CN109180910A - A kind of tetra functional carboxyl epoxy curing agent and preparation method thereof - Google Patents
A kind of tetra functional carboxyl epoxy curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN109180910A CN109180910A CN201810956023.8A CN201810956023A CN109180910A CN 109180910 A CN109180910 A CN 109180910A CN 201810956023 A CN201810956023 A CN 201810956023A CN 109180910 A CN109180910 A CN 109180910A
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- China
- Prior art keywords
- curing agent
- epoxy curing
- tetra functional
- preparation
- functional carboxyl
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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
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
- C08G59/4269—Macromolecular compounds obtained by reactions other than those involving unsaturated carbon-to-carbon bindings
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
- C08G65/3326—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic aromatic
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides tetra functional carboxyl epoxy curing agent and preparation method thereof, preparation method is the following steps are included: trimellitic anhydride, polyetherdiol and catalyst are added in reactor, in atmosphere of inert gases, heating is reacted, then it cools down, washing filters, the epoxy curing agent of carboxyl containing tetra functional is prepared.One-component epoxy resin system made of tetra functional carboxyl epoxy curing agent and epoxy resin mixed preparing that the present invention obtains and filler have good affinity, good mixing effect, good fluidity, and then improve the flow behavior, hot property and electrical characteristics of epoxy molding plastic.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically disclose a kind of tetra functional carboxyl epoxy curing agent
And preparation method thereof.
Background technique
Epoxy molding plastic (EMC) mainly have filler, epoxy resin, curing agent, curing accelerator, release agent, fire retardant with
And the groups such as other additives are grouped as.EMC be at a certain temperature by epoxy resin and curing agent curing accelerator work
It is made after carrying out prepolymerization under, the properties of EMC are mainly determined by prepolymerized degree.
Epoxy resin is one of important component of epoxy molding plastic, the type of epoxy resin and the ratio shared by it
Difference not only directly affects the flow behavior of epoxy molding plastic, also directly affects the hot property and electrical property of epoxy molding plastic
Energy.Currently used epoxy resin has bisphenol A-type, o-cresol type, biphenyl type, polyfunctional group type etc..Different types of asphalt mixtures modified by epoxy resin
Rouge has different characteristics, such as o-cresol type epoxy resin thermal stability with higher and chemical stability；Bisphenol type epoxy
Resin has low-shrinkage and low volatile ingredient；Polyfunctional group type epoxy resin has excellent thermal stability, rapidly-curable
The features such as with high Tg；Biphenyl type epoxy resin has the characteristics that lower viscosity, high fillibility.
The main function of curing agent is to react to form a kind of stable tridimensional network with epoxy resin.Curing agent and ring
Oxygen resin affects the flow behavior, hot property and electrical characteristics of epoxy molding plastic together.Common phenolic resin curing agent is affine
Power is poor, bad with the mixed effect of filler, leads to poor fluidity, and then influences the final performance of epoxy molding plastic.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, a kind of tetra functional carboxyl epoxy resin cure is provided
Agent and preparation method thereof, the tetra functional carboxyl epoxy curing agent and epoxy resin mixed preparing form single-component epoxy tree
Resin system, one-component epoxy resin system and filler have good affinity, good mixing effect and mobility, and then improve
Flow behavior, hot property and the electrical characteristics of epoxy molding plastic.
In order to realize that object above and other purposes, the present invention are by including that following technical scheme is realized: first party
Face, the present invention provide a kind of tetra functional carboxyl epoxy curing agent, and molecular characterization is as follows:
Wherein, R is
Wherein, n is the integer of 25-45.
Preferably, the softening point temperature of the tetra functional carboxyl epoxy curing agent is 70-80 DEG C.The present invention obtains
Curing agent softening point temperature it is low, be conducive to curing agent and the mixing of epoxy resin, react.
Second aspect, the present invention provide a kind of side for preparing tetra functional carboxyl epoxy curing agent as described above
Method, comprising the following steps: trimellitic anhydride, polyetherdiol and catalyst are added in reactor, in atmosphere of inert gases, heating
It is reacted, is then cooled down, washed, filtered, the epoxy curing agent of carboxyl containing tetra functional is prepared.
Preferably, the molar ratio of the trimellitic anhydride and the polyetherdiol is (2-2.5): 1.
Preferably, the polyetherdiol is any one in polyethylene glycol, polypropylene glycol and polytetrahydrofuran ether glycol
Kind is a variety of.
Preferably, the molecular weight of the polyethylene glycol is 1500~2000；The molecular weight of the polypropylene glycol be 1500~
2500；The molecular weight of the polytetrahydrofuran ether glycol is 1000~3000.
Preferably, the catalyst is selected from one of ceric sulfate and 2- methylamino pyridine.
Preferably, the additive amount of the catalyst is the 0.1- of the trimellitic anhydride and the polyetherdiol quality sum
2%.
Preferably, the temperature of the heating reaction is 120-150 DEG C, and the time for heating reaction is 1-2h.
Preferably, it is washed, is washed 3-5 times using 50-70 DEG C of hot water.
In conclusion the present invention provides a kind of tetra functional carboxyl epoxy curing agent and preparation method thereof, the present invention
The utility model has the advantages that the tetra functional carboxyl epoxy curing agent tool that obtains of the present invention improves solid there are four degree of functionality carboxyl
Reactivity between agent and epoxy resin.Tetra functional carboxyl epoxy curing agent and epoxy resin mixed preparing are formed
One-component epoxy resin system, between one-component epoxy resin system and filler have good affinity, mixed effect with
And mobility, and then improve the final flow behavior of epoxy molding plastic, hot property and electrical characteristics.The present invention, which has, simplifies production
The advantages that operating procedure prevents the pollution of the environment, and improves product quality, adapts to modern large-scale industrial production.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Embodiment 1
0.07moL polyethylene glycol 2000,0.14moL trimellitic anhydride are weighed, 0.79g 2- methylamino pyridine is mixed,
Pour into N in three-necked flask2The lower 150 DEG C of oil baths of atmosphere are stirred to react 2h.Cooling is stood after the reaction was completed, with 60 DEG C of distillation washings three
Secondary acquired solution filters to obtain product to remove unreacted raw material.Through detecting, the softening point temperature of product is 90 DEG C.According to state
The acid value that family standard GB2895-82 " measurement of unsaturated polyurethane resin acid value " measures product is 112.0mg (KOH)/g.
Embodiment 2
0.07moL polypropylene glycol 2025,0.15moL trimellitic anhydride are weighed, 1.64g ceric sulfate is mixed, pours into
N in three-necked flask2The lower 135 DEG C of oil baths of atmosphere are stirred to react 1.5h.Cooling is stood after the reaction was completed, is washed four times with 60 DEG C of distillations
Acquired solution filters to obtain product to remove unreacted raw material.Through detecting, the softening point temperature of product is 74 DEG C.According to country
The acid value that standard GB2895-82 " measurement of unsaturated polyurethane resin acid value " measures product is 110.6mg (KOH)/g.
Embodiment 3
Weigh 0.07moL polytetrahydrofuran ether glycol 2000,0.17moL trimellitic anhydride, 3.31g 2- methylamino pyridine
It is mixed, pours into N in three-necked flask2The lower 120 DEG C of oil baths of atmosphere are stirred to react 1h.Cooling is stood after the reaction was completed, with 60 DEG C
Distillation four acquired solutions of washing filter to obtain product divided by unreacted raw material is removed.Through detecting, the softening point of product is 70 DEG C.
It is 113.6mg according to the acid value that standard GB/T 2895-82 " measurement of unsaturated polyurethane resin acid value " measures product
(KOH)/g。
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of tetra functional carboxyl epoxy curing agent, it is characterised in that: its molecular characterization is as follows:
Wherein, R is
Wherein, n is the integer of 25-45.
2. tetra functional carboxyl epoxy curing agent as described in claim 1, it is characterised in that: the tetra functional carboxyl
The softening point temperature of epoxy curing agent is 70-80 DEG C.
3. a kind of method for preparing tetra functional carboxyl epoxy curing agent as described in claim 1, it is characterised in that: packet
It includes following steps: trimellitic anhydride, polyetherdiol and catalyst is added in reactor, in atmosphere of inert gases, heating is carried out
Reaction, then cools down, and washes, and filters, the epoxy curing agent of carboxyl containing tetra functional is prepared.
4. the preparation method of tetra functional carboxyl epoxy curing agent as claimed in claim 3, it is characterised in that: described inclined
The molar ratio of benzenetricarboxylic anhydride and the polyetherdiol is (2-2.5): 1.
5. the preparation method of tetra functional carboxyl epoxy curing agent as claimed in claim 3, it is characterised in that: described poly-
Any one or more of ether glycol in polyethylene glycol, polypropylene glycol and polytetrahydrofuran ether glycol.
6. the preparation method of tetra functional carboxyl epoxy curing agent as claimed in claim 5, it is characterised in that: described poly-
The molecular weight of ethylene glycol is 1500~2000；The molecular weight of the polypropylene glycol is 1500~2500；The polytetrahydrofuran ether
The molecular weight of glycol is 1000~3000.
7. the preparation method of tetra functional carboxyl epoxy curing agent as claimed in claim 3, it is characterised in that: described to urge
Agent is selected from one of ceric sulfate and 2- methylamino pyridine.
8. the preparation method of tetra functional carboxyl epoxy curing agent as claimed in claim 3, it is characterised in that: described to urge
The additive amount of agent is the 0.1-2% of the trimellitic anhydride and the polyetherdiol quality sum.
9. the preparation method of tetra functional carboxyl epoxy curing agent as claimed in claim 3, it is characterised in that: described to add
The temperature of thermal response is 120-150 DEG C, and the time for heating reaction is 1-2h.
10. the preparation method of tetra functional carboxyl epoxy curing agent as claimed in claim 3, it is characterised in that: use
50-70 DEG C of hot water is washed, and is washed 3-5 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810956023.8A CN109180910A (en) | 2018-08-21 | 2018-08-21 | A kind of tetra functional carboxyl epoxy curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810956023.8A CN109180910A (en) | 2018-08-21 | 2018-08-21 | A kind of tetra functional carboxyl epoxy curing agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109180910A true CN109180910A (en) | 2019-01-11 |
Family
ID=64919396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN201810956023.8A Pending CN109180910A (en) | 2018-08-21 | 2018-08-21 | A kind of tetra functional carboxyl epoxy curing agent and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1019568A (en) * | 1963-07-09 | 1966-02-09 | Hysol Corp | Hardeners for epoxy resins and epoxy resins including such hardeners |
| US3639345A (en) * | 1969-11-28 | 1972-02-01 | Minnesota Mining & Mfg | Shelf-stable epoxy resin composition of epoxy resin and adduct of trimellitic anhydride and polyalkylene glycol |
| US4347343A (en) * | 1981-01-21 | 1982-08-31 | The Dow Chemical Company | Thickened vinyl ester resin compositions |
| CN1255525A (en) * | 1998-12-01 | 2000-06-07 | 中国科学院化学研究所 | Encapsulating epoxy resin material |
| CN101747491A (en) * | 2009-12-11 | 2010-06-23 | 上海新天和树脂有限公司 | Fast thickening vinyl ester resin as well as preparation method and application thereof |
-
2018
- 2018-08-21 CN CN201810956023.8A patent/CN109180910A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1019568A (en) * | 1963-07-09 | 1966-02-09 | Hysol Corp | Hardeners for epoxy resins and epoxy resins including such hardeners |
| US3639345A (en) * | 1969-11-28 | 1972-02-01 | Minnesota Mining & Mfg | Shelf-stable epoxy resin composition of epoxy resin and adduct of trimellitic anhydride and polyalkylene glycol |
| US4347343A (en) * | 1981-01-21 | 1982-08-31 | The Dow Chemical Company | Thickened vinyl ester resin compositions |
| CN1255525A (en) * | 1998-12-01 | 2000-06-07 | 中国科学院化学研究所 | Encapsulating epoxy resin material |
| CN101747491A (en) * | 2009-12-11 | 2010-06-23 | 上海新天和树脂有限公司 | Fast thickening vinyl ester resin as well as preparation method and application thereof |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190111 |
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| RJ01 | Rejection of invention patent application after publication |