CN120137143A - A method for preparing organosilicon-modified multifunctional epoxy resin - Google Patents
A method for preparing organosilicon-modified multifunctional epoxy resin Download PDFInfo
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- CN120137143A CN120137143A CN202510418783.3A CN202510418783A CN120137143A CN 120137143 A CN120137143 A CN 120137143A CN 202510418783 A CN202510418783 A CN 202510418783A CN 120137143 A CN120137143 A CN 120137143A
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3281—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing silicon
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Emergency Medicine (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to the technical field of epoxy resin preparation, in particular to a preparation method of organosilicon modified polyfunctional epoxy resin. The method comprises the following steps of S1, enabling cyclotetrasiloxane to react with an alkenyl epoxy compound to obtain epoxidized cyclotetrasiloxane, S2, enabling the epoxidized cyclotetrasiloxane to react with anhydride to obtain carboxylated cyclotetrasiloxane epoxy resin, and S3, enabling the carboxylated cyclotetrasiloxane epoxy resin to react with epoxy resin. The prepared organosilicon modified multifunctional epoxy resin contains four epoxy groups and is branched, so that the crosslinking density of a cured product is ensured, and meanwhile, the addition of the organosilicon promotes the flexibility of the cured product of the epoxy resin and the heat resistance of a resin system. The prepared epoxy resin is suitable for the protective coating of various petroleum equipment, chemical equipment, power equipment and steel structures for buildings with requirements on high temperature resistance and corrosion resistance.
Description
Technical Field
The invention relates to the technical field of epoxy resin preparation, in particular to a preparation method of organosilicon modified polyfunctional epoxy resin.
Background
Epoxy resins are widely used in the fields of composite materials, adhesives, paints, electronic packages and the like because of excellent mechanical properties, adhesion, heat resistance and electrical insulation. However, its brittleness, insufficient toughness, and difficult processing after curing limit the application. To solve these problems, silicone-modified epoxy resins have become a research hotspot. The organosilicon can improve the internal stress, flexibility and corrosion resistance of the epoxy resin. The compatibility is improved by introducing the reactive functional groups, and the high-temperature resistant matrix is synthesized. The modification method such as side chain grafting, main chain extension and the like can improve the flexibility and the ageing resistance. There are problems of poor compatibility and unstable performance caused by phase separation. Researchers have proposed strategies to synthesize small molecule epoxy organosiloxane oligomers, control polymerization kinetics, physically blend, or develop silicon-containing curatives to optimize performance.
Chinese patent application CN 116179127a discloses a room temperature curable silicone modified epoxy resin pouring sealant, which consists of a component a (containing epoxy resin, epoxy oligosiloxane, reactive diluent, etc.) and a component B (organic amine curing agent). The compatibility problem of the traditional polyorganosiloxane and the epoxy resin is solved through physical blending, the adhesive can be cured in 24 hours at room temperature, and the flexibility, ageing resistance and moisture resistance (water contact angle 91-118 ℃) of the adhesive layer are obviously improved. However, bisphenol A epoxy resin is mainly relied on, epoxy oligosiloxane is physically mixed instead of chemically modified, so that the compatibility is insufficient and the overall strength of a cured product is reduced, and Chinese patent application CN 116179127A discloses an organosilicon modified epoxy resin adhesive suitable for LED encapsulation, which consists of organosilicon modified epoxy resin (A/B component), an anhydride curing agent and the like. The glass is characterized by high light transmittance (visible light > 90%), refractive index of 1.51, low moisture absorption and excellent thermal aging resistance and ultraviolet stability. However, bisphenol A epoxy resin is not used, and modified epoxy groups are provided by a diluent, resulting in further improvement in strength and thermal stability of the cured product.
Disclosure of Invention
The invention provides a preparation method of an organosilicon modified polyfunctional epoxy resin, which comprises the following steps:
S1, reacting cyclotetrasiloxane with an alkenyl epoxy compound to obtain epoxidized cyclotetrasiloxane;
s2, reacting the epoxy cyclotetrasiloxane with anhydride to obtain carboxylated cyclotetrasiloxane epoxy resin;
s3, reacting the carboxylated cyclotetrasiloxane epoxy resin with epoxy resin.
The organosilicon modified multi-functionality epoxy resin prepared by the method contains four epoxy groups and is a branched group, so that the crosslinking density of a cured product is ensured, meanwhile, carboxyl generated by the reaction of anhydride and the epoxy groups has high reactivity, the carboxyl can be used as a crosslinking point in the subsequent curing process of the epoxy resin to form more three-dimensional network structures, the crosslinking density is obviously improved, the coating film is more compact due to the high crosslinking density, and excellent salt spray resistance is realized. Carboxylation introduces soft segments or forms microphase separation structures, by introducing flexible siloxane segments, significantly increases elongation at break, disperses stresses and inhibits crack propagation. Meanwhile, the addition reaction of anhydride and epoxy group may generate ester bond structure with better toughness, further improving impact resistance and water resistance.
The alkenyl epoxy compound comprises at least one of Allyl Glycidyl Ether (AGE), 1, 2-epoxy-4-vinyl cyclohexane and allyl polyether epoxy compound.
The anhydride comprises at least one of phthalic anhydride, maleic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and nadic anhydride.
Alternatively, the tetramethyl cyclotetrasiloxane is selected from 1,3,5, 7-tetramethyl cyclotetrasiloxane.
The epoxy resin comprises at least one of bisphenol A epoxy resin, bisphenol F epoxy resin and phenolic epoxy resin.
Tetramethyl cyclo-tetra siloxane (S) tetramethyl cyclotetrasiloxane tetramethyl tetravinyl cyclotetrasiloxane at least one of octaphenyl cyclotetrasiloxane and chloromethyl heptamethyl cyclotetrasiloxane.
The molar ratio of the cyclotetrasiloxane to the alkenyl epoxy compound is 1 (4-6).
Alternatively, the molar ratio of cyclotetrasiloxane to alkenyl epoxy compound is 1 (4-5).
The S1 comprises the steps of dropwise adding an alkenyl epoxy compound into cyclotetrasiloxane for 1-3h under the condition of a catalyst, and reacting.
Alternatively, the catalyst in S1 is selected from Karstedt' S catalyst in an amount of 1-20ppm based on the mass of the cyclotetrasiloxane.
The reaction temperature in the S1 is 150-170 ℃ and the reaction time is 10-14h.
Optionally, the reaction temperature in the step S1 is 160-165 ℃ and the reaction time is 10-12h.
The molar ratio of the epoxy cyclotetrasiloxane to the anhydride is 1 (4-6).
Optionally, the molar ratio of the epoxidized cyclotetrasiloxane to the anhydride is 1 (4-5).
The temperature of the reaction in the S2 is 80-120 ℃.
The reaction raw materials in S2 and S3 also comprise a catalyst, wherein the catalyst comprises at least one of boron trifluoride complex, triphenylphosphine, triethanolamine and potassium persulfate.
The addition amount of the catalyst in the S2 is 0.1-0.5wt% of the epoxy cyclotetrasiloxane.
The addition amount of the catalyst in the S3 is 0.1-0.5wt% of the epoxy resin.
The mol ratio of the carboxylated cyclotetrasiloxane epoxy resin to the epoxy resin is 1 (4-6).
Optionally, the molar ratio of the carboxylated cyclotetrasiloxane epoxy resin to the epoxy resin is 1 (4-5).
Advantageous effects
1. The epoxy resin prepared by the invention effectively improves the strength and the thermal stability of the resin on the basis of keeping the compatibility.
2. According to the invention, the cyclotetrasiloxane and the alkenyl epoxy compound are introduced, and the prepared organosilicon modified polyfunctional epoxy resin contains four epoxy groups and is a branched group, so that the crosslinking density of a cured product is ensured.
3. The invention provides a carboxylated cyclotetrasiloxane epoxy resin obtained by reacting epoxidized cyclotetrasiloxane with anhydride, which can further improve the salt spray resistance, impact resistance and water resistance of the resin.
4. The invention can further improve the adhesive force and fracture toughness of the resin by the reaction of the carboxylated cyclotetrasiloxane epoxy resin and the epoxy resin.
5. The epoxy resin prepared by the invention is suitable for the protective coating of various petroleum equipment, chemical equipment, power equipment and steel structures for buildings which have requirements on high temperature resistance and corrosion resistance.
Detailed Description
In this embodiment, E-44, E-51, karstedt's catalyst are not limited to the manufacturer.
Example 1
The preparation method of the organosilicon modified polyfunctional epoxy resin comprises the following steps:
96g of 1,3,5, 7-tetramethyl cyclotetrasiloxane was weighed and added to the reaction vessel, followed by the Karstedt catalyst (5 ppm by mass of 1,3,5, 7-tetramethyl cyclotetrasiloxane) and after stirring well, AGE was started to be added dropwise, wherein the AGE amount was 90g. After the catalyst was added, the reaction began to exotherm and the reaction temperature was slowly raised to 82 ℃ by cooling water control. Continuously dripping alkenyl epoxy compound for 1h, heating to 160 ℃ after dripping, keeping the reaction for 10 h, and removing redundant alkenyl epoxy compound by reduced pressure distillation (the pressure is controlled to be-0.09 to-0.10 MPa) after the reaction is finished, thus obtaining the epoxidation cyclotetrasiloxane.
70G of epoxidized cyclotetrasiloxane is taken and added into a reaction vessel, 60g of phthalic anhydride is added for reaction for 3 hours, 0.1g of triphenylphosphine catalyst is added, the reaction temperature is 90 ℃, and the carboxylated cyclotetrasiloxane epoxy resin is obtained after the acid value is not reduced any more.
64G of carboxylated epoxy polysiloxane were added to the reaction vessel, heated to 120℃and 88g of liquid epoxy resin E-44 were added. 0.1g of triphenylphosphine is added for reaction for 2 hours, and when the acid value is less than 5mgKOH, the reaction reaches the end point, and the obtained product is the polyfunctional organosilicon modified epoxy resin.
Example 2
The preparation method of the organosilicon modified polyfunctional epoxy resin comprises the following steps:
96g of 1,3,5, 7-tetramethyl cyclotetrasiloxane was weighed and added to the reaction vessel, followed by the Karstedt catalyst (5 ppm by mass of 1,3,5, 7-tetramethyl cyclotetrasiloxane) and after stirring well, AGE was started to be added dropwise, wherein the AGE amount was 90g. After the catalyst was added, the reaction began to exotherm and the reaction temperature was slowly raised to 82 ℃ by cooling water control. Continuously dripping alkenyl epoxy compound for 1h, heating to 160 ℃ after dripping, and keeping the reaction for 10 h. After the reaction is completed, the excess alkenyl epoxy compound is removed by distillation under reduced pressure (the pressure is controlled to be-0.09 to-0.10 MPa), and the epoxidized cyclotetrasiloxane is obtained.
70G of epoxidized cyclotetrasiloxane is added into a reaction vessel, 62g of hexahydrophthalic anhydride is added for reaction for 3 hours, 0.1g of triphenylphosphine catalyst is added, the reaction temperature is 90 ℃, and the acid value is not reduced any more, so that the carboxylated cyclotetrasiloxane epoxy resin is obtained.
66G of carboxylated cyclotetrasiloxane epoxy resin were taken and added to the reaction vessel, heated to 120℃and 88g of liquid epoxy resin E-44 were added. 0.1g of triphenylphosphine is added for reaction for 2 hours, and when the acid value is less than 5mgKOH, the reaction reaches the end point, and the obtained product is the polyfunctional organosilicon modified epoxy resin.
Example 3
The preparation method of the organosilicon modified polyfunctional epoxy resin comprises the following steps:
96g of 1,3,5, 7-tetramethyl cyclotetrasiloxane was weighed and added to the reaction vessel, followed by the Karstedt catalyst (5 ppm by mass of 1,3,5, 7-tetramethyl cyclotetrasiloxane) and after stirring well, AGE was started to be added dropwise, wherein the AGE amount was 90g. After the catalyst was added, the reaction began to exotherm and the reaction temperature was slowly raised to 82 ℃ by cooling water control. Continuously dripping alkenyl epoxy compound for 1h, heating to 160 ℃ after dripping, and keeping the reaction for 10 h. After the reaction is completed, the excess alkenyl epoxy compound is removed by distillation under reduced pressure (the pressure is controlled to be-0.09 to-0.10 MPa), and the epoxidized cyclotetrasiloxane is obtained.
70G of epoxidized cyclotetrasiloxane is taken and added into a reaction vessel, 60g of phthalic anhydride is added for reaction for 3 hours, 0.1g of triphenylphosphine catalyst is added, the reaction temperature is 90 ℃, and the acid value is not reduced any more, thus obtaining the carboxylated cyclotetrasiloxane epoxy resin.
64G of carboxylated cyclotetrasiloxane epoxy resin were taken and charged into a reaction vessel, heated to 120℃and 80g of liquid epoxy resin E-51 were added. 0.1g of triphenylphosphine is added for reaction for 2 hours, and when the acid value is less than 5mgKOH, the reaction reaches the end point, and the obtained product is the polyfunctional organosilicon modified epoxy resin.
Comparative example 1
A preparation method of epoxy resin comprises weighing 96g of 1,3,5, 7-tetramethyl cyclotetrasiloxane, adding into a reaction vessel, then adding Karstedt catalyst (the dosage is 5ppm of the mass of 1,3,5, 7-tetramethyl cyclotetrasiloxane), stirring uniformly, and then beginning to drop AGE, wherein the dosage of AGE is 90g. After the catalyst was added, the reaction began to exotherm and the reaction temperature was slowly raised to 82 ℃ by cooling water control. Continuously dripping alkenyl epoxy compound for 1h, heating to 160 ℃ after dripping, and keeping the reaction for 10 h. After the reaction is completed, the excess alkenyl epoxy compound is removed by distillation under reduced pressure (the pressure is controlled to be-0.09 to-0.10 MPa), and the epoxidized cyclotetrasiloxane is obtained.
35G of the epoxidized cyclotetrasiloxane is taken and added into a beaker, 88g of liquid epoxy resin E44 is then added, and the mixture is stirred uniformly at 50 ℃.
Comparative example 2
A commercially available epoxy resin E44 (not limited to manufacturer) was used as a comparison.
Performance test method
Performance tests were performed in examples and comparative examples and the test data are listed in table 1.
Sample preparation:
The epoxy resins of examples 1-3 and comparative examples 1-2 were prepared by adding xylene as a solvent (controlling the solid content to 40-60%, optionally 50%) at the same time in a molar ratio of 1:0.9 of active hydrogen equivalent in the epoxy groups and the curing agent, and then spraying on PP plates to prepare free films for testing the crosslink density, glass transition temperature, and heat resistance at break. And meanwhile, the coating with the base material is prepared on a tinplate by spraying and is used for testing the water resistance, salt spray resistance, impact resistance and adhesive force resistance. Drying at 60 ℃ for 2 hours, and testing after adjusting at room temperature for 16 hours.
Detailed description of the test methods
1. Cross-link Density test
The method comprises immersing the sample in toluene for 24 hours, measuring the volume change before and after swelling, and calculating the crosslinking density by Flory-Rehner equation.
The device is characterized in that a swelling tester is used for controlling swelling conditions, and an electronic balance is used for accurately measuring mass change of a sample.
2. Glass transition temperature (Tg) test
The method comprises the steps of using a DSC instrument to rise from room temperature to 200 ℃ at a temperature rising rate of 10 ℃ per minute, recording a heat flow change curve, wherein Tg is the temperature corresponding to the inflection point of the curve.
A Differential Scanning Calorimeter (DSC) is used to accurately measure heat flow variation.
3. Fracture toughness test
The method comprises the steps of preparing a single-side notched beam sample, performing three-point bending test by using a universal material testing machine, recording load and displacement during fracture, and calculating fracture toughness.
The device is a universal material testing machine for loading and recording data, and the notch preparation device is used for preparing standard notches.
4. Impact resistance test
The method comprises the steps of using a drop hammer impact tester to impact a sample with a drop hammer with a certain height according to the GB/T1732 standard, and recording impact energy when the sample is broken.
The drop hammer impact tester is used for simulating impact conditions.
5. Salt spray resistance time test
The method comprises the steps of placing a sample into a salt fog box, spraying 5wt% NaCl solution, periodically observing the rust condition of a paint film, and recording the time of rust occurrence.
The equipment is a salt spray test box for simulating salt spray environment.
6. Water resistance test
The method comprises the steps of immersing a sample in normal-temperature water for 48 hours, and observing whether a paint film is foamed, rusted or whitened.
The device comprises: the constant temperature water tank is used for keeping the water temperature constant.
7. Adhesion test
According to the GB/T9286 standard, a cross-cut device is used for cutting square grids of 1mm multiplied by 1mm on the surface of a paint film, an adhesive tape is attached, and then the paint film is torn off, and the peeling condition of the paint film is observed.
The device, the cross-hatch machine, is used for preparing standard cross-hatch and the adhesive tape is used for peeling test.
Performance test data
TABLE 1
Claims (10)
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| CN202510418783.3A CN120137143A (en) | 2025-04-03 | 2025-04-03 | A method for preparing organosilicon-modified multifunctional epoxy resin |
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