CN106519188A - Abietyl hyper branched epoxy resin and preparation method and application thereof - Google Patents
Abietyl hyper branched epoxy resin and preparation method and application thereof Download PDFInfo
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- CN106519188A CN106519188A CN201610861045.7A CN201610861045A CN106519188A CN 106519188 A CN106519188 A CN 106519188A CN 201610861045 A CN201610861045 A CN 201610861045A CN 106519188 A CN106519188 A CN 106519188A
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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
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/12—Polycondensates containing more than one epoxy group per molecule of polycarboxylic acids with epihalohydrins or precursors thereof
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
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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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- 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
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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Abstract
The invention discloses abietyl hyper branched epoxy resin and a preparation method thereof. The method comprises the following steps: a) maleopimaric anhydride and bio-dihydric alcohol, a benzene solvent, and a catalyst are reacted, the benzene solvent is removed through pressure reduction to obtain the abietyl hyper branched polyester; and b) the abietyl hyper branched polyester and chloropropylene oxide are subjected to a reaction under the effect of an open loop reaction catalyst, the unreacted chloropropylene oxide is removed through pressure reduction, an organic solvent and an alkalescence catalyst are added for the reaction, and then processing is carried out to obtain the abietyl hyper branched epoxy resin. The invention also discloses an application of the resin. The rosin is introducecd into a hyper branched epoxy resin structure, a special hydrogen phenanthrene ring structure of rosin is used, rigidity, heat resistance and solidification speed are increased, viscosity is low, hydroxy is not contained, so that the epoxy resin can be used for the fields of high temperature resistance gluing agent, high temperature resistance paint, environmental protection low volatilization paint, low volatilization resin and routine epoxy resin.
Description
Technical field
The present invention relates to bio-based polymer resin technology field, and in particular to a kind of abietyl hyperbranched epoxy resin and
Preparation method and application.
Background technology
Colophonium is the most important product of chemistry of forest product industry, with many excellent characteristics, such as anti-corrosion, insulation, thickening, breast
Change etc..Used as a kind of valuable Renewable resource, Colophonium and its deep processed product are widely used in coating, ink, papermaking, gluing
The fields such as agent, electronics industry, food medicine and biological preparation.In recent years, chemical substance and material are being prepared using Renewable resource
Expect under this main trend, the applied research of Colophonium has obtained more rapidly developing.Colophonium is because its hydrogen phenanthrene ring structural rigidity is strong
With significant construction featuress, its rigidity can be matched in excellence or beauty with phenyl ring.The non-renewable resources such as current oil are day by day exhausted and people
Under situation to environmental conservation pay attention to day by day, become in recent years using Colophonium and its derivant synthesising biological based high molecular material
Carry out the focus of macromolecule research field.
There is substantial amounts of cavity structure inside dissaving polymer, with substantial amounts of end group, therefore live with higher reaction
Property.Due to winding less between hyperbranched polymer molecule, therefore which is difficult crystallization, and with good hydrodynamic performance, uniqueness
Viscosity behavior, the characteristic such as easy film forming so as to show wide application prospect in many fields.Containing a large amount of epoxy-terminated
Dissaving polymer (also referred to as hyperbranched epoxy resin) also there is excellent mechanical property, electrical property, adhesive property and low glutinous
The characteristics such as degree, it is expected to obtain extensively should in fields such as electronic material, LED Embedding Materials, the varnished insulation materials of wind-driven generator
With.Bio-based dissaving polymer is prepared with Colophonium and its derivant gradually to attract attention.Zhao Zhendong
Maleopimaric acid and epoxy prapanol reaction are obtained abietyl and are surpassed by (ZL201210246784.7, ZL201210516983.5) et al.
Branched polyester.Xie Hui (ZL201110000659.3；《Thermosetting resin》, 2013,28 (2):1-5.) et al. by maleopimaric acid
Three-glycidyl ester, maleopimaric acid, epichlorohydrin reaction obtain hyperbranched epoxy resin.The hyperbranched epoxy of these abietyls
The epoxide number not high (0.13～0.23) of resin, only with toughening functions.Therefore the simple low viscosity high epoxy value of development technology
Bio-based hyperbranched epoxy resin is to solve this area fundamental way of problems.
The content of the invention
It is an object of the present invention in view of the shortcomings of the prior art, there is provided a kind of hyperbranched asphalt mixtures modified by epoxy resin of abietyl
Fat.
Second object of the present invention is the preparation method for providing above-mentioned abietyl hyperbranched epoxy resin.
Third object of the present invention is to provide the application of above-mentioned abietyl hyperbranched epoxy resin.
For realizing above-mentioned first purpose, the structural formula of the abietyl hyperbranched epoxy resin that the present invention is provided is：
In formula, R1For R2For
For realizing second object of the present invention, the preparation side of the above-mentioned abietyl hyperbranched epoxy resin that the present invention is provided
Method comprises the steps：
A maleopimaric anhydride and bio-based dihydroxylic alcohols, benzene kind solvent, catalyst react 3 by () at 120 DEG C～180 DEG C～
6h, is then removed under reduced pressure benzene kind solvent at 100～120 DEG C, obtains abietyl hyper-branched polyester.
80～120 DEG C of reactions 3 in the presence of ring-opening reaction catalyst with epoxychloropropane of (b) abietyl hyper-branched polyester
～6h, is then removed under reduced pressure unreacted epoxychloropropane, adds organic solvent and base catalyst, in 0～50 DEG C of condition
3～8h of lower reaction, to neutrality, the organic solvent that reduces pressure away obtains abietyl hyperbranched epoxy resin for layering, aqueouss.
The mol ratio 1 of the maleopimaric anhydride, bio-based dihydroxylic alcohols and benzene kind solvent:(0.5～1):(1～5).
Described bio-based dihydroxylic alcohols are ethylene glycol, 1,3- Propylene Glycol, 1,4- butanediols；The catalyst is the positive fourth of metatitanic acid
Ester, titanium tetraethoxide, four normal propyl alcohol titaniums, titanium tetraisopropylate, four (2-Ethylhexyl Alcohol) titanium, butyl isopropyl titanate, zinc acetate, 4- (two
Methylamino) pyridine one or more, its quality is the 0.1～1% of maleopimaric anhydride and dihydroxylic alcohols gross mass.
Described benzene kind solvent is one or more in benzene, toluene and dimethylbenzene.
The mol ratio of the end carboxyl, epoxychloropropane and ring-opening reaction catalyst of described abietyl hyperbranched epoxy resin
For 1:(1～20):(0.001～0.1).
Described ring-opening reaction catalyst is tetrabutyl ammonium bromide, cetyl trimethylammonium bromide, three second of cetyl
One or more in base ammonium bromide, boron trifluoride etherate, stannum dichloride, butter of tin；
Described base catalyst is sodium hydroxide and/or potassium hydroxide, and the base catalyst is hyperbranched with abietyl
The mol ratio of the end carboxyl of polyester is 1:(1～3).
Described organic solvent is toluene, dioxane, ethyl acetate, tetrahydrofuran, the one kind or two in butyl acetate
More than kind, its consumption is 1 with the end carboxyl mol ratio of bio-based hyper-branched polyester:1～5.
For realizing above-mentioned 3rd purpose, the prepared abietyl with low viscosity, high epoxy value is overspend by the present invention
Change epoxy resin and be applied to high-temperature Resistance Adhesives, high-temperature resistant coating, the low volatilization coating of environmental protection, low volatilization resin and bisphenol A-type ring
The enhancing of oxygen tree fat and toughness reinforcing.
Technical scheme is had the advantage that and beneficial effect compared with prior art：
1st, the present invention is incorporated into biomass resource Colophonium in the structure of hyperbranched epoxy resin, using the special hydrogen of Colophonium
Phenanthrene ring structure, improves the rigid of resin, thermostability and curing rate, reduces the dependence to petroleum-type product.
2nd, the preparation process is simple of abietyl hyperbranched epoxy resin of the invention, cost of material are low, are suitable to industrial metaplasia
Produce.
3rd, the epoxide number of abietyl hyperbranched epoxy resin of the invention is in more than 0.28/100g, to different epoxy resin
With activeness and quietness function, the enhancing of high-temperature Resistance Adhesives, high-temperature resistant coating and bisphenol A type epoxy resin is can be widely applied to
With toughness reinforcing field.
4th, abietyl hyperbranched epoxy resin viscosity of the invention is low, not hydroxyl, significantly can drop as reactive diluent
The viscosity of low epoxy resin, can be widely applied to solvent-free, low volatilization epoxy coating field.
Specific embodiment
The present invention is described in detail below in conjunction with specific embodiments, but protection scope of the present invention is not limited to this
A little embodiments, equivalence changes or modification that all spirits according to technical solution of the present invention are done should all be covered by the present invention
Protection domain in.
The number-average molecular weight of product is determined and is determined using the PL-GPC-50 of PL companies of Britain, and epoxide number adopts salt according to GB
Sour acetone method is determined, and viscosity is determined under the conditions of 25 DEG C using Brookfield viscometers.
Embodiment 1
A () will be 40.00g maleopimaric anhydrides anti-at 120 DEG C with 4.65g ethylene glycol, 20g dimethylbenzene, 0.06g titanium tetraethoxides
6h is answered, dimethylbenzene is removed under reduced pressure at 100 DEG C then, obtain end carboxyl abietyl hyper-branched polyester (HBPE-1, every mole of HBPE-1
Carboxyl containing 6mol), number-average molecular weight is about 1340g/mol.
B 20.00g HBPE-1,41.21g epoxychloropropane, 120 DEG C of 0.04g tetrabutyl ammonium bromide are reacted 3h by (), then
Unreacted epoxychloropropane is removed under reduced pressure, 24.00g ethyl acetate, 4.46g sodium hydroxide is added, it is anti-under the conditions of 10 DEG C
After answering 7h, reaction to terminate, layering, organic layer aqueouss are dried to neutral and anhydrous magnesium sulfate, obtain pine after ethyl acetate is removed under reduced pressure
Perfume base hyperbranched epoxy resin (HBEE-1, every mole of HBEE-1 epoxy radicals containing 6mol), epoxide number is 0.34mol/100g, viscosity
For 620cp (25 DEG C).
Embodiment 2
A () is by 40.00g maleopimaric anhydrides with 5.58g ethylene glycol, 25g dimethylbenzene, 0.05g tetrabutyl titanates at 140 DEG C
Reaction 5h, dimethylbenzene is removed under reduced pressure at 110 DEG C then, obtain end carboxyl abietyl hyper-branched polyester (HBPE-2, per mole
HBPE-2 carboxyls containing 12mol), number-average molecular weight is about 2800g/mol.
B 20.00g HBPE-2,42.69g epoxychloropropane, 110 DEG C of 0.05g tetrabutylammonium chlorides are reacted 4h by (), then
Unreacted epoxychloropropane is removed under reduced pressure, 20.00g tetrahydrofurans, 4.62g sodium hydroxide is added, is reacted under the conditions of 0 DEG C
8h, reaction is layered after terminating, organic layer aqueouss are dried to neutral, anhydrous magnesium sulfate, obtains Colophonium after tetrahydrofuran is removed under reduced pressure
Base hyperbranched epoxy resin (HBEE-2, every mole of HBEE-2 epoxy radicals containing 12mol), epoxide number is 0.32mol/100g, viscosity
For 740cp (25 DEG C).
Embodiment 3
A 40.00g maleopimaric anhydrides are reacted at 160 DEG C by () with 5.92g ethylene glycol, 30g dimethylbenzene, 0.10g zinc acetates
4h, is then removed under reduced pressure dimethylbenzene at 120 DEG C, and (HBPE-3, every mole of HBPE-3 contain to obtain end carboxyl abietyl hyper-branched polyester
24mol carboxyls), number-average molecular weight is about 4850g/mol.
B () will be 20.00g HBPE-3,48.01g epoxychloropropane, 100 DEG C of 0.18g cetyl trimethylammonium bromide anti-
5h is answered, unreacted epoxychloropropane is then removed under reduced pressure, add 25.00g butyl acetates, 7.85g potassium hydroxide, at 30 DEG C
Under the conditions of react 5h, after reaction terminates, layering, organic layer aqueouss are dried to neutral, anhydrous magnesium sulfate, and butyl acetate is removed under reduced pressure
After obtain abietyl hyperbranched epoxy resin (HBEE-3, every mole of HBEE-3 epoxy radicals containing 24mol), epoxide number is 0.30mol/
100g, viscosity are 820cp (25 DEG C).
Embodiment 4
A () is by 40.00g maleopimaric anhydrides and 6.07g ethylene glycol, 40g dimethylbenzene, 0.10g4- (dimethylamino) pyridine
180 DEG C react 3h, dimethylbenzene is removed under reduced pressure at 120 DEG C then, obtain abietyl hyper-branched polyester (HBPE-4, per mole
HBPE-4 carboxyls containing 48mol), number-average molecular weight is about 10820g/mol.
B then 20.00g HBPE-4,54.86g epoxychloropropane, 90 DEG C of reaction 6h of 0.06g butters of tin ammonium are subtracted by ()
Pressure removes unreacted epoxychloropropane, adds 20.00g toluene, 7.74g potassium hydroxide, reacts 4h, instead under the conditions of 40 DEG C
Should be layered after terminating, organic layer aqueouss are dried to neutral, anhydrous magnesium sulfate, obtain the hyperbranched ring of abietyl after toluene is removed under reduced pressure
Oxygen tree fat (HBEE-4, every mole of HBEE-4 epoxy radicals containing 48mol), epoxide number are 0.28mol/100g, and viscosity is 760cp (25
℃)。
Embodiment 5
A () is by 40.00g maleopimaric anhydrides and 7.25g Propylene Glycol, 25g dimethylbenzene, 0.25g butyl isopropyl titanate 140
DEG C reaction 5h, dimethylbenzene is removed under reduced pressure at 110 DEG C then, obtain end carboxyl abietyl hyper-branched polyester (HBPP-3, per mole
HBPP-3 carboxyls containing 24mol), number-average molecular weight is about 5260g/mol.
B 20.00g HBPP-3,59,79g epoxychloropropane, 110 DEG C of 0.06g tetrabutyl ammonium bromide are reacted 4h by (), then
Unreacted epoxychloropropane is removed under reduced pressure, 16.00g dioxane, 4.06g sodium hydroxide is added, it is anti-under the conditions of 30 DEG C
After answering 5h, reaction to terminate, layering, organic layer aqueouss are dried to neutral, anhydrous magnesium sulfate, obtain pine after dioxane is removed under reduced pressure
Perfume base hyperbranched epoxy resin (HBEP-3, every mole of HBEP-3 epoxy radicals containing 24mol), epoxide number is 0.30mol/100g, is glued
Spend for 750cp (25 DEG C).
Embodiment 6
A () is by 40.00g maleopimaric anhydrides with 8.81g butanediols, 30g dimethylbenzene, 0.07g titanium tetraisopropylates at 180 DEG C
Reaction 3h, dimethylbenzene is removed under reduced pressure at 110 DEG C then, obtain end carboxyl abietyl hyper-branched polyester (HBPB-3, per mole
HBPB-3 carboxyls containing 24mol), number-average molecular weight is about 5310g/mol.
B 20.00g HBPB-3,68.33g epoxychloropropane, 80 DEG C of 0.05g tetrafluorides diethyl etherate are reacted by ()
3h, is then removed under reduced pressure unreacted epoxychloropropane, adds 24.00g tetrahydrofurans, 4.80g sodium hydroxide, in 20 DEG C of bars
6h is reacted under part, and reaction is layered after terminating, organic layer aqueouss are dried to neutral, anhydrous magnesium sulfate, after tetrahydrofuran is removed under reduced pressure
Abietyl hyperbranched epoxy resin (HBEB-3, every mole of HBEB-3 epoxy radicals containing 24mol) is obtained, epoxide number is 0.28mol/
100g, viscosity are 620cp (25 DEG C).
The abietyl hyperbranched epoxy resin that the embodiment 1～6 of this specific embodiment part is obtained and bisphenol A-type ring
Oxygen mixed with resin (NPEL 128, epoxide equivalent 184g/eq, viscosity is 11500cps under the conditions of 25 DEG C), wherein abietyl over-expense
Change epoxy resin and account for the 9% of two kinds of epoxy resin gross masses, then (consumption of firming agent is amine equivalent with firming agent polyetheramine D230
With epoxide equivalent equivalent reaction stoichiometry be defined) mix after room temperature evacuation removing bubble, be then cast in mould,
Cold curing 24h, room temperature carry out performance test after naturally cooling to room temperature, as a result as shown in table 1 to 120 DEG C of solidify afterwards 2h.Its
In, tensile property and bending property are determined according to ASTM 3039 and ASTM D790 respectively, and unnotched impact strength is according to ASTM
D256 is determined, and the fracture toughness of material is determined according to ASTM D5045.
Performance after 1 embodiment of table, 1～8 gained abietyl hyperbranched epoxy resin modified bisphenol A type epoxy resin
As it can be seen from table 1 synthesized low-viscosity high molecular abietyl hyperbranched epoxy resin effectively can strengthen
Toughness reinforcing bisphenol A type epoxy resin, the thermostability of epoxy resin are also improved.This is because the epoxy of abietyl hyperbranched epoxy resin
Value is high, molecular dimension is little, and be close to the property of bisphenol A type epoxy resin, can effectively be dispersed in bisphenol type epoxy tree
In resin system, and with certain molecular weight and molecular dimension, during solidification, the epoxy radicals of surrounding molecules participate in reaction, therefore whole
Individual abietyl hyperbranched epoxy resin molecule equivalent to homodisperse organic rigid-particle in situ, forms equal in resin matrix
Phase structure.Abietyl hyperbranched epoxy resin molecular structure has substantial amounts of hole and containing substantial amounts of rigid hydrogen phenanthrene ring structure,
The presence in intramolecular hole has a raising beneficial to toughness (or impact strength), the presence of rigid hydrogen phenanthrene ring structure have beneficial to intensity and
The increase of thermostability.
Claims (9)
1. a kind of abietyl hyperbranched epoxy resin, it is characterised in that：The resin has following structural formula：
In formula, R1For R2For
2. the preparation method of the abietyl hyperbranched epoxy resin described in claim 1, it is characterised in that：The method includes as follows
Step：
A maleopimaric anhydride is reacted 3～6h with bio-based dihydroxylic alcohols, benzene kind solvent, catalyst at 120 DEG C～180 DEG C by (), so
Benzene kind solvent is removed under reduced pressure afterwards at 100～120 DEG C, abietyl hyper-branched polyester is obtained；
(b) abietyl hyper-branched polyester and epoxychloropropane in the presence of ring-opening reaction catalyst 80～120 DEG C of reactions 3～
6h, is then removed under reduced pressure unreacted epoxychloropropane, adds organic solvent and base catalyst, under the conditions of 0～50 DEG C
3～8h of reaction, to neutrality, the organic solvent that reduces pressure away obtains abietyl hyperbranched epoxy resin for layering, aqueouss；
The mol ratio 1 of the maleopimaric anhydride, bio-based dihydroxylic alcohols and benzene kind solvent:(0.5～1):(1～5).
3. the preparation method of abietyl hyperbranched epoxy resin according to claim 2, it is characterised in that：Described biology
Base dihydroxylic alcohols are ethylene glycol, 1,3- Propylene Glycol, 1,4- butanediols；The catalyst be tetrabutyl titanate, titanium tetraethoxide, four positive third
Alcohol titanium, titanium tetraisopropylate, four (2-Ethylhexyl Alcohol) titanium, butyl isopropyl titanate, zinc acetate, one kind of 4- (dimethylamino) pyridine or
Two or more, its quality is the 0.1～1% of maleopimaric anhydride and dihydroxylic alcohols gross mass.
4. the preparation method of the abietyl hyperbranched epoxy resin according to Claims 2 or 3, it is characterised in that：Described
Benzene kind solvent is one or more in benzene, toluene and dimethylbenzene.
5. the preparation method of the abietyl hyperbranched epoxy resin according to Claims 2 or 3, it is characterised in that：Described
The mol ratio of the end carboxyl of abietyl hyperbranched epoxy resin, epoxychloropropane and ring-opening reaction catalyst is 1:(1～20):
(0.001～0.1).
6. the preparation method of the abietyl hyperbranched epoxy resin according to Claims 2 or 3, it is characterised in that：Described
Ring-opening reaction catalyst is tetrabutyl ammonium bromide, cetyl trimethylammonium bromide, cetyltriethylammonium bromide, borontrifluoride
One or more in diethyl etherate, stannum dichloride, butter of tin.
7. the preparation method of the abietyl hyperbranched epoxy resin according to Claims 2 or 3, it is characterised in that：Described
Base catalyst is sodium hydroxide and/or potassium hydroxide, the base catalyst and the end carboxyl of abietyl hyper-branched polyester
Mol ratio is 1:(1～3).
8. the preparation method of the abietyl hyperbranched epoxy resin according to Claims 2 or 3, it is characterised in that：Described
Organic solvent is toluene, dioxane, ethyl acetate, tetrahydrofuran, one or more in butyl acetate, its consumption with
The end carboxyl mol ratio of bio-based hyper-branched polyester is 1:1～5.
9. the abietyl hyperbranched epoxy resin described in claim 1 is in high-temperature Resistance Adhesives, high-temperature resistant coating, environmentally friendly low volatilization
Application in coating, low volatilization resin and bisphenol A type epoxy resin.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5939886A (en) * | 1982-08-30 | 1984-03-05 | Arakawa Chem Ind Co Ltd | Fumaropimaric acid triglycidyl ester |
| CN102766264A (en) * | 2012-07-17 | 2012-11-07 | 中国林业科学研究院林产化学工业研究所 | Preparation method for rosin-based hyperbranched polyester and application of rosin-based hyperbranched polyester to epoxy resin |
| CN104987499A (en) * | 2015-08-07 | 2015-10-21 | 中国林业科学研究院林产化学工业研究所 | Water-soluble maleopimaric acid hyperbranched polyester and preparation method therefor |
-
2016
- 2016-09-29 CN CN201610861045.7A patent/CN106519188B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5939886A (en) * | 1982-08-30 | 1984-03-05 | Arakawa Chem Ind Co Ltd | Fumaropimaric acid triglycidyl ester |
| CN102766264A (en) * | 2012-07-17 | 2012-11-07 | 中国林业科学研究院林产化学工业研究所 | Preparation method for rosin-based hyperbranched polyester and application of rosin-based hyperbranched polyester to epoxy resin |
| CN104987499A (en) * | 2015-08-07 | 2015-10-21 | 中国林业科学研究院林产化学工业研究所 | Water-soluble maleopimaric acid hyperbranched polyester and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| 赵丽 等: "松香基超支化环氧树脂的合成及性能研究", 《热固性树脂》 * |
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