CN111234148B - Maleimide modified p-tert-butyl phenol formaldehyde resin and synthetic method thereof - Google Patents
Maleimide modified p-tert-butyl phenol formaldehyde resin and synthetic method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention provides a maleimide modified p-tert-butylphenol formaldehyde resin and a synthesis method thereof, wherein the method comprises the following steps of 1: putting p-tert-butylphenol, 4-maleimide aminophenol, formaldehyde and a catalyst into a reaction vessel, and carrying out condensation reaction at 80-100 ℃; step 2: adding toluene, extracting an organic phase, adding alkali liquor, adjusting the reaction liquid to be neutral, draining the water phase, and evaporating the water phase and the solvent in the system; and step 3: heating to 160-190 deg.C, performing polycondensation reaction, distilling under reduced pressure, removing water and unreacted monomer, and obtaining maleimide modified p-tert-butylphenol formaldehyde resin. In the invention, part of R groups in the p-tert-butylphenol-formaldehyde resin are substituted by maleimide groups, and double bonds can react with double bonds in rubber, thereby reducing the migration of the resin in the rubber, reducing the heat generation and improving the anti-aging capability of the rubber. The carbonyl of the modifying group has strong hydrogen bond effect, can effectively improve the interaction force among molecules and improve the lasting viscosity.
Description
Technical Field
The invention relates to the technical field of tackifying resins, and particularly belongs to maleimide modified p-tert-butylphenol formaldehyde resin and a synthesis method thereof.
Background
In the production process of the tire, a laminating forming method is generally adopted, namely, rubber sheets of all parts are respectively prepared into unvulcanized rubber according to different performance requirements, and then laminating forming is carried out; this process requires the uncured compound to have a relatively high build viscosity. In order to improve the insufficient adhesion between the rubber sheets of different parts, a tackifier is usually added during the rubber mixing.
At present, the tackifier which is widely used is common tackifier resin, namely alkylphenol-formaldehyde resin, which has the advantages of simple process and low price, but after the tackifier resin is added into rubber, the tackifier resin is in a free state in the rubber, and can influence the crosslinking density of the rubber, which is mainly shown in that the tackifier resin has high heat generation and poor thermal aging performance in the use process of tires.
Koresin produced by Pasteur Germany not only can improve the self-adhesiveness of the film, but also can reduce the dynamic heat generation of the rubber material and improve the heat aging performance. However, the koresin is synthesized by reacting alkylphenol and acetylene, and the synthesis process is a gas-solid reaction, and has the disadvantages of complex process, high technical requirement and high cost. Therefore, the expensive cost limits the application area of the korein resin, which is currently used only in some high-end products.
Disclosure of Invention
The invention provides a maleimide modified p-tert-butylphenol formaldehyde resin, which aims to achieve the purposes of simple preparation process, low cost and excellent product performance.
Meanwhile, the invention also provides a synthetic method of the maleimide modified p-tert-butylphenol formaldehyde resin.
The maleimide modified p-tert-butyl phenol formaldehyde resin is characterized by having the following structural formula:
Preferably, the maleimide-modified p-tert-butylphenol formaldehyde resin has a weight average molar mass of from 1100 to 1500g/mol.
The method for synthesizing the maleimide modified p-tert-butylphenol formaldehyde resin is characterized by comprising the following steps:
step 1: putting p-tert-butylphenol, 4-maleimide aminophenol, formaldehyde and a catalyst into a reaction vessel, and carrying out condensation reaction for 1-3h at the temperature of 80-100 ℃; the molar ratio of the added p-tert-butyl phenol to the added formaldehyde is 1.0:0.7-0.9; the adding mass of the 4-maleimide aminophenol is 1-3% of the adding mass of the p-tert-butylphenol;
and 2, step: step 1, after the condensation reaction is finished, adding toluene, extracting an organic phase, then adding alkali liquor, adjusting the reaction liquid to be neutral, draining a water phase, heating to 110 ℃, and evaporating water and a solvent in the system; the using amount of the toluene is 150 percent of the mass of the p-tert-butylphenol;
and step 3: and 2, after the reaction is finished, heating to 160-190 ℃, carrying out polycondensation reaction for 1-3 hours under the condition of normal pressure, then carrying out reduced pressure distillation, and removing water and unreacted monomers to obtain the maleimide modified p-tert-butylphenol formaldehyde resin.
Preferably, the molar ratio of the p-tert-butyl phenol to the formaldehyde is 1.0:0.8-0.9.
Preferably, the catalyst is an organic acid or an inorganic acid; adding the mixture into a reaction system in a solid or liquid form; the dosage of the catalyst is 0.2-0.3% of the mass of the p-tert-butyl phenol.
Preferably, the catalyst is oxalic acid, concentrated sulfuric acid or p-toluenesulfonic acid.
Preferably, the formaldehyde is a formaldehyde aqueous solution, and is added into the reaction system in a dropping manner; the p-tert-butylphenol and the 4-maleimide aminophenol are solid raw materials, and the solid is fed at one time.
Preferably, the concentration of the aqueous formaldehyde solution is 37 to 40wt%.
Preferably, the alkali liquor has a concentration of 5% and is an aqueous solution of sodium hydroxide or potassium hydroxide.
The invention has the following beneficial effects:
(1) The invention takes formaldehyde and p-tert-butylphenol as raw materials and 4-maleimide phenol as a modifier, and the modifier and the raw materials are added simultaneously in the reaction process, so the operation steps are simple; the method has the advantages of mild reaction conditions, no solid waste, no washing, simple process, low cost and excellent product performance.
(2) In the maleimide modified resin synthesized by the invention, part of R groups in the p-tert-butylphenol-formaldehyde resin are replaced by maleimide groups, 4-maleimide group phenol containing maleimide groups is used as an initial raw material, and maleimide is not directly used as a raw material for modification, so that the reaction difficulty is reduced, and the product structure is easier to control; double bonds are introduced into the resin and can react with the double bonds in the rubber, so that the migration of the resin in the rubber is reduced, the heat generation is reduced, and the ageing resistance of the rubber is improved. The carbonyl of the modifying group has strong hydrogen bond effect, can effectively improve the interaction force among molecules and improve the lasting viscosity.
(3) The process has low requirement on equipment, can be completed by adopting common tackifying resin synthesis equipment, saves production cost and is suitable for industrial popularization.
Detailed Description
The technical scheme of the invention is further illustrated by the following specific examples, wherein the raw materials used in the following examples, such as p-tert-butylphenol, formaldehyde, concentrated sulfuric acid (98 wt%), 4-maleimidophenol, and the like, are all purchased from the market; the concentrations used are mass concentrations unless otherwise specified.
Example 1
A method for synthesizing maleimide modified p-tert butyl phenol formaldehyde resin comprises the following steps:
step 1: weighing 100g (0.67 mol) of p-tert-butylphenol, 1g of 4-maleimidophenol and 0.3g of concentrated sulfuric acid, adding the weighed materials into a 500ml four-neck round-bottom flask provided with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel, heating the flask to 90 ℃, dropwise adding 44g of formaldehyde aqueous solution (phenolic ratio is 1;
step 2: after the reaction, 150g of toluene was added, the organic phase was extracted, and the reaction solution was adjusted to neutrality by adding an alkali solution. The waste water is drained, and the temperature is slowly raised to 110 ℃ to evaporate water in the system. Then, slowly raising the temperature, and evaporating water and toluene;
and step 3: heating to 160 ℃ for polycondensation, keeping for 1h, distilling under reduced pressure, and distilling to remove small molecular substances and unreacted monomers. Discharging to obtain the maleimide modified p-tert butyl phenol formaldehyde resin. The product was weighed after cooling, and the yield was 99%.
The softening point of the resin was measured by a ring and ball softening point tester to be 125 ℃, the weight average molecular weight was 1250g/mol by Gel Permeation Chromatography (GPC), and the mass percentage content of free p-tert-butylphenol and the mass percentage content of moisture in the resin were measured by bromination to be 0.6% and 0.8%, respectively.
Example 2
A method for synthesizing maleimide modified p-tert butyl phenol formaldehyde resin comprises the following steps:
step 1: 100g (0.67 mol) of p-tert-butylphenol, 3g of 4-maleimidophenol and 0.2g of concentrated sulfuric acid were weighed, charged into a 500ml four-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel, heated to 100 ℃ and added dropwise with 49g of an aqueous formaldehyde solution (phenolic ratio 1.
And 2, step: after the reaction, 150g of toluene was added, the organic phase was extracted, and the reaction solution was adjusted to neutrality by adding an alkali solution. The waste water is drained, and the temperature is slowly raised to 110 ℃ to evaporate water in the system. Then, the temperature is slowly raised, water and toluene are distilled out,
and step 3: heating to 190 ℃ for polycondensation, and keeping for 2 hours; and (4) distilling under reduced pressure to remove small molecular substances and unreacted monomers. Discharging to obtain the maleimide modified p-tert butyl phenol formaldehyde resin. The product was weighed after cooling, and the yield was 98%.
The softening point of the resin is 142 ℃ measured by a ring and ball softening point instrument, the weight average molecular weight is 1460g/mol measured by a Gel Permeation Chromatography (GPC) method, and the mass percentage content of free p-tert-butylphenol in the resin is 0.7 percent and the mass percentage content of moisture is 0.8 percent measured by a bromination method.
Example 3
Step 1: 100g (0.67 mol) of p-tert-butylphenol, 2g of 4-maleimidophenol and 0.3g of p-toluenesulfonic acid were weighed, charged into a 500ml four-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel, heated to 95 ℃ and added dropwise with 44g of an aqueous formaldehyde solution (phenolic ratio 1.
Step 2: after the reaction, 150g of toluene was added, the organic phase was extracted, and the reaction solution was adjusted to neutrality by adding an alkali solution. The waste water is drained, and the temperature is slowly raised to 110 ℃ to evaporate water in the system. Then slowly raising the temperature, evaporating water and toluene,
and 3, step 3: performing polycondensation at 180 ℃ and keeping for 3h; and (4) distilling under reduced pressure to remove small molecular substances and unreacted monomers. Discharging to obtain the maleimide modified p-tert-butylphenol formaldehyde resin. The product was weighed after cooling, and the yield was 99%.
The softening point of the resin was 132 ℃ as measured by a ring and ball softening point apparatus, the weight average molecular weight was 1320g/mol as measured by Gel Permeation Chromatography (GPC), and the mass percent content of free p-tert-butylphenol and moisture in the resin was 0.7% and 0.7% as measured by bromination, respectively.
Comparative example 1
After the synthesis of common tackifying resin is finished, maleimide is directly added for modification, and the method comprises the following steps:
step 1: weighing 100g (0.67 mol) of p-tert-butylphenol and 0.2g of concentrated sulfuric acid, adding the weighed materials into a 250ml four-neck round-bottom reaction flask provided with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel, heating the mixture to 90 ℃, dropwise adding 43.3g of formaldehyde solution (phenolic ratio is 1;
and 2, step: after the reaction, sodium hydroxide solution (2.5%) was added to adjust the reaction solution PH =7. Subsequently, water and unreacted monomers were distilled off, and then the temperature was raised to 160 ℃ for 1 hour;
and step 3: adding maleimide for modification, continuing the reaction for 1 hour, and discharging. The product was weighed out by cooling, and the yield was 98%.
The softening point of the resin was 131 ℃ as measured by a ring and ball softening point apparatus, the weight average molecular weight was 1280g/mol as measured by Gel Permeation Chromatography (GPC), and the mass percent content of free p-tert-butylphenol and the mass percent content of moisture in the resin were 0.6% and 0.8% as measured by bromination, respectively.
Examples 1-3 in the course of resin synthesis, 4-maleimidophenol was used as a raw material for modification to give a maleimide-modified p-tert-butylphenol formaldehyde resin.
Comparative example 1 is that maleimide is directly added for modification after the synthesis of ordinary tackifying resin is finished, and phenolic hydroxyl structure is destroyed and product performance is affected due to exposure of imine functional group in the synthesis process.
Application example
The resin products respectively obtained in the embodiments 1-3 and the comparative example 1 of the invention and the existing product 1 German BASF chemical group product are as follows: tackifying resin Koresin and tackifying resin SC2066 (p-tert-butylphenol-formaldehyde resin) produced by Sanliko specialty chemical group of the existing product 2 belong to common tackifying resin; the resins were used as respective tackifier resins, and performance verification tests were carried out.
Adopting the formula of the all-steel load radial wheel shoulder wedge shown in the table 1 to rubber, and comparing the application performance of different tackifying resin samples; table 2 shows the detection items and the detection processing apparatuses:
TABLE 1
| Raw material | Parts by weight phr |
| Brominated butyl rubber | 80 |
| Natural rubber | 20 |
| Carbon Black N660 | 65 |
| Naphthenic oil | 4 |
| Zinc oxide | 3 |
| Stearic acid | 2 |
| Accelerant MBTS | 1 |
| DTDM | 1 |
| Sulfur | 0.5 |
| Tackifying resins | 4 (variety) |
TABLE 2 detection items and detection processing instrument
In the test, a two-stage mixing process is adopted, one-stage mixing of carbon black master batch is carried out in a 1.5L experimental internal mixer, and the charging sequence is as follows: carbon black N660, white carbon black, naphthenic oil, stearic acid, tackifying resin and zinc oxide. The two-stage mixing and vulcanizing system is carried out on a 6-inch open mill. Taking a section of master batch, coating the master batch on a roll mill, adding accelerators MBTS, sulfur and DTDM, cutting for 2 times in a left-right 3/4 mode, thinly passing for 4 times at a minimum roll spacing, rolling for 4 times at a 2mm roll spacing, discharging the sheet, and standing to be tested.
In the above rubber compounds, the tackifying resins used were the resins of example 1, example 2, example 3, comparative example 1, conventional product 1 and conventional product 2, respectively, and the quality index for each tackifying resin is shown in table 3 below:
TABLE 3 quality index
Note: heating to reduce weight refers to heating tackifying resin at 105 deg.C for 2h, burning tackifying resin at 550 + -25 deg.C for 4h, cooling to about 200 deg.C, taking out, cooling in a drier for 30min, and calculating ash content.
As can be seen from the data in Table 3, the tackifying resins of the examples, comparative examples and the existing products of the invention can meet the requirements that the heating loss of the tackifying resin for rubber is less than or equal to 1.0 percent, the ash content is less than or equal to 0.5 percent, the softening point is 120-145 ℃, and the free phenol is less than or equal to 1 percent.
The mechanical properties of the mixtures obtained with the different tackifying resins were tested and the results are shown in Table 4:
TABLE 4 mechanical Properties of the mixes obtained with the addition of different tackifying resins
From table 4, it can be seen from the mechanical property data of each rubber material that the tensile stress is reduced and the elongation at break is improved after the tackifying resin is added, compared with the blank, and the elongation at break is obviously improved by adding the rubber material of the product obtained in examples 1-3, which is higher than that of adding comparative example 1 and the existing product 2 (common tackifying resin), and is equivalent to the application property of the existing product 2. Particularly, after thermal-oxidative aging, the rubber materials added with the tackifying resins of examples 1 to 3 well maintain the elongation at break of the rubber sheet, which shows that the tackifying resin samples obtained in examples 1 to 3 improve the aging resistance of the rubber sheet.
The test dynamic compression heating data is formed as follows in table 5:
TABLE 5 dynamic compression Heat generation/. Deg.C
From the data in table 5, one can see: the addition of ordinary tackifying resin, namely the sizing material of the existing product 2, has obviously higher dynamic compression heat generation than the blank, because the resin molecules are in a free state in the sizing material, and the intermolecular friction increases the heat generation. The addition of the compounds of examples 1-3 effectively reduced the dynamic compression heat generation of the compounds, and was comparable to the Koresin, i.e., product 1, indicating that the maleimide-modified tackifying resin had the characteristic of effectively reducing the dynamic heat generation.
Cutting the obtained sizing materials into 180 x 65mm films, respectively storing the films for 1 day, 3 days, 5 days, 8 days and 15 days under the environment of the conventional room temperature (20 ℃ and 60 percent relative humidity), then pressing two films with the same storage days for 5s at the pressing speed of 20cm/min, then separating the two films at the tearing speed of 20cm/min, testing the force required for separating the two films, repeating the experiment for 5 times under the same condition for each storage day, and taking the average value of the adhesive force of the sample as the unit of Newton (N). The experimental instrument is a RZN-II rubber autohension tester (Beijing Wanhui Tech Co., ltd.).
The self-adhesion of the compounds was characterized by their adhesion, with greater adhesion indicating better self-adhesion, and the results are shown in table 6:
TABLE 6 autohension test (adhesion/N)
| Tackifying resins | 1d | 3d | 5d | 8d | 15d |
| Blank space | 6.41 | 7.00 | 6.59 | 6.11 | 5.21 |
| Example 1 | 15.28 | 15.63 | 14.42 | 13.32 | 13.17 |
| Example 2 | 14.71 | 15.14 | 14.53 | 13.38 | 13.12 |
| Example 3 | 15.35 | 14.68 | 13.33 | 13.21 | 13.11 |
| Comparative example 1 | 12.55 | 14.22 | 10.28 | 8.11 | 6.25 |
| Existing product 1 | 14.38 | 13.66 | 13.53 | 13.18 | 12.78 |
| Existing product 2 | 16.45 | 11.42 | 10.19 | 10.01 | 9.34 |
The data in table 6 show that after the rubber materials are left for 1 day, 3 days, 5 days, 8 days and 15 days, the self-adhesiveness of the rubber materials is obviously improved after the tackifying resin is added compared with that of the blank rubber materials without the tackifying resin. The rubber material of the existing product 2 has high initial viscosity, because the common tackifying resin is in a free state in rubber and is easy to migrate to the surface, the initial viscosity is high. In the process of tyre processing, the rubber sheet is generally required to be stored for 1-2 weeks, so that the lasting viscosity is significant for the rubber sheet processing. In terms of permanent tack, the sizing materials of examples 1-3 of the invention are equivalent to the sizing material of the existing product 1, and all show more excellent performance than the existing product 1; can be used as a substitute of the prior product 1-Koresin. The maleimide in comparative example 1 destroys the phenolic hydroxyl group structure, thereby affecting the tackifying property of the resin.
The results of the comprehensive application experiments show that the samples obtained by adding the samples obtained in the examples 1-3, the samples obtained by adding the comparative examples and the samples obtained by adding the existing products 1-2 are qualified in all indexes, and show good aging resistance in the aspect of the mechanical properties of rubber compounds. And can effectively reduce the dynamic compression heat generation of the sizing material. In terms of self-adhesive properties, the products of the invention exhibit higher permanent tack with Koresin. In addition, the method has the advantages of simple and easy operation process, low requirement on equipment, low raw material cost and high safety performance, and is suitable for industrial popularization and production.
Claims (7)
1. A method for synthesizing maleimide modified p-tert-butyl phenol formaldehyde resin is characterized in that the maleimide modified p-tert-butyl phenol formaldehyde resin has the following structural formula:
the weight-average molar mass of the maleimide-modified p-tert-butylphenol formaldehyde resin is 1100 to 1500g/mol;
the method for synthesizing the maleimide modified p-tert-butylphenol formaldehyde resin comprises the following steps:
step 1: putting p-tert-butylphenol, 4-maleimide aminophenol, formaldehyde and a catalyst into a reaction vessel, and carrying out condensation reaction for 1-3h at 80-100 ℃; the molar ratio of the added p-tert-butylphenol to the added formaldehyde is 1.0:0.7-0.9; the adding mass of the 4-maleimide aminophenol is 1-3% of the adding mass of the p-tert-butylphenol;
and 2, step: step 1, after the condensation reaction is finished, adding toluene, extracting an organic phase, then adding alkali liquor, adjusting the reaction liquid to be neutral, draining a water phase, heating to 110 ℃, and evaporating water and a solvent in the system; the using amount of the toluene is 150 percent of the mass of the p-tert-butylphenol;
and step 3: and 2, after the reaction is finished, heating to 160-190 ℃, carrying out polycondensation reaction for 1-3 hours under the normal pressure condition, then carrying out reduced pressure distillation, and removing water and unreacted monomers to obtain the maleimide modified p-tert-butylphenol formaldehyde resin.
2. The method for synthesizing maleimide-modified p-tert-butylphenol formaldehyde resin according to claim 1, wherein the molar ratio of p-tert-butylphenol to formaldehyde is 1.0:0.8-0.9.
3. The method for synthesizing maleimide-modified p-tert-butylphenol formaldehyde resin according to claim 1, wherein said catalyst is an organic acid or an inorganic acid; adding the mixture into a reaction system in a solid or liquid form; the dosage of the catalyst is 0.2-0.3% of the mass of the p-tert-butylphenol.
4. The method for synthesizing maleimide-modified p-tert-butylphenol formaldehyde resin according to claim 3, wherein said catalyst is oxalic acid, concentrated sulfuric acid or p-toluenesulfonic acid.
5. The method for synthesizing maleimide-modified p-tert-butylphenol formaldehyde resin according to claim 1, wherein said formaldehyde is an aqueous formaldehyde solution and is added dropwise to the reaction system; the p-tert-butylphenol and the 4-maleimide aminophenol are solid raw materials, and the solid is fed at one time.
6. The method for synthesizing maleimide-modified p-tert-butylphenol formaldehyde resin according to claim 5, wherein said concentration of said aqueous formaldehyde solution is 37 to 40% by weight.
7. The method for synthesizing maleimide-modified p-tert-butylphenol formaldehyde resin according to claim 1, wherein said alkali solution has a concentration of 5% and is an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide.
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Citations (3)
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|---|---|---|---|---|
| JPH0551425A (en) * | 1991-08-23 | 1993-03-02 | Hitachi Chem Co Ltd | Hydroxyl group-containing polymaleimide resin and its production |
| RO115639B1 (en) * | 1995-02-20 | 2000-04-28 | Inst Cercetari Chim | Process of preparing thermoreactive para-alkylphenolformaldehyde resins |
| JP2014080502A (en) * | 2012-10-16 | 2014-05-08 | Taoka Chem Co Ltd | Cocondensate and rubber composition containing the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0551425A (en) * | 1991-08-23 | 1993-03-02 | Hitachi Chem Co Ltd | Hydroxyl group-containing polymaleimide resin and its production |
| RO115639B1 (en) * | 1995-02-20 | 2000-04-28 | Inst Cercetari Chim | Process of preparing thermoreactive para-alkylphenolformaldehyde resins |
| JP2014080502A (en) * | 2012-10-16 | 2014-05-08 | Taoka Chem Co Ltd | Cocondensate and rubber composition containing the same |
Non-Patent Citations (1)
| Title |
|---|
| 对叔丁基酚醛树脂的合成与表征;李静等;《塑料工业》;20100720;第38卷(第07期);10-13 * |
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