CN107964088A - A kind of hypotoxicity is modified the preparation method of ethylenediamine curing agent - Google Patents
A kind of hypotoxicity is modified the preparation method of ethylenediamine curing agent Download PDFInfo
- Publication number
- CN107964088A CN107964088A CN201610907456.5A CN201610907456A CN107964088A CN 107964088 A CN107964088 A CN 107964088A CN 201610907456 A CN201610907456 A CN 201610907456A CN 107964088 A CN107964088 A CN 107964088A
- Authority
- CN
- China
- Prior art keywords
- ethylenediamine
- curing agent
- modified
- preparation
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses the preparation method that a kind of hypotoxicity is modified ethylenediamine curing agent, this method is that the benzyl alcohol solution containing epoxy resin and/or epoxy active diluent is added dropwise in the benzyl alcohol solution containing ethylenediamine to be reacted, up to modified ethylenediamine curing agent, the modification ethylenediamine curing agent of preparation reduces volatility and hygroscopicity, eliminate the phenomenon that ethylenediamine emits white cigarette in atmosphere, so as to substantially reduce the toxicity of ethylenediamine, can be used individually or with curing agent of other material mixings as epoxy resin.
Description
Technical field
The present invention relates to a kind of preparation method of modified ethylenediamine curing agent, more particularly to a kind of epoxy resin is modified second
The preparation method of diamine curing agent, belongs to epoxy curing agent preparation field.
Background technology
Ethylenediamine is simplest diamines, is aliphatic diamine, molecular weight 60, active hydrogen equivalent weight 15, colourless liquid, makees
For epoxy curing agent in use, 6~8 parts of ethylenediamines of every 100 parts of normal resins, viscosity is low, can room temperature fast-curing, use
In bonding, cast, coating etc..
In recent years, increase with the demand of epoxy resin, the domestic demand to ethylenediamine product is also to increase sharply, this is mainly
Because ethylenediamine is excellent epoxy curing agent；And common epoxy curing agent.
But ethylenediamine is poisonous, volatility is big, and hygroscopicity is strong, formed in atmosphere white smog, tool severe corrosive,
Strong and stimulating, can cause human body to burn.Steam toxicity is very strong, has intense irritation to mucous membrane and skin.Contacting the product steam can draw
Rise conjunctivitis, bronchitis, pneumonia orPulmonary edema, and can occurContact dermatitis.Can have liver,Renal damage.Skin and eye are direct
Contacting its liquid can cause to burn.The product can causeOccupational asthma.Wrongly take or suck high concentration ethylenediamine steam can cause headache,
Dizzy, short of breath, Nausea and vomiting, asthmatic breathing, or even mortality poisoning occurs.
Therefore, ethylenediamine cannot be used alone as epoxy curing agent.
In order to reduce its volatility and toxicity, it is changed using phenols (such as phenol, anacardol) and formaldehyde mostly
Property, the volatility and toxicity of ethylenediamine all substantially reduce.But simultaneously as the addition of phenol and formaldehyde, amine, phenol, the reaction of aldehyde are endless
Entirely, in curing agent product there are the unhindered amina of more amount, free phenol, free aldehyde, often there are free phenol, trip in commercial product
The phenomenon exceeded from content of formaldehyde, so as to add new toxicity, free phenol and content of free aldehyde are excessive, are storing and are curing
Free phenol, free aldehyde can be permeated into air in journey, larger to man and nature environmental hazards.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the purpose of the invention is to provide a kind of increase of viscosity, volatility
The preparation method for the modification ethylenediamine curing agent that small, toxicity reduces.
In order to realize above-mentioned technical purpose, the present invention provides the preparation side that a kind of hypotoxicity is modified ethylenediamine curing agent
Method, this method are that the benzyl alcohol solution containing epoxy resin and/or epoxy active diluent is added dropwise to the phenmethylol containing ethylenediamine
In solution, reacted at a temperature of 60~70 DEG C, up to modified ethylenediamine curing agent.
Technical scheme, key is that employing epoxy resin is modified ethylenediamine, in ethylenediamine molecule
Upper access epoxy resin or small molecule epoxy active diluent, epoxy group and reacting ethylenediamine activity are high, and reaction is thorough, makes modification
The molecular weight increase of ethylenediamine, viscosity increase, volatility reduce, and toxicity reduces, and effect is far superior to existing phenols or formaldehyde
Modified effect of the class to ethylenediamine.
Preferable scheme, active hydrogen equivalent weight and the epoxy resin and the epoxide equivalent ratio of/epoxy active diluent of ethylenediamine
Example is 4~9.When equivalent proportion is less than 4, the modified firming agent viscosity of preparation is excessive, it is difficult to meets the requirement of curing agent, equivalent
During than more than 9, reacting ethylenediamine is incomplete, volatile generation white cigarette.
Preferable scheme, the benzyl alcohol solution containing epoxy resin and/or epoxy active diluent are added dropwise to containing ethylenediamine
After in benzyl alcohol solution, the mass percentage content of phenmethylol is 30~50% in whole solution system.Used in reaction process
Suitable phenmethylol is diluted reaction raw materials, makes reaction more steady, thorough, reduces modified firming agent viscosity, be conducive to
Obtain the high modification ethylenediamine curing agent product of homogeneous transparent degree；And phenmethylol can be used as later cured accelerating agent, improve
Solidfied material brittleness.
Preferable scheme, during dropwise addition：Below 80 DEG C, time for adding controls in 2~5h temperature control.
Preferable scheme, reaction time are 1~3h.
Preferable scheme, epoxy resin are less than the bisphenol A type epoxy resin and/or Bisphenol F of 250g/mol for epoxide equivalent
Type epoxy resin.The epoxy resin of low molecular weight can effectively adjust the molecular weight of modified firming agent, be conducive to improve its follow-up
Application effect.
Preferable scheme, the epoxy active diluent are monocyclic oxygen and/or bis-epoxy glycidol ether.
Technical scheme is most preferably used to be modified ethylenediamine using epoxy resin, wherein being less than with epoxide equivalent
The bisphenol A type epoxy resin and/or bisphenol f type epoxy resin modified effect of 250g/mol is optimal.
Compared with the prior art, the advantageous effects that technical solution of the present invention is brought：1) technical scheme uses
Nontoxic higher boiling phenmethylol makees solvent, while is carried out modification using epoxy resin or epoxy micromolecular compound to ethylenediamine and changed
Property, increase the molecular weight of ethylenediamine, reduce the active hydrogen content of ethylenediamine, so as to reduce volatility and hygroscopicity, eliminate
Ethylenediamine emits the phenomenon of white cigarette in atmosphere, so as to substantially reduce the toxicity of ethylenediamine, can be mixed individually or with other materials
Conjunction is used to be used as the curing agent of epoxy resin.2) preparation method of modification ethylenediamine curing agent of the invention it is easy to operate,
Flow is short, and process conditions are gentle, obtained product homogeneous transparent.
Embodiment
Following embodiments are intended to further illustrate the present invention, rather than the scope of the protection of limitation the claims in the present invention.
The bisphenol A type epoxy resin that epoxide equivalent is 186 is mixed in a certain ratio uniformly with phenmethylol, is weighed by formula
Ethylenediamine and phenmethylol are added with stirring, in the four-hole boiling flask of condensing unit, under nitrogen protection, epoxy resin and benzene first are added dropwise
The mixture of alcohol, control temperature are no more than 80 DEG C, and time for adding is controlled in 3h, are added dropwise and reaction 2h is maintained after 60-70 DEG C.
1 embodiment 1~3 of table and comparative example 1 and 2
As can be seen from the table, ethylenediamine and active hydrogen equivalent weight and ring containing epoxy resin and/or epoxy active diluent
Oxygen equivalent proportion has to meet appropriate scope, and when ratio is less than 4, because amount of resin is bigger, molecular weight of product is big, so
It is big to show viscosity；When ratio be more than 9 when because amount of resin is small or ethylenediamine amount is big, the molecular weight of product it is relatively small or
Say that remaining ethylenediamine is more, so volatilization forms white cigarette in air.
Claims (6)
1. a kind of hypotoxicity is modified the preparation method of ethylenediamine curing agent, it is characterised in that：Epoxy resin will be contained and/or epoxy is lived
The benzyl alcohol solution of property diluent is added dropwise in the benzyl alcohol solution containing ethylenediamine, is reacted at a temperature of 60~70 DEG C, is changed to obtain the final product
Property ethylenediamine curing agent.
2. hypotoxicity according to claim 1 is modified the preparation method of ethylenediamine curing agent, it is characterised in that：Ethylenediamine
The epoxide equivalent ratio of active hydrogen equivalent weight and epoxy resin and/or epoxy active diluent is 4~9.
3. hypotoxicity according to claim 1 is modified the preparation method of ethylenediamine curing agent, it is characterised in that：Containing asphalt mixtures modified by epoxy resin
After the benzyl alcohol solution of fat and/or epoxy active diluent is added dropwise in the benzyl alcohol solution containing ethylenediamine, whole solution system
The mass percentage content of middle phenmethylol is 30~50%.
4. being modified the preparation method of ethylenediamine curing agent according to claims 1 to 3 any one of them hypotoxicity, its feature exists
In：During dropwise addition：Below 80 DEG C, time for adding controls in 2~5h temperature control.
5. being modified the preparation method of ethylenediamine curing agent according to claims 1 to 3 any one of them hypotoxicity, its feature exists
In：Reaction time is 1~3h.
6. being modified the preparation method of ethylenediamine curing agent according to claims 1 to 3 any one of them hypotoxicity, its feature exists
In：The epoxy resin is less than the bisphenol A type epoxy resin and/or bisphenol f type epoxy resin of 250g/mol for epoxide equivalent；
The epoxy active diluent is monocyclic oxygen and/or bis-epoxy glycidol ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610907456.5A CN107964088A (en) | 2016-10-18 | 2016-10-18 | A kind of hypotoxicity is modified the preparation method of ethylenediamine curing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610907456.5A CN107964088A (en) | 2016-10-18 | 2016-10-18 | A kind of hypotoxicity is modified the preparation method of ethylenediamine curing agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107964088A true CN107964088A (en) | 2018-04-27 |
Family
ID=61996232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610907456.5A Pending CN107964088A (en) | 2016-10-18 | 2016-10-18 | A kind of hypotoxicity is modified the preparation method of ethylenediamine curing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107964088A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109504234A (en) * | 2018-11-11 | 2019-03-22 | 中海油常州涂料化工研究院有限公司 | A kind of chemicals-resistant epoxy inside liner coating and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460689A (en) * | 2003-05-16 | 2003-12-10 | 广州秀珀化工有限公司 | Modified alicyclic amine solidifying agent and its preparation method |
| CN1931889A (en) * | 2006-09-27 | 2007-03-21 | 蓝星化工新材料股份有限公司无锡树脂厂 | Modified solid imidazole curing agent and its modification process |
| CN103224612A (en) * | 2013-05-15 | 2013-07-31 | 程梦喜 | Solvent-free self-leveling epoxy resin curing agent and preparation method thereof |
| CN103224611A (en) * | 2013-05-15 | 2013-07-31 | 程梦喜 | Modified alicyclic amine curing agent and preparation method thereof |
-
2016
- 2016-10-18 CN CN201610907456.5A patent/CN107964088A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460689A (en) * | 2003-05-16 | 2003-12-10 | 广州秀珀化工有限公司 | Modified alicyclic amine solidifying agent and its preparation method |
| CN1931889A (en) * | 2006-09-27 | 2007-03-21 | 蓝星化工新材料股份有限公司无锡树脂厂 | Modified solid imidazole curing agent and its modification process |
| CN103224612A (en) * | 2013-05-15 | 2013-07-31 | 程梦喜 | Solvent-free self-leveling epoxy resin curing agent and preparation method thereof |
| CN103224611A (en) * | 2013-05-15 | 2013-07-31 | 程梦喜 | Modified alicyclic amine curing agent and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109504234A (en) * | 2018-11-11 | 2019-03-22 | 中海油常州涂料化工研究院有限公司 | A kind of chemicals-resistant epoxy inside liner coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103554438B (en) | Preparation method of modified epoxy hardener for reducing bleaching | |
| CN100569826C (en) | A kind of self-emulsifying type aqueous latex of epoxy hardener and preparation method thereof | |
| CN106987194A (en) | A kind of non-ion aqueous epoxy resin latex and nonionic waterborne epoxy curing agent and its preparation method and aqueous epoxy resins varnish | |
| CN105440232B (en) | A kind of preparation technology of water-soluble methyl-etherified melamine resin | |
| US9346911B2 (en) | Liquid accelerator composition for hardeners | |
| CN104479110B (en) | A kind of nonionic waterborne epoxy curing agent and preparation method thereof | |
| CN103228696A (en) | One component epoxy resin composition | |
| Liu | Phosphorous‐containing epoxy resins from a novel synthesis route | |
| CN105727494A (en) | Formaldehyde scavenging agent | |
| CN103642002A (en) | Epoxy resin composite curing agent capable of being flexibly blended | |
| EP2180012A1 (en) | Curable epoxy resin and dicyandiamide solution | |
| CN107502256A (en) | A kind of high grade of transparency, high rigidity, color inhibition epoxy joint trimming agent and its construction technology | |
| CN107828311A (en) | The preparation method of aqueous epoxide resin paint | |
| CN107964088A (en) | A kind of hypotoxicity is modified the preparation method of ethylenediamine curing agent | |
| GB774663A (en) | Polyglycidyl ethers of tetraphenols | |
| CN102666649A (en) | Epoxy resin compositions | |
| GB702143A (en) | Cold-hardening compositions containing phenol-formaldehyde condensation products, and a process for making such compositions | |
| CN106957409A (en) | A kind of aqueous epoxy resin curing agent | |
| CN105330822A (en) | Water-borne epoxy resin curing agent | |
| CN101319125B (en) | Type 5 aqueous epoxide resin paint and preparation method thereof | |
| GB972988A (en) | Epoxy resin compositions | |
| EP4240803A1 (en) | Lignin-based bonding resin | |
| US3546169A (en) | Curable compositions based on oxirane polyepoxides and liquid eutectic mixtures of o-tolylenediamine,m-tolylenediamine,and bis(aminophenyl)methane | |
| CN111849358A (en) | Environment-friendly negative ion zeolite surface coating agent and preparation method thereof | |
| CN106905904A (en) | Digestion resistant adhesive and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180427 |