阅读说明：本技术 一种促进剂m改性烷基酚-甲醛树脂及其制备方法和应用 (Accelerator M modified alkylphenol-formaldehyde resin and preparation method and application thereof ) 是由 杜孟成 李庆朝 黄存影 王文博 宋彦哲 张朋龙 董瑞国 师利龙 于 2019-09-30 设计创作，主要内容包括：本发明公开一种促进剂M改性烷基酚-甲醛树脂及其制备方法和应用,该树脂由促进剂M和氯气的反应产物与烷基酚-甲醛树脂在碱性条件下反应而得。本发明以促进剂M作为改性剂,先通过一步反应生成易与树脂反应的中间体化合物Z,然后与烷基酚-甲醛树脂混合进行改性。本发明方法工艺简单、原子利用率高,所得改性树脂的粘合性能显著提高,性能明显优于传统增粘树脂,其增粘的持久性和湿热粘性性能显著提高。(The invention discloses an accelerant M modified alkylphenol-formaldehyde resin and a preparation method and application thereof. The invention takes an accelerant M as a modifier, firstly generates an intermediate compound Z which is easy to react with resin through one-step reaction, and then is mixed with alkylphenol-formaldehyde resin for modification. The method has simple process and high atom utilization rate, the adhesive property of the obtained modified resin is obviously improved, the performance of the modified resin is obviously superior to that of the traditional tackifying resin, and the tackifying durability and the hot and humid adhesive property of the modified resin are obviously improved.)

1. An accelerator M modified alkylphenol-formaldehyde resin is characterized in that: has a structural formula shown in the following formula I:

in the formula I, R is p-tert-octyl, p-tert-butyl, p-cyclohexyl, p-dodecyl or p-cumyl, and is preferably p-tert-butyl.

2. An accelerator M-modified alkylphenol-formaldehyde resin as claimed in claim 1, characterized in that: the number average molecular weight of the promoter M modified alkylphenol-formaldehyde resin is 2000-2500.

3. A process for preparing an accelerator M-modified alkylphenol-formaldehyde resin as claimed in claim 1, characterized by comprising: the compound Z reacts with alkylphenol-formaldehyde resin under alkaline condition to obtain the compound Z; the structural formulas of the compound Z and the alkylphenol-formaldehyde resin are as follows:

；

wherein R is one of p-tert-octyl, p-tert-butyl, p-cyclohexyl, p-dodecyl or p-cumyl, and is preferably p-tert-butyl.

4. The method of claim 3, wherein: the compound Z is obtained by reacting an accelerant M with chlorine under an alkaline condition; preferably, the molar ratio of promoter M to chlorine is 1: 1.

5. The method according to claim 3 or 4, wherein: reacting the compound Z with alkylphenol-formaldehyde resin in the presence of sodium hydroxide; the promoter M is reacted with chlorine in the presence of sodium hydroxide.

6. The method of claim 3, wherein: the method comprises the following steps:

(1) dissolving an accelerator M in an organic solvent, adjusting the pH value to 8-11 by using a sodium hydroxide solution, introducing chlorine gas for reaction, and treating a reaction solution to obtain a compound Z;

(2) carrying out condensation reaction on alkylphenol and formaldehyde under the action of a catalyst, adjusting the pH to 6.5-7 after reaction, adding an organic solvent to extract a product, distilling an obtained organic phase to remove the organic solvent and water, and then heating to carry out condensation polymerization reaction to obtain alkylphenol-formaldehyde resin;

(3) and (2) dissolving the alkylphenol-formaldehyde resin by using an organic solvent, adjusting the pH value to 7.5-8.5, then dripping the compound Z prepared in the step (1), carrying out reflux reaction after finishing dripping, and removing the organic solvent after reaction to obtain the promoter M modified alkylphenol-formaldehyde resin.

7. The method of claim 6, wherein: the molar ratio of the alkylphenol to the accelerator M is 1.0:0.09-0.3, preferably 1: 0.09-0.2; the molar ratio of alkylphenol to formaldehyde is 1: 0.6-1, preferably 1: 0.8-0.9.

8. The method of claim 6, wherein: in the step (2), the catalyst is acid, preferably p-toluenesulfonic acid or sulfuric acid; preferably, the amount of catalyst used is 0.5 to 1.0% by mass of alkylphenol.

9. The method of claim 6, wherein:

preferably, in the step (1), chlorine is introduced at the temperature of-5-20 ℃, and after the chlorine is introduced, the temperature is raised to 40-60 ℃ for reaction for 1-2 hours;

preferably, in the step (2), the alkylphenol is firstly mixed with the catalyst, then the temperature is raised to 80-100 ℃, the formaldehyde aqueous solution is dripped, and the reflux reaction is carried out for 1-3h to carry out the condensation reaction;

preferably, in the step (2), the polycondensation reaction is carried out at 170-180 ℃ for 0.5-1 h;

preferably, in the step (3), the alkylphenol-formaldehyde resin is dissolved in the organic solvent at 100-110 ℃, then the compound Z is dropped in, and the reflux reaction is carried out for 1-2h at the temperature.

10. Use of an accelerator M-modified alkylphenol-formaldehyde resin as claimed in claim 1 or 2 as a tackifying resin for rubber.

Technical Field

The invention relates to a modified alkylphenol-formaldehyde resin, in particular to a modified alkylphenol-formaldehyde resin which has strong tackifying persistence, high hot and humid viscosity performance and small influence on rubber material vulcanization performance, a preparation method thereof and application thereof as a tackifying resin for rubber, belonging to the technical field of alkyl phenolic tackifying resins.

Background

The radial ply tyre is commonly called as 'steel wire tyre', and is a new type tyre in which the tyre body cord lines are arranged according to the radial direction, and the cord lines are circumferentially arranged or nearly circumferentially arranged, and the buffer layer is tightly hooped on the tyre body. The adhesion strength of rubber to steel cords in tires greatly affects the quality of radial tires. Therefore, self-adhesion is important in the molding process and is therefore also referred to as molding tack. Furthermore, if there is a lack of adhesion between the compounds, particularly in the case of elastomeric compounds, creep of the semi-finished part deforms the dimensions, causing the part to detach from the adhesive. In the design of all-steel radial tire products, a plurality of parts such as tire bead parts, belt ply edges and the like use thin rubber sheets with better viscosity, and if the phenomenon of non-sticking occurs, air is trapped in a tire blank during molding, so that the quality of a finished product is influenced.

The natural rubber has good self-adhesion, so the process performance is good; synthetic rubbers, while having abrasion resistance, aging resistance and some special advantages, lack sufficient self-adhesiveness and present difficulties in the molding process, and one of the common solutions is to add tackifying resins to increase the tack. The tackifying resin should have the following four conditions: the compatibility with the rubber matrix is good; the adhesive has strong adhesiveness; the tackifying effect is durable and the change along with the time is small; the vulcanization speed and the physical properties of the vulcanized rubber are not reduced. The synthetic resin has better initial viscosity and durability, so the application of the synthetic resin is more and more extensive, wherein the alkyl phenolic resin has the most excellent tackifying effect and is one of the main rubber auxiliary agents for tire molding. However, when an alkylphenol resin is added, the vulcanization rate is reduced and the scorch time is shortened. Therefore, the invention discloses tackifying resin which has simple process, good performance, low cost and small influence on the processing performance of rubber materials, and becomes a research hotspot of rubber auxiliary agent related industries.

Disclosure of Invention

Aiming at the defects of the existing tackifying resin, the invention provides an accelerator M modified alkylphenol-formaldehyde resin which has a special structure, and the obtained resin has better tackifying performance and the influence of the resin on the vulcanization performance of rubber materials is weakened by improving the resin structure.

The invention also provides a preparation method of the promoter M modified alkylphenol-formaldehyde resin, and the method has the advantages of simple process, low cost and industrial popularization and application value.

The invention also provides the application of the promoter M modified alkylphenol-formaldehyde resin as tackifying resin for rubber, the tackifying resin has strong tackifying durability, high hot and humid adhesiveness, small influence on the vulcanization performance of rubber materials, and good application prospect.

The accelerator M (2-mercaptobenzothiazole) is a moderate-speed accelerator of natural rubber, has the efficacy of a plasticizer, can be used alone or in combination with other accelerators, and is suitable for tires, rubber shoes and industrial rubber products. It is not suitable for rubber products in food industry due to bitter taste. The structure is as follows. In the research process, the inventor unexpectedly finds that the performance of the phenolic resin can be well improved after the phenolic resin is modified by the accelerator M, and an unexpected effect is achieved. At present, no relevant report that the phenolic resin is modified by the accelerator M is found, and the invention belongs to the initiative.

The specific technical scheme of the invention is as follows:

an accelerator M-modified alkylphenol-formaldehyde resin (modified resin, the same applies below) having a structural formula shown in formula I below:

in the above formula I, R is p-tert-octyl, p-tert-butyl, p-cyclohexyl, p-dodecyl or p-cumyl, preferably p-tert-butyl.

Wherein, when R is p-tert-butyl, formula I is:

when R is p-tert-octyl, formula I is:

when R is p-cyclohexyl, formula I is:

when R is p-dodecyl, formula I is:

when R is p-cumyl, formula I is:

further, in the formula I, n is the number of the repeating units, and the number average molecular weight of the modified alkylphenol-formaldehyde resin is 2000-2500. When the molecular weight is within this range, the resulting modified resin is more excellent in tackiness and other properties, and is more suitable as a rubber tackifier resin.

The invention also provides a preparation method of the promoter M modified alkylphenol-formaldehyde resin, the modified resin is obtained by reacting a compound Z with alkylphenol-formaldehyde resin under alkaline conditions, and the structural formulas of the compound Z and the alkylphenol-formaldehyde resin are as follows:

further, in the above alkylphenol-formaldehyde resin, the R is one of p-tert-octyl, p-tert-butyl, p-cyclohexyl, p-dodecyl and p-cumyl, preferably p-tert-butyl. The molecular weight of the alkylphenol-formaldehyde resin is selected according to the molecular weight requirements of the final accelerator M modified alkylphenol-formaldehyde resin of formula i.

Further, the compound Z is obtained by reacting the promoter M with chlorine gas under alkaline conditions provided by a base, preferably sodium hydroxide.

Further, the molar ratio of the accelerator M to chlorine gas is 1: 1.

Further, compound Z is reacted with the alkylphenol-formaldehyde resin under basic conditions provided by a base, preferably sodium hydroxide.

Further, the alkylphenol-formaldehyde resin is prepared according to the preparation method of the phenolic resin reported in the prior art, namely, the alkylphenol-formaldehyde resin is prepared by condensation reaction of alkylphenol and formaldehyde and then polycondensation reaction, and a person skilled in the art can select a proper preparation process according to needs. Of course, suitable phenolic resins may also be purchased directly from the market.

Further, the molar ratio of the alkylphenol to the compound Z in the alkylphenol-formaldehyde resin is 1.0:0.09 to 0.3, preferably 1:0.09 to 0.2, wherein the molar amount of the alkylphenol-formaldehyde resin is based on the molar amount of the alkylphenol monomer.

Further, the invention provides a preparation method of a preferable promoter M modified alkylphenol-formaldehyde resin, and the process route is as follows:

further, the method specifically comprises the following steps:

(1) dissolving an accelerator M in an organic solvent, adjusting the pH value to 8-11 by using a sodium hydroxide solution, introducing chlorine gas for reaction, and treating a reaction solution to obtain a compound Z;

(2) carrying out condensation reaction on alkylphenol and formaldehyde under the action of a catalyst, adjusting the pH to 6.5-7 after reaction, adding an organic solvent to extract a product, distilling an obtained organic phase to remove the organic solvent and water, and then heating to carry out condensation polymerization reaction to obtain alkylphenol-formaldehyde resin;

(3) and (2) dissolving the alkylphenol-formaldehyde resin by using an organic solvent, adjusting the pH value to 7.5-8.5, then dripping the compound Z prepared in the step (1), carrying out reflux reaction after finishing dripping, and removing the organic solvent after reaction to obtain the promoter M modified alkylphenol-formaldehyde resin.

Further, in the step (1), the organic solvent is an alcohol, and the alcohol may be an alcohol commonly used as an organic solvent, such as methanol, ethanol, and the like.

Further, in the step (1), the sodium hydroxide solution is a dilute sodium hydroxide solution, and the concentration is preferably 2-5 wt%.

Further, in the step (1), the molar ratio of the promoter M to the chlorine gas is 1: 1. The introduction temperature of the chlorine is different from the reaction temperature, the chlorine is introduced at-5 to 20 ℃, and the temperature is raised to 40 to 60 ℃ after the introduction for reaction for 1 to 2 hours. Preferably, chlorine is introduced at the temperature of-5 to 12 ℃.

Further, in the step (1), after the reaction is finished, water is added into the reaction solution to adjust the polarity of the solvent, so that the product is crystallized and precipitated, and then the crystal is filtered and washed by water, so as to obtain the compound Z.

Further, in the step (2), the alkylphenol has a structural formula shown as the following, wherein R is one of p-tert-octyl, p-tert-butyl, p-cyclohexyl, p-dodecyl and p-cumyl, and is preferably p-tert-butyl. The alkyl phenol and formaldehyde are subjected to condensation reaction under the action of a catalyst, wherein the catalyst is acid, preferably p-toluenesulfonic acid or sulfuric acid. Preferably, the amount of catalyst used is 0.5 to 1.0% by mass of alkylphenol.

Further, in the step (2), formaldehyde is added in the form of an aqueous solution, preferably, the concentration of the aqueous formaldehyde solution is 37 to 40 wt%. During reaction, mixing alkylphenol and a catalyst, heating to 80-100 ℃, dripping formaldehyde aqueous solution, performing reflux reaction for 1-3h, and performing condensation reaction. After the condensation reaction, the temperature is raised to 170-180 ℃ for condensation polymerization reaction, and the reaction is generally 0.5-1.0 h.

Further, in the step (2), the molar ratio of the alkylphenol to the formaldehyde is 1: 0.6-1, preferably 1: 0.8-0.9.

Further, in the step (2), the organic solvent is an aromatic hydrocarbon solvent such as benzene, toluene or xylene.

Further, in the step (3), sodium hydroxide solution is added to adjust the pH to 7.5-8.5. The concentration of the sodium hydroxide solution is preferably 2 to 5% by weight.

Further, in the step (3), the compound Z and the alkylphenol-formaldehyde resin are added in such an amount that the molar ratio of the alkylphenol to the accelerator M is 1.0:0.09-0.3, preferably 1: 0.09-0.2.

Further, in the step (3), the alkylphenol-formaldehyde resin is dissolved by the organic solvent at the temperature of 100-110 ℃, then the compound Z is dropped, and the reflux reaction is carried out for 1-2h at the temperature, thus completing the modification. The organic solvent is aromatic solvent such as benzene, toluene or xylene.

Further, in the step (3), after the reflux reaction is finished, the organic solvent is removed by distillation to obtain the promoter M modified alkylphenol-formaldehyde resin. The modified resin is yellow to brown solid, has strong tackifying performance, has excellent tackifying durability and hot and humid tackifying performance, has little influence on the vulcanization performance of rubber materials, and can be used as tackifying resin for rubber.

The invention takes an accelerant M as a modifier, firstly generates an intermediate compound Z which is easy to react with resin through one-step reaction, and then is mixed with alkylphenol-formaldehyde resin for modification. The method has simple process and high atom utilization rate, and can obtain the alkyl phenolic resin with good performance. Compared with the prior art, the invention has the following advantages:

1. the rubber accelerator M is selected as a modifier, so that the compatibility of resin and rubber can be increased, and the influence of the resin on the vulcanization performance of rubber materials can be weakened.

2. The obtained modified resin has obviously improved adhesive property, obviously better property than the traditional tackifying resin, and obviously improved tackifying durability and hot and humid adhesive property.

3. The benzotriazole and mercapto structure in the accelerator M can effectively prevent metal such as copper from corroding, and is an effective metal corrosion inhibitor.

Detailed Description

The present invention is further illustrated by the following specific examples, which are intended to be exemplary only and are not intended to be limiting. In the following examples, the raw materials used were commercially available, such as alkylphenol, formaldehyde, chlorine, catalyst, and accelerator M.

In the following examples, unless otherwise specified, each concentration is a weight percent concentration.