CN105542126A - Bisphenol-A glycidyl-ester type epoxy resin and preparing method thereof - Google Patents
Bisphenol-A glycidyl-ester type epoxy resin and preparing method thereof Download PDFInfo
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- CN105542126A CN105542126A CN201511033257.8A CN201511033257A CN105542126A CN 105542126 A CN105542126 A CN 105542126A CN 201511033257 A CN201511033257 A CN 201511033257A CN 105542126 A CN105542126 A CN 105542126A
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- China
- Prior art keywords
- epoxy resin
- type epoxy
- ester type
- bisphenol
- dihydroxyphenyl propane
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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
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a bisphenol-A glycidyl-ester type epoxy resin. The structural formula is shown in the specification. The invention further provides a preparing method of the bisphenol-A glycidyl-ester type epoxy resin. The preparing method includes the steps that bisphenol A and sodium hydroxide solid are added into a reaction kettle, fatty alcohol serves as a solvent, stirring and temperature rising are carried out, then haloacetic acid is added, the mixture is reacted, acidized, washed and layered in a standing mode, and an organic phase is taken in a liquid-separating mode; bisphenol monobasic acid is obtained in a vacuumizing mode; the bisphenol monobasic acid and epoxy chloropropane are stirred and mixed, a sodium hydroxide aqueous solution is added to be reacted, and washing, extracting and vacuumizing are carried out, and the bisphenol glycidyl-ester type epoxy resin is obtained. By means of the bisphenol-A glycidyl-ester type epoxy resin and the preparing method, toughness is improved, adhesive force is increased, and meanwhile quite good heat resistance is achieved.
Description
Technical field
The invention belongs to chemical field, relate to a kind of epoxy resin, specifically a kind of dihydroxyphenyl propane glycidyl ester type epoxy resin and preparation method thereof.
Background technology
Glycidyl ester type epoxy resin of the prior art is synthesized by acid anhydrides and epoxy chloropropane or is synthesized under sodium hydroxide effect by phthalic anhydride, water, epoxy chloropropane.Glycidyl ester type epoxy resin and solidifying agent (MD650 Shanghai Mei Dong biomaterial limited-liability company produces) making sheet in prior art, thick 50 microns of mould, toughness 4mm, sticking power 3 grades, hardness HB, thermotolerance 80 DEG C.
Summary of the invention
The object of the present invention is to provide a kind of bis-phenol glycidyl ester type epoxy resin and preparation method thereof, described this bis-phenol glycidyl ester type epoxy resin and preparation method thereof will solve glycidyl ester type epoxy resin toughness of the prior art and the not good technical problem of resistance toheat.
The invention provides a kind of dihydroxyphenyl propane glycidyl ester type epoxy resin, its structural formula is as follows,
Present invention also offers its preparation method of above-mentioned a kind of dihydroxyphenyl propane glycidyl ester type epoxy resin, add dihydroxyphenyl propane and strong basic solid in a kettle., and add alcohol as solvent, described dihydroxyphenyl propane and the mol ratio of highly basic are 1:2 ~ 10, stirring is warming up to 50 ~ 70 DEG C, then in 20 ~ 50 minutes, halogen acetic acid is added, described dihydroxyphenyl propane and the mol ratio of halogen acetic acid are 1:2 ~ 10, after adding, 60 DEG C ~ 80 DEG C reactions 2 ~ 6 hours, then add water and ethylene dichloride, and add hydrochloric acid adjustment pH=7, washing, stratification, separatory gets organic phase; Then organic phase is vacuumized to obtain bis-phenol base monoprotic acid at 80 DEG C ~ 100 DEG C; Again this bis-phenol monoprotic acid and epoxy chloropropane are uniformly mixed, described bis-phenol monoprotic acid and the mol ratio of epoxy chloropropane are 1:2 ~ 100, be cooled to 40 ~ 65 DEG C, add the strong alkali aqueous solution that mass percent concentration is 30 ~ 65%, described bis-phenol monoprotic acid and the mol ratio of aqueous sodium hydroxide solution are 1:1 ~ 10,85 ~ 105 DEG C are reacted 1 ~ 5 hour, remove moisture and excess reagent, obtain bis-phenol glycidyl ester type epoxy resin after washing extraction.
Further, the mass percent concentration of described aqueous sodium hydroxide solution is 50%;
Further, described halogen acetic acid is Mono Chloro Acetic Acid, bromoacetic acid or iodoacetic acid;
Further, that described highly basic can be NaOH or KOH;
Further, described alcohol is ethanol, n-propyl alcohol or propyl carbinol.
The reaction process of its preparation method of a kind of bis-phenol glycidyl ester type epoxy resin of the present invention describes as follows:
By bis-phenol glycidyl ester type epoxy resin of the present invention and MD650 making sheet, thick 50 microns of mould, toughness 1mm, adhesion 1 grade, hardness HB, thermotolerance 100 DEG C, is ensureing under the condition that hardness does not decline, improve sticking power, toughness is obviously improved, and thermotolerance improves 20 DEG C.
The invention belongs to a kind of esterification and epoxidation reaction of bis-phenol.Utilize the constitutional features of bis-phenol to synthesize a kind of epoxy resin with ether, ester group and epoxy group(ing), make this epoxy resin have the denominator of ester class, ethers and epoxy group(ing) simultaneously.In bis-phenol ethylene oxidic ester epoxy resin of the present invention, except the phenyl ring in conventional epoxy and epoxy group(ing), also containing Racemic glycidol ester group, and ether, toughness and the sticking power of epoxy resin can be improved, there is good thermotolerance simultaneously.
The present invention compares with prior art, and its technique effect is actively with obvious.The present invention improves the thermotolerance after epoxy resin cure after being added by benzene ring structure, there is the toughening effect of ester class and ethers simultaneously, improve the toughness after epoxy resin cure and sticking power, there is small-molecular-weight, high epoxy value, low viscous feature simultaneously, easy to use.
Embodiment
Embodiment 1
228 grams of dihydroxyphenyl propanes and 120 grams of sodium hydrate solids are added in autoclave, 2000mL propyl carbinol is solvent, stirring is warming up to 60 DEG C, then in 30 minutes, is slowly added dropwise to Mono Chloro Acetic Acid 95 grams, dropwises 60 DEG C of reactions 4 hours, add hcl acidifying to pH=7,1000 grams of water again, 5000mL ethylene dichloride, washing, stratification, organic phase is got in shunting.At 80 DEG C, vacuumize 4 hours obtain bis-phenol base monoprotic acid, again this cardanol monoprotic acid and epoxy chloropropane 500 grams are uniformly mixed and are cooled to 60 DEG C, drip 50% aqueous sodium hydroxide solution 160 grams slowly, 100 DEG C are reacted 3 hours, washing extraction, remove moisture and excess reagent, obtain bis-phenol glycidyl ester type epoxy resin.Oxirane value 0.37, viscosity 20000CPS and MD650 making sheet, thick 50 microns of mould, toughness 1mm, adhesion 1 grade, hardness HB, thermotolerance 100 DEG C.
Embodiment 2
228 grams of dihydroxyphenyl propanes and 120 grams of sodium hydrate solids are added in autoclave, 2000mL ethanol is solvent, stirring is warming up to 60 DEG C, then in 30 minutes, be slowly added dropwise to Mono Chloro Acetic Acid 114 grams, dropwise 80 DEG C of reactions 4 hours, add hcl acidifying to pH=7, add 1000 grams of water again, 5000mL ethylene dichloride washs, stratification, and organic phase is got in shunting.At 80 DEG C, vacuumize 4 hours obtain bis-phenol base monoprotic acid, again this bis-phenol monoprotic acid and epoxy chloropropane 600 grams are uniformly mixed and are cooled to 60 DEG C, drip 50% aqueous sodium hydroxide solution 180 grams slowly, 100 DEG C are reacted 3 hours, washing extraction, remove moisture and excess reagent, obtain bis-phenol glycidyl ester type epoxy resin.Oxirane value 0.35 viscosity: 26000CPS, with MD650 making sheet, thick 50 microns of mould, toughness 1mm, adhesion 1 grade, hardness HB, thermotolerance 100 DEG C.
Embodiment 3
228 grams of dihydroxyphenyl propanes and 80 grams of sodium hydrate solids are added in autoclave, 2000mL propyl alcohol is solvent, stirring is warming up to 60 DEG C, then in 30 minutes, be slowly added dropwise to Mono Chloro Acetic Acid 95 grams, dropwise 60 DEG C of reactions 4 hours, add hcl acidifying to pH=7, add 1000 grams of water again, 5000mL ethylene dichloride washs, stratification, and organic phase is got in shunting.At 100 DEG C, vacuumize 4 hours obtain bis-phenol base monoprotic acid, again this bis-phenol monoprotic acid and epoxy chloropropane 1000 grams are uniformly mixed and are cooled to 60 DEG C, drip 50% aqueous sodium hydroxide solution 250 grams slowly, 100 DEG C are reacted 3 hours, washing extraction, remove moisture and excess reagent, obtain bis-phenol glycidyl ester type epoxy resin.Oxirane value 0.40, viscosity: 15500CPS and MD650 making sheet, thick 50 microns of mould, toughness 1mm, adhesion 1 grade, hardness HB, thermotolerance 100 DEG C.
Claims (6)
1. a dihydroxyphenyl propane glycidyl ester type epoxy resin, is characterized in that, its structural formula is as follows,
2. the preparation method of a kind of dihydroxyphenyl propane glycidyl ester type epoxy resin according to claim 1, it is characterized in that: add dihydroxyphenyl propane and strong basic solid in a kettle., and add fatty alcohol as solvent, described dihydroxyphenyl propane and the mol ratio of highly basic are 1:2 ~ 10, stirring is warming up to 50 ~ 70 DEG C, then in 20 ~ 50 minutes, halogen acetic acid is added, described dihydroxyphenyl propane and the mol ratio of halogen acetic acid are 1:2 ~ 10, after adding, 60 DEG C ~ 80 DEG C reactions 2 ~ 6 hours, add hydrochloric acid and regulate pH=7, add water and ethylene dichloride washing again, stratification, separatory gets organic phase, then organic phase is vacuumized to obtain bis-phenol base monoprotic acid at 80 DEG C ~ 100 DEG C, again this bis-phenol monoprotic acid and epoxy chloropropane are uniformly mixed, described bis-phenol monoprotic acid and the mol ratio of epoxy chloropropane are 1:2 ~ 100, be cooled to 40 ~ 65 DEG C, add the strong alkali aqueous solution that mass percent concentration is 30 ~ 65%, described bis-phenol monoprotic acid and the mol ratio of aqueous sodium hydroxide solution are 1:1 ~ 10,85 ~ 105 DEG C are reacted 1 ~ 5 hour, remove moisture and excess reagent, obtain bis-phenol glycidyl ester type epoxy resin after washing extraction.
3. the preparation method of a kind of dihydroxyphenyl propane glycidyl ester type epoxy resin according to claim 2, is characterized in that: the mass percent concentration of described strong alkali aqueous solution is 50%.
4. according to the preparation method of a kind of dihydroxyphenyl propane glycidyl ester type epoxy resin described in claim 2, it is characterized in that: described halogen acetic acid is Mono Chloro Acetic Acid, bromoacetic acid or iodoacetic acid.
5. according to the preparation method of a kind of dihydroxyphenyl propane glycidyl ester type epoxy resin described in claim 2, it is characterized in that: described highly basic can be NaOH or KOH.
6. according to the preparation method of a kind of dihydroxyphenyl propane glycidyl ester type epoxy resin described in claim 2, it is characterized in that: described aliphatic alcohol solvent is ethanol, n-propyl alcohol or propyl carbinol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511033257.8A CN105542126A (en) | 2015-12-31 | 2015-12-31 | Bisphenol-A glycidyl-ester type epoxy resin and preparing method thereof |
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| CN201511033257.8A CN105542126A (en) | 2015-12-31 | 2015-12-31 | Bisphenol-A glycidyl-ester type epoxy resin and preparing method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679703A (en) * | 2020-12-24 | 2021-04-20 | 温州大学 | Epoxy resin curing agent and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2839494A (en) * | 1954-03-24 | 1958-06-17 | Albert Ag Chem Werke | Resinous condensation products and their production |
| JP2011046623A (en) * | 2009-08-25 | 2011-03-10 | Honshu Chem Ind Co Ltd | New epoxy compound |
| CN104364289A (en) * | 2012-06-15 | 2015-02-18 | 陶氏环球技术有限责任公司 | Transmission for a motor vehicle |
| CN104803867A (en) * | 2014-11-28 | 2015-07-29 | 上海美东生物材料股份有限公司 | Preparation method of cardanol modified epoxy resin curing agent |
-
2015
- 2015-12-31 CN CN201511033257.8A patent/CN105542126A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2839494A (en) * | 1954-03-24 | 1958-06-17 | Albert Ag Chem Werke | Resinous condensation products and their production |
| JP2011046623A (en) * | 2009-08-25 | 2011-03-10 | Honshu Chem Ind Co Ltd | New epoxy compound |
| CN104364289A (en) * | 2012-06-15 | 2015-02-18 | 陶氏环球技术有限责任公司 | Transmission for a motor vehicle |
| CN104803867A (en) * | 2014-11-28 | 2015-07-29 | 上海美东生物材料股份有限公司 | Preparation method of cardanol modified epoxy resin curing agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112679703A (en) * | 2020-12-24 | 2021-04-20 | 温州大学 | Epoxy resin curing agent and preparation method and application thereof |
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Application publication date: 20160504 |