CN109232862A - A kind of flame-retardant hyperbranched epoxy resin and preparation method thereof - Google Patents
A kind of flame-retardant hyperbranched epoxy resin and preparation method thereof Download PDFInfo
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- CN109232862A CN109232862A CN201811082956.5A CN201811082956A CN109232862A CN 109232862 A CN109232862 A CN 109232862A CN 201811082956 A CN201811082956 A CN 201811082956A CN 109232862 A CN109232862 A CN 109232862A
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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
- C08G59/3263—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing sulfur
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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
- C08G59/40—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
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- 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
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
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Abstract
The invention belongs to Epoxy Resin Technology fields, it specifically discloses a kind of flame-retardant hyperbranched epoxy resin and preparation method thereof: three-functionality-degree epoxy resin containing sulfur nitrogen heterocycle, dihydric alcohol being carried out to atom transfer polymerization reaction under the action of catalyst and prepare heat-resisting flame-retardant hyperbranched epoxy resin, molecular weight 3000-35000g/mol.Nitrogen-containing heterocycle is introduced into the structure of hyperbranched epoxy resin by the present invention, and heat resistance can be improved, and the introducing with flame retarding function nitrogen improves the anti-flammability of epoxy resin, realizes the function of halogen-free flameproof；Sulphur atom is introduced into the structure of hyperbranched epoxy resin, can promote the solidification of epoxy resin, improve the efficiency of epoxy resin cure and reduces solidification temperature, plays energy-saving function.The features such as present invention process is simple, reaction condition is mild, yield is high, product has the function of fire-retardant and activeness and quietness, it is expected to for the halogen-free flameproof activeness and quietness of epoxy resin, the fields such as solventless coatings.
Description
Technical field
The present invention relates to hyperbranched epoxy resin and preparation method thereof technical fields, and in particular to a kind of flame-retardant hyperbranched
Epoxy resin and preparation method thereof.
Background technique
The study on the synthesis of hyperbranched epoxy resin originate from 1993, PCT International Application WO9317060 disclose with
Dihydromethyl propionic acid, trimethylolpropane are that raw material and epichlorohydrin reaction can synthesize the higher aliphatic sulfur-bearing of viscosity and overspend
Change epoxy resin.Present inventor (Zhang Daohong) prepares super using trimellitic anhydride, diglycol as primary raw material
The viscosity of branch epoxy resins is low, but heat resistance not high (European Polymer Journal, 2006,42 (3): 711-
714).Present inventor also studied the high azacyclo- hyperbranched epoxy resin and silicon framework hyperbranched epoxy of heat resisting temperature
Resin (ZL200910029024.9, ZL200910029026.8, ZL200910062871.5, ZL201010224451.5).This
The preparation process for the hyperbranched epoxy resin reported a bit usually requires that a large amount of organic solvent is added, and big Alternative is completed in reaction
After require water-washing step, have certain pollution to environment, the sulfur-bearing hyperbranched epoxy resin furthermore reported in the prior art
The efficiency of technology of preparing (esterification, hydrosilylation, graft reaction) is relatively low, yield is not high, energy consumption is high for reaction time length,
Temperature height, time are long when solidification.Present inventor, which has invented, thus prepares sulfur-bearing epoxy using mercaptan-alkene hydrocarbon click-reaction
The technology of resin (ZL201310091452.0) and sulfur-bearing hyperbranched epoxy resin (ZL201210566173.0), improves
Preparation efficiency, but the epoxy resin of its preparation does not have flame retarding function.The epoxy resin technology of all technology preparations at present
Process is partially complicated, and the epoxy resin heat resistance of preparation is low, curing rate is slow, does not have flame retarding function.Therefore development technology it is simple,
High yield, the technology of preparing of flame-retardant hyperbranched epoxy resin are the fundamental ways for solving the problems, such as the current field and existing.
Summary of the invention
It is an object of the invention to be directed to the deficiencies in the prior art, a kind of new flame-retardant hyperbranched ring is provided
Oxygen resin, structural formula are as follows:
R in formula2Structure be Wherein m, n are each independently selected from any integer in 0~8；Preferably, n=2, m=0.
R1=-CH2CH2SCH2CH2CH2OCH2CH(OH)CH2-；
R3=-CH2(CH2)jOr-CH2CH2(OCH2CH2)j, wherein j=1,2,3,4 or 5.
A kind of synthetic method of above-mentioned flame-retardant hyperbranched epoxy resin, steps are as follows:
Three-functionality-degree epoxy monomer containing sulfur nitrogen heterocycle, dihydric alcohol and organic solvent are added to according to a certain percentage
It is uniformly mixed in reaction vessel equipped with mechanical stirring, condenser pipe and thermometer, then catalyst is added thereto, in 100-140
It is stirred to react under the conditions of DEG C 8-20 hours, steams organic solvent to get to hyperbranched epoxy resin, molecular weight is in 3000-
35000g/mol, preferably 3500-25000g/mol.
The molar ratio of the three-functionality-degree epoxy monomer containing sulfur nitrogen heterocycle, dihydric alcohol and organic solvent be (1.0~
1.5): 1:(1.0~5.0).
Further, the catalyst be tetrabutylammonium bromide, tetrabutylammonium chloride, cetyl trimethylammonium bromide and
The one or more of hexadecyltrimethylammonium chloride, dosage are three-functionality-degree epoxy monomer containing sulfur nitrogen heterocycle matter
The 0.5-5% of amount, preferably 2-5%.
Further, the organic solvent are as follows: one or more of benzene,toluene,xylene and tetrahydrofuran.
The dihydric alcohol is HO-R3- OH, R3=-CH2(CH2)jOr-CH2CH2(OCH2CH2)j, wherein j=1,2,
3,4 or 5.
Further, the dihydric alcohol is ethylene glycol, diglycol, butanediol or triethylene-glycol.
The structural formula of three-functionality-degree epoxy monomer containing sulfur nitrogen heterocycle are as follows:
Wherein R2For the R in flame-retardant hyperbranched epoxy resin structural formula2。
Further, the three-functionality-degree epoxy monomer containing sulfur nitrogen heterocycle is three (2- ethoxy) chlorinated isocyanurates-
Three (mercaptopropionic acid ester) triglycidyl ethers
Or melamine-three (mercaptopropionyl amine) triglycidyl ether
The synthesis step of three-functionality-degree epoxy monomer containing sulfur nitrogen heterocycle in the present invention can refer to inventor and disclose hair
The paper (Progress in Organic Coatings, 2016,101:178-185) of table.
Flame-retardant hyperbranched epoxy resin prepared by the present invention has lower viscosity, high temperature resistant and rapid curing etc. excellent
Point, it is expected to the fields such as activeness and quietness applied to the low volatilization coating of environmental protection, low volatilization resin, epoxy resin.
Technical solution of the present invention is had the following advantages and beneficial effects: compared with prior art
1, nitrogen-containing heterocycle is introduced into the structure of hyperbranched epoxy resin by the present invention, and the heat-resisting of epoxy resin can be improved
Property, the introducing with flame retarding function nitrogen improves the anti-flammability of epoxy resin, realizes the function of halogen-free flameproof；
2, sulphur atom is introduced into the structure of hyperbranched epoxy resin by the present invention, be can promote the solidification of epoxy resin, is mentioned
The cured efficiency of high epoxy resin and reduction solidification temperature, play energy-saving function；
3, the preparation process of hyperbranched epoxy resin of the invention is simple, and cost of material is low, is suitable for industrialized production；
4, hyperbranched epoxy resin of the invention has the function of activeness and quietness to ordinary epoxy resin, it is expected to be widely used in
The activeness and quietness field of epoxy resin；
5, hyperbranched epoxy resin viscosity of the invention is low, it can significantly be lowered by being added in bisphenol A type epoxy resin glues
Degree, plays the role of reactive diluent, it is expected to be applied to solvent-free, low volatilization epoxy coating field.
Specific embodiment
Below with reference to specific embodiment, the present invention is described in detail, but these embodiments should not limit in any way
Protection scope of the present invention processed.
The molecular weight determination of product using PL company of Britain GPC, epoxide number use national standard hydrochloric acid acetone
Method measurement, viscosity are measured under the conditions of 25 DEG C using Brookfield viscosimeter.
The three-functionality-degree epoxy monomer containing sulfur nitrogen heterocycle in all embodiments is present inventor's self-control below
(Progress in Organic Coatings, 2016,101:178-185), to prepare three (2- ethoxy) chlorinated isocyanurates-
Three (mercaptopropionic acid ester) triglycidyl ethers (THGEP) and melamine-three (mercaptopropionyl amine) triglycidyl ether (MGEP)
For introduce its process.
(1) synthesis of THGEP
0.2mol tri- (2- ethoxy) isocyanide is sequentially added in the 250mL four-hole boiling flask equipped with magnetic agitation and water segregator
Urate, 0.7mol3- mercaptopropionic acid, 0.3g p-methyl benzenesulfonic acid and solvent toluene be heated to reflux anti-under nitrogen protection
It answers, when the acid value in reaction system no longer reduces, when remaining unchanged, stops reaction.It is washed instead with sodium hydroxide solution (5wt%)
It answers liquid to neutrality, organic layer is evaporated off after toluene, product three (2- ethoxy) (mercaptopropionic acid of chlorinated isocyanurates-three can be obtained
Ester) (THMP), it is colorless and transparent liquid, yield is about 98.0%.
0.1molTHMP and 0.3mol allyl glycidyl ether (AGE) are added in the single port bottle equipped with magnetic agitation,
Organic solvents, chloroform is added and accounts for 2% photoinitiator benzophenone of THMP mass, stirs lower ultraviolet lighting 5min, revolving
Organic solvent is removed, colorless and transparent, low viscosity three (2- ethoxy) chlorinated isocyanurates-three-glycidyl thioethers can be obtained
(THGEP), yield about 98%.
(2) synthesis of MGEP
0.2mol melamine, 0.75mol3- mercapto are sequentially added in the four-hole boiling flask equipped with magnetic agitation and water segregator
Base propionic acid, 0.25g p-methyl benzenesulfonic acid and solvent toluene carry out heating reflux reaction, when in reaction system under nitrogen protection
Acid value no longer reduces, and when remaining unchanged, stops reaction.It, will be organic with sodium hydroxide solution (5wt%) washing reaction liquid to neutrality
Product melamine-three (mercaptopropionic acid ester) (MMP) can be obtained after toluene is evaporated off in layer, is colorless and transparent liquid, yield is about
It is 95.0%.
0.1molMMP and 0.3mol allyl glycidyl ether (AGE) are added in the single port bottle equipped with magnetic agitation, adds
Enter organic solvents, chloroform and account for the 2% of MMP mass photoinitiator benzophenone, stir lower ultraviolet lighting 5min, revolving is removed
Organic solvent is removed, colorless and transparent, low viscosity melamine-three (mercaptopropionyl amine) triglycidyl ether can be obtained
(MGEP), yield about 99%.
A kind of flame-retardant hyperbranched epoxy resin of embodiment 1, preparation methods steps are as follows:
By 0.4mol tri- (2- ethoxy) chlorinated isocyanurates-three (epihydric alcohol sulfide) (THGEP), 0.3mol ethylene glycol and
0.3mol dimethylbenzene is added in the three-necked flask equipped with mechanical stirring, condenser pipe and thermometer and is uniformly mixed, and is then added
The tetrabutylammonium bromide of THGEP mass 0.5% is slowly warming up under the conditions of 140 DEG C, is stirred to react 8 hours, is steamed dimethylbenzene,
Hyperbranched epoxy resin (the first structure, HEP-6, every mole of HEP-6 epoxy group containing 6mol in claim 1 can be obtained
Group), epoxide number 0.16mol/100g, number-average molecular weight is about 3600g/mol, and viscosity is 6000cp (25 DEG C).
A kind of flame-retardant hyperbranched epoxy resin of embodiment 2, preparation methods steps are as follows:
By 0.5mol tri- (2- ethoxy) chlorinated isocyanurates-three (epihydric alcohol sulfide) (THGEP), the contracting of 0.45mol mono- two
Ethylene glycol and 2.25mol toluene, which are added in the three-necked flask equipped with mechanical stirring, condenser pipe and thermometer, to be uniformly mixed, then
The cetyl trimethylammonium bromide of THGEP mass 5% is added, is slowly warming up under the conditions of 110 DEG C, is stirred to react 15 hours,
Toluene is steamed, hyperbranched epoxy resin can be obtained, and (second of structure, HEP-12, every mole of HEP-12 contain in claim 1
12mol epoxy group), epoxide number 0.12mol/100g, number-average molecular weight is about 11000g/mol, viscosity 7200cp
(25℃)。
A kind of flame-retardant hyperbranched epoxy resin of embodiment 3, preparation methods steps are as follows:
By 0.22mol tri- (2- ethoxy) chlorinated isocyanurates-three (epihydric alcohol sulfide) (THGEP), 0.21mol 1,4-
Butanediol, 0.1mol toluene and 0.2mol benzene, which are added in the three-necked flask equipped with mechanical stirring, condenser pipe and thermometer, to be mixed
Uniformly, the hexadecyltrimethylammonium chloride of THGEP mass 2% is then added, is stirred to react under the conditions of being slowly warming up to 110 DEG C
20 hours, organic solvent is steamed, hyperbranched epoxy resin (the third structure in claim 1, wherein R can be obtained2StructureN=2, HEP-24, every mole of HEP-24 epoxy group containing 24mol), epoxide number 0.10mol/
100g, number-average molecular weight are about 22900g/mol, and viscosity is 8600cp (25 DEG C).
A kind of flame-retardant hyperbranched epoxy resin of embodiment 4, preparation methods steps are as follows:
By 0.22mol melamine-three (mercaptopropionyl amine) triglycidyl ether (MGEP), three second two of contracting of 0.21mol bis-
Alcohol, 0.4mol dimethylbenzene, which are added in the three-necked flask equipped with mechanical stirring, condenser pipe and thermometer, to be uniformly mixed, is then added
The hexadecyltrimethylammonium chloride of MGEP mass 3% is slowly warming up under the conditions of 140 DEG C, is stirred to react 10 hours, has been steamed
Hyperbranched epoxy resin (the third structure in claim 1, wherein R can be obtained in solvent2StructureM=0, HMEP-24, every mole of HMEP-24 epoxy group containing 24mol), epoxide number is
0.11mol/100g, number-average molecular weight are about 23100g/mo, and viscosity is 9200cp (25 DEG C).
Hyperbranched epoxy resin, bisphenol A type epoxy resin (E51, the epoxide number that Examples 1 to 4 is obtained respectively
0.51mol/100g) mixed respectively with methylnadic anhydride, the dosage of methylnadic anhydride and epoxy resin according to
The molar ratio of anhydride group and epoxy group is 1.1:1.Then mixture is cast in mold, it is small is warming up to 170-180 DEG C of solidification 6
When, it is demoulded after taking out sample cooling, the performance of test material is distinguished after being placed at room temperature for 12 hours.The results are shown in Table 1.Wherein,
The tensile strength of material is tested according to ASTM D638-82a, the bending property of material according to ASTM D790M-92 standard into
The impact strength of row test, material is tested according to ASTM D256-81 standard, and the fracture toughness of material is according to ASTM
D5045-91a standard is tested, and the hot property (glass transition temperature) of material is surveyed according to ASTM 3418-82 by DSC
Examination, the heating rate of test are 10 DEG C/min.The flame retardant property (oxygen index (OI)) of material is according to standard GB/T/T 2406-1993
It is measured.Cure cycle is tested by DSC, and the heating rate of test is 10 DEG C/min.
The performance of hyperbranched epoxy resin product obtained by 1 embodiment 1-4 of table
Claims (10)
1. a kind of flame-retardant hyperbranched epoxy resin, structural formula are as follows:
R in formula2Structural formula be Wherein m, n are each independently selected from any integer in 0~8；
R1=-CH2CH2SCH2CH2CH2OCH2CH(OH)CH2,
R3=-CH2(CH2)jOr-CH2CH2(OCH2CH2)j, wherein j=1,2,3,4 or 5.
2. a kind of flame-retardant hyperbranched epoxy resin according to claim 1, it is characterised in that: the m=0, n=2.
3. a kind of flame-retardant hyperbranched epoxy resin according to claim 1, it is characterised in that: the R2Structural formula beWherein n=2.
4. the preparation method of flame-retardant hyperbranched epoxy resin described in a kind of claims 1 or 2 or 3, include the following steps: by
Three-functionality-degree epoxy monomer containing sulfur nitrogen heterocycle, dihydric alcohol and organic solvent are uniformly mixed, then catalyst is added thereto,
It is stirred to react under the conditions of 100-140 DEG C 8-20 hours, steams organic solvent, obtain flame-retardant hyperbranched epoxy resin.
5. the preparation method according to claim 4, it is characterised in that: three-functionality-degree epoxy resin containing the sulfur nitrogen heterocycle list
The molar ratio of body, dihydric alcohol and organic solvent is (1.0~1.5): 1.0:(1.0~5.0).
6. preparation method according to claim 5, which is characterized in that three-functionality-degree epoxy resin containing the sulfur nitrogen heterocycle list
The structural formula of body are as follows:
7. preparation method according to claim 6, it is characterised in that: the catalyst is tetrabutylammonium bromide, the tetrabutyl
The one or more of ammonium chloride, cetyl trimethylammonium bromide and hexadecyltrimethylammonium chloride, dosage three
The 0.5-5% of the degree of functionality quality of epoxy monomer containing sulfur nitrogen heterocycle.
8. preparation method according to claim 7, it is characterised in that: the organic solvent be benzene,toluene,xylene and
One or more of tetrahydrofuran.
9. preparation method according to claim 8, it is characterised in that: three-functionality-degree epoxy resin containing the sulfur nitrogen heterocycle list
Body is three (2- ethoxy) chlorinated isocyanurates-three (mercaptopropionic acid ester) triglycidyl ethers or the (mercaptopropionyl of melamine-three
Amine) triglycidyl ether.
10. the preparation method according to claim 4, it is characterised in that: the molecule of the flame-retardant hyperbranched epoxy resin
Amount is in 3000-35000g/mol.
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Cited By (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 |
| CN111961075A (en) * | 2020-08-24 | 2020-11-20 | 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 |
| CN115011294A (en) * | 2022-06-07 | 2022-09-06 | 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 |
| CN116113179A (en) * | 2023-02-01 | 2023-05-12 | 江苏贺鸿电子有限公司 | Multilayer printed circuit board and preparation method thereof |
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| CN105925130A (en) * | 2016-05-23 | 2016-09-07 | 北京化工大学 | Hyper-branched polyether epoxy resin/epoxy resin composite anti-corrosion coating and preparation method thereof |
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| CN105925130A (en) * | 2016-05-23 | 2016-09-07 | 北京化工大学 | Hyper-branched polyether epoxy resin/epoxy resin composite anti-corrosion coating and preparation method thereof |
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Cited By (7)
| 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 |
| CN111961075A (en) * | 2020-08-24 | 2020-11-20 | 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 |
| CN115011294A (en) * | 2022-06-07 | 2022-09-06 | 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 |
| 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 |
| CN116113179A (en) * | 2023-02-01 | 2023-05-12 | 江苏贺鸿电子有限公司 | Multilayer printed circuit board 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 |
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| CN109232862B (en) | 2021-05-25 |
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