CN109232862B - Flame-retardant hyperbranched epoxy resin and preparation method thereof - Google Patents
Flame-retardant hyperbranched epoxy resin and preparation method thereof Download PDFInfo
- Publication number
- CN109232862B CN109232862B CN201811082956.5A CN201811082956A CN109232862B CN 109232862 B CN109232862 B CN 109232862B CN 201811082956 A CN201811082956 A CN 201811082956A CN 109232862 B CN109232862 B CN 109232862B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- flame
- retardant
- hyperbranched epoxy
- hyperbranched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08G59/3263—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing sulfur
-
- 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
- C08G59/40—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 curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of epoxy resin, and particularly discloses flame-retardant hyperbranched epoxy resin and a preparation method thereof, wherein the flame-retardant hyperbranched epoxy resin comprises the following steps: the heat-resistant flame-retardant hyperbranched epoxy resin is prepared by carrying out atom transfer polymerization reaction on trifunctional sulfur-nitrogen heterocyclic epoxy resin and dihydric alcohol under the action of a catalyst, wherein the molecular weight is 3000-35000 g/mol. According to the invention, the nitrogen-containing heterocycle is introduced into the structure of the hyperbranched epoxy resin, so that the heat resistance can be improved, the flame retardance of the epoxy resin is improved by introducing the nitrogen element with the flame retardant function, and the halogen-free flame retardant function is realized; the sulfur atoms are introduced into the structure of the hyperbranched epoxy resin, so that the curing of the epoxy resin can be promoted, the curing efficiency of the epoxy resin is improved, the curing temperature is reduced, and the functions of energy conservation and consumption reduction are achieved. The invention has the characteristics of simple process, mild reaction condition, high yield and the like, and the product has the functions of flame retardance, reinforcement and toughening, and is expected to be used in the fields of halogen-free flame retardance, reinforcement and toughening of epoxy resin, solvent-free coating and the like.
Description
Technical Field
The invention relates to the technical field of hyperbranched epoxy resin and a preparation method thereof, in particular to flame-retardant hyperbranched epoxy resin and a preparation method thereof.
Background
The research on the synthesis of hyperbranched epoxy resin originated from 1993, and PCT international application WO9317060 discloses that aliphatic sulfur-containing hyperbranched epoxy resin with higher viscosity can be synthesized by reacting dimethylolpropionic acid and trimethylolpropane as raw materials with epichlorohydrin. Hyperbranched epoxy resins prepared from trimellitic anhydride and diethylene glycol as main raw materials by the inventors of the present application have low viscosity but low heat resistance (European Polymer Journal,2006,42(3): 711-. The inventors of the present application also studied nitrogen heterocyclic hyperbranched epoxy resins and silicon skeleton hyperbranched epoxy resins (ZL200910029024.9, ZL200910029026.8, ZL200910062871.5, ZL201010224451.5) having high heat-resistant temperature. In addition, the preparation technology (esterification reaction, hydrosilylation reaction and grafting reaction) of the sulfur-containing hyperbranched epoxy resin reported in the prior art has low efficiency, low yield, long reaction time, high energy consumption, high curing temperature and long curing time. Therefore, the inventor of the application finds that the process technology for preparing the sulfur-containing epoxy resin (ZL201310091452.0) and the sulfur-containing hyperbranched epoxy resin (ZL201210566173.0) by utilizing the mercaptan-olefin click reaction improves the preparation efficiency, but the prepared epoxy resin does not have the flame retardant function. The epoxy resin prepared by all the prior art technologies has complex process, low heat resistance, slow curing speed and no flame retardant function. Therefore, the development of a preparation technology of the flame-retardant hyperbranched epoxy resin with simple process, high yield and flame retardance is a fundamental way for solving the problems existing in the field at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a novel flame-retardant hyperbranched epoxy resin, which has the following structural formula:
in the formula R2Is structured as
Wherein m and n are independently selected from any integer of 0-8; preferably, n is 2 and m is 0.
R1＝-CH2CH2SCH2CH2CH2OCH2CH(OH)CH2-；
R3＝-CH2(CH2)j-or-CH2CH2(OCH2CH2)j-, where j is 1, 2, 3, 4 or 5.
A synthetic method of the flame-retardant hyperbranched epoxy resin comprises the following steps:
adding a trifunctional sulfur-containing nitrogen heterocyclic epoxy resin monomer, dihydric alcohol and an organic solvent into a reaction vessel provided with a mechanical stirring pipe, a condensing pipe and a thermometer according to a certain proportion, uniformly mixing, adding a catalyst into the reaction vessel, stirring and reacting for 8-20 hours at the temperature of 140 ℃, and evaporating the organic solvent to obtain the hyperbranched epoxy resin, wherein the molecular weight of the hyperbranched epoxy resin is 3000-35000g/mol, preferably 3500-25000 g/mol.
The molar ratio of the trifunctional sulfur-nitrogen heterocyclic epoxy resin monomer to the diol to the organic solvent is (1.0-1.5): 1: (1.0-5.0).
Furthermore, the catalyst is one or more than two of tetrabutylammonium bromide, tetrabutylammonium chloride, hexadecyltrimethylammonium bromide and hexadecyltrimethylammonium chloride, and the dosage of the catalyst is 0.5-5% of the mass of the trifunctional sulfur-containing nitrogen heterocyclic epoxy resin monomer, and is preferably 2-5%.
Further, the organic solvent is: one or more of benzene, toluene, xylene and tetrahydrofuran.
The dihydric alcohol is HO-R3-OH，R3＝-CH2(CH2)j-or-CH2CH2(OCH2CH2)j-, where j is 1, 2, 3, 4 or 5.
Further, the dihydric alcohol is ethylene glycol, diethylene glycol, butanediol or triethylene glycol.
The structural formula of the trifunctional sulfur-containing nitrogen heterocyclic epoxy resin monomer is as follows:
wherein R is2R in the structural formula of flame-retardant hyperbranched epoxy resin2。
Further, the trifunctional sulfur-containing nitrogen heterocyclic epoxy resin monomer is tris (2-hydroxyethyl) isocyanurate-tris (mercaptopropionate) triglycidyl ether
Or melamine-tris (mercaptopropionamide) triglycidyl ether
The synthetic procedure of the trifunctional sulfur-containing azacyclic epoxy resin monomer of the present invention can be referred to the published article of the inventor (Progress in Organic Coatings,2016,101: 178-185).
The flame-retardant hyperbranched epoxy resin prepared by the invention has the advantages of low viscosity, high temperature resistance, rapid curing and the like, and is expected to be applied to the fields of environment-friendly low-volatility coating, low-volatility resin, enhancement and toughening of epoxy resin and the like.
Compared with the prior art, the technical scheme of the invention has the following advantages and beneficial effects:
1. according to the invention, the nitrogen-containing heterocycle is introduced into the structure of the hyperbranched epoxy resin, so that the heat resistance of the epoxy resin can be improved, the introduction of nitrogen element with a flame-retardant function can improve the flame retardance of the epoxy resin, and the function of halogen-free flame retardance can be realized;
2. according to the invention, sulfur atoms are introduced into the structure of the hyperbranched epoxy resin, so that the curing of the epoxy resin can be promoted, the curing efficiency of the epoxy resin is improved, the curing temperature is reduced, and the functions of energy conservation and consumption reduction are achieved;
3. the hyperbranched epoxy resin has simple preparation process and low raw material cost, and is suitable for industrial production;
4. the hyperbranched epoxy resin has the functions of strengthening and toughening common epoxy resin, and is expected to be widely applied to the field of strengthening and toughening epoxy resin;
5. the hyperbranched epoxy resin has low viscosity, can obviously reduce the viscosity when added into bisphenol A epoxy resin, plays a role of an active diluent, and is expected to be applied to the field of solvent-free and low-volatility epoxy resin coatings.
Detailed Description
The present invention is described in detail below with reference to specific examples, but these examples should not be construed as limiting the scope of the present invention in any way.
The molecular weight of the product was determined by GPC from PL, UK, the epoxy value was determined by the national standard acetone hydrochloride method, and the viscosity was determined by Brookfield viscometer at 25 ℃.
The trifunctional sulfur-containing azacyclic epoxy resin monomer in the following examples was prepared by the inventors of the present application (Progress in Organic Coatings,2016,101: 178-.
(1) Synthesis of THGEP
0.2mol of tris (2-hydroxyethyl) isocyanurate, 0.7mol of 3-mercaptopropionic acid, 0.3g of p-toluenesulfonic acid and a solvent toluene are sequentially added into a 250mL four-neck flask provided with a magnetic stirring device and a water separator, heating reflux reaction is carried out under the protection of nitrogen, and the reaction is stopped when the acid value in a reaction system is not reduced and is kept unchanged. The reaction solution was washed with sodium hydroxide solution (5 wt%) to neutrality, and the organic layer was distilled to remove toluene to obtain the product tris (2-hydroxyethyl) isocyanurate-tris (mercaptopropionate) (THMP) as a colorless transparent liquid with a yield of about 98.0%.
Adding 0.1mol of THMP and 0.3mol of Allyl Glycidyl Ether (AGE) into a single-neck flask with magnetic stirring, adding an organic solvent of chloroform and a photoinitiator of benzophenone accounting for 2 percent of the mass of the THMP, carrying out ultraviolet irradiation for 5min under stirring, and carrying out rotary evaporation to remove the organic solvent, thereby obtaining the colorless and transparent tris (2-hydroxyethyl) isocyanurate-triglycidyl sulfide (THGEP) with low viscosity, wherein the yield is about 98 percent.
(2) Synthesis of MGEP
0.2mol of melamine, 0.75mol of 3-mercaptopropionic acid, 0.25g of p-toluenesulfonic acid and a solvent toluene are sequentially added into a four-neck flask provided with a magnetic stirring device and a water separator, heating reflux reaction is carried out under the protection of nitrogen, and the reaction is stopped when the acid value in a reaction system is not reduced any more and is kept unchanged. The reaction solution was washed with sodium hydroxide solution (5 wt%) to neutrality, and the organic layer was evaporated to remove toluene to obtain melamine-tris (mercaptopropionate) (MMP) as a colorless transparent liquid with a yield of about 95.0%.
Adding 0.1mol of MMP and 0.3mol of Allyl Glycidyl Ether (AGE) into a single-mouth bottle with magnetic stirring, adding an organic solvent of chloroform and a photoinitiator of benzophenone accounting for 2 percent of the mass of the MMP, irradiating for 5min by ultraviolet under stirring, and removing the organic solvent by rotary evaporation to obtain the colorless, transparent and low-viscosity melamine-tris (mercaptopropionamide) triglycidyl ether (MGEP), wherein the yield is about 99 percent.
Embodiment 1a flame-retardant hyperbranched epoxy resin, which is prepared by the following steps:
adding 0.4mol of tris (2-hydroxyethyl) isocyanurate-tris (glycidyl sulfide) (THGEP), 0.3mol of ethylene glycol and 0.3mol of xylene into a three-neck flask provided with a mechanical stirring device, a condenser tube and a thermometer, uniformly mixing, then adding tetrabutylammonium bromide with the mass of 0.5% of THGEP, slowly heating to 140 ℃, stirring and reacting for 8 hours, and distilling off the xylene to obtain the hyperbranched epoxy resin (the first structure in claim 1, HEP-6, containing 6mol of epoxy groups per mol of HEP-6), wherein the epoxy value is 0.16mol/100g, the number average molecular weight is about 3600g/mol, and the viscosity is 6000cp (25 ℃).
Embodiment 2a flame-retardant hyperbranched epoxy resin, which is prepared by the following steps:
adding 0.5mol of tris (2-hydroxyethyl) isocyanurate-tris (glycidyl sulfide) (THGEP), 0.45mol of diethylene glycol and 2.25mol of toluene into a three-neck flask provided with a mechanical stirrer, a condenser and a thermometer, uniformly mixing, then adding 5 mass percent of hexadecyl trimethyl ammonium bromide of THGEP, slowly heating to 110 ℃, stirring for reaction for 15 hours, and distilling off the toluene to obtain the hyperbranched epoxy resin (the second structure in claim 1, HEP-12, containing 12mol of epoxy groups per mol of HEP-12), wherein the epoxy value is 0.12mol/100g, the number average molecular weight is about 11000g/mol, and the viscosity is 7200cp (25 ℃).
Embodiment 3 a flame-retardant hyperbranched epoxy resin, which is prepared by the following steps:
0.22mol of tris (2-hydroxyethyl) isocyanurate-tris (glycidylthioether) (THGEP), 0.21mol of 1, 4-butanediol, 0.1mol of toluene andadding 0.2mol of benzene into a three-neck flask provided with a mechanical stirring device, a condenser pipe and a thermometer, uniformly mixing, adding hexadecyl trimethyl ammonium chloride with the mass of 2 percent of THGEP, slowly heating to 110 ℃, stirring and reacting for 20 hours, and evaporating the organic solvent to obtain the hyperbranched epoxy resin (the third structure in claim 1, wherein R is R)2Structure of (1)
n-2, HEP-24 containing 24mol epoxy groups per mole of HEP-24), an epoxy value of 0.10mol/100g, a number average molecular weight of about 22900g/mol, and a viscosity of 8600cp (25 ℃).
Embodiment 4 a flame-retardant hyperbranched epoxy resin, which is prepared by the following steps:
adding 0.22mol of melamine-tri (mercaptopropionamide) triglycidyl ether (MGEP), 0.21mol of triethylene glycol and 0.4mol of xylene into a three-neck flask provided with a mechanical stirrer, a condenser pipe and a thermometer, uniformly mixing, adding hexadecyltrimethylammonium chloride accounting for 3 percent of the weight of MGEP, slowly heating to 140 ℃, stirring for reaction for 10 hours, and evaporating an organic solvent to obtain the hyperbranched epoxy resin (the third structure in claim 1, wherein R is R2Structure of (1)
m is 0, HMEP-24, 24mol epoxy groups per mol HMEP-24), an epoxy value of 0.11mol/100g, a number average molecular weight of about 23100g/mo and a viscosity of 9200cp (25 ℃).
The hyperbranched epoxy resins and bisphenol A type epoxy resins (E51, epoxy value 0.51mol/100g) obtained in examples 1 to 4 were mixed with methylnadic anhydride, respectively, in such amounts that the molar ratio of anhydride groups to epoxy groups was 1.1: 1. and then pouring the mixture into a mold, heating to 170-180 ℃ for curing for 6 hours, taking out a sample, cooling, demolding, and standing at room temperature for 12 hours to respectively test the performance of the material. The results are shown in Table 1. Wherein the tensile strength of the material is tested according to ASTM D638-82a, the bending property of the material is tested according to ASTM D790M-92 standard, the impact strength of the material is tested according to ASTM D256-81 standard, the fracture toughness of the material is tested according to ASTM D5045-91a standard, the thermal property (glass transition temperature) of the material is tested by DSC according to ASTM 3418-82, and the temperature rise rate of the test is 10 ℃/min. The flame retardant property (oxygen index) of the material is determined according to the national standard GB/T2406-1993. The cure cycle was measured by DSC, with a temperature rise rate of 10 deg.C/min.
TABLE 1 Properties of hyperbranched epoxy resin products obtained in examples 1 to 4
Claims (7)
1. A preparation method of flame-retardant hyperbranched epoxy resin is disclosed, wherein the structural formula of the flame-retardant hyperbranched epoxy resin is as follows:
in the formula R2Has the structural formula
Wherein m and n are independently selected from any integer of 0-8;
R1＝-CH2CH2SCH2CH2CH2OCH2CH(OH)CH2-，
R3＝-CH2(CH2)j-or-CH2CH2(OCH2CH2)j-, wherein j is 1, 2, 3, 4 or 5;
the preparation method comprises the following steps: uniformly mixing a trifunctional sulfur-nitrogen heterocyclic epoxy resin monomer, dihydric alcohol and an organic solvent, adding a catalyst, stirring and reacting for 8-20 hours at the temperature of 100 ℃ and 140 ℃, and evaporating the organic solvent to obtain the flame-retardant hyperbranched epoxy resin;
the molecular weight of the flame-retardant hyperbranched epoxy resin is 3000-35000 g/mol;
the structural formula of the trifunctional sulfur-containing nitrogen heterocyclic epoxy resin monomer is as follows:
2. the method of claim 1, wherein: and m is 0, and n is 2.
3. The method of claim 1, wherein: the R is2Has the structural formula
Wherein n is 2.
4. The method of claim 1, wherein: the molar ratio of the trifunctional sulfur-nitrogen heterocyclic epoxy resin monomer to the diol to the organic solvent is (1.0-1.5): 1.0: (1.0-5.0).
5. The method of claim 4, wherein: the catalyst is one or more than two of tetrabutylammonium bromide, tetrabutylammonium chloride, hexadecyltrimethylammonium bromide and hexadecyltrimethylammonium chloride, and the dosage of the catalyst is 0.5-5% of the mass of the trifunctional sulfur-containing nitrogen heterocyclic epoxy resin monomer.
6. The method of claim 5, wherein: the organic solvent is one or more than two of benzene, toluene, xylene and tetrahydrofuran.
7. The method of claim 6, wherein: the tri-functionality sulfur-containing nitrogen heterocyclic epoxy resin monomer is melamine-tri (mercaptopropionamide) triglycidyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811082956.5A CN109232862B (en) | 2018-09-17 | 2018-09-17 | Flame-retardant hyperbranched epoxy resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811082956.5A CN109232862B (en) | 2018-09-17 | 2018-09-17 | Flame-retardant hyperbranched epoxy resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109232862A CN109232862A (en) | 2019-01-18 |
| CN109232862B true CN109232862B (en) | 2021-05-25 |
Family
ID=65059009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811082956.5A Active CN109232862B (en) | 2018-09-17 | 2018-09-17 | Flame-retardant hyperbranched epoxy resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109232862B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836588A (en) * | 2019-02-27 | 2019-06-04 | 济南大学 | A kind of synthesis of hyperbranched epoxy resin and its application in waterproof roll |
| CN111961075B (en) * | 2020-08-24 | 2022-09-16 | 万华化学集团股份有限公司 | Silicon-nitrogen flame-retardant precursor and preparation method thereof, silicon-nitrogen hybridized flame-retardant sol and preparation method thereof |
| CN114196291A (en) * | 2021-12-31 | 2022-03-18 | 株洲飞鹿高新材料技术股份有限公司 | Low-surface-treatment fireproof coating and preparation method thereof |
| CN115011294B (en) * | 2022-06-07 | 2023-02-10 | 道尔化成电子材料(上海)有限公司 | Sintered nano silver conductive adhesive for chip packaging and preparation method thereof |
| CN116113179B (en) * | 2023-02-01 | 2023-09-05 | 江苏贺鸿电子有限公司 | Multilayer printed circuit board and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105925130B (en) * | 2016-05-23 | 2018-05-25 | 北京化工大学 | A kind of hyperbranched polyether type epoxy resin/epoxy resin composite anticorrosion coating and preparation method thereof |
| CN106832219B (en) * | 2017-01-22 | 2019-01-29 | 中南民族大学 | A kind of containing phosphorus-nitrogen halogen-free flame-retardant hyperbranched epoxy resin and preparation method thereof |
-
2018
- 2018-09-17 CN CN201811082956.5A patent/CN109232862B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109232862A (en) | 2019-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109232862B (en) | Flame-retardant hyperbranched epoxy resin and preparation method thereof | |
| CA1141769A (en) | Diglycidyl ethers of di-secondary alcohols, their preparation, and curable compositions containing them | |
| US5494977A (en) | Compositions, epoxized compositions, a heat curable resin composition, an epoxy resin composition, radically polymerized compositions, a curable resin composition and a polymer having epoxy groups | |
| KR101668301B1 (en) | Long chain alkylene group-containing epoxy compound | |
| CN105440261B (en) | A kind of degradable self-crosslinking hyperbranched epoxy resin and preparation method thereof | |
| Zhang et al. | Highly efficient preparation of hyperbranched epoxy resins by UV-initiated thiol-ene click reaction | |
| WO2019206200A1 (en) | Sulphur-containing degradable hyperbranched epoxy resin and preparation method therefor | |
| CN111825829A (en) | Triazine ring structure-containing bio-based epoxy resin and preparation method thereof | |
| JP6769540B2 (en) | Epoxy resin composition, curable resin composition and fiber reinforced composite material | |
| US3676397A (en) | Oxazolidinone-containing epoxy resins and process for their preparation | |
| CN109320688B (en) | High-temperature-resistant hyperbranched epoxy resin and preparation method thereof | |
| EP0458296B1 (en) | Modified epoxy resins having acetylenically unsaturated functions | |
| US4296231A (en) | Curable epoxide resin mixtures | |
| CA1262992A (en) | Branched polyesters | |
| CA1290483C (en) | Thermoplastic polymer composition having thermosetting processing characteristics | |
| WO2015044757A9 (en) | A self-healing epoxy resin composition | |
| Zhang et al. | A novel method for preparation of epoxy resins using thiol–ene click reaction | |
| TW202100602A (en) | Curable composition and cured product of same | |
| US4879414A (en) | Polythiols and use as epoxy resin curing agents | |
| WO2009143038A1 (en) | Adducts of epoxy resins derived from alkanolamides and a process for preparing the same | |
| US3714198A (en) | Polyglycidyl esters | |
| EP2283059A1 (en) | Epoxy resins derived from non-seed oil based alkanolamides and a process for preparing the same | |
| US4927902A (en) | Polythiols and use as epoxy resin curing agents | |
| JPH04128279A (en) | Glycidyl ether compound containing triple bond | |
| JPS5910737B2 (en) | Compositions containing half-esters of organic polyols, unsaturated monomers, epoxides and reinforcing fibers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |