CN110643008B

CN110643008B - Accelerator M modified alkylphenol-formaldehyde resin and preparation method and application thereof

Info

Publication number: CN110643008B
Application number: CN201910942538.7A
Authority: CN
Inventors: 杜孟成; 李庆朝; 黄存影; 王文博; 宋彦哲; 张朋龙; 董瑞国; 师利龙
Original assignee: Shandong Dairuike New Materials Co ltd; Shandong Yanggu Huatai Chemical Co Ltd
Current assignee: Shandong Dairuike New Materials Co ltd; Shandong Yanggu Huatai Chemical Co Ltd
Priority date: 2019-09-30
Filing date: 2019-09-30
Publication date: 2022-07-15
Anticipated expiration: 2039-09-30
Also published as: CN110643008A

Abstract

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.

Description

Accelerator M modified alkylphenol-formaldehyde resin and preparation method and application thereof

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 'steel wire tyre', and is one new type of tyre with radially arranged tyre body cords and circumferentially arranged or near circumferentially arranged buffering layers. The adhesion strength of rubber to steel wires in a tire greatly affects the quality of a radial tire. 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, thin rubber sheets with good viscosity are used at a tire bead part, a belt ply edge part and other parts, and if the phenomenon of non-sticking occurs, air is trapped during molding of a tire blank, so that the quality of a finished product is influenced.

The natural rubber has good self-adhesion, so the process performance is good; although synthetic rubbers have some particular advantages in terms of abrasion resistance, aging resistance, and lack sufficient self-adhesion, which presents difficulties in the molding process, 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 per se; 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 the alkylphenol resin is added, the vulcanization rate is lowered 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 promoter M can well improve the performance of the resin after modifying the phenolic resin, and has unexpected effects. 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 for use 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 the 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 alkylphenol-formaldehyde resin modified with the accelerator M 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, the 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 and formaldehyde are subjected to condensation reaction and then to 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 value to 6.5-7 after the reaction, adding an organic solvent to extract a product, distilling the obtained organic phase to remove the organic solvent and water, and then heating to carry out polycondensation 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, 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 with 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 a yellow to brown solid, has extremely 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 invention is further illustrated by the following specific examples, which are intended to be exemplary only and not 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.

Example 1

(1) A100 ml four-neck round bottom reaction flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a tail gas absorption device is added with 10g (0.06mol) of accelerator M and 50ml of absolute ethyl alcohol, after complete dissolution, sodium hydroxide solution (2 wt%) is added, the pH is adjusted to 11, the temperature is kept at 10-12 ℃, chlorine is slowly introduced, and the feeding is carried out according to the molar ratio of the accelerator M to the chlorine being 1: 1. After the gas introduction was completed, the temperature was raised to 45 ℃ to react for 1 hour. During the reaction, sodium hydroxide is continuously added, and a weak alkaline environment (pH 8-11) is maintained. Then the reaction solution is poured into 500g of cold water, stands for 1 hour, is filtered, washed by cold water and dried at 50 ℃ to obtain the intermediate compound Z.

(2) To a 250ml four necked round bottom reaction flask equipped with a mechanical stirrer, thermometer, reflux condenser and dropping funnel was added 100g (0.67mol) of p-tert-butylphenol and 0.5g of p-toluenesulfonic acid. The temperature was raised to 90 ℃ and 48.7g of formaldehyde solution (37 wt%) was slowly added dropwise in a phenol formaldehyde ratio of 1:0.9, followed by reflux reaction at this temperature. After 2.0h of reaction, sodium hydroxide solution (2 wt%) was added to adjust the pH to neutral, 80g of toluene was added, and the mixture was allowed to stand for separation to separate the aqueous phase. Distilling the organic phase, and when no obvious distillate is produced, heating to 175 ℃ for polycondensation for 0.5 hour.

(3) After the resin is cooled to 100 ℃, 80g of toluene is added, the temperature is raised for dissolution, sodium hydroxide solution (2 wt%) is added for adjusting the pH value to 8, then the prepared intermediate compound Z is dropwise added, and the reflux reaction is carried out for 1 hour after the dropwise addition is finished. After the reaction, distilling to remove the solvent and the small molecular unreacted substance until no distillate is generated, stopping the distillation, and discharging. The product was weighed by cooling, and the yield based on alkylphenol was 95%. The softening point of the resin is 135 ℃ measured by a ring and ball softening point instrument, the number average molecular weight is 2434g/mol measured by a Gel Permeation Chromatography (GPC) method, the mass percentage content of free p-tert-butylphenol in the resin is 0.9 percent measured by a bromination method, and the mass content of water is lower than 1 percent.

Example 2

(1) A100 ml four-neck round bottom reaction flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a tail gas absorption device is added with 10g (0.06mol) of accelerator M and 50ml of absolute ethanol, after complete dissolution, sodium hydroxide solution (2 wt%) is added, the pH is adjusted to 10, the temperature is kept at 10-12 ℃, chlorine is slowly introduced, and feeding is carried out according to the molar ratio of the accelerator M to the chlorine being 1: 1. After the gas introduction was completed, the temperature was raised to 40 ℃ to react for 1 hour. During the reaction, sodium hydroxide was continuously added to maintain a weakly alkaline environment (pH 8-11). The reaction solution was then poured into 500g of cold water, allowed to stand for 1 hour, filtered, washed with cold water, and dried at 50 ℃ to give intermediate compound Z.

(2) To a 250ml four necked round bottom reaction flask equipped with a mechanical stirrer, thermometer, reflux condenser and dropping funnel was added 100g (0.67mol) of p-tert-butylphenol and 0.5g of p-toluenesulfonic acid. The temperature was raised to 100 ℃ and 43.3g of formaldehyde solution (37 wt%) was slowly added dropwise in a phenol formaldehyde ratio of 1:0.8, followed by reflux reaction at this temperature. After 2.0h of reaction, sodium hydroxide solution (2 wt%) was added to adjust the pH to neutral, 80g of toluene was added, and the mixture was allowed to stand for separation to separate the aqueous phase. Distilling the organic phase, and raising the temperature to 170 ℃ for polycondensation for 0.5 hour after no obvious distillate is generated.

(3) After the resin is cooled to 100 ℃, 80g of toluene is added, the temperature is raised for dissolution, sodium hydroxide solution (2 wt%) is added for adjusting the pH to 8, then the prepared intermediate compound Z is dropwise added, and the reflux reaction is carried out for 1 hour after the dropwise addition is finished. After the reaction, distilling to remove the solvent and the small molecule unreacted substance until no distillate is generated, stopping the distillation, and discharging. The product was weighed by cooling, giving a yield of 94% based on alkylphenol. The softening point of the resin is 132 ℃ measured by a ring and ball softening point instrument, the number average molecular weight is 2083g/mol measured by a Gel Permeation Chromatography (GPC) method, the mass percentage content of free p-tert butyl phenol in the resin is 0.9 percent measured by a bromination method, and the mass content of water is lower than 1 percent.

Example 3

(1) Adding 10g (0.06mol) of accelerator M and 50ml of absolute ethyl alcohol into a 100ml four-neck round-bottom reaction flask provided with a mechanical stirrer, a thermometer, a reflux condenser and a tail gas absorption device for dissolving, adding a sodium hydroxide solution (2 wt%) after complete dissolution, adjusting the pH to 11, keeping the temperature at-5-0 ℃, slowly introducing chlorine, and feeding according to the molar ratio of the accelerator M to the chlorine being 1: 1. After the gas introduction is finished, the temperature is raised to 60 ℃ and the reaction is carried out for 1 hour. During the reaction, sodium hydroxide solution was continuously added to maintain a weakly alkaline environment (pH 8-11). The reaction solution was then poured into 500g of cold water, allowed to stand for 1 hour, filtered, washed with cold water, and dried at 50 ℃ to give intermediate compound Z.

(2) To a 250ml four necked round bottom reaction flask equipped with a mechanical stirrer, thermometer, reflux condenser and dropping funnel was added 100g (0.67mol) of p-tert-butylphenol and 0.5g of p-toluenesulfonic acid. The temperature was raised to 90 ℃ and 48.7g of formaldehyde solution (37 wt%) was slowly added dropwise in a phenol formaldehyde ratio of 1:0.9, followed by reflux reaction at this temperature. After 2.0h of reaction, sodium hydroxide solution (2 wt%) was added to adjust the pH to neutral, 80g of toluene was added, and the mixture was allowed to stand for separation to separate the aqueous phase. Distilling the organic phase, and when no obvious distillate is produced, heating to 180 ℃ for polycondensation for 0.5 hour.

(3) After the resin is cooled to 110 ℃, 80g of toluene is added, the temperature is raised for dissolution, sodium hydroxide solution (2 wt%) is added for adjusting the pH value to 8, then the prepared intermediate compound Z is dropwise added, and the reflux reaction is carried out for 1 hour after the dropwise addition is finished. After the reaction, distilling to remove the solvent and the small molecular unreacted substance until no distillate is generated, stopping the distillation, and discharging. The product was weighed with cooling, giving a yield of 94% based on alkylphenol. The softening point of the resin is 135 ℃ measured by a ring and ball softening point instrument, the number average molecular weight is 2401g/mol measured by a Gel Permeation Chromatography (GPC) method, the mass percentage content of free p-tert butyl phenol in the resin is 0.8 percent measured by a bromination method, and the mass content of water is lower than 1 percent.

Example 4

(1) 22.4g (0.134mol) of accelerator M and 50ml of absolute ethyl alcohol are added into a 100ml four-neck round-bottom reaction flask provided with a mechanical stirrer, a thermometer, a reflux condenser and a tail gas absorption device for dissolving, after complete dissolution, sodium hydroxide solution (2 wt%) is added, the pH value is adjusted to 8, the temperature is kept between-5 ℃ and 0 ℃, chlorine is slowly introduced, and feeding is carried out according to the mol ratio of the accelerator M to the chlorine being 1: 1. After the gas introduction was completed, the temperature was raised to 45 ℃ to react for 1 hour. During the reaction, sodium hydroxide solution is continuously added to keep a weak alkaline environment (pH 8-11). The reaction solution was poured into 500g of cold water, allowed to stand for 1 hour, filtered, washed with cold water, and dried at 50 ℃ to obtain intermediate compound Z.

(2) To a 250ml four necked round bottom reaction flask equipped with a mechanical stirrer, thermometer, reflux condenser and dropping funnel was added 100g (0.67mol) of p-tert butyl phenol and 1.0g of concentrated sulfuric acid. The temperature was raised to 80 ℃ and 48.7g of formaldehyde solution (37 wt%) was slowly added dropwise in a phenol formaldehyde ratio of 1:0.9, followed by reflux reaction at this temperature. After 2.0h of reaction, sodium hydroxide solution (2 wt%) was added to adjust the pH to neutral, 80g of toluene was added, and the mixture was allowed to stand for layering, and the aqueous phase was separated. Distilling the organic phase, and when no obvious distillate is produced, heating to 180 ℃ for polycondensation for 0.5 hour.

(3) After the resin is cooled to 110 ℃, 80g of toluene is added, the temperature is raised for dissolution, sodium hydroxide solution (2 wt%) is added for adjusting the pH to 8, then the prepared intermediate compound Z is dropwise added, and the reflux reaction is carried out for 1 hour after the dropwise addition is finished. After the reaction, distilling to remove the solvent and the small molecule unreacted substance until no distillate is generated, stopping the distillation, and discharging. The product was weighed with cooling, giving a yield of 94% based on alkylphenol. The softening point of the resin is 128 ℃ through the measurement of a ring and ball softening point instrument, the number average molecular weight is 2221g/mol through a Gel Permeation Chromatography (GPC) method, the mass percentage content of free p-tert butyl phenol in the resin is 0.8 percent through a bromination method, and the mass content of water is lower than 1 percent.

Comparative example 1

Preparing morpholine modified p-tert-butyl phenol-formaldehyde resin by taking p-toluenesulfonic acid as an acidic catalyst, p-tert-butyl phenol and formaldehyde as raw materials, and preparing the p-tert-butyl phenol: formaldehyde: morpholine (molar ratio) 1:0.9: 0.1. The structural formula of morpholine is as follows:

the method comprises the following specific steps:

(1) to a 250ml four necked round bottom reaction flask equipped with a mechanical stirrer, thermometer, reflux condenser and dropping funnel was added 100g (0.67mol) of p-tert-butylphenol and 0.5g of p-toluenesulfonic acid. The temperature was raised to 90 ℃ and 48.7g of formaldehyde solution (37 wt%) was slowly added dropwise in a phenol formaldehyde ratio of 1:0.9, followed by reflux reaction at this temperature. After 2.0h of reaction, sodium hydroxide solution (2 wt%) was added to adjust the pH to neutral, 80g of toluene was added, and the mixture was allowed to stand for separation to separate the aqueous phase. Distilling the organic phase, and raising the temperature to 175 ℃ for polycondensation for 0.5 hour after no obvious distillate is generated.

(2) After the resin is cooled to 100 ℃, 80g of toluene is added, the temperature is raised for dissolution, sodium hydroxide solution (2%) is added for adjusting the pH value to 8, then morpholine is dropwise added, and after the morpholine is dropwise added, reflux reaction is carried out for 1 hour. After the reaction, distilling to remove the solvent and the small molecule unreacted substance until no distillate is produced, stopping distilling, and pouring out the product. The product was weighed with cooling, and the yield based on alkylphenol was 95%. The softening point of the resin is 132 ℃ through the measurement of a ring and ball softening point instrument, the number average molecular weight is 2212g/mol through the Gel Permeation Chromatography (GPC), the mass percentage content of free p-tert butyl phenol in the resin is 0.9 percent through the measurement of a bromination method, and the mass content of water is lower than 1 percent.

Comparative example 2

The procedure for the preparation of p-tert-butylphenol-formaldehyde resin was the same as in (2) in example 1.

The yield of the product obtained, based on alkylphenol, was 95%. The softening point of the resin is 137 ℃ measured by a ring and ball softening point instrument, the mass percentage content of free p-tert-butylphenol in the resin is 0.9 percent measured by a bromination method, and the mass content of water is lower than 1 percent.

Application example 1

The modified alkylphenol-formaldehyde resins obtained in the above examples and comparative examples of the present invention can be used as tackifier resins, and the following verification tests were conducted in order to verify their performances.

The following formula of the all-steel load radial wheel shoulder wedge rubber compound shown in the table 1 is adopted to prepare rubber compounds, the application performance of different tackifying resin samples is compared, and the tackifying resin is prepared by the following resins prepared in the following examples and comparative examples:

TABLE 1

A two-stage mixing process is adopted, one-stage mixing of carbon black master batch is carried out in a 1.5L experimental internal mixer, and the charging sequence is as follows: NR, carbon black N550, white carbon black, TDAE, stearic acid, an anti-aging agent RD, an anti-aging agent 4020, tackifying resin and zinc oxide. The two-stage mixing and vulcanizing system is carried out on a 6-inch open mill. Taking a section of master batch, coating the master batch on an open mill, adding an accelerator NS, an accelerator D, insoluble sulfur HDOT20 and DTDM, cutting for 2 times in a left-right 3/4 mode, passing through for 4 times at a minimum roll distance, rolling for 4 times at a 2mm roll distance, discharging sheets, and standing to be tested.

The quality indexes of the tackifying resin used in the above rubber compound are shown in the following table 2:

TABLE 2

Note: heating to reduce weight refers to heating tackifying resin at 65 deg.C for 2h with mass loss rate, and burning tackifying resin at 550 + -25 deg.C for 4h with ash content, cooling to about 200 deg.C, taking out, cooling in a drier for 30min, and calculating ash content. The detection of free phenol is carried out by bromination. The softening point was determined by the ring and ball method.

The viscosity properties of the mixes are shown in Table 3 below.

TABLE 3

As can be seen from tables 2 and 3, the samples obtained in the examples of the present invention and the samples obtained in the comparative examples all passed but showed a large difference in the tack retention rate. Compared with the rubber material added with the comparative resin, the rubber material added with the promoter M modified alkylphenol-formaldehyde resin has the advantages that the Mooney viscosity of the rubber material is reduced, and the processability of the rubber material is improved. As can be seen from the viscosity retention rate data of different storage conditions, the rubber compound added with the promoter M modified alkylphenol-formaldehyde resin can obviously improve the humidity resistance and heat resistance and long-term storage viscosity of the rubber compound, and is obviously superior to the resin in the comparative example.

Scorch characteristics of rubber compounds obtained by adding different tackifying resins were tested according to GB/T1233-2008 using a Mooney viscosity tester GT-7080-S manufactured by high-speed railway instruments as shown in Table 4.

TABLE 4 scorch characteristics of the rubber mixtures

As can be seen from the 140 ℃ Mooney scorch test data t5 in Table 4: compared with the blank, the scorch time t5 of the rubber compound is shortened after the tackifying resin is added. However, the scorch time of the rubber material added with the tackifying resin of the embodiment of the invention is reduced less than that of the rubber material added with the tackifying resin of the comparative example, which shows that the scorch performance of the rubber material is less affected by the tackifying resin modified by the accelerator M of the invention.

Application example 2

To verify the difference in performance of the alkylphenol-formaldehyde resin modified with the accelerator M and the unmodified alkylphenol-formaldehyde resin physically mixed with the accelerator M, the following verification test was performed.

The following all-steel truck radial tire shoulder wedge formula shown in table 5 was used for rubber mixing:

TABLE 5

A two-stage mixing process is adopted, one-stage mixing of carbon black master batch is carried out in a 1.5L experimental internal mixer, and the charging sequence is as follows: NR, carbon black N550, white carbon black, TDAE, stearic acid, an anti-aging agent RD, an anti-aging agent 4020, tackifying resin and zinc oxide. The two-stage mixing and vulcanizing system is carried out on a 6-inch open mill. Taking a section of master batch, coating the master batch on an open mill, adding an accelerator NS, an accelerator D, an accelerator M (if any), insoluble sulfur HDOT20 and DTDM, cutting for 2 times in a left-right 3/4 mode, passing through for 4 times at a minimum roll distance, rolling for 4 times at a 2mm roll distance, discharging, and standing to be tested.

The viscosity properties of the mixes are shown in Table 6 below.

TABLE 6

Scorch characteristics of rubber compounds obtained by adding different tackifying resins were examined by using a Mooney viscosity tester GT-7080-S manufactured by high-speed railway instruments according to GB/T1233-2008 standard, as shown in Table 7.

TABLE 7 scorch characteristics of the mixes

As can be seen from tables 6 and 7, the structural modification of the alkylphenol tackifying resins with the accelerator M (formulation 1) has a higher retention of tack and a higher resistance to wet heat than the physical mixing of the two (formulation 2). In addition, in the aspect of the scorching performance of the rubber compound, the scorching time of the rubber compound is longer, and the processing safety is better. This is because: after the alkylphenol tackifying resin is modified by the accelerator M, a new structure is formed, and the structure is more favorable for reducing the negative influence of common tackifying resin on the film vulcanization performance. If the accelerator M is merely physically mixed with the alkylphenol tackifying resin, the dispersing performance of the auxiliary in the film is poor and the functionality is poor.

The above is only a part of the embodiments of the present invention, and the embodiments of the present invention are not limited by the examples, and any other changes and substitutions, such as the substitution of p-tert-butylphenol for p-tert-octylphenol, p-cyclohexylphenol, p-dodecylphenol, p-cumylphenol, to prepare corresponding p-tert-octylphenol-formaldehyde resin, p-cyclohexylphenol-formaldehyde resin, p-dodecylphenol-formaldehyde resin, p-cumylphenol-formaldehyde resin, should be equivalent substitutions, should be included in the protection scope of the present invention.

Claims

1. An alkylphenol-formaldehyde resin modified by an accelerator M, which 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.

2. An alkylphenol-formaldehyde resin modified with an accelerator M as claimed in claim 1, characterized in that: in the formula I, R is p-tert-butyl.

3. 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.

4. 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.

5. The method according to claim 4, wherein: in the structural formula of the alkylphenol-formaldehyde resin, R is p-tert-butyl.

6. The method according to claim 4, wherein: the compound Z is obtained by reacting an accelerant M with chlorine under alkaline conditions.

7. The method for preparing a polycarbonate resin composition according to claim 6, wherein: the molar ratio of the promoter M to the chlorine gas is 1: 1.

8. The method according to claim 4 or 5, 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.

9. The method for preparing a polycarbonate resin composition according to claim 4, wherein: the method comprises the following steps:

10. The method of claim 9, wherein: the molar ratio of the alkylphenol to the accelerator M is 1.0: 0.09-0.3; the molar ratio of alkylphenol to formaldehyde is 1: 0.6-1.

11. The method of claim 10, wherein: the molar ratio of the alkylphenol to the accelerator M is 1: 0.09-0.2.

12. The method of claim 10, wherein: the molar ratio of the alkylphenol to the formaldehyde is 1: 0.8-0.9.

13. The method of claim 9, wherein: in the step (2), the catalyst is acid.

14. The method of claim 13, wherein: in the step (2), the catalyst is p-toluenesulfonic acid or sulfuric acid.

15. The method of claim 13, wherein: in the step (2), the dosage of the catalyst is 0.5-1.0% of the mass of the alkylphenol.

16. The method of claim 9, wherein: in the step (1), chlorine gas is introduced at the temperature of-5-20 ℃, and after the chlorine gas is introduced, the temperature is raised to 40-60 ℃ for reaction for 1-2 hours.

17. The method of claim 9, wherein: 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.

18. The method of claim 9, wherein: in the step (2), the polycondensation reaction is carried out at 170-180 ℃ for 0.5-1 h.

19. The method of claim 9, wherein: 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 into the solution, and the reflux reaction is carried out for 1 to 2 hours at the temperature.

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