KR20210005919A - 4-tert-alkylphenol-(morpholinyl) formaldehyde resin and its manufacturing method and application - Google Patents

Abstract

The present invention provides a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin in which N-formylmorpholine and alkylphenol are prepared through condensation and polycondensation reactions, and methods and applications for preparing the same. The method of the present invention is simple in operation and easy to implement, the condition is mild, high pressure is not required, stability is high, controllability is strong, the product yield is high, the quality is excellent, energy saving and environmentally friendly. It is an excellent adhesive resin because it has excellent initial viscosity and continuous viscosity by connecting a morpholine group to the methyl group of the obtained resin, has excellent moist heat resistance, antioxidant performance, and is particularly used as a continuous adhesive resin for rubber in the manufacture and production of tires. Suitable for When the resin of the present invention is added, the initial viscosity and viscous endurance of the rubber compound are greatly improved, thereby reducing the defective rate of tires or rubber products, improving the quality of tires or rubber products, reducing production cost, and improving production efficiency. It has excellent economic and social benefits as it can reduce the dynamic heat generation of rubber and has a broad market prospect.

Description

4-tert-alkylphenol-(morpholinyl) formaldehyde resin and its manufacturing method and application

The present invention relates to a phenol resin containing a morpholinyl group, and specifically to a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin, as well as a method for producing the same and its application as an adhesive resin for rubber. It belongs to the field of phenolic resin technology.

In the process of processing rubber tires or products, especially radial tires and bias tires, they are often molded using a bonding method, which requires that the unvulcanized rubber compound has a high molding viscosity. Natural rubber has excellent processing performance because it has excellent self-adhesiveness, and synthetic rubber has abrasion resistance, aging resistance and some other advantages, but its self-adhesiveness is bad, which causes difficulties in the molding process, limiting the use of synthetic rubber. .

In the case of insufficient viscosity between rubber compounds, especially in the case of synthetic rubber compounds, semi-finished rubber parts are not only deformed in size by creep, but also part of the rubber part is separated due to expansion during molding, so the unvulcanized rubber compound has high molding viscosity. Must be equipped. In order to solve this problem, gasoline or an adhesive is generally applied in the initial process. This method is high in cost and causes environmental pollution and production safety risks due to volatilization of solvents. The adhesiveness of each rubber part is improved by using a method of excluding and adding an adhesive resin directly to the rubber.

Initial adhesive resins used in tire factories include petroleum hydrocarbon resins, coumarone resins, and rosin resins. Since natural rubber has excellent self-adhesiveness, the use of this kind of resin can satisfy the demand, but since synthetic rubber has poor self-adhesiveness, this kind cannot satisfy the demand. Later, p-tert-butylphenol formaldehyde resin, p-tert-octylphenol formaldehyde resin, and p-tert-butylphenol acetylene resin were used as adhesive resins, but these adhesive resins have some disadvantages in the process of use. For example, the addition of p-tert-butylphenolformaldehyde resin and p-tert-octylphenolformaldehyde resin to a rubber compound provides a high initial viscosity, but the adhesive property rapidly decreases in storage, aeration or humid and hot environments, and p- Production of tert-butylphenol acetylene resin requires high temperature and high pressure, and production safety is poor. Therefore, there is an urgent need to introduce an adhesive resin that is resistant to moisture and heat and is anti-oxidant in the market.

In terms of the disadvantages of low moisture and heat resistance and antioxidant properties existing in the existing adhesive resin for rubber, the present invention is a phenol resin containing a new morpholinyl group --4-tert-alkylphenol-(morpholinyl) formaldehyde resin In order to provide, the resin has excellent initial viscosity and can be stored for a long time or still maintain high viscosity even in a humid heat environment, making it an excellent lasting adhesive resin.

The present invention further provides a method for preparing the 4-tert-alkylphenol-(morpholinyl) formaldehyde resin, the raw material of which is easy to obtain, has strong process control, does not require high pressure, has mild production conditions, and is safe. It is high and suitable for industrial production.

The present invention further provides the application of the 4-tert-alkylphenol-(morpholinyl) formaldehyde resin as an adhesive resin, and the 4-tert-alkylphenol-(morpholinyl) formaldehyde resin of the present invention is an excellent initial It is an excellent adhesive resin because it has viscous properties and has continuous performance of storage resistance and heat resistance, and can be used especially as an adhesive resin for rubber.

Specific technical solutions of the present invention are as follows.

The 4-tert-alkylphenol-(morpholinyl) formaldehyde resin researched and prepared by the present invention has a structural formula represented by the following formula, wherein m is an integer of 1-10, and preferably an integer of 3-6. . R is a tert-alkyl group having a carbon number greater than or equal to 4 and less than or equal to 12 and is preferably a tert-butyl group or a tert-octyl group.

Preferably, the weight average molecular weight of the 4-tert-alkylphenol-(morpholinyl) formaldehyde resin is between 1140-2580 when preferred conditions for m and R are selected. The molecular weight size has a certain influence on the viscosity of the product, and in practical applications, an appropriate molecular weight can be selected according to the needs.

The 4-tert-alkylphenol-(morpholinyl) formaldehyde resin of the above structure of the present invention contains a morpholine group, has excellent initial self-adhesiveness and lasting adhesion, moisture-heat resistance and anti-oxidation, and the performance is conventional p-tert -Excellent than adhesive resins such as alkylphenol formaldehyde resins. The 4-tert-alkylphenol-(morpholinyl) formaldehyde resin of the present invention is synthesized using the method for preparing a phenol resin disclosed in the prior art, and in a specific embodiment of the present invention, the present invention is the 4-tert-alkyl Provides a preferred method for preparing a phenol-(morpholinyl) formaldehyde resin, which is a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin through condensation and polycondensation reaction of N-formylmorpholine and alkylphenol. It includes the step of preparing. Here, the structural formulas of N-formylmorpholine and alkylphenol are as follows, wherein R is a tert-alkyl group having a carbon number greater than or equal to 4 and less than or equal to 12, preferably a tert-butyl group or a tert-octyl group.

N-formylmorpholine alkylphenol

라디칼이 있는 것을 의미하는 바, 즉 R는

라디칼을 함유하는 알킬기이다.Furthermore, the tert-alkyl group is attached to the substituent R

Means there is a radical, i.e. R is

It is an alkyl group containing a radical.

Furthermore, N-formylmorpholine and alkylphenol obtained the 4-tert-alkylphenol-(morpholinyl) formaldehyde resin of the present invention through condensation and polycondensation reaction, and the method of condensation and polycondensation reaction is of the prior art. Reference may be made to a method for producing a phenolic resin. For example, the reaction of N-formylmorpholine and alkylphenol should proceed in the presence of a catalyst, and the catalyst used is an acid and the acid may be an organic acid or an inorganic acid. As the acid catalyst used in the present invention, any acid catalyst disclosed in the prior art phenol resin production process, such as oxalic acid, concentrated sulfuric acid, p-toluenesulfonic acid, and the like can be used. The acid can be added in the form of a solid or aqueous solution. The amount of the catalyst used may be the amount of the catalyst used in the prior art phenolic resin production process.

Furthermore, as the condensation reaction continues to proceed, the material becomes increasingly viscous and it is very difficult to stir uniformly, and in order to prevent the phenomenon that the part reacts excessively by making the reaction material uniform, a certain amount in the middle and late stages of the condensation reaction. Of organic solvent can be added. When the polycondensation reaction begins, an organic solvent must be added to completely dissolve the material, and as the polycondensation reaction continues, the material continues to become viscous, making it very difficult to remove moisture generated by the polycondensation from the viscous material. It is difficult, where the solvent not only acts as a dissolving agent, but also acts as a moisture remover. The organic solvent may be any organic solvent that can be used in the preparation of a phenol resin as reported in the prior art, and the organic solvent used in a specific embodiment of the present invention is toluene, benzene, xylene, etc., and the effect of each organic solvent Is similar.

Further, the molar ratio of N-formylmorpholine and alkylphenol is 0.75 to 0.99:1, preferably 0.85:1.

Furthermore, when N-formylmorpholine and alkylphenol react, first proceed with a condensation reaction (also referred to as methylolation reaction), and then form a methylol product (R is greater than or equal to 4 carbon atoms and less than 12). Or the same tert-alkyl group, preferably a tert-butyl group or tert-octyl group), and a polycondensation reaction with the remaining alkylphenol to obtain a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin.

The reaction formula of the condensation reaction is as follows, and the catalyst is the acid catalyst mentioned above.

Further, the temperature of the condensation reaction is 95 ~ 110 ℃; The time for the condensation reaction is generally 2-6 h.

Furthermore, the end temperature of the polycondensation reaction is 150 to 200°C, and the time for the total polycondensation reaction is 2 to 6 h.

Furthermore, it specifically includes the following steps.

(1) Put the alkylphenol in the reactor, heat it up, melt it, add a catalyst, add N-formylmorpholine dropwise under reflux and agitation conditions, and increase the temperature to 95~110℃ after the dropwise addition is completed to proceed with condensation reaction. To obtain a methylol product that becomes;

(2) Add an organic solvent to the reactor to dissolve and dilute the material, raise the temperature to dehydrate while polycondensation reaction, and basically, if water is not distilled, continue to increase the temperature to proceed with the polycondensation reaction, and the temperature will reach 150-200℃. In this case, the reaction is stopped to obtain a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin product.

Further, in step (1), the N-formylmorpholine is added dropwise and the dropwise addition is preferably completed within 30-60 minutes.

Furthermore, in step (1), when the material becomes viscous in the intermediate and late stages of the reaction, an organic solvent may be appropriately added to dissolve and dilute it, and the organic solvent is toluene, xylene or benzene.

Furthermore, in step (2), the organic solvent is toluene, xylene or benzene.

Preferably, the temperature of the condensation reaction is 95 to 105°C.

Preferably, the time for the condensation reaction is 3 to 4 h.

Preferably, the end temperature of the polycondensation reaction is 150 to 170°C.

Preferably, the time for the entire polycondensation reaction is 3 to 4 h.

Furthermore, the present invention provides an application of a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin as an adhesive resin, and preferably, the adhesive resin is an adhesive resin for rubber, and the manufacture of a tire And used in production.

Furthermore, the present invention further provides an adhesive resin containing the 4-tert-alkylphenol-(morpholinyl) formaldehyde resin of the present invention as an active ingredient.

The present invention provides a new phenolic resin, which is obtained through methylolation and polycondensation reaction of N-formylmorpholine and alkylphenol under catalytic conditions. The method is simple in operation and easy to implement, the condition is mild, high pressure is not required, stability is high, controllability is strong, the product yield is high, the quality is excellent, energy saving and environmentally friendly. It has excellent initial viscosity and lasting viscosity by connecting a morpholine group to the methyl group of the phenolic resin, and it is an excellent adhesive resin because it has excellent storage, moisture and heat resistance, antioxidant performance, and especially in tire manufacturing and production. It is suitable for use as a resin. When the resin of the present invention is added, the initial viscosity and viscous endurance of the rubber compound are greatly improved, thereby reducing the defective rate of tires or rubber products, improving the quality of tires or rubber products, reducing production cost, and improving production efficiency. It has excellent economic and social benefits as it can reduce the dynamic heat generation of rubber and has a broad market prospect.

The present invention discloses a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin, has a special initial viscosity and long-term adhesion, is an excellent adhesive resin, and the structural formula is as follows.

In the above structural formula, m is an integer of 1-10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and preferably 3-6. R is a tert-alkyl group having a carbon number greater than or equal to 4 and less than or equal to 12 and is preferably a tert-butyl group or a tert-octyl group. Preferably, the weight average molecular weight of the resin is preferably 1140-2580.

The 4-tert-alkylphenol-(morpholinyl) formaldehyde resin can be prepared by the following method.

1.Put the alkylphenol into the reactor, heat it up to melt it, add the catalyst, add N-formylmorpholine dropwise within 30 to 60 minutes under reflux and stirring conditions, and then proceed by controlling the temperature to proceed with the reaction If the material becomes viscous as it progresses, the reaction can be made uniform by diluting it by appropriately adding an organic solvent). The reaction scheme is as follows.

2. After the reaction is completed in step 1, add an organic solvent to dissolve and dilute the material, increase the temperature, and dehydrate while polycondensation reaction. If water is not distilled basically, continue to increase the temperature to reach 150-200℃. After stopping, pouring the material and cooling to obtain the 4-tert-alkylphenol-(morpholinyl) formaldehyde resin product of the present invention.

The reaction equation is as follows.

Furthermore, N-formylmorpholine can be purchased directly from the market or can be prepared by itself.In a preferred embodiment of the present invention, N-formylmorpholine is prepared using a method of dehydrating formic acid and morpholine, and a specific production method Is as follows.

Formic acid, morpholine, and toluene, which is a moisture removing agent, are put in a reactor and reacted under reflux under heating and stirring conditions.Toluene removes the produced water, separates and reuses toluene, and reaches the reaction end point when the amount of water produced is no longer increased. The ratio of the amount of the substance of formic acid and morpholine is 1.05 to 1.5:1, such as 1.05:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, and preferably 1.05:1. The time for the reflux reaction is 4 to 5 h. The reaction equation is as follows.

Furthermore, in step 1, the ratio of the amount of the substance of alkylphenol and N-formylmorpholine is 1:0.75 to 0.99, for example 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95, 1 :0.99, preferably 1:0.85. The reaction temperature is 95 to 110°C, for example 95°C, 100°C, 105°C, 110°C, and preferably 95 to 105°C. The reaction time is 2 to 6 hours, for example 2h, 3h, 4h, 5h, 6h, preferably 3 to 4 hours.

Further, in step 2, the end temperature of the polycondensation reaction is 150 to 200°C, such as 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, preferably 150-170°C. The reaction time for the total polycondensation reaction is 2 to 6 hours, for example 2h, 3h, 4h, 5h, 6h, preferably 3 to 4 hours.

Furthermore, in steps 1 and 2, the organic solvent is toluene, xylene, benzene, and the like, preferably toluene. The organic solvent provides an environment for the reaction and allows the reaction to proceed in the direction of the formation of the resin in order to remove water generated during the reaction.

Hereinafter, various specific embodiments of the present invention are listed so that those skilled in the art can better understand the present invention, but the implementation of the present invention is not limited thereto. In the examples below, unless otherwise specified, all concentrations are mass concentrations.

In the examples below, the ring and ball softening points were tested according to standard GB/T4507-2014 and the instrument used was SYD-2806E and the rate of temperature rise was 1° C./min.

In the examples below, the weight average molecular weight is tested by gel chromatography 1260, the column temperature is 35° C., the chromatography column model is Agilent Plgel 3um MLXED-E, the solvent is tetrahydrofuran and the flow rate is 1 ml/min.

In the following examples, free phenol is tested by high performance liquid chromatography, the instrument is Shimadzu liquid chromatography LC-20AT, the chromatography column model is a C18 packed column, the detection wavelength is 275 nm, and the mobile phase is methanol: KH ₂ PO ₄ =36 :64 (volume ratio), flow rate 1ml/min, column temperature 35℃.

Example 1

41.3 g of 99.5 wt% formic acid, 74.4 g of 99.5 wt% morpholine (a ratio of the amount of formic acid to morpholine: 1.05:1) and 180 g of toluene were added to the reactor and reacted under reflux for 6 h under heating and stirring conditions. The produced water is removed by toluene through a water separator, and then condensed with a condenser to obtain a mixture of toluene and water, and the mixture is statically partitioned, and the toluene is separated and reused until no more water is produced, and then under vacuum conditions. If toluene is removed from, N-formylmorpholine can be obtained. If N-formylmorpholine is not enough, this method can be repeated to produce more N-formylmorpholine.

Weigh 158.1 g of 95 wt% p-tert-butylphenol, put it in a new reactor, heat up to melt it, add 8.0 g of oxalic acid, stir evenly, and N-formylmorpholine (p-tert-butylphenol and The ratio of the amount of the substance of N-methylmorpholine is 1:0.85) after dropwise addition within 30 minutes and reflux condensation reaction at 98-100°C for 3 hours (if the material becomes viscous, add an appropriate amount of toluene and dilute. Make the reaction uniform) After the condensation reaction is completed, add toluene to dissolve and dilute it, and increase the temperature to dehydrate the polycondensation reaction. If water is not distilled, continue to increase the temperature to proceed with the polycondensation reaction. And the polycondensation reaction time was all 3 hours. After completion of the polycondensation reaction, the material of the reactor was poured and cooled to obtain the 4-tert-butylphenol-(morpholinyl) formaldehyde resin product of the present invention, and the softening point detected by the ring and ball softening point instrument was 135°C and high performance liquid chromatography. The free phenol detected by chromatography was 0.15% and the weight average molecular weight detected by gel chromatography was 1880.

Example 2

99.5 wt% of formic acid 48.3 g, 99.5% wt% of morpholine 83.2 g (amount of material ratio 1.1: 1) and 200 g of toluene were added to the reactor and refluxed for 5 h under heating and stirring conditions. After being removed by toluene through a water separator and condensed with a condenser to obtain a mixture of toluene and water, the mixture is statically partitioned, and then toluene is separated and reused until no more water is produced, and toluene is removed under vacuum. N-formylmorpholine can be obtained. If N-formylmorpholine is not enough, this method can be repeated to produce more N-formylmorpholine.

Weigh 158.1 g of 95 wt% p-tert-butylphenol, put it in a new reactor, heat up to melt, add 11 g of oxalic acid, and stir evenly, and N-methylmorpholine (p-tert-butylphenol and N -The ratio of the amount of the material of methylmorpholine is 1:0.95) dropwise addition within 40 minutes, and then reflux condensation reaction at 99-102°C for 4 hours (if the material becomes viscous during the reaction period, an appropriate amount of toluene is added. After the condensation reaction is completed, toluene is added to dissolve and dilute, and the temperature is raised to dehydrate the polycondensation reaction. If water is not distilled by default, continue to increase the temperature to proceed with the polycondensation reaction at 180℃ The reaction was stopped and the polycondensation reaction time was all 3 hours. After completion of the polycondensation reaction, the material of the reactor was poured and cooled to obtain the 4-tert-butylphenol-(morpholinyl) formaldehyde resin product of the present invention. The softening point detected by the ring and ball softening point instrument is 132°C and high performance liquid chromatography The free phenol detected by chromatography was 0.21% and the weight average molecular weight detected by gel chromatography was 1370.

Example 3

99.5 wt% of formic acid 54.1 g, 99.5% wt% of morpholine 78.8 g (amount of material ratio 1.3:1) and 200 g of toluene were added to the reactor and refluxed for 7 h under heating and stirring conditions, and the resulting water was After being removed by toluene through a water separator and condensed with a condenser to obtain a mixture of toluene and water, the mixture is statically partitioned, and then toluene is separated and reused until no more water is produced, and toluene is removed under vacuum. N-formylmorpholine can be obtained. If N-formylmorpholine is not sufficient, this method can be repeated to produce more N-formylmorpholine.

Weigh 99.5 wt% of p-tert-butylphenol 158.1, put it in a reactor, heat up to melt it, add 8 g of 98 wt% sulfuric acid, and stir evenly, and then N-methylmorpholine (p-tert-butylphenol and The ratio of the amount of the substance of N-methylmorpholine is 1:0.90) was added dropwise within 40 minutes, followed by reflux condensation reaction at 97-102℃ for 4 hours (if the material becomes viscous during the reaction period, an appropriate amount of toluene) After the condensation reaction is completed, toluene is added to dissolve and dilute, and the temperature is raised to dehydrate the polycondensation reaction. If water is not distilled, continue to increase the temperature to proceed with the polycondensation reaction at 180℃ In case the reaction is stopped, the polycondensation reaction time is all 3 hours. After completion of the polycondensation reaction, the material of the reactor was poured and cooled to obtain a 4-tert-butylphenol-(morpholinyl) formaldehyde resin product of the present invention. The softening point detected by the ring and ball softening point instrument was 146° C., the free phenol detected by high performance liquid chromatography was 0.11%, and the weight average molecular weight detected by gel chromatography was 1140.

Example 4

99.5 wt% of formic acid 47.2 g, 99.5% wt% of morpholine 74.4 g (amount of material ratio 1.2: 1) and toluene were added to a reactor and refluxed for 4 h under heating and stirring conditions, and the resulting water was toluene. After being removed through a water separator by means of a water separator and condensed with a condenser to obtain a mixture of toluene and water, the mixture is statically partitioned, and then toluene is separated and reused until no more water is produced, and toluene is removed under vacuum. -You can get formylmorpholine. If N-formylmorpholine is not sufficient, this method can be repeated to produce more N-formylmorpholine.

95 wt% of p-tert-octylphenol 217.2 g was weighed, put in a reactor, heated to melt, and 10.8 g of p-toluenesulfonic acid was added to uniformly agitate the N-methylmorpholine (p-tert-octyl) prepared above. The ratio of the amount of phenol and N-methylmorpholine is 1:0.85) dropwise addition within 50 minutes and reflux condensation reaction at 100-104°C for 4.5 hours (if the material becomes viscous during the reaction period, an appropriate amount of Add toluene and dilute to make the reaction uniform) After the condensation reaction is complete, add toluene to dissolve and dilute and dehydrate the polycondensation reaction by raising the temperature. If water is not distilled by default, continue to increase the temperature to proceed with the polycondensation reaction at 180℃ In the case of, the reaction is stopped and the polycondensation reaction time is all 3.5 hours. After completion of the polycondensation reaction, the material of the reactor was poured and cooled to obtain a 4-tert-octylphenol-(morpholinyl) formaldehyde resin product of the present invention. The softening point detected by the ring and ball softening point instrument was 124°C, the free phenol detected by high performance liquid chromatography was 0.17%, and the weight average molecular weight detected by gel chromatography was 1560.

Comparative example

100 g of p-tert-butylphenol, 46 g of formaldehyde solution, 0.5 g of alkaline solution, 10 g of morpholine solution and 1 g of p-toluenesulfonic acid are weighed. First, p-tert-butylphenol and p-toluenesulfonic acid are placed in a flask, stirred, and heated. After the temperature rose to 110° C., some formaldehyde solution was slowly added dropwise, and after the dropwise addition was completed, the reaction was continued for 2 h. Distillation is started, and after the temperature rises to 110° C., distillation is stopped. Sodium hydroxide is added to adjust the pH to weakly alkaline, and 10 g of morpholine is slowly added dropwise, followed by reflux reaction for 30 minutes. Add p-toluenesulfonic acid to adjust it to weak acidity, add the remaining formaldehyde solution dropwise, continue to react for 2 h after dropwise addition, and start distillation. After the temperature rises to 140 ℃, distill under reduced pressure and distillate is no longer produced. Stop distillation and spill the product. The softening point detected by the ring and ball softening point instrument was 128° C., the free phenol detected by high performance liquid chromatography was 0.35%, and the weight average molecular weight detected by gel chromatography was 850.

Effect Example

The following experiment was conducted to verify the adhesive effect of the resin of the present invention.

The product of Example 1 of the present invention, the product of Example 2, the product of Example 3, the product of Example 4, the product of the comparative example, and the product of p-tert-butylphenol formaldehyde resin (marketing number 204) are respectively adhesive. It is applied to rubber as a resin and the self-adhesion of each resin is detected.

Master batch compound (parts by weight): 100 parts of SBR (styrene butadiene rubber), 35 parts of carbon black N550, 2 parts of TDAE (aromatic oil), 7.5 parts of zinc oxide-80, 1 part of stearic acid, 1 part of anti-aging agent RD, aging 1.5 parts of inhibitor 4020, 1.2 parts of accelerator NS-80, 0.2 parts of accelerator DPG-80, 3 parts of insoluble sulfur HDOT20-80, 0.8 parts of accelerator DTDM-80, and 6 parts of adhesive resin.

Rubber mixing process:

The first stage mixing is carried out in a 1.5L half-bar remixer. Styrene-butadiene rubber, carbon black, zinc oxide, stearic acid, anti-aging agent, adhesive resin, and TDAE are added and mixed to 135° C. to increase the pressure, and then mixed to 155° C. and discharged.

The two-stage mixing takes place in an open mill. After taking the master batch from step 1 and winding the roll in an open mill, add insoluble sulfur and accelerator, cut 3/4 of the left and right two times, and the minimum roll distance is 4 thin passes, and the distance of 2 mm rolls is 4 It is rolled twice, loaded, stored for 24 hours, and prepared for testing.

The adhesion of the non-vulcanized rubber compound is indicated by measuring the adhesive force formed by contacting and compressing the rubber films for a certain period of time. The method is as follows.

1. The rubber compound obtained above was cut into a 180mm×65mm film, and the film was cut in a normal room temperature (20°C, 50% relative humidity) for 1, 3, 5, 8, and 15 days, respectively. After storage, two films with the same storage time are taken and compressed for 5 s at a pressing speed of 20 cm/min, and then the two films are separated at a pull-off speed of 20 cm/min, and the force required to separate the two films is tested. And repeat the experiment 5 times under the same condition for each storage time. The average value is taken as the adhesive force of the sample, and the unit is Newton (N). The experimental device is RZN-II rubber self-adhesiveness meter (Beijing Wanhuifang Science Co., Ltd.).

Table 1 shows the adhesive strength of the rubber compound after storage for different times in a conventional environment.

Viscosity test results under typical conditions of different adhesive resin rubber compounds Adhesive resin Adhesion (N) 1d 3d 5d 8d 15d p-tert-butylphenol formaldehyde resin (204) 13.32 12.04 10.52 8.76 7.11 Product of Example 1 16.61 16.35 16.04 15.70 15.33 Product of Example 2 15.93 15.66 15.31 14.90 14.42 Product of Example 3 15.62 15.35 14.97 14.56 14.05 Product of Example 4 16.28 15.98 15.65 15.28 14.87 Comparative Example Sample 14.73 13.57 12.14 10.67 9.11

As can be seen from Table 1 above, the initial viscosity and viscous endurance of the product of the present invention is superior to that of the p-tert-butylphenolformaldehyde resin 204 and the comparative sample on the market.

2. The rubber compound obtained above was cut into a 180mm×65mm film, and the film was stored for 1, 3, 5, and 7 days in an environment of 60°C and 95% relative humidity, respectively. Take two films and press them for 5 s at a pressing speed of 20 cm/min, and then separate the two films at a pull-off speed of 20 cm/min. Test the force required to separate the two films, and each storage time is the same. The experiment is repeated 5 times under conditions, and the average value is taken as the adhesive strength of the sample, and the unit is Newton (N). The experimental device is RZN-II rubber self-adhesiveness meter (Beijing Wanhuifang Science Co., Ltd.).

Table 2 shows the adhesive strength of the rubber compound after being stored for different times in a humid heat environment.

Moisture and heat resistance test results of different adhesive resin rubber compounds Adhesive resin Adhesion (N) 1d 3d 5d 7d p-tert-butylphenol formaldehyde resin (204) 11.76 9.92 8.01 6.27 Product of Example 1 16.13 15.59 15.00 14.46 Product of Example 2 15.38 14.79 14.24 13.65 Product of Example 3 15.07 14.49 13.95 13.48 Product of Example 4 15.73 15.11 14.49 13.97 Comparative Example Sample 13.55 12.10 10.56 9.08

As can be seen from Table 2 above, the moisture and heat resistance of the product of the present invention is superior to that of the p-tert-butylphenolformaldehyde resin 204 in the market and the comparative sample.

Claims (10)

It has the structural formula represented by the following formula, wherein m is an integer of 1-10 and R is a tert-alkyl group having a carbon number greater than or equal to 4 and less than or equal to 12 4-tert-alkylphenol-(morphopoly Neil) formaldehyde resin.

The method of claim 1,
m is an integer of 3-6, R is a tert-butyl group or a tert-octyl group, and preferably, the weight average molecular weight of the 4-tert-alkylphenol-(morpholinyl) formaldehyde resin is 1140-2580. 4-tert-alkylphenol-(morpholinyl) formaldehyde resin as described above. Including the step of preparing a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin through condensation and polycondensation reactions of N-formylmorpholine and alkylphenol, wherein the structural formula of the N-formylmorpholine and alkylphenol Where R is a tert-alkyl group having a carbon number greater than or equal to 4 and less than or equal to 12, preferably a tert-butyl group or a tert-octyl group, 4-tert-alkylphenol-(morpholinyl) formaldehyde Method of making resin.

N-formylmorpholine alkylphenol The method of claim 3,
The reaction proceeds in the presence of a catalyst, and the catalyst is an acid, and the acid is an inorganic acid or an organic acid, preferably oxalic acid, concentrated sulfuric acid, or p-toluenesulfonic acid, characterized in that 4-tert-alkylphenol-(Mor Polynyl) method for producing formaldehyde resin. The method of claim 3,
The method for producing a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin, wherein the molar ratio of N-formylmorpholine and alkylphenol is 0.75-0.99:1, and preferably 0.85:1. The method of claim 3,
When N-formylmorpholine and alkylphenol react, a condensation reaction is performed first, a methylol product described later is formed, and then a polycondensation reaction is performed to obtain a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin. In formula I, R is a tert-alkyl group having a carbon number greater than or equal to 4 and less than or equal to 12, and preferably a tert-butyl group or a tert-octyl group. 4-tert-alkylphenol-(morpholinyl) Method for producing formaldehyde resin.

The method of claim 3,
After adding the alkylphenol to the reactor, heating it up, melting it, adding a catalyst, adding N-formylmorpholine dropwise under reflux and stirring conditions, and increasing the temperature to 95~110℃ after completion of the dropwise addition to proceed with the condensation reaction, methylol represented by the following formula I. Obtaining a product (1);

Add organic solvent to the reactor to dissolve and dilute the material, and then increase the temperature to dehydrate while polycondensation reaction. Basically, if water does not distill, continue to increase the temperature to proceed with the polycondensation reaction and stop the reaction when the temperature reaches 150-200℃. A method for producing a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin, characterized in that it specifically comprises the step (2) of obtaining a 4-tert-alkylphenol-(morpholinyl) formaldehyde resin. The method of claim 7,
In step (1), when the material becomes viscous in the intermediate and late stages of the reaction, an organic solvent is added to dissolve and dilute it, and the organic solvent is toluene, xylene or benzene; In step (2), the organic solvent is toluene, xylene, or benzene, wherein the 4-tert-alkylphenol-(morpholinyl) formaldehyde resin is produced. The application of the 4-tert-alkylphenol-(morpholinyl) formaldehyde resin according to claim 1 or 2 as an adhesive resin, preferably as an adhesive resin for rubber. The active ingredient is an adhesive resin comprising the 4-tert-alkylphenol-(morpholinyl) formaldehyde resin according to claim 1 or 2.