CN112442157B - Epoxy resin and rosin modified alkylphenol-formaldehyde resin and preparation method and application thereof - Google Patents
Epoxy resin and rosin modified alkylphenol-formaldehyde resin and preparation method and application thereof Download PDFInfo
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- CN112442157B CN112442157B CN201910835500.XA CN201910835500A CN112442157B CN 112442157 B CN112442157 B CN 112442157B CN 201910835500 A CN201910835500 A CN 201910835500A CN 112442157 B CN112442157 B CN 112442157B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/34—Chemically modified polycondensates by natural resins or resin acids, e.g. rosin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
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Abstract
The invention discloses an epoxy resin and rosin modified alkylphenol-formaldehyde resin, which is prepared by adding alkylphenol, epoxy resin and rosin in a certain proportion in the presence of a catalyst, reacting at 90-100 ℃ for a period of time, heating to 100-. The resin prepared by the invention has the advantage of high viscosity, and can be applied to the fields of rubber products and the like.
Description
Technical Field
The invention relates to a structure of epoxy resin and rosin modified alkylphenol-formaldehyde resin and a preparation method thereof.
Background introduction
Alkylphenol-phenolic resin is used as tackifying resin in the field of rubber products, and is an indispensable additive. The rubber tire sheet adhesive has the main functions of improving the self-adhesion in the rubber processing process and ensuring that the rubber tire sheets have good adhesion. Natural rubber has good self-adhesiveness, but for non-natural rubber, a certain tackifying resin is needed to increase the self-adhesiveness, and alkylphenol resin is generally selected for tackifying. Due to the existence of alkyl chains of the alkylphenol, the alkylphenol has good compatibility with non-aromatic ring rubber such as ethylene propylene rubber and the like, and the tackifying effect is good, but the tackifying effect of the rubber containing styrene is poor. Therefore, the invention develops a tackifying resin for increasing the viscosity of the rubber with an aromatic ring system.
For modifying the thickening effect of the rubber having an aromatic ring, the following patents are available: us4073826 patent: the epoxy resin is reacted with bisphenol A epoxy resin (epoxy value equivalent is 58-4000) to enhance the adhesive property of the elastomer with alpha olefin structure and ensure that the rigidity of the elastomer is slightly changed. CA1055643A realizes the tackifying effect of the alkylphenol resin containing epoxy group and the epoxy equivalent is more than 4000. The modification of alkylphenol tackifying resins with morpholine in the US4146513 patent mainly improves the adhesion between elastomer (rubber) and fiber. Patent CN201210315677.5, also modified with an alkylphenol with epoxy group, gives a resin with improved adhesion of natural rubber and compounded rubber. The main method is to prepare a prepolymer of alkylphenol resin in a solution of toluene or xylene, then wash the prepolymer with water, remove a solvent, add epoxy resin to prepare the resin, and the final product is mainly prepared by physical mixing; in patent CN201210315677.5, a small molecule with epoxy group reacts with phenolic resin to obtain a resin with epoxy functional group, which is chemically modified. Both vary in the manner of implementation and in the final structure. But both adopt a water washing process to generate more wastewater.
In the field of epoxy and alkylphenol modification, mixing is mainly used, and the alkylphenol-mixed epoxy is applied to the field of electronic packaging or composite materials, for example, JP1984030820A discloses a preparation method based on phenol and alkylphenol epoxidation for application of molding compounds. EP0506080B1 discloses a process for the modification of epoxy resins with alkyl phenols, for the use of curing agents for epoxy resins. WO2009155747a1 discloses a method of blending rosin with fatty acid-modified alkylphenol to improve the tackifying performance of alkylphenol resin and the like.
Disclosure of Invention
The invention mainly uses the material with epoxy group to chemically modify the alkylphenol, can obtain the alkylphenol resin modified by the chemically modified epoxy group under the condition of not changing the prior process, and simultaneously introduces the rosin to improve the processing performance of the rubber.
The invention adopts epoxy resin and rosin to modify alkylphenol-formaldehyde resin, which can improve the adhesive property and rubber processing property of rubber. Compared with the method in the prior art, the method can improve the bonding property of the rubber and improve the scorching time of the rubber.
The invention provides epoxy resin and rosin modified alkylphenol-formaldehyde resin, which has a structure shown in a formula (1):
wherein the content of the first and second substances,
r is an alkyl chain of C4-C15; preferably, R is an alkyl chain of C8-C12; further preferably, the compound is one or more of tert-butyl, p-tert-octyl or nonyl;
r' is epoxy resin;
r' is rosin;
x is an integer of 1 or more.
Wherein the iodine value of the rosin is between 180 and 220.
Wherein, the structure of the epoxy resin is one or more of the following formulas (2):
the invention provides a preparation method of epoxy resin and rosin modified alkylphenol-formaldehyde resin, wherein in the presence of a catalyst, alkylphenol, epoxy resin and rosin react, formaldehyde is gradually added after a period of time, and after the addition is finished, excessive moisture is removed, a terminator is added to terminate the reaction, so that the epoxy resin and rosin modified alkylphenol-formaldehyde resin is prepared.
The steps of the epoxy resin and rosin modified alkylphenol-formaldehyde resin prepared by the invention are as follows:
under the action of a catalyst, alkylphenol reacts with epoxy resin and rosin at the temperature of 90-100 ℃, then the temperature is raised to 100-minus ice-110 ℃, formaldehyde is added for polycondensation, then the temperature is raised to 140-minus ice-160 ℃, distillation reaction is carried out to distill off redundant moisture, and after vacuum pumping, a terminator is added to terminate the reaction, thus obtaining the epoxy resin and rosin modified alkylphenol-formaldehyde resin.
The catalyst comprises, by weight, 60-120 parts of alkylphenol, 20-80 parts of formaldehyde, 1-50 parts of epoxy resin, 1-50 parts of rosin, 0.1-5 parts of catalyst and 0.1-5 parts of terminator.
Preferably, the alkylphenol is used in an amount of 70-110 parts by weight, the formaldehyde is used in an amount of 30-70 parts by weight, the epoxy resin is used in an amount of 10-40 parts by weight, the rosin is used in an amount of 10-40 parts by weight, the catalyst is used in an amount of 1-3 parts by weight, and the terminator is used in an amount of 1-3 parts by weight.
Wherein the softening point of the epoxy resin and rosin modified alkylphenol-formaldehyde resin is between 95 and 105 ℃.
Wherein the catalyst is an acid catalyst and is selected from one or more of dodecyl benzene sulfonic acid, p-methyl benzene sulfonic acid, p-hydroxybenzene sulfonic acid, benzene sulfonic acid, oxalic acid, hydrochloric acid, sulfuric acid and the like; preferably, it is dodecylbenzenesulfonic acid.
Wherein the terminator is alkali, and is selected from one or more of sodium hydroxide, potassium hydroxide, N-methyl triethanolamine, diazabicyclo and the like; preferably, it is N-methyltriethanolamine.
Wherein the vacuum pumping condition is that the vacuum degree is-0.04 to-0.08 MPa; preferably, -0.05 MPa.
Wherein the time for vacuum pumping is 10-60 min; preferably, it is 30 min.
Wherein alkylphenol reacts with epoxy resin as shown in the following formula (I),
wherein R is an alkyl chain of C4-C15; preferably, R is an alkyl chain of C8-C12; further preferably, the compound is one or more of tert-butyl, p-tert-octyl or nonyl;
r' is epoxy resin, and the structure of the epoxy resin is one or more than one of the following formulas (2):
wherein, the reaction of alkylphenol and rosin is shown as formula (II), mainly takes place alkylation reaction:
in the invention, the main reason for introducing the epoxy resin is to increase the compatibility of the epoxy resin with rubber containing aromatic rings, and the main reason is that the epoxy resin contains rigid aromatic ring structures, and the compatibility of the epoxy resin with the rubber can be increased according to the principle of similar compatibility, so that the self-adhesion of the rubber is increased. In addition, in the aspect of prolonging the scorching time of rubber processing, the rosin acid is selectively added for improvement, firstly, because the rosin contains an aromatic ring structure, the poor compatibility after the rosin is introduced can not be caused, and secondly, the rosin is also used in the field of rubber tires.
In the invention, the structure of the alkylphenol is shown as the formula (3):
wherein R is an alkyl chain of C4-C15;
preferably, R is an alkyl chain of C8-C12;
further preferably, the compound is one or more of tert-butyl, p-tert-octyl or nonyl.
The rosin used in the present invention needs to have a certain double bond in order to ensure the reactivity with alkylphenol, and the iodine value can be generally used to measure the amount of the double bond, the iodine value of the rosin used in the present invention is limited to 180-220, the too low iodine value affects the reactivity, and the too high iodine value is not suitable to control the softening point of the finally obtained resin.
The invention also provides epoxy resin and rosin modified alkylphenol-formaldehyde resin prepared by the method.
The invention also provides application of the epoxy resin and rosin modified alkylphenol-formaldehyde resin in the field of rubber products.
The invention has the beneficial effects that: the compatibility of the tackifying resin and the rubber is improved, the processability is improved, the scorching time of rubber processing is prolonged, and the operation safety is improved.
Detailed Description
The present invention will be described in further 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. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1
Adding 1.5 parts by weight of acid catalyst dodecyl benzene sulfonic acid, 103 parts by weight of p-tert-octylphenol, 30 parts by weight of rosin and 20 parts by weight of bisphenol A epoxy resin at 90 ℃, reacting for 1 hour at 105 ℃, heating to 108 ℃, gradually adding 37 parts by weight of formaldehyde, distilling to 140 ℃, extracting for vacuum reaction for 30min, keeping the vacuum degree at-0.05 MPa, adding 1.5 parts by weight of terminator triethanolamine to terminate the reaction, and testing the softening point to be 102 ℃ to obtain 161 parts by weight of epoxy resin and rosin modified alkylphenol-formaldehyde resin.
Comparative example 1
Adding 1.5 parts by weight of acid catalyst dodecyl benzene sulfonic acid, 103 parts by weight of p-tert-octylphenol and 20 parts by weight of bisphenol A epoxy resin at 90 ℃, reacting for 1 hour at 105 ℃, heating to 108 ℃, gradually adding 37 parts by weight of formaldehyde, distilling to 140 ℃, vacuumizing to react for 30min under the vacuum degree of-0.05 MPa, adding 1.5 parts by weight of terminator triethanolamine to terminate the reaction, testing the softening point to be 98 ℃, obtaining 131 parts by weight of epoxy resin and rosin modified alkylphenol-formaldehyde resin, wherein the structural formula of the used epoxy resin is shown in formula V, and the secondary epoxy resin is used in the subsequent examples unless particularly specified.
Comparative example 2
Adding 1.5 parts by weight of acid catalyst dodecyl benzene sulfonic acid, 103 parts by weight of p-tert-octylphenol and 30 parts by weight of rosin at 90 ℃, reacting for 1h at 105 ℃, heating to 108 ℃, gradually adding 37 parts by weight of formaldehyde, distilling to 140 ℃, performing vacuum reaction for 30min, stopping the reaction by adding 1.5 parts by weight of terminator triethanolamine, testing the softening point to be 109 ℃, and obtaining 142 parts by weight of epoxy resin and rosin modified alkylphenol-formaldehyde resin.
Example 2
Adding 1.5 parts by weight of acid catalyst dodecyl benzene sulfonic acid, 70 parts by weight of p-tert-octylphenol, 10 parts by weight of rosin and 10 parts by weight of epoxy resin at 90 ℃, reacting for 1 hour at 105 ℃, heating to 108 ℃, gradually adding 30 parts by weight of formaldehyde, distilling to 140 ℃, vacuumizing to react for 30 minutes at a vacuum degree of-0.05 MPa, adding 1.5 parts by weight of terminator triethanolamine to terminate the reaction, and testing the softening point to be 105 ℃ to obtain 102 parts by weight of epoxy resin and rosin modified alkylphenol-formaldehyde resin.
Example 3
Adding 1.5 parts by weight of acid catalyst dodecyl benzene sulfonic acid, 110 parts by weight of p-tert-octylphenol, 40 parts by weight of rosin and 40 parts by weight of epoxy resin at 90 ℃, reacting for 1 hour at 105 ℃, heating to 108 ℃, gradually adding 70 parts by weight of formaldehyde, distilling to 140 ℃, vacuumizing to react for 30min at the vacuum degree of-0.05 MPa, adding 1.5 parts by weight of terminator triethanolamine to terminate the reaction, and testing the softening point to be 115 ℃ to obtain 215 parts by weight of epoxy resin and rosin modified alkylphenol-formaldehyde resin.
Example 4
The reaction reagents/reaction raw materials, the amount and the preparation process are the same as those in example 1, p-tert-octylphenol is replaced by dodecylphenol, the catalyst is replaced by p-toluenesulfonic acid 1 part by weight and benzenesulfonic acid 0.5 part by weight, and the terminator is replaced by DBu 1 part by weight and N-methyltriethanolamine 0.5 part by weight, so that the alkylphenol-formaldehyde resin with the low phenol content of 159 parts by weight is finally obtained; wherein the softening points of the epoxy resin and the rosin modified alkylphenol-formaldehyde resin are 103 ℃.
Example 5
The reaction reagents/reaction raw materials, the amounts thereof and the preparation process were the same as in example 1, and 103 parts by weight of tert-octylphenol were replaced with 50 parts by weight of tert-butylphenol and 53 parts by weight of nonylphenol, to finally obtain 159 parts by weight of an alkylphenol-formaldehyde resin; wherein the softening point of the epoxy resin and rosin modified alkylphenol-formaldehyde resin is 104 ℃.
Examples 6-9 as shown in table 1 below, the epoxy resin, rosin modified alkylphenol-formaldehyde resin can be prepared by replacing different epoxy resins with different rosin having different double bond content.
TABLE-1
In order to test the application performance of the epoxy resin and the rosin-modified alkylphenol-formaldehyde resin prepared by the invention in the rubber compound, the epoxy resin and the rosin-modified alkylphenol-formaldehyde resin (hereinafter referred to as tackifying resin) prepared by the invention in the examples 1-4, the comparative example 1 and the comparative example 2 are selected for the application performance test, the formula of the rubber composition is shown in the table-2, wherein the rest filler is an auxiliary agent commonly used in the rubber industry.
The final test results are shown in tables-3 and-4, which are comparative examples (commercially available tackifier SL 1801).
Table-2 formula table
| Serial number | Raw material | Formulation(s) |
| 1 | Natural rubber | 30 |
| 2 | EPDM | 70 |
| 3 | Carbon Black N375 | 80 |
| 4 | Oil | 4 |
| 5 | Stearic acid | 2 |
| 6 | Zinc oxide | 3 |
| 7 | Sulphur (80%) (OT2O) | 1 |
| 8 | Tackifying resins | 4 |
| 9 | Sulfenamide NS | 2.2 |
| 10 | Anti-aging agent TMQ | 1.5 |
| 11 | Anti-aging agent 4020 | 1.6 |
TABLE-3 results of tack testing of examples and comparative examples
TABLE-4 mechanical Property test results of examples and comparative examples
TABLE-5 scorch test results for examples and comparative examples 1 and 2
The self-adhesion of rubber is an index for inspecting the processability of rubber, and is generally expressed by self-adhesion, and the larger the self-adhesion is, the better the processability is. As is clear from Table-3, the alkylphenol-formaldehyde resins (tackifying resins) obtained in examples 1 to 4 of the present invention have better self-adhesion to rubber than or equal to the control (commercial tackifying resin SL 1801). From the results of the mechanical property tests in Table-4, the breaking strength of the alkylphenol-formaldehyde resins prepared in examples 1 and 2 of the present invention is improved, which shows that the epoxy resin and rosin-modified alkylphenol-formaldehyde resin prepared in the present invention can improve the mechanical properties of rubber.
Meanwhile, in order to comparatively illustrate the application test properties of the epoxy resin, rosin-modified alkylphenol-formaldehyde resin prepared by the method of example 1 of the present invention and the resins prepared in comparative examples 1 and 2, wherein comparative example 1 is an epoxy resin-modified alkylphenol resin and comparative example 2 is a rosin-modified alkylphenol resin, see tables-3 and-4. The mechanical property of the epoxy resin and rosin modified alkylphenol-formaldehyde resin prepared by the method of the invention is slightly better than that of the epoxy resin prepared by the comparative example 1, and the self-adhesion is better than that of the epoxy resin prepared by the comparative example 1. Meanwhile, the scorching time is prolonged by 20%. In addition, the self-adhesion of example 1 is significantly superior to that of comparative example 2, and the scorch is comparable or slightly longer than that, indicating that rosin alone does not improve the self-adhesion of the rubber. Therefore, the alkylphenol-formaldehyde resin modified by epoxy and rosin can increase the self-adhesiveness of the rubber and prolong the scorching time.
The protection of the present invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art are intended to be included within the invention without departing from the spirit and scope of the inventive concept, and the scope of the invention is to be determined by the appended claims.
Claims (9)
1. An epoxy resin and rosin modified alkylphenol-formaldehyde resin is characterized in that the structure is shown as formula (1):
wherein, the first and the second end of the pipe are connected with each other,
r is an alkyl chain of C4-C15;
r' is an epoxy resin residue; the structure of the epoxy resin is one or more of the following formulas (2):
r' is rosin; the iodine value of the rosin is between 180 and 220;
x is an integer of 1 or more.
2. The process for producing an epoxy resin, rosin-modified alkylphenol-formaldehyde resin according to claim 1, wherein the alkylphenol, the epoxy resin and the rosin are reacted in the presence of a catalyst, the formaldehyde is gradually added after a certain period of time, and after the completion of the addition, the excess water is removed, and then the reaction is terminated by adding a terminator to obtain the epoxy resin, rosin-modified alkylphenol-formaldehyde resin.
3. The method as claimed in claim 2, wherein in the presence of a catalyst, the alkylphenol reacts with the epoxy resin and the rosin at 90-100 ℃, then the temperature is raised to 100-110 ℃, formaldehyde is added for polycondensation, then the temperature is raised to 140-160 ℃ for distillation to evaporate excess moisture, and after vacuum pumping, a terminator is added to terminate the reaction, thus obtaining the epoxy resin and rosin modified alkylphenol-formaldehyde resin.
4. The method as claimed in claim 2 or 3, wherein the iodine value of the rosin is between 180 and 220; the structure of the alkylphenol is shown as the formula (3):
wherein R is an alkyl chain of C4-C15.
5. A method according to claim 2 or 3, characterized in that the epoxy resin, rosin-modified alkylphenol-formaldehyde resin has a softening point between 95 and 115 ℃.
6. The method according to claim 3, wherein the condition of vacuum extraction is a vacuum degree of-0.04 MPa to-0.08 MPa, and the time of vacuum extraction is 10-60 min.
7. The method according to claim 2 or 3, wherein the catalyst is an acid catalyst selected from one or more of dodecylbenzene sulfonic acid, p-methyl benzene sulfonic acid, p-hydroxybenzene sulfonic acid, oxalic acid, sulfuric acid, hydrochloric acid and benzene sulfonic acid; and/or the terminator is alkali and is selected from one or more of sodium hydroxide, potassium hydroxide, N-methyl triethanolamine and diaza-dicyclo.
8. The method according to claim 2 or 3, wherein the alkylphenol is used in an amount of 60 to 120 parts by weight, the formaldehyde is used in an amount of 20 to 80 parts by weight, the epoxy resin is used in an amount of 1 to 50 parts by weight, the rosin is used in an amount of 1 to 50 parts by weight, the catalyst is used in an amount of 0.1 to 5 parts by weight, and the terminator is used in an amount of 0.1 to 5 parts by weight.
9. Use of the epoxy resin, rosin-modified alkylphenol-formaldehyde resin according to claim 1 in the field of rubber articles.
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| CN1233680C (en) * | 2003-06-03 | 2005-12-28 | 山西省应用化学研究所 | Phenol-formaldehyde resin by colophony modified with alkyl phenol being mixed and its preparation method |
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