CN113956414B - Epoxy modified phenolic resin and preparation method and application thereof - Google Patents
Epoxy modified phenolic resin and preparation method and application thereof Download PDFInfo
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- CN113956414B CN113956414B CN202111256447.1A CN202111256447A CN113956414B CN 113956414 B CN113956414 B CN 113956414B CN 202111256447 A CN202111256447 A CN 202111256447A CN 113956414 B CN113956414 B CN 113956414B
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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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- 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
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/20—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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Abstract
The invention provides an epoxy modified phenolic resin and a preparation method and application thereof, wherein the preparation method of the epoxy modified phenolic resin mainly comprises the following steps: adding phenol and an acid catalyst into a reactor, heating to 120-140 ℃, then dropwise adding a modifier with an epoxy group for reaction, cooling to 80-100 ℃, dropwise adding formaldehyde, and carrying out heat preservation reaction; and then distilling at normal pressure to remove water and phenol, and decompressing to obtain the epoxy modified phenolic resin. The epoxy modified phenolic resin prepared by the invention is applied to rubber, can ensure the bonding effect, and has lower heat generation and better processing performance.
Description
Technical Field
The invention relates to the field of rubber tires, in particular to epoxy modified phenol-formaldehyde resin and a preparation method and application thereof.
Background
In rubber tire products, nylon, steel wires and the like are usually used as a supporting framework structure to improve the strength of rubber, a bonding system of a metacresol system is commonly used for bonding the supporting framework structure and the rubber, however, resorcinol volatilizes in the rubber mixing process, generates heavy odor and toxic smoke, is harmful to human bodies, is highly polluted in the production process, is very easy to absorb water, has non-renewable property, and is replaced by resorcinol-formaldehyde prepolymer. However, when the resorcinol-formaldehyde prepolymer is used as a resorcinol substitute for an adhesive system, the heat generation of rubber is obviously increased, so that the temperature of the rubber tire is higher in the movement process, and the service life of the tire is greatly shortened.
At present, the improvement direction of the prior art is to insert an alkyl chain into a side chain of a prepolymer to improve the rigidity of molecules, for example, the side chain of cardanol is inserted into the molecules, so that a rubber product is not fuming in the processing process, and the rubber product has the advantages of high modulus, high hardness, low heat generation and the like; or the phenolic compound containing carbon-carbon double bonds and alkylphenol are subjected to co-condensation reaction to prepare the modified alkyl phenolic resin containing the double bond structure, and the modified alkyl phenolic resin provides enough initial self-adhesion and long-acting adhesion force for the rubber composition provided by the invention and reduces the dynamic heat generation of the rubber. However, in the above method, double bonds are introduced into the phenolic resin, and gelation is likely to occur during polymerization with formaldehyde, which is difficult to synthesize and complicated in process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the epoxy modified phenolic resin, the modifier with the epoxy group is connected between main chain molecules of the phenol prepolymer, a flexible branched chain is introduced between two phenol molecules through a ring opening reaction, the molecular weight of the polymer is increased, the affinity of the polymer with rubber in the processing process is increased, the intermolecular interaction friction is reduced, and therefore, the rubber product is easy to process, the heat generation is reduced. When the adhesive is applied to rubber, the adhesive can ensure the adhesion effect, and has lower heat generation and better processing performance.
The method is realized by the following technical scheme:
an epoxy modified phenolic resin, characterized by having the following structural formula:
wherein R is aryl, aralkyl or phenyl, preferably methyl or ethyl benzene;
n is an integer of 2 to 6.
The reaction formula for forming the epoxy modified phenolic resin is as follows:
the invention also provides a preparation method of the epoxy modified phenolic resin, which comprises the following steps:
s1: adding phenol and an acidic catalyst into a reactor;
s2: heating to 120-140 ℃, and dropwise adding a modifier with an epoxy group for reaction;
s3: cooling to 80-100 ℃, dripping formaldehyde, and carrying out heat preservation reaction;
s4: distilling at normal pressure to remove water and phenol;
s5: and decompressing to obtain the epoxy modified phenolic resin.
Further, in step S1, the acidic catalyst is one or more of oxalic acid, hydrochloric acid and p-toluenesulfonic acid.
Further, in step S1, the amount of the acid catalyst is 0.3 to 0.8wt% of the phenol, and the reaction rate is controlled by controlling the amount of the acid catalyst, and if the amount of the acid catalyst is less than 0.3wt%, the reaction rate is low and the reaction time is long; if the amount of the acid catalyst is more than 0.8wt%, the reaction rate is too fast and the reaction degree is severe.
Further, in step S2, the modifier with an epoxy group is an aromatic hydrocarbon or an alkane with an epoxy group.
In the step S2, the temperature is controlled to be 120-140 ℃, which is beneficial to ensuring that the modifier with epoxy groups can completely modify phenol.
Preferably, in step S2, the reaction time is 1-2h.
Preferably, the molar ratio of formaldehyde in step S3 to phenol in step S1 is from 0.5 to 0.8. If the molar ratio of the formaldehyde to the phenol is lower than the range, the prepared phenolic resin has low viscosity and is difficult to form; if the amount is more than this range, the resulting phenol resin tends to gel, and the resin loses its function of use and cannot be processed and used.
In the step S3, the temperature is reduced to 80-100 ℃, formaldehyde is dripped into the mixture and then the mixture is subjected to heat preservation reaction, the temperature of the heat preservation reaction is controlled to be 80-100 ℃, if the temperature is lower than 80 ℃, the reaction in the step S3 is not carried out, and if the temperature is higher than 100 ℃, the pressure is generated, and the reaction phenomenon is abnormal; preferably, the reaction is maintained for 1-2h to complete the reaction.
Further, in step S5, the reduced pressure distillation temperature is 160-180 ℃, the reduced pressure distillation time is 30-60min, and the reduced pressure distillation pressure is-0.07 to-0.09 Mpa.
Compared with the prior art, the invention has the following advantages:
1. volatile resorcinol is avoided, and the epoxy modified phenolic resin is added into the rubber composition for rubber mixing, so that volatile toxic substances are not generated;
2. compared with the traditional adhesive resin, the epoxy modified phenolic resin has lower heat generation and better processing performance on the basis of maintaining adhesion.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is an IR spectrum of an epoxy-modified phenolic resin prepared in example 1 of the present invention;
FIG. 2 is an infrared hydrogen spectrum of a phenol-formaldehyde resin prepared in comparative example 4;
FIG. 3 is a graph comparing the infrared hydrogen spectra of example 1 and comparative example 4.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The invention provides epoxy modified phenol formaldehyde resin and a preparation method and application thereof. Mainly through getting into the modifier that has the epoxy group between phenol performed polymer main chain molecule, introduce a flexible branch chain between two phenol molecules through ring-opening reaction, when the molecular weight of increase polymer, increase its affinity with rubber in the course of working, intermolecular interaction friction reduces to reach the easy processing of rubber goods, the effect that the themogenesis reduces, use the modifier that has the epoxy group, low toxicity, the smoking problem that uses resorcinol can be solved in the environmental protection, simple process is easy to operate.
Example 1
Adding 94g (1 mol) of phenol and 0.5g (0.5 percent of the mass of the phenol) of p-toluenesulfonic acid into a 1L four-neck flask provided with a temperature control, stirring, reflux condenser and a constant pressure dropping funnel, heating to 120-140 ℃, then dropwise adding 120g of styrene oxide, carrying out heat preservation reaction for 2h, cooling to 80-100 ℃, dropwise adding 50g (0.6 mol) of 37wt% of formaldehyde, carrying out heat preservation reaction for 2h, heating to 160 ℃ under normal pressure, carrying out reduced pressure distillation under 0.08MPa until the temperature in a kettle is 180 ℃, and keeping for 30min to obtain 192g of epoxy modified phenolic resin.
Example 2
141g (1.5 mol) of phenol and 1g (0.7 percent of the mass of the phenol) of oxalic acid are added into a 1L four-neck flask provided with a temperature control, stirring and reflux condenser tube and a constant pressure dropping funnel, the temperature is raised to 120-140 ℃, then 139g of epoxy hexane is dripped, the temperature is kept for reaction for 1.5h, the temperature is lowered to 80-100 ℃, 83g (1 mol) of 37wt% formaldehyde is dripped, the temperature is kept for reaction for 1.5h, the temperature is raised to 160 ℃ under normal pressure, the temperature is kept for reaction for 30min, and 206g of epoxy modified phenolic resin is obtained after-0.07 Mpa reduced pressure distillation is carried out until the temperature in the kettle is 180 ℃.
Example 3
Adding 141g (1.5 mol) of phenol and 0.6g (0.4% of phenol mass) of p-toluenesulfonic acid into a 1L four-neck flask provided with a temperature control, stirring, reflux condenser and a constant pressure dropping funnel, heating to 120-140 ℃, then dropwise adding 139g of epoxy hexane, carrying out heat preservation reaction for 2h, cooling to 80-100 ℃, dropwise adding 83g (1 mol) of 37wt% formaldehyde, carrying out heat preservation reaction for 2h, heating to 160 ℃ under normal pressure, distilling to 180 ℃ under reduced pressure of-0.08 MPa, and keeping for 30min to obtain 198g of epoxy modified phenolic resin.
Example 4
Adding 141g (1.5 mol) of phenol, 0.6g (0.4% of phenol mass) of p-toluenesulfonic acid and 0.5g (0.4% of phenol mass) of oxalic acid into a 1L four-neck flask provided with a temperature control, stirring and reflux condenser and a constant pressure dropping funnel, heating to 120-140 ℃, then dropwise adding 113g of glycidyl methacrylate, carrying out heat preservation reaction for 1.5h, cooling to 80-100 ℃, dropwise adding 83g (1 mol) of 37wt% of formaldehyde, carrying out heat preservation reaction for 1.5h, heating to atmospheric distillation to 160 ℃, carrying out reduced pressure distillation under 0.08MPa until the temperature in the kettle is 180 ℃, and keeping for 60min to obtain 224g of epoxy modified phenolic resin.
Comparative example 1
94g (1 mol) of phenol and 0.5g (0.5 percent of the mass of the phenol) of p-toluenesulfonic acid are added into a 1L four-neck flask provided with a temperature control, stirring and reflux condenser tube and a constant pressure dropping funnel, the temperature is increased to 80-100 ℃, 50g (0.6 mol) of formaldehyde with the weight percent of 37 is added dropwise, the temperature is kept for reaction for 2 hours, the temperature is increased to 160 ℃ under normal pressure, the temperature is increased to 180 ℃ under the pressure of-0.08 MPa, and the mixture is kept for 30 minutes after the temperature is increased to 160 ℃, the temperature is reduced to 180 ℃ in a kettle, so that 118g of phenol-formaldehyde resin is obtained.
Comparative example 2
141g (1.5 mol) of phenol, 0.6g (0.4 percent of the mass of the phenol) of p-toluenesulfonic acid and 0.5g (0.4 percent of the mass of the phenol) of oxalic acid are added into a 1L four-neck flask provided with a temperature control, stirring and reflux condenser and a constant pressure dropping funnel, the temperature is increased to 80-100 ℃, 83g (1 mol) of formaldehyde with the weight percent of 37 is dropwise added, the temperature is kept for 1.5h, the temperature is increased to 160 ℃ under normal pressure, the temperature is reduced to 180 ℃ under the pressure of-0.08 MPa, the temperature is kept for 30min, and 182g of phenol-formaldehyde resin is obtained.
Comparative example 3
Adding 141g (1.5 mol) of phenol and 1g (0.3% of the mass of the phenol) of oxalic acid into a 1L four-neck flask provided with a temperature control, stirring, reflux condenser and a constant pressure dropping funnel, heating to 80-100 ℃, dropwise adding 81g (1 mol) of formaldehyde with the weight percent of 37, reacting for 1.5h under heat preservation, heating to 160 ℃ under normal pressure, distilling under reduced pressure of-0.08 MPa until the temperature in the kettle is 180 ℃, and keeping for 60min to obtain 203g of phenol-formaldehyde resin.
Comparative example 4
110g (1 mol) of resorcinol and 0.6g (0.5% of phenol mass) of p-toluenesulfonic acid are added into a 1L four-neck flask provided with a temperature control, stirring, reflux condenser and a constant pressure dropping funnel, the temperature is raised to 80-100 ℃, 44g (0.55 mol) of 37% formaldehyde is added dropwise, the mixture is kept warm and reacted for 2 hours, the temperature is raised to 160 ℃ under normal pressure, the mixture is distilled to 180 ℃ under 0.08Mpa, and the mixture is kept for 60 minutes to obtain 115g of resorcinol formaldehyde resin.
< application test >
Application of epoxy modified phenolic resin in rubber tire products
The experimental formulation is shown in Table 1 below
TABLE 1 Experimental formulation
The rubber composition comprises the following specific preparation steps:
in the first step, natural rubber and carbon black are mixed in a Farrel internal mixer at about 150 ℃ to prepare a master batch.
In the second step, the resins prepared in comparative examples 1 to 4 and examples 1 to 4, respectively, were mixed with a cobalt salt at a temperature of about 145 ℃ into a master batch obtained by mixing in a Farrel internal mixer.
Thirdly, the rest components listed in the table 1 are added and mixed at the temperature of 90-100 ℃, and the product of the mixing and mixing is the modified vulcanized rubber mixture which is placed in the environment with the constant temperature of about 23-25 ℃ and the relative humidity of 40-80 percent overnight. Then, the mechanical properties were evaluated by measuring the vulcanization, shape, and optimum vulcanization degree at 150 ℃.
The test data for the modified vulcanized rubber compositions are shown in tables 2 to 4. Vulcanization conditions adopted for steel cord adhesion properties (N): multiplying by 20min at 160 ℃, and the specification of a steel cord; 2+2 0.25HT, tested in accordance with the standard ASTM D1871-2004; the DMA was tested using an Shimadzu DMA tester.
TABLE 2.T pull-out force comparison (number of samples N > 5) N/2+3 × 0.3HT wire
As can be seen from Table 2, the adhesion properties of the synthesized epoxy-modified phenolic resin of the present invention and the conventional phenolic resin (comparative example 4) are substantially not different.
TABLE 3 comparison of the vulcanization rates of the rubbers
As can be seen from Table 3, the resins of comparative examples 1 to 3 had higher Mooney viscosities than the resorcinol-formalin resin (comparative example 4), but the resins of examples 1 to 4 had significantly lower Mooney viscosities and better processability.
TABLE 4DMA Performance comparison
As can be seen from Table 4, the epoxy modified phenolic resin synthesized by the invention overcomes the problem of high heat buildup (Tan delta 60 ℃) of unmodified phenol formaldehyde resin, and the comparison of examples 1-4 and comparative examples 1-4 shows that the epoxy modified phenolic resin synthesized by the process of the invention applied to rubber can ensure the bonding effect, and has lower heat buildup and better processing performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. An epoxy-modified phenolic resin, comprising the following structural formula:
wherein R is aryl or aralkyl;
n is an integer of 2 to 6;
the preparation method of the epoxy modified phenolic resin comprises the following steps:
s1: adding phenol and an acidic catalyst into a reactor;
s2: heating, and dropwise adding a modifier with an epoxy group for reaction;
s3: cooling, dripping formaldehyde, and carrying out heat preservation reaction;
s4: removing water and phenol by atmospheric distillation;
s5: and decompressing to obtain the epoxy modified phenolic resin.
2. The epoxy-modified phenolic resin of claim 1, wherein R is phenyl.
3. A method for preparing the epoxy-modified phenolic resin according to claim 1 or 2, comprising the steps of:
s1: adding phenol and an acidic catalyst into a reactor;
s2: heating to 120-140 ℃, and dropwise adding a modifier with an epoxy group for reaction;
s3: cooling to 80-100 ℃, dripping formaldehyde, and carrying out heat preservation reaction;
s4: removing water and phenol by atmospheric distillation;
s5: and decompressing to obtain the epoxy modified phenolic resin.
4. The method for preparing epoxy modified phenolic resin according to claim 3, wherein in step S1, the acidic catalyst is one or more of oxalic acid, hydrochloric acid and p-toluenesulfonic acid.
5. The method of claim 3, wherein the acidic catalyst is used in an amount of 0.3 to 0.8wt% based on the phenol in step S1.
6. The method of claim 3, wherein the modifier having an epoxy group in step S2 is an aromatic hydrocarbon or an aromatic alkane having an epoxy group.
7. The method of claim 3, wherein the molar ratio of formaldehyde in step S3 to phenol in step S1 is 0.5 to 0.8.
8. The method for preparing epoxy modified phenolic resin according to claim 3, wherein in step S3, the reaction time is kept for 1-2h.
9. The method of claim 3, wherein in step S5, the temperature of the reduced pressure distillation is 160-180 ℃, the time of the reduced pressure distillation is 30-60min, and the pressure of the reduced pressure distillation is-0.07 to-0.09 MPa.
10. Use of the epoxy-modified phenolic resin according to any one of claims 1 to 2 or prepared by the preparation method according to any one of claims 3 to 9 in rubber tires.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2254379A1 (en) * | 1972-11-07 | 1974-05-22 | Reichhold Albert Chemie Ag | METHOD FOR MANUFACTURING NOVOLACES |
| CN104822722A (en) * | 2012-11-12 | 2015-08-05 | Dic株式会社 | Phenolic-hydroxyl-containing resin, epoxy resin, curable resin composition, substance obtained by curing same, and semiconductor sealant |
| CN108192053A (en) * | 2018-01-25 | 2018-06-22 | 杜广新 | A kind of method that high-performance Alkylphenolic Tackifying Resin is produced using phenol waste as raw material |
| CN111484588A (en) * | 2020-06-10 | 2020-08-04 | 山东阳谷华泰化工股份有限公司 | Epoxy oleate modified alkylphenol-formaldehyde resin rubber tackifier and preparation method thereof |
| CN111548467A (en) * | 2020-06-10 | 2020-08-18 | 山东阳谷华泰化工股份有限公司 | Epoxy-modified alkylphenol-formaldehyde resin rubber tackifier and preparation method thereof |
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- 2021-10-27 CN CN202111256447.1A patent/CN113956414B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2254379A1 (en) * | 1972-11-07 | 1974-05-22 | Reichhold Albert Chemie Ag | METHOD FOR MANUFACTURING NOVOLACES |
| CN104822722A (en) * | 2012-11-12 | 2015-08-05 | Dic株式会社 | Phenolic-hydroxyl-containing resin, epoxy resin, curable resin composition, substance obtained by curing same, and semiconductor sealant |
| CN108192053A (en) * | 2018-01-25 | 2018-06-22 | 杜广新 | A kind of method that high-performance Alkylphenolic Tackifying Resin is produced using phenol waste as raw material |
| CN111484588A (en) * | 2020-06-10 | 2020-08-04 | 山东阳谷华泰化工股份有限公司 | Epoxy oleate modified alkylphenol-formaldehyde resin rubber tackifier and preparation method thereof |
| CN111548467A (en) * | 2020-06-10 | 2020-08-18 | 山东阳谷华泰化工股份有限公司 | Epoxy-modified alkylphenol-formaldehyde resin rubber tackifier and preparation method thereof |
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