CN109880031B - Preparation method of mixed alkylphenol-formaldehyde resin rubber tackifier - Google Patents
Preparation method of mixed alkylphenol-formaldehyde resin rubber tackifier Download PDFInfo
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Abstract
The invention provides a preparation method of a mixed alkylphenol-formaldehyde resin rubber tackifier, which uses C4Adding mixture of fraction, phenol and formaldehyde as raw materials, and adding C4Distilling and cutting the fraction addition mixture to obtain diisobutylene; mixing diisobutylene and phenol, and synthesizing an alkylation reaction solution under the catalytic action of a strong-acid cation exchange resin; distilling out light components and leaving heavy components to continue reacting; mixing the mixed alkylphenol and formaldehyde, and carrying out catalytic condensation and polycondensation to obtain the product. The process of the invention omits the rectification and purification process of alkylphenol, the mixed alkylphenol after alkylation is reacted with formaldehyde to obtain mixed alkylphenol-formaldehyde resin, phenols are effectively utilized, the generation of a large amount of solid wastes is avoided, and because a small amount of disubstituted phenol exists, better rubber compatibility is shown, the elongation at break is improved, and the adhesion increasing performance and the adhesion increasing durability which are equivalent to those of p-tert-octylphenol-formaldehyde resin are provided.
Description
Technical Field
The invention belongs to the technical field of rubber tackifiers, and particularly relates to a preparation method of a mixed alkylphenol-formaldehyde resin rubber tackifier, which mainly comprises p-tert-octylphenol-formaldehyde resin.
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 synthetic rubber compounds, the semi-finished part creeps to deform in size, causing the part to come loose due to swelling during molding. 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, wherein the alkylbenzene phenolic resin has the most excellent effect and is one of the main rubber auxiliary materials for tire molding.
However, compared with the traditional tackifying resin, the production process of the alkyl benzene phenolic resin is complex and the price is higher. The reason is mainly that the complicated and high-energy-consumption alkylphenol purification process restricts the wide application of the alkylphenol phenolic resin. Therefore, the development of a simple and low-cost synthesis process of alkylphenol-formaldehyde resin becomes a research hotspot of rubber auxiliary related industries.
Chinese patent document CN 101190961B discloses a preparation method of rubber tackifier p-tert-octylphenol formaldehyde resin, which adopts C4 fraction addition mixture as raw material; isobutene dimer with the content of target distillate more than 98 percent obtained by fractional distillation and cutting at the temperature of 75-105 ℃ is used as an alkylating agent; na-type sulfonated styrene-ethylene diene copolymer with 50 percent of water is used for strongly alkalifying anion exchange resin and is converted into H-type sulfonated styrene-ethylene diene copolymer strong acid cation exchange resin used as an alkylation catalyst through acidification; preparing an alkylation solution by alkylation reaction at 90-100 ℃, and then performing fractional steaming and cutting at 220-270 ℃ to prepare p-tert-octylphenol with the melting point of 87.5-89.5 ℃; then the p-tert-octylphenol and formaldehyde aqueous solution are subjected to acid catalysis condensation reaction in a toluene medium to prepare the p-tert-octylphenol formaldehyde resin. Through verification, the production process can obtain p-tert-octyl phenol-formaldehyde resin with better quality. However, the production process described in the above patent documents is complicated in operation, long in process flow, and high in energy consumption, and accordingly, the cost of the resin is high. Therefore, the development of the alkylphenol formaldehyde resin production process with relatively simplified process, short flow and low production cost has important significance.
Disclosure of Invention
The preparation method of the mixed alkylphenol-formaldehyde resin rubber tackifier provided by the invention achieves the purposes of simplifying the process, shortening the flow and reducing the production cost.
The preparation method of the mixed alkylphenol-formaldehyde resin rubber tackifier is characterized by comprising the following steps:
step 1, preparation of diisobutylene: by a sulfation-degassing process C4The distillate addition mixture is used as a raw material; distilling and cutting at 75-105 ℃ to obtain a distillate which is diisobutylene with the content of more than or equal to 98 percent;
step 2, preparation of mixed alkylphenol: diisobutylene and phenol solution are taken as raw materials, the reaction temperature is controlled to be 85-95 ℃, the reaction is carried out for 3-4 hours under the catalysis of strong acid cation exchange resin, alkylation reaction liquid is synthesized, light components with the temperature of 180 ℃ below 190 ℃ are distilled out, and the rest heavy components containing p-tert-octylphenol are reserved; the general structural formula of the mixed alkylphenol in the heavy component is as follows:
wherein R is1、R2、R3、R4、R5Is H or tert-butyl or tert-octyl: when R is1、R2、R4、R5Is H, R3When the alkyl phenol is tert-butyl, the alkyl phenol is p-tert-butyl phenol; when R is1、R2、R4、R5Is H, R3When the alkyl phenol is tert-octyl, the alkyl phenol is p-tert-octyl phenol;
step 3, synthesizing mixed alkylphenol-formaldehyde resin: keeping the temperature at 90-100 ℃, dropwise adding formaldehyde into the heavy component, reacting for 2-3 hours under the catalysis of p-toluenesulfonic acid to complete condensation reaction, then adding a buffer solution, and adjusting the reaction solution to be neutral; then taking toluene as an extraction liquid, extracting an organic phase in the condensation liquid, transferring the organic phase to a polycondensation reaction kettle, and heating for polycondensation; after the reaction is finished, discharging to obtain the mixed alkylphenol-formaldehyde resin, wherein the structure of the mixed alkylphenol-formaldehyde resin is as follows:
R2、R3、R5can be H or tert-butyl or tert-octyl; from the structure of the mixed alkylphenol-formaldehyde resin, it is known that the synthesized mixed alkylphenol-formaldehyde resin is a mixed alkylphenol-formaldehyde resin synthesized with p-tert-octylphenol as a main reactant, and contains a trace amount of alkylphenol containing an ortho-substituent which cannot participate in the reaction.
Preferably, in step 2, the molar ratio of the diisobutylene to the phenol is from 1:1 to 1.1: 1.
Preferably, in the polycondensation reaction in the step 3, the polycondensation reaction temperature is 140-150 ℃, and the polycondensation time is controlled to be 30-50min, so that the softening point of the obtained mixed alkylphenol-formaldehyde resin is 85-100 ℃, and the corresponding molecular weight is 800-1200.
Preferably, the formaldehyde solution used in step 3 is an aqueous formaldehyde solution with a content of 35% to 37%.
Preferably, the molar ratio of the mixed alkylphenol to formaldehyde is 1.0: 0.8-1.0:0.9.
Preferably, the strong-acid cation exchange resin is a D001 type cation exchange resin.
The reaction mechanism of the present invention:
the invention uses C4A fraction addition mixture, phenol and formaldehyde as raw materials, wherein C4The distillate addition mixture is a colorless transparent liquid; firstly, C is4Distilling and cutting the fraction addition mixture to obtain diisobutylene; then mixing diisobutylene with phenol, and synthesizing under the catalysis of strong acid cation exchange resinAn alkylating liquor; distilling out light components, and leaving heavy components for continuous reaction, wherein the heavy components are mixed alkylphenol and are white crystals at room temperature; mixing the mixed alkylphenol and formaldehyde, and carrying out catalytic condensation and polycondensation to obtain the product, wherein the condensation liquid is milky white liquid. After the polycondensation is completed, the product is obtained as a yellow to brown flaky solid.
The invention has the beneficial effects that:
1. compared with the production process of rubber tackifier p-tert-octylphenol-formaldehyde resin in the prior art, the invention adopts C4The distillate addition mixture, the phenol and the formaldehyde are used as basic raw materials, so that the production cost is effectively saved.
2. The technological process of the present invention has no alkyl phenol rectifying and purifying process, low power consumption, less investment in apparatus and simple operation.
3. The invention reacts alkylated mixed alkylphenol with formaldehyde to obtain mixed alkylphenol-formaldehyde resin, effectively utilizes phenols, and avoids the generation of a large amount of solid wastes.
4. The production process provided by the invention perfectly combines the synthesis of the mixed alkylphenol and the synthesis of the tackifying resin, simplifies the production process, saves the cost investment and reduces the solid waste rate on the premise of not influencing the product quality, and is a green, energy-saving and environment-friendly production process.
5. Compared with the p-tert-octyl phenol-formaldehyde resin, the mixed alkylphenol-formaldehyde resin prepared by the invention has better rubber compatibility and improved elongation at break due to the existence of a small amount of disubstituted phenol, and has the equivalent tackifying performance and tackifying durability to the p-tert-octyl phenol-formaldehyde resin.
Detailed Description
Example 1
A preparation method of a mixed alkylphenol-formaldehyde resin rubber tackifier comprises the following steps:
step 1, preparation of diisobutylene: to a 500ml four-necked round bottom reaction flask equipped with a mechanical stirrer, thermometer, reflux condenser and dropping funnel was added a solution obtained by the sulfation-degassing processC4250g of distillate addition mixture is used as a raw material; distilling and cutting at 75-105 ℃ to obtain a distillate which is diisobutylene with the content of more than or equal to 98 percent;
step 2, preparation of mixed alkylphenol: according to diisobutylene: weighing 153g of diisobutylene, 127g of phenol and 10g of D001 type cation exchange resin according to a molar ratio of 1:1, putting the weighed materials into a 500ml four-neck round-bottom reaction flask provided with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel, heating to 85 ℃, continuously reacting for 4 hours to obtain an alkylation reaction solution, starting distillation, stopping the distillation when the temperature is raised to 180 ℃, and filtering to remove the catalyst while the temperature is hot;
analyzing the components in the heavy components, wherein the components in the heavy components and the mass fraction of the components are as follows: p-tert-octylphenol: 85.0 percent; p-tert-butylphenol: 10.0 percent; di-substituted phenols: 4.0 percent; and others: 1.0 percent.
Step 3, synthesizing mixed alkylphenol-formaldehyde resin: the mass of the heavy components remaining in the flask was weighed to be 238g and calculated to be 1.16mol based on the total amount of p-tert-octylphenol. 1.2g of p-toluenesulfonic acid was added to the heavy component, the temperature was raised to 90 ℃, 75.3g of formaldehyde solution (phenolic ratio 1:0.8) was added dropwise, and the reaction was continued for 2 hours. The reaction solution was adjusted to pH 7 by adding (2.5%) sodium hydroxide solution. 190g of toluene were added, the organic phase was extracted and the aqueous phase was discharged. Subsequently, distillation and polycondensation were started. The temperature is raised to 140 ℃, the temperature is kept for 0.5h, and the material is discharged, namely the mixed alkylphenol-formaldehyde resin rubber tackifier which takes the p-tert-octylphenol-formaldehyde resin as the main component.
The product was weighed out with cooling, the yield was 99%. The resin was determined to have a softening point of 88 deg.C, a molecular weight of 825g/mol by Gel Permeation Chromatography (GPC), and a free phenol content of 0.9% by mass and a moisture content of 0.8% by mass in the resin by bromination.
Example 2
A preparation method of a mixed alkylphenol-formaldehyde resin rubber tackifier comprises the following steps:
step 1, preparation of diisobutylene: to a container equipped with a mechanical stirrer, thermometer, reflux condenser and droppingA500 ml four-neck round-bottom reaction flask with a liquid funnel is added with C which is processed by sulfation-degassing4250g of distillate addition mixture is used as a raw material; distilling and cutting at 75-105 ℃ to obtain a distillate which is diisobutylene with the content of more than or equal to 98 percent;
step 2, preparation of mixed alkylphenol: according to diisobutylene: 168g of diisobutylene, 127g of phenol, and 10g of a D001 type cation exchange resin were weighed in a ratio of 1.1:1 (molar ratio), and the weighed materials were put into a 500ml four-neck round-bottom reaction flask equipped with a mechanical stirrer, a thermometer, a reflux condenser, and a dropping funnel, and the temperature was raised to 90 ℃ to carry out a continuous reaction for 3 hours, thereby obtaining an alkylated alkylphenol solution. Subsequently, the distillation was started, the distillation was stopped after the temperature had risen to 185 ℃ and the catalyst was removed by filtration while hot.
Analyzing the components in the heavy components, wherein the components in the heavy components and the mass fraction of the components are as follows: p-tert-octylphenol: 87.0 percent; p-tert-butylphenol: 9.0 percent; di-substituted phenols: 3.0 percent; and others: 1.0 percent.
Step 3, synthesizing mixed alkylphenol-formaldehyde resin: the mass of the heavy component remaining in the flask was weighed to 245g and calculated to be 1.19mol based on the total amount of p-tert-octylphenol. 1.2g of p-toluenesulfonic acid was added to the heavy component, the temperature was raised to 90 ℃, 86.9g of formaldehyde solution (phenolic ratio 1:0.9) was added dropwise, and the reaction was continued for 2 hours. The reaction solution was adjusted to pH 7 by adding (2.5%) sodium hydroxide solution. 190g of toluene were added, the organic phase was extracted and the aqueous phase was discharged. Subsequently, distillation and polycondensation were started. The temperature is raised to 150 ℃, the temperature is kept for 40min, and the material is discharged, namely the mixed alkylphenol-formaldehyde resin rubber tackifier which takes the p-tert-octyl phenol-formaldehyde resin as the main component.
The product was weighed out by cooling, and the yield was 100%. The resin was determined to have a softening point of 96 deg.C, a molecular weight of 895g/mol by Gel Permeation Chromatography (GPC), and a free phenol content of 0.7% by mass and a moisture content of 0.9% by mass in the resin by bromination.
Example 3
A preparation method of a mixed alkylphenol-formaldehyde resin rubber tackifier comprises the following steps:
step 1, preparation of diisobutylene: to a 500ml four-necked round bottom reaction flask equipped with a mechanical stirrer, thermometer, reflux condenser and dropping funnel was added C which had undergone the sulfation-degassing process4250g of distillate addition mixture is used as a raw material; distilling and cutting at 75-105 ℃ to obtain a distillate which is diisobutylene with the content of more than or equal to 98 percent;
step 2, preparation of mixed alkylphenol: according to diisobutylene: 159g of diisobutylene, 127g of phenol, and 10g of a D001 type cation exchange resin were weighed in a ratio of 1.05:1 (molar ratio), and the weighed materials were put into a 500ml four-neck round-bottom reaction flask equipped with a mechanical stirrer, a thermometer, a reflux condenser, and a dropping funnel, and the temperature was raised to 85 ℃ to conduct a reaction continuously for 3.5 hours, thereby obtaining an alkylated solution. Subsequently, the distillation was started, the distillation was stopped after the temperature had risen to 190 ℃ and the catalyst was removed by filtration while hot.
Analyzing the components in the heavy components, wherein the components in the heavy components and the mass fraction of the components are as follows: p-tert-octylphenol: 86.0 percent; p-tert-butylphenol: 11.0 percent; di-substituted phenols: 2.0 percent; and others: 1.0 percent.
Step 3, synthesizing mixed alkylphenol-formaldehyde resin: the mass of the heavy components remaining in the flask was weighed to 240g and calculated to be 1.17mol based on the total amount of p-tert-octylphenol. 1.2g of p-toluenesulfonic acid was added to the heavy component, the temperature was raised to 95 ℃, 80.7g of formaldehyde solution (phenolic ratio 1:0.85) was added dropwise, and the reaction was continued for 2.5 hours. The reaction solution was adjusted to pH 7 by adding (2.5%) sodium hydroxide solution. 190g of toluene were added, the organic phase was extracted and the aqueous phase was discharged. Subsequently, distillation and polycondensation were started. The temperature is raised to 145 ℃, the temperature is kept for 50min, and the mixed alkylphenol-formaldehyde resin rubber tackifier which takes the p-tert-octylphenol-formaldehyde resin as the main component is discharged.
The product was weighed out by cooling, and the yield was 99.6%. The resin was determined to have a softening point of 100 deg.C, a molecular weight of 1050g/mol by Gel Permeation Chromatography (GPC), and a free phenol content of 0.9% by mass and a moisture content of 0.8% by mass in the resin by bromination.
Example 4
A preparation method of a mixed alkylphenol-formaldehyde resin rubber tackifier comprises the following steps:
step 1, preparation of diisobutylene: to a 500ml four-necked round bottom reaction flask equipped with a mechanical stirrer, thermometer, reflux condenser and dropping funnel was added C which had undergone the sulfation-degassing process4250g of distillate addition mixture is used as a raw material; distilling and cutting at 75-105 ℃ to obtain a distillate which is diisobutylene with the content of more than or equal to 98 percent;
step 2, preparation of mixed alkylphenol: according to diisobutylene: 153g of diisobutylene, 127g of phenol, and 10g of a D001 type cation exchange resin were weighed in a ratio of 1:1 (molar ratio) and put into a 500ml four-necked round-bottomed reaction flask equipped with a mechanical stirrer, a thermometer, a reflux condenser, and a dropping funnel, and the temperature was raised to 95 ℃ to continuously react for 4 hours, thereby obtaining an alkylated solution. Subsequently, the distillation was started, the distillation was stopped after the temperature had risen to 190 ℃ and the catalyst was removed by filtration while hot.
Analyzing the components in the heavy components, wherein the components in the heavy components and the mass fraction of the components are as follows: p-tert-octylphenol: 88.0 percent; p-tert-butylphenol: 10.0 percent; di-substituted phenols: 1.5 percent; and others: 0.5 percent.
Step 3, synthesizing mixed alkylphenol-formaldehyde resin: the mass of the heavy components remaining in the flask was weighed to be 238g and calculated to be 1.16mol based on the total amount of p-tert-octylphenol. 1.2g of p-toluenesulfonic acid was added to the heavy component, the temperature was raised to 100 ℃, 75.3g of formaldehyde solution (phenolic ratio 1:0.8) was added dropwise, and the reaction was continued for 3 hours. The reaction solution was adjusted to pH 7 by adding (2.5%) sodium hydroxide solution. 190g of toluene were added, the organic phase was extracted and the aqueous phase was discharged. Subsequently, distillation and polycondensation were started. The temperature is raised to 150 ℃, the temperature is kept for 45min, and the material is discharged, namely the mixed alkylphenol-formaldehyde resin rubber tackifier which takes the p-tert-octyl phenol-formaldehyde resin as the main component.
The product was weighed out by cooling, and the yield was 99.2%. The resin was determined to have a softening point of 92 ℃ and a molecular weight of 868g/mol by Gel Permeation Chromatography (GPC) and 0.8% by mass free phenol and 0.8% by mass moisture in the resin by bromination.
The p-tert-octylphenol-formaldehyde resin rubber tackifier was prepared as a comparative example by using p-tert-octylphenol and formaldehyde as raw materials, p-toluenesulfonic acid as an acid catalyst, and toluene as a solvent.
Comparative example 1
238g (1.16mol) of p-tert-octylphenol and 1.2g of p-toluenesulfonic acid were weighed, charged into a 500ml four-necked round-bottomed reaction flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel, heated to 100 ℃ and added dropwise with 75.3g of a formaldehyde solution (phenol/formaldehyde ratio: 1:0.8) to carry out continuous reaction for 3 hours. The reaction solution was adjusted to pH 7 by adding (2.5%) sodium hydroxide solution. 190g of toluene were added, the organic phase was extracted and the aqueous phase was discharged. Subsequently, distillation and polycondensation were started. And (3) raising the temperature to 150 ℃, keeping the temperature for 45min, and discharging to obtain the p-tert-octyl phenol-formaldehyde resin rubber tackifier.
The product was weighed out by cooling, and the yield was 99.3%. The resin was determined to have a softening point of 90 deg.C, a weight average molecular weight of 845g/mol by Gel Permeation Chromatography (GPC), a free phenol content of 0.6% by mass and a moisture content of 0.8% by mass in the resin by bromination.
Comparative example 2
238g (1.16mol) of p-tert-octylphenol and 1.2g of p-toluenesulfonic acid were weighed, charged into a 500ml four-necked round-bottomed reaction flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel, heated to 90 ℃ and added dropwise with 75.3g of a formaldehyde solution (phenol/formaldehyde ratio: 1:0.8) to carry out continuous reaction for 2 hours. The reaction solution was adjusted to pH 7 by adding (2.5%) sodium hydroxide solution. 190g of toluene were added, the organic phase was extracted and the aqueous phase was discharged. Subsequently, distillation and polycondensation were started. And (3) raising the temperature to 140 ℃, keeping the temperature for 30min, and discharging to obtain the p-tert-octyl phenol-formaldehyde resin rubber tackifier.
The product was weighed out by cooling, and the yield was 99.6%. The resin was determined to have a softening point of 95 deg.C, a weight average molecular weight of 882g/mol by Gel Permeation Chromatography (GPC), and a free phenol content of 0.5% by mass and a moisture content of 0.8% by mass in the resin by bromination.
Comparative example 3
245g (1.19mol) of p-tert-octylphenol and 1.2g of p-toluenesulfonic acid were weighed, charged into a 500ml four-necked round-bottomed reaction flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel, heated to 90 ℃ and added dropwise with 86.9g of a formaldehyde solution (phenol/formaldehyde ratio 1:0.9) to carry out continuous reaction for 2 hours. The reaction solution was adjusted to pH 7 by adding (2.5%) sodium hydroxide solution. 190g of toluene were added, the organic phase was extracted and the aqueous phase was discharged. Subsequently, distillation and polycondensation were started. And (3) raising the temperature to 150 ℃, keeping the temperature for 40min, and discharging to obtain the p-tert-octyl phenol-formaldehyde resin rubber tackifier.
The product was weighed out by cooling, and the yield was 99.5%. The resin was determined to have a softening point of 99 deg.C, a weight average molecular weight of 910g/mol by Gel Permeation Chromatography (GPC), and a free phenol content of 0.5% by mass and a moisture content of 0.8% by mass in the resin by bromination.
Comparative example 4
245g (1.19mol) of p-tert-octylphenol and 1.2g of p-toluenesulfonic acid were weighed, charged into a 500ml four-necked round-bottomed reaction flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel, heated to 95 ℃ and added dropwise with 86.9g of a formaldehyde solution (phenol/formaldehyde ratio 1:0.9) to carry out continuous reaction for 2.5 hours. The reaction solution was adjusted to pH 7 by adding (2.5%) sodium hydroxide solution. 190g of toluene were added, the organic phase was extracted and the aqueous phase was discharged. Subsequently, distillation and polycondensation were started. And (3) raising the temperature to 145 ℃, keeping the temperature for 50min, and discharging to obtain the p-tert-octyl phenol-formaldehyde resin rubber tackifier.
The product was weighed out by cooling, and the yield was 99.5%. The resin was determined to have a softening point of 100 deg.C, a weight average molecular weight of 1080g/mol by Gel Permeation Chromatography (GPC), a free phenol content of 0.5% by mass and a moisture content of 0.8% by mass in the resin by bromination.
The product quality indicators obtained in examples 1 to 4 and comparative examples 1 to 4 are formed in table 1:
TABLE 1 quality index
As shown in Table 1, the product obtained by the production process has a slightly high content of free phenol in the product due to the fact that the raw material contains a small amount of phenols which do not participate in the reaction, but the content of free phenol in the product is less than 1% of the index (refer to standard HG/T4388-2012) requirement, so that the product is used as the raw material to produce other products, and the application performance of the other products is not affected.
The products obtained in examples 1-4 and comparative examples 1-4 were used as rubber tackifiers to verify the performance.
Table 2 shows the formula of the shoulder wedge of the all-steel radial truck tire, and the products obtained in examples 1-4 and comparative examples 1-4 are applied to rubber mixing:
TABLE 2 all-steel load radial tire shoulder wedge formula
A two-stage mixing process is adopted, wherein one-stage mixing of carbon black master batch is carried out in a 1.5L experimental internal mixer, and 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 a roll mill, adding insoluble sulfur and an accelerant, cutting for 2 times at 3/4 left and right, thinly passing for 4 times at the minimum roll spacing, rolling for 4 at the 2mm roll spacing, discharging the sheets, and standing to be tested.
The scorch characteristics of the rubber compounds were measured, and 140 ℃ Mooney scorch test was conducted to obtain the data shown in Table 3
TABLE 3 scorch characteristics of the mixes
From the Mooney scorch test data t5 at 140 ℃: compared with the blank, the scorch time t5 of the compound was reduced by about 20% after the addition of the products of examples 1-4 and comparative examples 1-4. And the scorch times t5 for each group of compounds in groups 2-9 were close, indicating that the mixed alkylphenol-formaldehyde resin produced by the process of the present application was consistent with the standard p-tert-octylphenol-formaldehyde resin in terms of scorch characteristics of the rubber compound.
Vulcanizate physical property data form table 4:
TABLE 4 vulcanizate physical Properties
Analysis of the mechanical property data of each rubber material before thermal oxidative aging shows that the tensile strength and the stress at definite elongation of each rubber material are consistent with those of the blank, which indicates that the tackifying resins of examples 1-4 and comparative examples 1-4 have no difference in performance. After thermo-oxidative aging, the compounds to which the products of examples 1-4 were added exhibited a slight increase in elongation at break compared to the compounds to which the products of comparative examples 1-4 were added, because the resins synthesized in examples 1-4 contained other types of alkylphenols, such as disubstituted phenols, which resulted in higher branching degree of the resins and better compatibility with rubbers, and thus exhibited higher elongation at break.
The autohension test was tested and the resulting data are reported in table 5:
TABLE 5 self-adhesion test (adhesion/N)
| Number of sizing materials | Additive product | 1d | 3d | 5d | 8d | 15d |
| 1 | Blank space | 5.61 | 7.02 | 6.57 | 6.41 | 7.30 |
| 2 | Example 1 | 14.32 | 12.33 | 12.42 | 11.27 | 13.97 |
| 3 | Example 2 | 14.61 | 12.64 | 12.53 | 11.48 | 14.05 |
| 4 | Example 3 | 14.31 | 12.48 | 12.73 | 11.29 | 14.18 |
| 5 | Example 4 | 14.25 | 12.52 | 12.50 | 11.31 | 14.05 |
| 6 | Comparative example 1 | 14.27 | 12.30 | 12.39 | 11.30 | 13.89 |
| 7 | Comparative example 2 | 14.53 | 12.59 | 12.49 | 11.44 | 14.02 |
| 8 | Comparative example 3 | 14.40 | 12.53 | 12.63 | 11.26 | 14.21 |
| 9 | Comparative example 4 | 14.38 | 12.47 | 12.58 | 11.33 | 13.80 |
As shown in Table 5, after the rubber materials are parked for 1d, 3d, 5d, 8d and 15d, the self-adhesiveness of the rubber materials is obviously improved by analyzing data compared with that of the blank rubber materials after the tackifying resin is added. Examples 1-4 perform similarly in terms of self-adhesion as compared to comparative examples 1-4, indicating that the resins perform similarly in tackifying applications.
The comprehensive application experiment results show that all indexes of the samples obtained in the embodiments of the invention and the samples obtained in the comparative examples are qualified, and the samples show the same performance in the aspects of the application performances such as scorching characteristic of rubber compound, physical performance of vulcanized rubber, self-adhesiveness and the like. The mixed alkylphenol-formaldehyde resin rubber tackifier synthesized by the method not only can save energy consumption and reduce production cost, but also can ensure that the product quality and the application performance can reach the performance of the similar products.
Claims (5)
1. The preparation method of the mixed alkylphenol-formaldehyde resin rubber tackifier is characterized by comprising the following steps:
step 1, preparation of diisobutylene: by a sulfation-degassing process C4The distillate addition mixture is used as a raw material; distilling and cutting at 75-105 ℃ to obtain a distillate which is diisobutylene with the content of more than or equal to 98 percent;
step 2, preparation of mixed alkylphenol: diisobutylene and phenol solution are taken as raw materials, the reaction temperature is controlled to be 85-95 ℃, the reaction is carried out for 3-4 hours under the catalysis of strong acid cation exchange resin, alkylation reaction liquid is synthesized, light components with the temperature of 180 ℃ below 190 ℃ are distilled out, and the rest heavy components containing p-tert-octylphenol are reserved; the general structural formula of the mixed alkylphenol in the heavy component is as follows:
wherein R is1、R2、R3、R4、R5Is H or tert-butyl or tert-octyl: when R is1、R2、R4、R5Is H, R3When the alkyl phenol is tert-butyl, the alkyl phenol is p-tert-butyl phenol; when R is1、R2、R4、R5Is H, R3When the alkyl phenol is tert-octyl, the alkyl phenol is p-tert-octyl phenol;
step 3, synthesizing mixed alkylphenol-formaldehyde resin: keeping the temperature at 90-100 ℃, dropwise adding formaldehyde into the heavy component, reacting for 2-3 hours under the catalysis of p-toluenesulfonic acid to complete condensation reaction, then adding a buffer solution, and adjusting the reaction solution to be neutral; then taking toluene as an extraction liquid, extracting an organic phase in the condensation liquid, transferring the organic phase to a polycondensation reaction kettle, and heating for polycondensation; after the reaction is finished, discharging to obtain the mixed alkylphenol-formaldehyde resin, which comprises the following structure:
R2、R3、R5can be H or tert-butyl or tert-octyl; the synthesized mixed alkylphenol-formaldehyde resin is a mixed alkylphenol-formaldehyde resin synthesized by taking p-tert-octylphenol as a main reactant, and contains trace alkylphenol containing ortho-substituent which can not participate in the reaction; in the polycondensation reaction, the polycondensation reaction temperature is 140-85-100 ℃, and the corresponding molecular weight is between 800-1200.
2. The method of claim 1, wherein in step 2, the ratio of the diisobutylene to phenol is in the range of 1:1 to 1.1: 1.
3. The method for preparing the mixed alkylphenol-formaldehyde resin rubber tackifier according to claim 1, wherein the formaldehyde used in the step 3 is a formaldehyde aqueous solution with a content of 35% to 37%.
4. The method of claim 1, wherein the molar ratio of the mixed alkylphenol to formaldehyde is 1.0: 0.8-1.0:0.9.
5. The method of claim 1, wherein the strong acid cation exchange resin is a D001 cation exchange resin.
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