CN106916283B - A kind of preparation method of branched structure anhydride curing accelerator - Google Patents
A kind of preparation method of branched structure anhydride curing accelerator Download PDFInfo
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- CN106916283B CN106916283B CN201710155560.8A CN201710155560A CN106916283B CN 106916283 B CN106916283 B CN 106916283B CN 201710155560 A CN201710155560 A CN 201710155560A CN 106916283 B CN106916283 B CN 106916283B
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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
- C08G59/68—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 catalysts used
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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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
-
- 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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
Abstract
The present invention relates to a kind of preparation methods of branched structure anhydride curing accelerator, belong to the synthesis technical field of thermosetting resin auxiliary agent in fine chemistry industry.Specific step is as follows: the polynary amine monomers of 50 to 90 parts by weight being taken to react at 0-5 DEG C 2-4 hours with the trifunctional unsaturation acrylate of 10 to 50 parts by weight, then with 20 to 40 parts by weight of acrylic ester monomer and 20 to 40 parts by weight mixed solution of anhydrous methanol between 20-25 DEG C, after reaction 4-8 hours, distillation 6-8 hours, temperature is controlled between 120-130 DEG C, the pressure control of water pump obtains branched structure anhydride curing accelerator between -0.05 to -0.1MPa.The promotor is the use of epoxy resin promotor, making epoxy resin at normal temperature has longer working life, the curing reaction of acid anhydride type curing agent and epoxy resin can be improved again at high temperature, and obtained solidfied material has preferable mechanics and thermodynamic property, is a kind of epoxyeicosatrienoic acid anhydride curing accelerator for being suitable for industrialized production.
Description
Technical field
The invention belongs to chemical technology fields, are related to a kind of preparation method of branched structure anhydride curing accelerator.
Background technique
Epoxy resin is a kind of one of most common thermosetting resin, it must be by being reacted with curing agent, ability
Obtain high molecular material with practical value.The most common curing agent of epoxy resin mainly has anhydride, amine and polyisocyanate cyanogen
Acid esters curing agent etc..Various curing agent have respective advantage and disadvantage.The wherein solidification of acid anhydride type curing agent and epoxy resin is and hydroxyl
Base is reacted, and is reacted very slow, is often needed hot setting, or even carry out at 200 DEG C, if in the presence of acid or base catalyst,
It reacts quickly, so being often equipped with curing accelerator using acid anhydride type curing agent.It is several solid for epoxy resin-anhydride system
Change pours into agent and mainly has tertiary amine, alcohol, phenol, acid, boron amide network platform object and other subsidence feeds.Ideal promotor should have
Higher activity can participate in curing reaction again, while must also have environmental protection, efficient, ease for operation energy.It uses currently on the market
Promotor have and more or less there are problems that, such as Tertiary amine accelerators are that nonreactive small molecule is residual since they are acted on
It is left in polymer network, they will lead to Tg significant decrease.In addition, since they are used as the latent of the presoma of chemical weapons
In possibility, now several such ethanolamine derivant is by the control of institute, the government.
Summary of the invention
Present invention aims to overcome that the shortcomings that prior art and deficiency, provide a kind of branched structure epoxy resin-acid anhydrides
The preparation method of curing accelerator, and the auxiliary agent is applied in cycloaliphatic epoxy resin-acid anhydrides fixed line system material, the auxiliary agent
Epoxy resin-anhydride system storage time is improved, improves epoxy resin-anhydride system hot setting speed, simultaneously
Improve epoxy resin-anhydride system solidfied material mechanical property.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of branched structure anhydride curing accelerator, comprising steps of
1) polynary 50 to 90 parts by weight of amine monomers is taken to be placed in blender, thermometer, condenser pipe and isobaric funnel
Four-hole boiling flask in；
2) four-hole boiling flask is placed in the oil bath of temperature programmed control；
3) 10 to 50 parts by weight of trifunctional unsaturation acrylic ester monomer are weighed to be placed in isobaric funnel；
4) blender is under stirring, and in nitrogen protection, isobaric funnel starts that trifunctional unsaturation acrylic acid is added dropwise
Esters monomer；After being added dropwise, the temperature in four-hole boiling flask is controlled between 0-5 DEG C.After reaction 2-4 hours, intermediate compound I is obtained.
5) 20 to 40 parts by weight of acrylic ester monomer and 20 to 40 parts by weight of anhydrous methanol is taken to be uniformly mixed postposition
In isobaric funnel；
6) under blender stirring, in nitrogen protection, isobaric funnel starts acrylic ester monomer to be added dropwise and without water beetle
The mixed liquor of alcohol；After being added dropwise, the temperature in four-hole boiling flask is controlled between 20-25 DEG C, the reaction was continued 4-8 hours, obtains
Mesosome II；
7) under blender stirring, nitrogen is closed, opens water pump, intermediate II is evaporated under reduced pressure 6-8 hours；It distilled
Cheng Zhong controls the temperature in four-hole bottle between 120-130 DEG C, and the pressure control of water pump obtains between -0.05 to -0.1MPa
Branched structure anhydride curing accelerator.
Further, the trifunctional unsaturation acrylic ester monomer refers to trimethylolpropane tris acrylic acid
One of ester, trimethylol-propane trimethacrylate or two kinds.
Further, the polynary amine monomers refer to ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, four
One of five amine of ethylene, pentaethylene hexamine are several.
Further, the acrylic ester monomer refers to methyl acrylate, methyl methacrylate.
Compared with prior art, the present invention provides a kind of branched structure, be used to prepare stable storing, epoxy resin-
Anhydride-cured promotor, this promotor, which makes epoxy resin at normal temperature, longer working life, can be improved again at high temperature
The curing reaction of acid anhydride type curing agent and epoxy resin participates in the solidification of epoxy resin, improves the mechanics and thermodynamics of solidfied material
Performance is a kind of epoxyeicosatrienoic acid anhydride curing accelerator for being suitable for industrialized production.
Detailed description of the invention
Fig. 1 is the SEM photograph for having dosed the impact fracture surface of the epoxy resin-anhydride-cured system after 0.5 part of BPNH-10.
Fig. 2 is the SEM photograph of the impact fracture surface of the epoxy resin-anhydride-cured system of no curing accelerator.
Fig. 3 is the SEM photograph for having dosed the impact fracture surface of the epoxy resin-anhydride-cured system after 0.5 part of acetylacetone,2,4-pentanedione neodymium
Piece.
Fig. 4 is the relation curve of branched structure anhydride curing accelerator BPNH-10 content and viscosity.
Specific embodiment:
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that following embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, the people that is skilled in technique in the field
Member can make some nonessential modifications and adaptations to the present invention according to the content of foregoing invention.
Test method explanation:
1) bending property examination is tested by GB/T 9341-2000 standard
2) Izod notched impact strength is tested by GB/T 1843-1996 standard.
3) glass transition temperature is tested, and is tested using differential scanning calorimeter.Test condition: the sample of about 8.0mg is set
It is tested under nitrogen atmosphere in crucible, is raised to 250 DEG C by room temperature with 5 DEG C/min heating rate.
4) viscosity measurement: utilizing rotational viscometer, tests 135 DEG C of viscosity changes for solidifying lower system.
5) epoxy resin cured product sem test, using the impact fracture surface of solidfied material, in Flied emission after the metal spraying of surface
It is tested under scanning electron microscope.
Embodiment 1
Diethylenetriamine 50g is taken to be placed in four mouthfuls of burnings of the 250ml with blender, thermometer, condenser pipe and isobaric funnel
In bottle.Four-hole boiling flask is placed in the oil bath of temperature programmed control.It weighs trimethylolpropane trimethacrylate 50g and is placed in isobaric funnel
In.Blender is under stirring, and in nitrogen protection, isobaric funnel starts that trimethylolpropane trimethacrylate is added dropwise.It is added dropwise
After, the temperature in four-hole boiling flask is controlled at 0 DEG C.After reaction 4 hours, intermediate compound I is obtained.Take methyl acrylate 20g and anhydrous
Methanol 20g is uniformly mixed and is placed in isobaric funnel.Under blender stirring, in nitrogen protection, isobaric funnel starts to be added dropwise
The mixed liquor of methyl acrylate and anhydrous methanol.After being added dropwise, the temperature in four-hole boiling flask is controlled at 20 DEG C, the reaction was continued 8
Hour, obtain intermediate II.Under blender stirring, nitrogen is closed, opens water pump, intermediate II is evaporated under reduced pressure 8 hours.It steams
During evaporating, the temperature in four-hole bottle is controlled at 120 DEG C, the pressure of water pump is controlled in -0.10MPa, obtains branched structure anhydride
Curing accelerator BPNH-1.
Embodiment 2
Diethylenetriamine 60g is taken to be placed in four mouthfuls of burnings of the 250ml with blender, thermometer, condenser pipe and isobaric funnel
In bottle.Four-hole boiling flask is placed in the oil bath of temperature programmed control.It weighs trimethylolpropane trimethacrylate 40g and is placed in isobaric funnel
In.Blender is under stirring, and in nitrogen protection, isobaric funnel starts that trimethylolpropane trimethacrylate is added dropwise.It is added dropwise
After, the temperature in four-hole boiling flask is controlled at 0 DEG C.After reaction 4 hours, intermediate compound I is obtained.Take methyl acrylate 20g and anhydrous
Methanol 20g is uniformly mixed and is placed in isobaric funnel.Under blender stirring, in nitrogen protection, isobaric funnel starts to be added dropwise
The mixed liquor of methyl acrylate and anhydrous methanol.After being added dropwise, the temperature in four-hole boiling flask is controlled at 20 DEG C, the reaction was continued 8
Hour, obtain intermediate II.Under blender stirring, nitrogen is closed, opens water pump, intermediate II is evaporated under reduced pressure 8 hours.It steams
During evaporating, the temperature in four-hole bottle is controlled at 120 DEG C, the pressure of water pump is controlled in -0.10MPa, obtains branched structure anhydride
Curing accelerator BPNH-2.
Embodiment 3
Diethylenetriamine 90g is taken to be placed in four mouthfuls of burnings of the 250ml with blender, thermometer, condenser pipe and isobaric funnel
In bottle.Four-hole boiling flask is placed in the oil bath of temperature programmed control.It weighs trimethylolpropane trimethacrylate 10g and is placed in isobaric funnel
In.Blender is under stirring, and in nitrogen protection, isobaric funnel starts that trimethylolpropane trimethacrylate is added dropwise.It is added dropwise
After, the temperature in four-hole boiling flask is controlled at 0 DEG C.After reaction 4 hours, intermediate compound I is obtained.Take methyl acrylate 20g and anhydrous
Methanol 20g is uniformly mixed and is placed in isobaric funnel.Under blender stirring, in nitrogen protection, isobaric funnel starts to be added dropwise
The mixed liquor of methyl acrylate and anhydrous methanol.After being added dropwise, the temperature in four-hole boiling flask is controlled at 20 DEG C, the reaction was continued 8
Hour, obtain intermediate II.Under blender stirring, nitrogen is closed, opens water pump, intermediate II is evaporated under reduced pressure 8 hours.It steams
During evaporating, the temperature in four-hole bottle is controlled at 120 DEG C, the pressure of water pump is controlled in -0.10MPa, obtains branched structure anhydride
Curing accelerator BPNH-3.
Embodiment 4
Ethylenediamine 50g is taken to be placed in the four-hole boiling flask of the 250ml with blender, thermometer, condenser pipe and isobaric funnel.
Four-hole boiling flask is placed in the oil bath of temperature programmed control.Trimethylolpropane trimethacrylate 50g is weighed to be placed in isobaric funnel.It stirs
Device is mixed under stirring, in nitrogen protection, isobaric funnel starts that trimethylolpropane trimethacrylate is added dropwise.It is added dropwise
Afterwards, the temperature in four-hole boiling flask is controlled at 0 DEG C.After reaction 4 hours, intermediate compound I is obtained.Take methyl acrylate 20g and anhydrous methanol
20g is uniformly mixed and is placed in isobaric funnel.Under blender stirring, in nitrogen protection, isobaric funnel starts that propylene is added dropwise
The mixed liquor of sour methyl esters and anhydrous methanol.After being added dropwise, the temperature in four-hole boiling flask is controlled at 20 DEG C, the reaction was continued 8 hours,
Obtain intermediate II.Under blender stirring, nitrogen is closed, opens water pump, intermediate II is evaporated under reduced pressure 8 hours.It distilled
Cheng Zhong controls the temperature in four-hole bottle at 120 DEG C, and the pressure control of water pump obtains the solidification of branched structure anhydride in -0.10MPa
Accelerant B PNH-4.
Embodiment 5
Ethylenediamine 60g is taken to be placed in the four-hole boiling flask of the 250ml with blender, thermometer, condenser pipe and isobaric funnel.
Four-hole boiling flask is placed in the oil bath of temperature programmed control.Trimethylolpropane trimethacrylate 40g is weighed to be placed in isobaric funnel.It stirs
Device is mixed under stirring, in nitrogen protection, isobaric funnel starts that trimethylolpropane trimethacrylate is added dropwise.It is added dropwise
Afterwards, the temperature in four-hole boiling flask is controlled at 0 DEG C.After reaction 4 hours, intermediate compound I is obtained.Take methyl acrylate 20g and anhydrous methanol
20g is uniformly mixed and is placed in isobaric funnel.Under blender stirring, in nitrogen protection, isobaric funnel starts that propylene is added dropwise
The mixed liquor of sour methyl esters and anhydrous methanol.After being added dropwise, the temperature in four-hole boiling flask is controlled at 20 DEG C, the reaction was continued 8 hours,
Obtain intermediate II.Under blender stirring, nitrogen is closed, opens water pump, intermediate II is evaporated under reduced pressure 8 hours.It distilled
Cheng Zhong controls the temperature in four-hole bottle at 120 DEG C, and the pressure control of water pump obtains the solidification of branched structure anhydride in -0.10MPa
Accelerant B PNH-5.
Embodiment 6
Ethylenediamine 90g is taken to be placed in the four-hole boiling flask of the 250ml with blender, thermometer, condenser pipe and isobaric funnel.
Four-hole boiling flask is placed in the oil bath of temperature programmed control.Trimethylolpropane trimethacrylate 10g is weighed to be placed in isobaric funnel.It stirs
Device is mixed under stirring, in nitrogen protection, isobaric funnel starts that trimethylolpropane trimethacrylate is added dropwise.It is added dropwise
Afterwards, the temperature in four-hole boiling flask is controlled at 0 DEG C.After reaction 4 hours, intermediate compound I is obtained.Take methyl acrylate 20g and anhydrous methanol
20g is uniformly mixed and is placed in isobaric funnel.Under blender stirring, in nitrogen protection, isobaric funnel starts that propylene is added dropwise
The mixed liquor of sour methyl esters and anhydrous methanol.After being added dropwise, the temperature in four-hole boiling flask is controlled at 20 DEG C, the reaction was continued 8 hours,
Obtain intermediate II.Under blender stirring, nitrogen is closed, opens water pump, intermediate II is evaporated under reduced pressure 8 hours.It distilled
Cheng Zhong controls the temperature in four-hole bottle at 120 DEG C, and the pressure control of water pump obtains the solidification of branched structure anhydride in -0.10MPa
Accelerant B PNH-6.
Embodiment 7 takes diethylenetriamine 50g to be placed in the 250ml's with blender, thermometer, condenser pipe and isobaric funnel
In four-hole boiling flask.Four-hole boiling flask is placed in the oil bath of temperature programmed control.Trimethylol-propane trimethacrylate 50g is weighed to set
In isobaric funnel.Blender is under stirring, and in nitrogen protection, isobaric funnel starts that trimethylol propane trimethyl is added dropwise
Acrylate.After being added dropwise, the temperature in four-hole boiling flask is controlled at 0 DEG C.After reaction 4 hours, intermediate compound I is obtained.Take acrylic acid
Methyl esters 40g and anhydrous methanol 40g is uniformly mixed and is placed in isobaric funnel.It is isobaric in nitrogen protection under blender stirring
Funnel starts the mixed liquor that methyl acrylate and anhydrous methanol is added dropwise.After being added dropwise, the temperature in four-hole boiling flask is controlled 20
DEG C, the reaction was continued 8 hours, obtains intermediate II.Under blender stirring, nitrogen is closed, opens water pump, intermediate II is depressurized
Distillation 8 hours.In distillation process, the temperature in four-hole bottle is controlled at 120 DEG C, the pressure of water pump is controlled in -0.10MPa, must be propped up
Change structure anhydride curing accelerator BPNH-7.
Embodiment 8
Diethylenetriamine 60g is taken to be placed in four mouthfuls of burnings of the 250ml with blender, thermometer, condenser pipe and isobaric funnel
In bottle.Four-hole boiling flask is placed in the oil bath of temperature programmed control.It weighs trimethylol-propane trimethacrylate 40g and is placed in equipressure
In funnel.Blender is under stirring, and in nitrogen protection, isobaric funnel starts that trimethylol propane trimethyl acrylic acid is added dropwise
Ester.After being added dropwise, the temperature in four-hole boiling flask is controlled at 5 DEG C.After reaction 2 hours, intermediate compound I is obtained.Take methyl acrylate 30g
It is uniformly mixed and is placed in isobaric funnel with anhydrous methanol 30g.Under blender stirring, in nitrogen protection, isobaric funnel is opened
Begin the mixed liquor that methyl acrylate and anhydrous methanol is added dropwise.After being added dropwise, the temperature in four-hole boiling flask is controlled at 25 DEG C, is continued
Reaction 8 hours, obtains intermediate II.Under blender stirring, nitrogen is closed, opens water pump, it is small to intermediate II vacuum distillation 8
When.In distillation process, the temperature in four-hole bottle is controlled at 130 DEG C, the pressure control of water pump obtains branched structure acid in -0.05MPa
Anhydride curing accelerator BPNH-8.
Embodiment 9
Diethylenetriamine 90g is taken to be placed in four mouthfuls of burnings of the 250ml with blender, thermometer, condenser pipe and isobaric funnel
In bottle.Four-hole boiling flask is placed in the oil bath of temperature programmed control.It weighs trimethylol-propane trimethacrylate 10g and is placed in equipressure
In funnel.Blender is under stirring, and in nitrogen protection, isobaric funnel starts that trimethylol propane trimethyl acrylic acid is added dropwise
Ester.After being added dropwise, the temperature in four-hole boiling flask is controlled at 0 DEG C.After reaction 3 hours, intermediate compound I is obtained.Take methyl acrylate 30g
It is uniformly mixed and is placed in isobaric funnel with anhydrous methanol 30g.Under blender stirring, in nitrogen protection, isobaric funnel is opened
Begin the mixed liquor that methyl acrylate and anhydrous methanol is added dropwise.After being added dropwise, the temperature in four-hole boiling flask is controlled at 20 DEG C, is continued
Reaction 8 hours, obtains intermediate II.Under blender stirring, nitrogen is closed, opens water pump, it is small to intermediate II vacuum distillation 6
When.In distillation process, the temperature in four-hole bottle is controlled at 125 DEG C, the pressure control of water pump obtains branched structure acid in -0.10MPa
Anhydride curing accelerator BPNH-9.
Embodiment 10
Diethylenetriamine 60g is taken to be placed in four mouthfuls of burnings of the 250ml with blender, thermometer, condenser pipe and isobaric funnel
In bottle.Four-hole boiling flask is placed in the oil bath of temperature programmed control.It weighs trimethylol-propane trimethacrylate 40g and is placed in equipressure
In funnel.Blender is under stirring, and in nitrogen protection, isobaric funnel starts that trimethylol propane trimethyl acrylic acid is added dropwise
Ester.After being added dropwise, the temperature in four-hole boiling flask is controlled at 5 DEG C.After reaction 2 hours, intermediate compound I is obtained.Take butyl acrylate 30g
It is uniformly mixed and is placed in isobaric funnel with anhydrous methanol 30g.Under blender stirring, in nitrogen protection, isobaric funnel is opened
Begin the mixed liquor that methyl acrylate and anhydrous methanol is added dropwise.After being added dropwise, the temperature in four-hole boiling flask is controlled at 25 DEG C, is continued
Reaction 8 hours, obtains intermediate II.Under blender stirring, nitrogen is closed, opens water pump, it is small to intermediate II vacuum distillation 8
When.In distillation process, the temperature in four-hole bottle is controlled at 130 DEG C, the pressure control of water pump obtains branched structure acid in -0.05MPa
Anhydride curing accelerator BPNH-10.
It the results are shown in Table using application of the branching curing accelerator prepared in the above embodiments in epoxy resin-anhydride system
1, Fig. 4 and Fig. 1, Fig. 2, Fig. 3.
From table 1 it follows that the branching curing accelerator use obtained according to the present invention is in epoxy resin-anhydride system
In, mechanical property, glass transition temperature and the 135 DEG C of gel times of solidfied material are substantially better than acetylacetone,2,4-pentanedione neodymium and do not fill out
Add the solidfied material of promotor.As can be seen from Figure 4 as branching curing accelerator BPNH-10 content increases, gel time is gradually decreased.
It can be seen that with no curing accelerator and compared with having dosed acetylacetone,2,4-pentanedione neodymium from Fig. 1, Fig. 2, Fig. 3, dosed BPNH-10 0.5
The impact fracture surface of epoxy resin-anhydride-cured system after part is fuzzy, illustrates impact property better than no curing accelerator and doses
There is the impact property of acetylacetone,2,4-pentanedione neodymium epoxy resin-anhydride-cured system.
Table 1: epoxy resin/acid anhydrides/branching curing accelerator curing materials performance indicator
Claims (4)
1. a kind of preparation method of branched structure anhydride curing accelerator, which comprises the steps of:
1) take polynary 50 to 90 parts by weight of amine monomers be placed in blender, thermometer, condenser pipe and isobaric funnel four
In mouth flask；
2) four-hole boiling flask is placed in the oil bath of temperature programmed control；
3) 10 to 50 parts by weight of trifunctional unsaturation acrylic ester monomer are weighed to be placed in isobaric funnel；
4) blender is under stirring, and in nitrogen protection, isobaric funnel starts that trifunctional unsaturation esters of acrylic acid is added dropwise
Monomer；After being added dropwise, the temperature in four-hole boiling flask is controlled between 0-5 DEG C；After reaction 2-4 hours, intermediate I is obtained；
5) it takes 20 to 40 parts by weight of acrylic ester monomer and 20 to 40 parts by weight of anhydrous methanol to be uniformly mixed to be placed on
It presses in funnel；
6) under blender stirring, in nitrogen protection, isobaric funnel starts that acrylic ester monomer and anhydrous methanol is added dropwise
Mixed liquor after being added dropwise, controls the temperature in four-hole boiling flask between 20-25 DEG C, the reaction was continued 4-8 hours, obtains intermediate
Ⅱ；
7) under blender stirring, nitrogen is closed, opens water pump, intermediate II is evaporated under reduced pressure 6-8 hours；Distillation process
In, the temperature in four-hole bottle is controlled between 120-130 DEG C, and the pressure control of water pump must prop up between -0.05 to -0.1MPa
Change structure anhydride curing accelerator.
2. a kind of preparation method of branched structure anhydride curing accelerator according to claim 1, it is characterised in that: institute
The trifunctional unsaturation acrylic ester monomer stated refers to trimethylolpropane trimethacrylate, trimethylol propane trimethyl
One of acrylate or two kinds.
3. a kind of preparation method of branched structure anhydride curing accelerator according to claim 1, it is characterised in that: institute
The polynary amine monomers stated refer to ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylene hexamine
One of or it is several.
4. a kind of preparation method of branched structure anhydride curing accelerator according to claim 1, it is characterised in that: institute
The acrylic ester monomer stated refers to one of methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate
Or it is several.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250319A (en) * | 2008-04-01 | 2008-08-27 | 南京航空航天大学 | Use of hyperbranched polyamine as curing agent in thermosetting resin |
| CN102834372A (en) * | 2010-03-25 | 2012-12-19 | 太阳化学有限公司 | Amine synergists and application inradiation curing |
| CN106432584A (en) * | 2016-09-18 | 2017-02-22 | 江南大学 | Synthesis of imidazole latent epoxy curing accelerator having toughening effect and application of accelerator in epoxy modification |
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2017
- 2017-03-16 CN CN201710155560.8A patent/CN106916283B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101250319A (en) * | 2008-04-01 | 2008-08-27 | 南京航空航天大学 | Use of hyperbranched polyamine as curing agent in thermosetting resin |
| CN102834372A (en) * | 2010-03-25 | 2012-12-19 | 太阳化学有限公司 | Amine synergists and application inradiation curing |
| CN106432584A (en) * | 2016-09-18 | 2017-02-22 | 江南大学 | Synthesis of imidazole latent epoxy curing accelerator having toughening effect and application of accelerator in epoxy modification |
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