber materials is generally in the interval 22-26, while the surface tension of inks is generally in the interval 38-42. The surface tension of the rubber material is not less than that of the ink by a surface treatment technology, so that the ink can be firmly attached to the surface of the rubber material after the rubber material is effectively wetted. The single-component rubber treating agent is specially used for surface pretreatment of nonpolar rubber materials, can effectively improve the surface polarity of the rubber materials, greatly improves the surface adhesive force of the rubber materials, has good effects on paint spraying and screen printing of the rubber pretreated by the treating agent, and has no phenomenon of water absorption and whitening.

Further, the SBR rubber is selected from one or more of kraton 1105, yuanization 792 and the like; the analogs are thermoplastic elastomers with styrene and butadiene contents, and polymer molecular structures similar to kraton 1105 or yuenation 792.

Kraton 1105 is a product sold under the mark 1105 by kraton corporation in the united states; the product is named 792 from Yueyanization 792, chemical industries, south of lake, Inc. The two products have proper contents of styrene and butadiene, and have good comprehensive performance and good chemical stability. After grafting modification by MMA and HEMA, chlorinated polyolefin, modified EVM, anti-skinning agent and the like are introduced and applied to the surface of the rubber material, so that the treated rubber material has better bondability and stability and can inhibit later yellowing.

Further, the modified EVM rubber is an ethylene-vinyl acetate copolymer rubber modified by organic silicon, and the mass ratio of ethylene to vinyl acetate of the modified EVM rubber is 6: (3-5). The modified EVM rubber is a solid rubber-like elastomer, and can be better cross-linked and wound with the SBR graft copolymer by virtue of the reaction residual temperature by limiting the mass ratio of ethylene to vinyl acetate, so that the modified EVM rubber has better adsorption effect on 'oil' substances such as softeners, plasticizers and the like in the SBR rubber.

Furthermore, in the raw material formula of the single-component rubber treating agent, the mass ratio of the modified EVM rubber to the chlorinated polyolefin is 7 (2-4). The rubber treating agent with the proportion is not easy to delaminate in the storage process, the stability is higher, and the chlorination end is surrounded to a certain extent, so that yellowing can be inhibited.

Further, the chlorinated polyolefin is selected from one or two of chlorinated polypropylene and chlorinated polyethylene; the anti-skinning agent is selected from one or more of mercapto compounds and oxime compounds. The antiskinning agent can be a new Hunan-K material product with the brand number of H-3544, and can also be ethanol-ethylene glycol monobutyl ether solution (the water content is less than or equal to 800ppm) containing 10% of butyraldehyde oxime by weight, and the control of the water content can inhibit the water absorption whitening of the rubber treating agent.

Further, the single-component rubber treating agent is used for the pretreatment of printing ink of rubber.

The preparation method of the single-component rubber treating agent comprises the following steps:

(1) adding dimethyl carbonate, methylcyclohexane, SBR rubber and ethyl acetate with the formula amount of 10-15% into a reaction kettle according to the formula amount, heating to 80-90 ℃, and stirring for 0.5-1.5 hours;

(2) adjusting the temperature in the reaction kettle to 70-80 ℃, adding MMA according to the formula amount, and reacting for 20-40 minutes;

(3) adjusting the temperature in the reaction kettle to 80-90 ℃, adding BPO with the formula amount of 50%, and stirring for reaction for 1-1.5 hours;

(4) adding HEMA and BPO with the formula amount of 50% to continue the reaction, and closing the heater when the materials are in a conglobation state;

(5) and transferring the materials in the reaction kettle into a high-speed dispersing machine while the materials are hot, sequentially adding chlorinated polyolefin, modified EVM rubber, an anti-skinning agent, ethyl acetate and butanone according to the formula amount, performing high-speed dispersion and tail-end reaction, filtering and packaging to obtain a finished product, wherein the addition amount of the ethyl acetate is the formula residual amount.

In the method, in the first half of the reaction, ethyl acetate is used as a solvent to obtain SBR dissolved solution with a certain concentration, and the SBR dissolved solution with the concentration and BPO are matched to achieve the optimal reaction rate; the ethyl acetate can be matched with butanone by adding the ethyl acetate in the later section of the reaction, the solubility parameter of the reaction liquid is adjusted, and the viscosity of the product is adjusted, so that the brushing performance of the rubber treating agent is better. The addition of excessive butanone can make the rubber treating agent easily absorb water and whiten, so that the use of ethyl acetate and butanone can control and reduce the consumption of ketone solvent.

In the preparation process, MMA is added into a reaction solution of dimethyl carbonate, methylcyclohexane, SBR rubber and ethyl acetate at a stable temperature for reaction, HEMA and BPO with the formula amount of 50% are added for reaction, and a better graft product with a ternary graft structure can be obtained by limiting the adding sequence of MMA and HEMA, so that the rubber surface dyne value can be effectively improved, the treated rubber surface dyne value can be closer to that of ink, and the ink has better adhesive force. The BPO is added twice to control the reaction speed and the chain segment structure, and the rubber treating agent can further improve the surface tension of the rubber.

In the step (5), the material dissolution is accelerated by utilizing the reaction waste heat, the efficiency is improved, the chlorinated polyolefin and the modified EVM rubber are added at the end of the preparation process, and the chlorinated polyolefin and the modified EVM rubber are mixed with the ternary grafting system and participate in the tail-end reaction, so that the better compounding stability is achieved.

Further, in the step (1), the stirring speed is 80-120 r/min; in the step (3), the stirring speed is 40-80 rpm. The reaction in the reaction liquid can be fully and stably realized by limiting the stirring speed, and a high-performance product can be obtained.

Further, in the step (4), the reaction is carried out for 1.5 to 2.5 hours, when the materials are agglomerated and the viscosity is measured to be 13 to 18 ten thousand CPS/25 ℃, the heater is closed. The reaction process is limited by the reaction time and the viscosity, and the reaction is more conveniently controlled.

Further, in the step (5), the rotation speed of the high-speed dispersion is 800-. The higher rotating speed can improve the uniform mixing speed, ensure the dispersion sufficiency by limiting the dispersion time and accelerate the completion of the tail-stage reaction at the residual temperature.

The invention is further illustrated by the following examples and comparative examples.