CN108503759B - Synthesis method of alkyl phenolic resin - Google Patents
Synthesis method of alkyl phenolic resin Download PDFInfo
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Abstract
The invention discloses an alkyl phenolic resin and a synthesis method thereof. Compared with the similar alkyl phenolic resin, the alkyl phenolic resin has obviously better tackifying effect and the content of free phenol is reduced. The invention also discloses the application of the alkyl phenolic resin in the production and manufacture of tires and rubber products.
Description
The application is filed on 5/29/2014, has an application number of 201410235452.8 and is named as: the invention discloses a synthesis method of alkyl phenolic resin, which is a divisional application of Chinese patent application.
Technical Field
The invention belongs to the technical field of rubber manufacturing, and particularly relates to a synthetic method of alkyl phenolic resin.
Technical Field
Tackifying resins are important compounding agents in rubber processing, and the importance of tackifying resins is increasing due to insufficient self-adhesion as the amount of synthetic rubber used increases. In the tire industry, various types of rubber parts need to be adhered closely to each other before being vulcanized in a line, so a tackifying resin is indispensable in the tire formulation.
The tackifying resins are hydrocarbon resins, rosin resins, alkyl phenolic resins and modified products thereof. Because the tackifying effect is good, the influence on the dynamic performance of the mechanical property of the rubber is small, and the alkyl phenolic tackifying resin becomes a main industrial rubber tackifying resin. The alkyl phenolic tackifying resin mainly comprises octyl phenol and butyl phenol resin, generally alkyl phenol formaldehyde resin, and a few kinds of acetaldehyde and acetylene resin. Still a few products are modifications on the basis of the above-mentioned alkylphenol-formaldehyde resins.
The alkyl phenolic tackifying resin is a linear oligomer, the number average molecular weight is generally between 500 and 1500, the weight average molecular weight is generally not more than 2500, because the reaction degree of the condensation reaction is low, so that more phenolic monomers are inevitably remained in the resin, and the free phenol can be brought into the rubber product and continuously migrate out of the rubber product during the use of the rubber product, thereby polluting the environment. The general methods for removing free phenol mainly include: water washing, long-time vacuum, steam distillation and the like all need to consume a lot of working hours and energy sources, or have high requirements on equipment, are difficult to realize, and have poor economic benefits.
The invention relates to an alkyl phenolic tackifying resin and a preparation method thereof, which simply and effectively reduces free phenol in the resin, improves the environmental protection of the product, has narrow molecular weight distribution, and improves the tackifying effect compared with the common alkyl phenolic tackifying resin.
Disclosure of Invention
In order to reduce the content of free alkylphenol in alkylphenol phenolic tackifying resin and increase the environmental protection of products, the invention provides a synthetic method of tackifying resin, namely alkylphenol phenolic resin. The tackifying resin synthesized by the method has the advantages of low free phenol monomer content, simple and convenient synthesis method, reduced molecular weight distribution width and improved tackifying effect.
The invention provides a method for synthesizing alkyl phenolic resin, which comprises the steps of adding raw materials of mono-substituted alkylphenol and di-substituted alkylphenol (for example, the total mole ratio of the mono-substituted alkylphenol to the di-substituted alkylphenol is 1: 0.05-1) into a reactor according to a certain proportion (for example, the mole ratio of the mono-substituted alkylphenol to the di-substituted alkylphenol is 1: 0.05-1), reacting with a certain amount of aldehyde (for example, 0.5-1.2 moles of aldehyde) at 70-180 ℃ under the action of an acid catalyst, further removing residual moisture after reaching a target softening point (for example, 80-150 ℃), and completely neutralizing to obtain the alkyl phenolic resin. Wherein the molecular weight distribution of the alkyl phenolic resin is 1.4-1.8; the content of free alkylphenol in the alkyl phenolic resin is 0.5-3%.
In the synthetic method, the monosubstituted alkylphenol is R as a substituent1The monosubstituted alkylphenol of (1); the disubstituted alkylphenol has a substituent R2、R3、R4、R5Any one or two of them.
The reaction process of the synthetic method of the invention is as follows:
wherein R is hydrogen or methyl; r1Is alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 18 carbon atoms or aryl with 6 to 18 carbon atoms; r2、R3、R4、R5Respectively is alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 18 carbon atoms or aryl with 6 to 18 carbon atoms. Preferably, R is hydrogen or methyl; r1Is an alkyl group of 4 to 9 carbon atoms; r2、R3、R4、R5Each alkyl group having 4 to 9 carbon atoms.
The synthesized product alkyl phenolic resin contains 0.5 to 3 percent of free alkylphenol. The molecular weight distribution of the synthesized product alkyl phenolic resin is 1.4-1.8. The softening point of the synthesized product alkyl phenolic resin is 80-150 ℃.
The synthesized product alkyl phenolic resin comprises the following structure:
wherein R is hydrogen or methyl. R1Is alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 18 carbon atoms or aryl with 6 to 18 carbon atoms. Preferably, R1Is preferably an alkyl group of 4 to 9 carbon atoms. More preferably, R1Is tert-butyl or tert-octyl. R2、R3、R4、R5Respectively is alkyl with 1 to 18 carbon atoms, cycloalkyl with 5 to 18 carbon atoms or aryl with 6 to 18 carbon atoms. R2、R3、R4、R5The groups may be the same or different substituents. Preferably, R2、R3、R4、R5Each alkyl group having 4 to 9 carbon atoms.
In the synthetic method, the molar ratio of the mono-substituted alkylphenol to the di-substituted alkylphenol of the raw materials is 1: 0.05-1. Preferably, the molar ratio of the mono-substituted alkylphenol to the di-substituted alkylphenol is 1: 0.05-0.5.
Wherein the raw material monosubstituted alkylphenol has a substituent R1The monosubstituted alkylphenols of (1). The raw material mono-substituted alkylphenol includes but is not limited to one or more of p-methyl phenol, p-n-butyl phenol, p-tert-octyl phenol, nonyl phenol, dodecyl phenol and octadecyl phenol. Preferably, the raw material mono-substituted alkylphenol is p-tert-butylphenol, p-tert-octylphenol, p-nonylphenol.
Wherein the raw material disubstituted alkylphenol has a substituent R2、R3、R4、R5Any one or two of them. The raw material disubstituted alkylphenol includes but is not limited to one or more of 2, 4-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 2, 4-di-tert-octylphenol, 2, 6-di-tert-octylphenol, 2, 4-di-octylphenol, 2-tert-butyl-4-tert-butylphenol, 2-tert-butyl-4-octylphenol, 2-octyl-4-tert-butylphenol.
Wherein the acidic catalyst is one or a mixture of more than two of sulfuric acid, hydrochloric acid, benzenesulfonic acid or alkyl substituent thereof, phenyl sulfate and oxalic acid. Preferably, the acidic catalyst is benzenesulfonic acid or its alkyl substituent, oxalic acid.
Wherein the aldehyde is one or mixture of 10-37% concentration formaldehyde water solution or paraformaldehyde, or one or mixture of acetaldehyde or paraldehyde.
The invention also provides the alkylphenol formaldehyde resin prepared by the synthesis method, and the content of free alkylphenol in the product alkylphenol formaldehyde resin is 0.5-3%; the molecular weight distribution is 1.4-1.8.
When the alkyl phenolic resin (dialkyl phenol-alkyl phenolic resin) is prepared by adopting the method, because the dialkyl phenol only has one functional group, the end capping effect can be realized when the dialkyl phenol is connected to a phenolic resin molecular chain, and the polymerization degree is prevented from increasing. During the chain growth of the macromolecule, monomers (including alkylphenol and dialkyl phenol) are continuously attached to the molecular chain of the phenolic resin. In view of the reaction probability, the alkylphenol concentration is high and the functional group is large at the initial stage of the reaction, so that the alkylphenol resin is formed in many cases. As the degree of reaction increases, the longer the molecular chain of the phenolic resin, the higher the chance of capping with dialkylphenols is naturally, while the chance of capping with free phenols and small molecules that do not undergo chain growth is relatively low. In the synthesis method, in the later reaction stage with higher conversion rate, the macromolecules are mostly blocked and cannot continue to grow, so that the softening point is prevented from exceeding the application range. And simultaneously, the added aldehyde mainly reacts with free alkylphenol and micromolecules, so that the content of the free alkylphenol in the final product, namely the alkylphenol formaldehyde resin is reduced.
Compared with the commercial alkylphenol formaldehyde tackifying resin, the free phenol content is lower at the same softening point, and the product is synthesized by the simple method, so that the content of the free phenol can reach below 1% without post-treatment processes such as vacuum, water washing and the like, the energy consumption, the working hour and the monomer conversion rate are reduced, and the environmental pollution caused by the post-treatment process is reduced. Meanwhile, the molecular weight distribution of the product is narrower than that of normal alkylphenol formaldehyde resin, and the tackifying effect of the product is superior to that of the similar existing alkylphenol formaldehyde tackifying resin.
The content of free phenol in the existing alkylphenol formaldehyde resin with the same brand and the same softening point is 1-3 percent lower, for example, the content of free phenol in p-tert-butyl phenol formaldehyde resin with the softening point of 118-125 ℃ is 3-4 percent, and the vacuum can reduce the content of free phenol to 2-3 percent at most. Compared with the commercial alkylphenol formaldehyde tackifying resin, the alkylphenol formaldehyde tackifying resin is modified by introducing dialkyl phenol, and after the synthesis by a simple method, the post-treatment processes such as vacuum, water washing and the like are not needed, so that the content of free phenol in the alkylphenol formaldehyde tackifying resin can reach below 1 percent, the energy consumption, the working hours and the monomer conversion rate are reduced, and the environmental pollution caused by the post-treatment process is reduced. Moreover, the molecular weight distribution of the product of the invention is narrower than that of the prior alkylphenol formaldehyde resin, and the molecular weight distribution index PDI is 1.4-1.9 according to the dosage of the dialkyl phenol, while the molecular weight distribution index of the prior alkylphenol formaldehyde resin is generally 1.8-2.2.
The alkyl phenolic resin synthesized by the invention has obvious and excellent tackifying effect. According to the invention, by adding part of disubstituted alkylphenol in the resin synthesis process, the content of free phenol in the phenolic resin is effectively reduced, and the environmental protection of the product is improved.
The reason for the significant reduction of free phenol in the alkylphenol-formaldehyde resin of the product of the invention is the introduction of the dialkyl phenol. Both alkylphenols and formaldehyde are difunctional monomers, and lowering free phenol necessitates an increase in the conversion of the alkylphenol, but higher conversions result in too high a molecular weight and softening point to make the resin unusable. According to the condensation reaction theory, molecular weight
The reaction degree P and the equivalent coefficient gamma have the following relationship:
the type of alkylphenol and the softening point of the resin require a limited molecular weight range. Molecular weight
The degree of reaction P and the equivalent coefficient γ are always the same.
After the introduction of monofunctional dialkylphenols, the equivalent coefficient γ decreases and the degree of reaction P increases, leading to a decrease in free phenol in the resin.
The tackifying resin has a good tackifying effect within a certain molecular weight range. When the molecular weight is too small, the anchoring effect of the alkyl segment in the rubber is insufficient; when the molecular weight is too large, the mobility in the resin is poor and sufficient orientation cannot be formed at the rubber interface to obtain a thickening effect by hydrogen bonding. The alkyl phenolic resin (dialkyl phenol-alkyl phenolic tackifying resin) synthesized by the preparation method utilizes the end capping function of dialkyl phenol, and the end capping probability of long-chain molecules is higher in the chain growth process, so that the molecular weight of macromolecules is reduced, and the proportion of macromolecules with the number of chain links more than 10 is obviously reduced. And when the second stage is supplemented with aldehyde, the monomer conversion rate is increased, so that the content of small molecules in the resin, namely oligomers containing 2-3 chain units is reduced. The molecular weight distribution is concentrated in a more reasonable range, namely the proportion of phenolic resin molecules containing 6-9 chain links is increased, so that the performance of the product of the invention is improved compared with the prior alkylphenol tackifying resin.
The invention also provides the application of the synthesized alkyl phenolic resin as a tackifier in the manufacture of rubber products and the application of the synthesized alkyl phenolic resin as a tackifier in tire rubber. The alkyl phenolic resin synthesized by the invention is applied to rubber mixtures, improves the self-adhesion of rubber, improves the tackifying performance compared with similar products in the prior art, and has low content of free phenol and obvious environmental protection. Compared with other modification methods, other modification substances are not introduced into the benzene product, the structure of the benzene product is similar to that of the existing alkylphenol formaldehyde resin, other unknown influences on the rubber performance can not be generated, and the benzene product is particularly suitable for being applied to tire rubber materials.
Detailed Description
The present invention will be further described in detail with reference to the following specific examples, but the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.
Reference ratio 1
A1000 ml four-necked reaction flask was equipped with a stirrer, a thermometer, and a reflux condenser. 300g of p-tert-butylphenol, 105g of a 37% formalin solution and 1.0g of p-toluenesulfonic acid were charged. 20g of toluene as a solvent, and raising the temperature to 100 ℃. The reaction was refluxed at 100 ℃ for 2 hours. The temperature is raised to 190 ℃ under normal pressure to remove toluene and water, and 0.7g of sodium hydroxide 20% aqueous solution is added for neutralization. The temperature was raised to 200 ℃ and maintained at this temperature for 2 hours. The resin melt was discharged into a stainless steel pan and cooled to room temperature. The product is transparent, has a softening point of 127 ℃ and is orange, and the structure of the product is as follows:
the free phenol, molecular weight distribution data are shown in Table 2.
Reference ratio 2
On a 1000ml four-necked reaction flask, a stirrer, a thermometer, a reflux condenser and an addition funnel were mounted. 412g of p-tert-octylphenol and 80g of a 37% formaldehyde aqueous solution were charged, and 2g of dodecylbenzenesulfonic acid was added thereto. The temperature is raised to 100 ℃, and the reflux reaction is carried out for 2 hours at 100 ℃. Dehydrating under normal pressure. When the temperature rises to 140 ℃, 11g of aldehyde is gradually supplemented. The temperature is raised to 160 ℃ for dehydration, 1.1g of sodium hydroxide 20% aqueous solution is added for neutralization, and the temperature is kept for 2 hours. The resin melt was discharged into a stainless steel pan and cooled to room temperature. The product is transparent, has a softening point of 94 ℃ and is brownish yellow.
The free phenol, molecular weight distribution data are shown in Table 3.
Example 1
On a 1000ml four-necked reaction flask, a stirrer, a thermometer, a reflux condenser and an addition funnel were mounted. 285g of p-tert-butylphenol, 20.6g of 2, 4-di-tert-butylphenol, 1.0g of p-toluenesulfonic acid, 20g of toluene as a solvent and 110g of 37% formaldehyde aqueous solution were added, the temperature was raised to 100 ℃ and a reflux reaction was carried out for 2 hours. The temperature is raised to 190 ℃ under normal pressure for dehydration and toluene, and 0.7g of sodium hydroxide 20% aqueous solution is added for neutralization. The temperature was raised to 200 ℃ and maintained at this temperature for 2 hours. The resin melt was discharged into a stainless steel pan and cooled to room temperature. The product is orange in color and has a softening point of 126 ℃. The molecular weight of the resin is higher during dehydration, and the toluene solvent is added to reduce the viscosity of the reaction system during dehydration.
Example 2
On a 1000ml four-necked reaction flask, a stirrer, a thermometer, a reflux condenser and an addition funnel were mounted. 255g of p-tert-butylphenol, 61.8g of 2, 4-di-tert-butylphenol, 1.2g of p-methylbenzenesulfonic acid, and 90g of 37% formalin were charged, and the mixture was heated to 100 ℃ and refluxed for 2 hours. Heating to 140 ℃ under normal pressure for dehydration, then gradually supplementing 16g of reinforced aldehyde, heating to 190 ℃ for dehydration, and adding 0.8g of sodium hydroxide 20% aqueous solution for neutralization. The temperature was raised to 200 ℃ and maintained at this temperature for 2 hours. The resin melt was discharged into a stainless steel pan and cooled to room temperature. The product is orange in color and has a softening point of 127 ℃.
Example 3
On a 1000ml four-necked reaction flask, a stirrer, a thermometer, a reflux condenser and an addition funnel were mounted. 180g of p-tert-butylphenol, 164.8g of 2, 4-di-tert-butylphenol, 1.2g of p-methylbenzenesulfonic acid, 20g of toluene as a solvent, and 120g of a 37% formaldehyde aqueous solution were charged, and the mixture was heated to 100 ℃ and subjected to a reflux reaction for 2 hours. The atmospheric temperature was raised to 190 ℃ for dehydration and toluene, and 0.8g of a 20% aqueous solution of sodium hydroxide was added for neutralization. The temperature was raised to 200 ℃ and maintained at this temperature for 2 hours. The resin melt was discharged into a stainless steel pan and cooled to room temperature. The product is orange in color and has a softening point of 125 ℃.
Example 4
On a 1000ml four-necked reaction flask, a stirrer, a thermometer, a reflux condenser and an addition funnel were mounted. 150g of p-tert-butylphenol, 206g of 2, 4-di-tert-butylphenol, 1.2g of p-toluenesulfonic acid and 90g of 37% formaldehyde aqueous solution are added, the temperature is raised to 100 ℃, and reflux reaction is carried out for 2 hours. Dehydrating under normal pressure. The temperature is raised to 140 ℃, then 22g of aldehyde is gradually supplemented, the temperature is raised to 190 ℃ to remove residual water, and 0.8g of sodium hydroxide 20% aqueous solution is added for neutralization. The temperature was raised to 200 ℃ and maintained at this temperature for 2 hours. The resin melt was discharged into a stainless steel pan and cooled to room temperature. The product is orange in color and has a softening point of 120 ℃.
Example 5
On a 1000ml four-necked reaction flask, a stirrer, a thermometer, a reflux condenser and an addition funnel were mounted. 370.8g of p-tert-octylphenol, 63.6g of 2, 4-di-tert-octylphenol, 0.8g of p-toluenesulfonic acid, 1g of oxalic acid and 85g of 37% formaldehyde aqueous solution were charged, and the mixture was heated to 100 ℃ and reacted at 100 ℃ for 2 hours under reflux. Dehydrating under normal pressure. When the temperature rises to 140 ℃, 12g of aldehyde is gradually supplemented. The temperature is raised to 160 ℃ for dehydration, 1.2g of sodium hydroxide 20% aqueous solution is added for neutralization, and the temperature is kept for 2 hours. The resin melt was discharged into a stainless steel pan and cooled to room temperature. The product is transparent, the softening point is 95 ℃, and the product is brownish yellow.
Example 6
On a 1000ml four-necked reaction flask, a stirrer, a thermometer, a reflux condenser and an addition funnel were mounted. 309g of p-tert-octylphenol, 159g of 2, 4-di-tert-octylphenol, 1.6g of dodecylbenzenesulfonic acid and 85g of 37% formaldehyde aqueous solution were charged, the temperature was raised to 100 ℃ and the mixture was refluxed at 100 ℃ for 2 hours. Dehydrating under normal pressure. When the temperature rises to 140 ℃, 15g of aldehyde is gradually supplemented. The temperature is raised to 160 ℃ for dehydration, 1.2g of sodium hydroxide 20% aqueous solution is added for neutralization, and the temperature is kept for 2 hours. The resin melt was discharged into a stainless steel pan and cooled to room temperature. The product is transparent, has a softening point of 96 ℃ and is brownish yellow.
Example 7
Alkylating phenol with excess diisobutylene using cation exchange resin as catalyst to obtain an alkylation solution, analyzing the composition of the alkylation solution: 43% of p-tert-octylphenol, 7% of p-tert-butylphenol, 38% of 2, 4-di-tert-octylphenol, 12% of 2-tert-butyl-4-tert-octylphenol, and the molar ratio of alkylphenol to dialkylphenol in the alkylation solution was about 0.6:0.4, and a stirrer, a thermometer, a reflux condenser and an addition funnel were attached to a 1000ml four-necked reaction flask. 400g of the above alkylation mixture, 0.8g of p-toluenesulfonic acid, 1g of oxalic acid, and 91g of 37% aqueous formaldehyde solution were added, and the mixture was heated to 100 ℃ and reacted at 100 ℃ under reflux for 2 hours. Dehydrating under normal pressure. When the temperature rises to 140 ℃, 19g of aldehyde is gradually supplemented. The temperature is raised to 160 ℃ for dehydration, 1.2g of sodium hydroxide 20% aqueous solution is added for neutralization, and the temperature is kept for 2 hours. The resin melt was discharged into a stainless steel pan and cooled to room temperature. The product is transparent, the softening point is 95 ℃, and the product is brownish yellow.
Example 8
Alkylating phenol with excess octene using cation exchange resin as catalyst to obtain an alkylation solution, analyzing the composition of the alkylation solution: there was 68% p-octylphenol, 4-butylphenol, 23% 2, 4-dioctylphenol, 5% 2-butyl-6-octylphenol, and a molar ratio of alkylphenol to dialkylphenol of about 0.8: 0.2. On a 1000ml four-necked reaction flask, a stirrer, a thermometer, a reflux condenser and an addition funnel were mounted. 400g of the above alkylation mixture, 0.8g of p-toluenesulfonic acid, 1g of oxalic acid and 90g of 37% aqueous formaldehyde solution were added, the temperature was raised to 100 ℃ and the mixture was refluxed at 100 ℃ for 2 hours. Dehydrating under normal pressure. When the temperature rises to 140 ℃, 14g of aldehyde is gradually supplemented. The temperature is raised to 160 ℃ for dehydration, 1.2g of sodium hydroxide 20% aqueous solution is added for neutralization, and the temperature is kept for 2 hours. The resin melt was discharged into a stainless steel pan and cooled to room temperature. The product is transparent, has a softening point of 94 ℃ and is brownish yellow.
Example 9
Using cation exchange resin as a catalyst, alkylating phenol by using excessive nonene and octene to obtain an alkylation solution, and analyzing the composition of the alkylation solution: there was 36% p-octylphenol, 28% p-nonylphenol, 3% 4-butylphenol, 2% 4-pentylphenol, 18% 2, 6-dioctylphenol, 11% 2, 4-dinonylphenol, 2% 2-butyl-4-octylphenol, and a molar ratio of alkylphenol to dialkylphenol of about 0.78: 0.22. On a 1000ml four-necked reaction flask, a stirrer, a thermometer, a reflux condenser and an addition funnel were mounted. 400g of the above alkylation mixture, 0.8g of p-toluenesulfonic acid, 1g of oxalic acid, and 83g of 37% aqueous formaldehyde solution were added, and the mixture was heated to 100 ℃ and reacted at 100 ℃ under reflux for 2 hours. Dehydrating under normal pressure. When the temperature rises to 140 ℃, 17g of aldehyde is gradually supplemented. The temperature is raised to 160 ℃ for dehydration, 1.2g of sodium hydroxide 20% aqueous solution is added for neutralization, and the temperature is kept for 2 hours. The resin melt was discharged into a stainless steel pan and cooled to room temperature. The product is transparent, the softening point is 92 ℃, and the product is brownish yellow.
Example 10 testing of resin tack
The resin viscosity detection method comprises the following steps:
firstly, mixing butadiene rubber, natural rubber, carbon black, process oil, stearic acid and zinc oxide in an internal mixer at about 150 ℃ to obtain master batch; secondly, respectively adding the product from the reference ratio and the tackifying resin from the embodiment into a certain amount of master batch, additionally adding anti-aging agents TMQ and 4020, and mixing in an internal mixer at about 140 ℃; and thirdly, adding sulfur and an accelerator NS into the rubber material obtained in the second step, and mixing and tabletting on an open mill to obtain the rubber sheet. These films were stored at 23 ℃ and 50% humidity and tested for self-adhesion for 24 hours, 48 hours and 72 hours, respectively. The tackiness was measured by a tack tester model P-2 from Toyo Seiki Seisaku-Sho Ltd.
The following table 1 shows the rubber mixture formulations. The characteristics of the product synthetic resin alkylphenol-formaldehyde resins prepared in the above examples 1-9 are shown in tables 2-4. The results of the self-adhesion tests of rubber sheets using different tackifying resins are shown in Table 5.
TABLE 1 formulation of rubber film in resin tack testing
| Serial number | Raw material | Formulation of |
| 1 | Natural rubber | 30.0 |
| 2 | Cis-polybutadiene rubber | 70.0 |
| 3 | Carbon Black N375 | 80.0 |
| 4 | Oil | 4.0 |
| 5 | Stearic acid | 2.0 |
| 6 | Zinc oxide | 3.0 |
| 7 | Sulphur (80%) (OT20) | 1.0 |
| 8 | Products obtained in reference example 1 or 2, or products obtained in examples 1 to 9 | 4.0 |
| 9 | Sulfenamide NS | 2.2 |
| 10 | Anti-aging agent TMQ | 1.5 |
| 11 | Anti-aging agent 4020 | 1.6 |
TABLE 2 results of resin testing
TABLE 3 results of resin testing
| Content (%) | Reference ratio 2 | Example 5 | Example 6 |
| Free Ptop | 2.8％ | 2.0％ | 1.4％ |
| Free 2, 4-ditert-octylphenol | 0 | 0.1％ | 0.2％ |
| Molecular weight distribution index PDI | 2.2 | 1.8 | 1.7 |
| Number averageMolecular weight Mn | 1036 | 1195 | 1260 |
TABLE 4 results of resin testing
| Content (%) | Example 7 | Example 8 | Example 9 |
| Free p-octylphenol | 0.7％ | 1.4％ | 1.1％ |
| Free p-butylphenol | 0.1％ | 0.1％ | 0.1％ |
| Free p-nonyl phenol | 0 | 0 | 0.8％ |
| Total free dialkylphenols | 0.5％ | 0.2％ | 0.2％ |
| Molecular weight distribution index PDI | 1.6 | 1.7 | 1.8 |
| Number average molecular weight Mn | 1320 | 1247 | 1154 |
TABLE 5 tackifying Performance results of rubber application test
Table 2 shows that the free phenol content of the resin is reduced by the copolymeric modification of PTBP with a dialkylphenol and the molecular weight distribution becomes narrower as the amount of dialkylphenol is increased, compared to the prior art p-tert-butylphenol (PTBP) -formaldehyde tackifying resin.
Table 3 shows that the free phenol content of the resin is reduced by the copolymeric modification of PTOP with dialkylphenols and the molecular weight distribution is narrowed as the amount of dialkylphenol is increased, compared to the prior art p-tert-octylphenol (PTOP) -formaldehyde tackifying resin.
Table 4 illustrates that other types of alkylphenol-formaldehyde resins can be co-modified with a dialkylphenol to achieve the same results of the present invention, and that the disubstituted alkylphenol includes, but is not limited to, one or more of 2, 4-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 2, 4-di-tert-octylphenol, 2, 6-di-tert-octylphenol, 2, 4-dioctylphenol, 2-tert-butyl-4-tert-octylphenol, 2-tert-butyl-4-octylphenol, 2-octyl-4-tert-butylphenol.
Table 5 shows that the synthesized resin of the product has better tackifying effect than the prior alkylphenol-formaldehyde resin product.
The results show that the tackifying resin synthesized by copolymerizing the dialkyl phenol and the alkylphenol can effectively reduce the content of free phenol in a resin product, improve the environmental protection property of the product, reduce the molecular weight distribution of the resin by the end capping effect of the dialkyl phenol, concentrate most of the molecular weight in the resin polymer in an optimal range, and improve the viscosity performance of the resin.
Claims (5)
1. The method for synthesizing the alkylphenol formaldehyde resin is characterized by comprising the steps of adding raw materials of monoalkylphenol and dialkylphenol into a reactor, reacting with aldehyde at 70-180 ℃ under the action of an acid catalyst, removing water after the reaction is completed, and neutralizing to obtain the alkylphenol formaldehyde resin, wherein the molar ratio of the monoalkylphenol to the dialkylphenol is 3: 2-1: 1;
the monoalkylphenol is one or more of p-methyl phenol, p-n-butyl phenol, p-tert-octyl phenol, nonyl phenol, dodecyl phenol and octadecyl phenol;
the dialkyl phenol is one or more of 2, 4-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 2, 4-di-tert-octylphenol, 2, 6-di-tert-octylphenol, 2, 4-di-octylphenol, 2-tert-butyl-4-tert-octylphenol, 2-tert-octyl-4-tert-butylphenol, 2-tert-butyl-4-octylphenol and 2-octyl-4-tert-butylphenol;
the molecular weight distribution of the alkyl phenolic resin is 1.4-1.6; the content of free alkylphenol in the alkyl phenolic resin is 0.5-0.9%.
2. The synthesis method according to claim 1, wherein the acidic catalyst is one or a mixture of two or more of sulfuric acid, hydrochloric acid, benzenesulfonic acid or its alkyl substituent, phenyl sulfate, and oxalic acid; the aldehyde is one or the mixture of 10 to 37 percent of formaldehyde aqueous solution or paraformaldehyde, or one or the mixture of acetaldehyde or paraldehyde.
3. A method for synthesizing alkyl phenolic resin is characterized by comprising the following steps: using cation exchange resin as a catalyst, alkylating phenol by using excessive nonene and octene to obtain an alkylation solution, and analyzing the composition of the alkylation solution: 36 percent of p-octylphenol, 28 percent of p-nonylphenol, 3 percent of 4-butylphenol, 2 percent of 4-pentylphenol, 18 percent of 2, 6-dioctylphenol, 11 percent of 2, 4-dinonylphenol, 2 percent of 2-butyl-4-octylphenol, and the molar ratio of alkylphenol to dialkylphenol of 0.78:0.22, a 1000ml four-neck reaction bottle is provided with a stirring thermometer, a reflux condenser tube and a charging funnel, 400g of the mixture of the alkylation solution, 0.8g of p-toluenesulfonic acid, 1g of oxalic acid and 83g of 37 percent aqueous solution of formaldehyde are charged, the mixture is heated to 100 ℃, the mixture is refluxed and reacted for 2 hours at 100 ℃, the mixture is dehydrated under normal pressure, the temperature is raised to 140 ℃, 17g of reinforced aldehyde is gradually supplemented, the mixture is heated to 160 ℃ to remove residual water, 1.2g of aqueous solution of sodium hydroxide 20 percent is added for neutralization, the mixture is kept warm for 2 hours at the temperature, and the resin melt is discharged into a stainless, when the temperature is cooled to room temperature, the product is transparent, the softening point is 92 ℃, and the color is brownish yellow.
4. An alkylphenol-formaldehyde resin prepared by the process of any one of claims 1 to 3.
5. Use of an alkylphenol aldehyde resin as claimed in claim 4 as a tackifier in the manufacture of rubber articles.
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| CN106967204B (en) * | 2016-03-28 | 2020-03-31 | 华奇（中国）化工有限公司 | Synthesis and application of long-acting tackifying phenolic resin |
| CN108329444B (en) * | 2018-01-31 | 2020-04-28 | 山东阳谷华泰化工股份有限公司 | Solid acid catalytic synthesis method of tackifying alkyl phenolic resin |
| CN109456454B (en) * | 2018-08-23 | 2021-07-09 | 彤程化学（中国）有限公司 | Low-phenol alkylphenol-formaldehyde resin and preparation method and application thereof |
| CN109880031B (en) * | 2018-12-07 | 2021-11-02 | 山东阳谷华泰化工股份有限公司 | Preparation method of mixed alkylphenol-formaldehyde resin rubber tackifier |
| CN109810231B (en) * | 2019-01-24 | 2021-11-23 | 山东阳谷华泰化工股份有限公司 | 4-tert-alkylphenol- (phenol group) formaldehyde resin and preparation method and application thereof |
| KR20230022064A (en) * | 2021-08-06 | 2023-02-14 | 코오롱인더스트리 주식회사 | A process of preparing the alkyl phenolic resin, an alkyl phenolic resin, and a rubber composition including the same |
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