CN109666118B - Preparation method of flame-retardant multi-arm epoxy resin - Google Patents
Preparation method of flame-retardant multi-arm epoxy resin Download PDFInfo
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- CN109666118B CN109666118B CN201811531734.7A CN201811531734A CN109666118B CN 109666118 B CN109666118 B CN 109666118B CN 201811531734 A CN201811531734 A CN 201811531734A CN 109666118 B CN109666118 B CN 109666118B
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
- C08G18/584—Epoxy resins having nitrogen
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3246—Polyamines heterocyclic, the heteroatom being oxygen or nitrogen in the form of an amino group
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
A preparation method of flame-retardant multi-arm epoxy resin belongs to the technical field of material chemistry. The preparation method specifically comprises the steps of preparing a flame-retardant multi-arm monomer and preparing the flame-retardant multi-arm epoxy resin, wherein amino in melamine reacts with NCO in HDT (trimer of HDI) to generate a rigid monomer with six amino groups, and then the rigid monomer and bisphenol A diglycidyl ether undergo a ring-opening reaction to generate the flame-retardant multi-arm epoxy resin. The flame-retardant epoxy resin is halogen-free, low-toxicity, smokeless, low-pollution and low-corrosion flame-retardant epoxy resin and efficient multifunctional composite flame-retardant epoxy resin.
Description
Technical Field
The invention relates to a preparation method of flame-retardant multi-arm type epoxy resin, particularly relates to preparation of a flame-retardant multi-arm monomer and preparation of flame-retardant multi-arm type epoxy resin, and belongs to the technical field of material chemistry.
Background
With the widespread use of resins, the flame retardancy of resins is receiving more and more attention worldwide. The traditional halogen-containing flame retardant has excellent flame retardant effect, but releases toxic and corrosive gases during combustion to generate larger smoke, and can cause 'secondary disaster' while inhibiting combustion, thereby being gradually eliminated. In recent years, researchers in various countries strive for the development of flame retardants with halogen free, low toxicity, smoke free, low pollution, low corrosion, and efficient multifunctional composite flame retardants.
Disclosure of Invention
The invention aims to provide a preparation method of flame-retardant multi-arm epoxy resin. In the method, amino in melamine reacts with NCO in HDT to generate rigid monomer with six amino, and then the rigid monomer reacts with bisphenol A diglycidyl ether to generate multi-arm flame-retardant epoxy resin.
The technical scheme of the invention is as follows: a preparation method of flame-retardant multi-arm epoxy resin comprises the following steps:
(1) preparation of flame-retardant six-arm monomer: weighing a proper amount of melamine in a four-neck flask, adding a certain amount of dimethyl sulfoxide, dissolving in an oil bath kettle at 80 ℃, adding a certain amount of HDT (HDI trimer) after complete dissolution, adding a small amount of DBTDL, raising the temperature to 100 ℃, introducing nitrogen, and reacting for 12 hours; after the reaction is finished, performing suction filtration on the product, then washing the solid for three times respectively by using ethanol and deionized water, centrifuging, performing suction filtration, and finally drying in a vacuum oven at the temperature of 80 ℃ for 48 hours to obtain yellow powder;
(2) preparation of flame-retardant multi-arm epoxy resin: adding a proper amount of bisphenol A diglycidyl ether into a four-neck flask provided with a stirring rod, adding a small amount of triethanolamine as a catalyst, heating an oil bath kettle to 165 ℃, stirring at a low speed, finally dissolving the flame-retardant six-arm monomer self-prepared in the step (1) by using dimethyl sulfoxide, dropwise adding the dissolved flame-retardant six-arm monomer into the four-neck flask, and reacting for a certain time to obtain the flame-retardant multi-arm epoxy resin.
The invention has the beneficial effects that: in the method, rigid monomers with six amino groups are generated by the reaction of amino groups in melamine and NCO in HDT (trimer of HDI), and then the rigid monomers and bisphenol A diglycidyl ether are subjected to ring-opening reaction to generate the multi-arm flame-retardant epoxy resin. The flame-retardant epoxy resin is halogen-free, low-toxicity, smokeless, low-pollution and low-corrosion flame-retardant epoxy resin and efficient multifunctional composite flame-retardant epoxy resin.
Detailed Description
Example 1 preparation of flame-retardant Multi-arm epoxy resin
(1) Preparation of flame-retardant six-arm monomer: weighing 11.34 g of melamine into a four-neck flask, adding 20mL of dimethyl sulfoxide, dissolving in an oil bath kettle at 80 ℃, adding 15.12g of HDT (trimer of HDI) after complete dissolution, adding 7-9 drops of DBTDL, raising the temperature to 100 ℃, introducing nitrogen, and reacting for 12 hours. And after the reaction is finished, performing suction filtration on the product, washing the solid for three times respectively by using ethanol and deionized water, centrifuging, performing suction filtration, and finally placing in a vacuum oven at 80 ℃ for 48 hours to obtain yellow powder.
(2) Preparation of flame-retardant multi-arm epoxy resin: adding 16.24g of bisphenol A diglycidyl ether into a four-necked flask provided with a stirring rod, adding 2mL of triethanolamine serving as a catalyst, heating an oil bath to 165 ℃, stirring at a low speed, dissolving 9.86g of self-made flame-retardant six-arm monomer with 20mL of dimethyl sulfoxide, dropwise adding the dissolved monomer into the four-necked flask, and reacting for 4 hours to obtain the flame-retardant multi-arm epoxy resin.
Claims (1)
1. A preparation method of flame-retardant multi-arm epoxy resin is characterized by comprising the following steps:
(1) preparation of flame-retardant six-arm monomer: weighing 11.34 g of melamine in a four-neck flask, adding 20mL of dimethyl sulfoxide, dissolving in an oil bath kettle at 80 ℃, adding 15.12g of HDI trimer after complete dissolution, adding 7-9 drops of DBTDL, raising the temperature to 100 ℃, introducing nitrogen, and reacting for 12 hours; after the reaction is finished, performing suction filtration on the product, then washing the solid for three times respectively by using ethanol and deionized water, centrifuging, performing suction filtration, and finally placing in a vacuum oven at 80 ℃ for 48 hours to obtain yellow powder, namely the flame-retardant six-arm monomer;
(2) preparation of flame-retardant multi-arm epoxy resin: adding 16.24g of bisphenol A diglycidyl ether into a four-necked flask provided with a stirring rod, adding 2mL of triethanolamine serving as a catalyst, heating an oil bath to 165 ℃, stirring at a low speed, dissolving 9.86g of the flame-retardant six-arm monomer prepared in the step (1) by using 20mL of dimethyl sulfoxide, dropwise adding the dissolved monomer into the four-necked flask, and reacting for 4 hours to obtain the flame-retardant multi-arm epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811531734.7A CN109666118B (en) | 2018-12-14 | 2018-12-14 | Preparation method of flame-retardant multi-arm epoxy resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811531734.7A CN109666118B (en) | 2018-12-14 | 2018-12-14 | Preparation method of flame-retardant multi-arm epoxy resin |
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| Publication Number | Publication Date |
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| CN109666118A CN109666118A (en) | 2019-04-23 |
| CN109666118B true CN109666118B (en) | 2021-02-09 |
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| CN201811531734.7A Active CN109666118B (en) | 2018-12-14 | 2018-12-14 | Preparation method of flame-retardant multi-arm epoxy resin |
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Citations (7)
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| CN101423602A (en) * | 2008-12-18 | 2009-05-06 | 江南大学 | Method for preparing ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer |
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| WO2018075656A1 (en) * | 2016-10-21 | 2018-04-26 | Basf Se | Methods for preparation of functional waterborne dispersions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160166480A1 (en) * | 2009-09-18 | 2016-06-16 | International Flavors & Fragrances Inc. | Microcapsule compositions |
| US9175117B2 (en) * | 2013-03-15 | 2015-11-03 | Covestro Llc | Dual cure composite resins containing uretdione and unsaturated sites |
-
2018
- 2018-12-14 CN CN201811531734.7A patent/CN109666118B/en active Active
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| CN101423602A (en) * | 2008-12-18 | 2009-05-06 | 江南大学 | Method for preparing ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer |
| CN102585148A (en) * | 2011-12-28 | 2012-07-18 | 烟台万华聚氨酯股份有限公司 | Composition for preparing highly fire-resistant polyisocyanurate foam |
| CN104829809A (en) * | 2014-02-11 | 2015-08-12 | 王祖文 | High-molecular foam material |
| CN104650136A (en) * | 2015-03-06 | 2015-05-27 | 苏州阳桥化工科技有限公司 | Preparation method of flame retardant, namely tris (dimethylchloropropoxy silicon acyloxy ethyl) triazine compound |
| CN104766932A (en) * | 2015-04-22 | 2015-07-08 | 电子科技大学 | Biodegradable substrate for flexible optoelectronic device and method for manufacturing same |
| WO2018075656A1 (en) * | 2016-10-21 | 2018-04-26 | Basf Se | Methods for preparation of functional waterborne dispersions |
| CN106519643A (en) * | 2016-12-29 | 2017-03-22 | 安徽浩丰特种电子材料有限公司 | High-strength heat-resistant corrosion-resistant polyurethane board and preparation method thereof |
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| CN109666118A (en) | 2019-04-23 |
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