CN103435781A - Epoxy resin curing agent, and preparation method and application of epoxy resin curing agent - Google Patents
Epoxy resin curing agent, and preparation method and application of epoxy resin curing agent Download PDFInfo
- Publication number
- CN103435781A CN103435781A CN2013103287314A CN201310328731A CN103435781A CN 103435781 A CN103435781 A CN 103435781A CN 2013103287314 A CN2013103287314 A CN 2013103287314A CN 201310328731 A CN201310328731 A CN 201310328731A CN 103435781 A CN103435781 A CN 103435781A
- Authority
- CN
- China
- Prior art keywords
- curing agent
- epoxy resin
- epoxy curing
- polyamine
- preparation
- 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.)
- Granted
Links
Abstract
The invention provides an epoxy resin curing agent which is prepared by polyamine, a mercaptan acid compound and amino polyether. The invention further provides a preparation method and an application of the epoxy resin curing agent. The epoxy resin curing agent is simple in preparation method and low in cost, and has the advantages of low-temperature curing, good toughening effect, simplicity in preparation, environmental protection and the like.
Description
Technical field
The invention belongs to building material field, particularly a kind of low temperature and good epoxy curing agent of toughening effect and preparation method thereof of being applicable to, also relate to the application of this solidifying agent in preparing epoxy resin cured product.
Background technology
Epoxy resin cured product have cohesive force strong, can ambient cure, cure shrinkage is little, mechanical property is high and the characteristics such as excellent anti-corrosion performance, therefore as sizing agent, coating, injection material etc., is widely used in the various fields such as building, machinery, electronics.But the epoxide resin material low-temperature curing is difficult and large these two shortcomings of fragility, become the greatest problem of restriction epoxide resin material application.
Epoxy resin cured product, in existing application, usually adopts and adds the method for curing catalyst to realize its low-temperature curing, adopts and adds toughner or realize the toughness reinforcing of epoxy-resin systems by the method for polyamide-based solidifying agent.Yet epoxy-based material can show all the more fragility under cold condition, had a strong impact on use safety and the life-span of epoxies material under the cold condition.Therefore, how to realize low-temperature curing and an efficient toughness reinforcing large difficult point that becomes epoxide resin material research, current research only is confined to use curing catalyst and toughner to solve this problem simultaneously, has the poor shortcoming of toughner consistency under cold condition.If therefore can realize low-temperature curing and efficient toughness reinforcing unification, will greatly expand the range of application of epoxide resin material, solve actual engineering roadblock.
Summary of the invention
Goal of the invention: the first purpose of the present invention is to provide a kind of low-temperature curing and good epoxy curing agent of toughening effect and preparation method thereof of being applicable to.
What the second purpose of the present invention was to provide above-mentioned epoxy curing agent is preparing the application of epoxy resin cured product.
Technical scheme: a kind of epoxy curing agent provided by the invention, by polyamine, mercaptan acid compounds and amino-polyether, made.
Wherein, described polyamine is selected from one or more in polyethylene polyamine compounds, polynary aliphatic cyclic amine compounds, excellent ground, described polyamine be selected from diethylenetriamine, triethylene tetramine, tetraethylene pentamine, isophorone diamine, the Meng alkane diamines and two (4-aminocyclohexyl) methane in one or more.
Wherein, one or more in described mercaptan acid compounds selected from mercapto acetic acid and thiohydracrylic acid.
Wherein, described amino-polyether is selected from one or more in the amino-polyether that molecular weight is 150～5000.
Wherein, described polyamine and mercaptan acid compounds mol ratio are 1:(0.2～0.5), the mass ratio of described polyamine and mercaptan acid compounds total mass and amino-polyether is 1:(0.2～0.5).
The present invention also provides the preparation method of above-mentioned epoxy curing agent, comprises the following steps:
(1) polyamine and the reaction of mercaptan acid compounds, obtain amidated sulfhydryl modified compound;
(2) after amidated sulfhydryl modified compound and amino-polyether mix, obtain.
Wherein, in step (1), temperature of reaction is 160-200 ℃, and the reaction times is 3-6h.
The present invention also provides the application of above-mentioned epoxy curing agent in preparing epoxy resin cured product.This epoxy curing agent can be applied in the preparation of the functional type epoxy resin cured products such as epoxy structural rubber, epoxy mortar, epoxy protective paint.During practical application, the stoichiometric reacted with epoxy resin according to the number calculating of amine active hydrogen is then tested to determine best proportioning in the scope of theoretical proportioning ± 10%.
Beneficial effect: epoxy curing agent preparation method provided by the invention is simple, with low cost, have low-temperature curing, toughening effect good, prepare the plurality of advantages such as simple and easy and environmental friendliness.
The applicant finds by great many of experiments, sulfhydryl compound has and promotes preferably curing effect under cold condition, therefore, epoxy curing agent of the present invention utilizes the above-mentioned characteristic of sulfhydryl compound, employing contain the group that can react with amino as the sulfhydryl compound of carboxyl as the epoxy curing agent raw material, realize that itself and organic amine carry out chemical bonding, thereby prepare the modified amine curing agent that contains sulfydryl, realize the low-temperature curing of epoxy resin.
The applicant finds by great many of experiments, amino-polyether has submissive longer polyether chain, after epoxy resin generation curing reaction, can effectively reduce the cross-linking density of curable epoxide thing, and the cured article structure rigidity descends, therefore can carry out the curable epoxide thing effectively toughness reinforcing.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition, after having read content of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
The preparation of epoxy curing agent comprises the following steps:
(1) polyamine and mercaptan acid compounds are measured to weighing according to certain molar ratio, first add polyamine in being furnished with the flask of stirring, then add excessive silica-gel drier in reaction flask, be warming up to 100 ℃, drip the mercaptan acid compounds, dripped off in 30 minutes, be warming up to 160～200 ℃ of reactions 3～6 hours after dripping off, after removing silica-gel drier after filtration, obtain amidated sulfhydryl modified compound;
(2) after amidated sulfhydryl modified compound and amino-polyether are mixed in reactor, stirring at normal temperature 20-40min, obtain.
Wherein, in step (1), reaction conditions is in Table 1.
The reaction conditions of table 1 step (1)
Wherein, in step (2), reaction conditions is in Table 2.
The reaction conditions of table 2 step (2)
Embodiment 2
The preparation of epoxy resin cured product:
Use prepared 7 kinds of solidifying agent, commercially available phenol aldehyde modified T31 solidifying agent (Changsha chemical industry low-temperature curing special use), diethylenetriamine (DETA) and the isophorone diamine (IPDA) of embodiment 1 to be mixed with epoxy resin cured product with E51 epoxy resin according to the optimum response proportioning respectively.
Test respectively its surface drying time, tensile strength, elongation, tension Young's modulus and steel under cold condition-steel stretching slip resistance.
Testing method: the epoxy resin cured product performance is according to GB50367-2006 " concrete structure reinforcement design specifications ", GB/T2567-2008 " casting resin method for testing performance ", the relevant regulations in the standards such as GB/T7124-2008 " mensuration of sizing agent tensile shear strength " is carried out.
The results are shown in Table 3.
The performance of the curable epoxide thing that table 3 is used solidifying agent of the present invention to prepare
Annotate: moulding, maintenance and test are all at 5 ℃.
The performance test results by table 3 can find, 7 kinds of prepared solidifying agent of the present invention all show excellent low-temperature curing and the toughness reinforcing effect of low temperature.With commercially available low temperature curing agent T31, compare, its set time and tensile strength are suitable, but the elongation of the material of use solidifying agent of the present invention is large, the tension Young's modulus is less, the prepared solidifying agent of this explanation the present invention is compared commercially available low temperature curing agent and is had suitable low-temperature curing performance, but the low temperature toughening effect obviously is better than commercially available prod; With the unmodified organic amine contrast such as diethylenetriamine and isophorone diamine, its low-temperature curing and low temperature toughening effect are outstanding.Owing to being rich in the functional type groups such as amide group, hydroxyl in epoxy curing agent of the present invention, cured article after itself and epoxy resin react has the adhesive property stronger with inorganic substrate, the low temperature shearing resistance data of upper table show, the prepared solidifying agent of the present invention under cold condition to improving the adhesive property successful of curable epoxide thing.
Claims (8)
1. an epoxy curing agent, is characterized in that: by polyamine, mercaptan acid compounds and amino-polyether, made.
2. a kind of epoxy curing agent according to claim 1, it is characterized in that: described polyamine is selected from one or more in polyethylene polyamine compounds, polynary aliphatic cyclic amine compounds.
3. a kind of epoxy curing agent according to claim 1, is characterized in that: one or more in described mercaptan acid compounds selected from mercapto acetic acid and thiohydracrylic acid.
4. a kind of epoxy curing agent according to claim 1, it is characterized in that: described amino-polyether is selected from one or more in the amino-polyether that molecular weight is 150～5000.
5. a kind of epoxy curing agent according to claim 1, it is characterized in that: described polyamine and mercaptan acid compounds mol ratio are 1:(0.2～0.5), the mass ratio of described polyamine and mercaptan acid compounds total mass and amino-polyether is 1:(0.2～0.5).
6. the preparation method of an epoxy curing agent is characterized in that: comprise the following steps:
(1) polyamine and the reaction of mercaptan acid compounds, obtain amidated sulfhydryl modified amine compound;
(2) after amidated sulfhydryl modified amine compound and amino-polyether mix, obtain.
7. the preparation method of a kind of epoxy curing agent according to claim 6, it is characterized in that: in step (1), temperature of reaction is 160-200 ℃, and the reaction times is 3-6h.
8. the application of the described epoxy curing agent of claim 1-5 any one in preparing epoxy resin cured product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310328731.4A CN103435781B (en) | 2013-07-31 | 2013-07-31 | A kind of epoxy curing agent and preparation method thereof and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310328731.4A CN103435781B (en) | 2013-07-31 | 2013-07-31 | A kind of epoxy curing agent and preparation method thereof and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103435781A true CN103435781A (en) | 2013-12-11 |
| CN103435781B CN103435781B (en) | 2016-05-11 |
Family
ID=49689508
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310328731.4A Active CN103435781B (en) | 2013-07-31 | 2013-07-31 | A kind of epoxy curing agent and preparation method thereof and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103435781B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837798A (en) * | 2015-01-14 | 2016-08-10 | 中国科学院宁波材料技术与工程研究所 | Latent polythiol curing agent, and synthetic method and application of latent polythiol curing agent |
| CN107383366A (en) * | 2016-09-21 | 2017-11-24 | 东莞市舜天实业有限公司 | Polyamide Epoxy curing agent |
| CN108676148A (en) * | 2018-06-07 | 2018-10-19 | 安徽匠星联创新材料科技有限公司 | A kind of epoxy curing agent and preparation method thereof applied to porous pavement material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040935A (en) * | 2010-12-21 | 2011-05-04 | 同济大学 | Weak-exothermic room temperature curing epoxy adhesive |
| CN102181042A (en) * | 2011-04-06 | 2011-09-14 | 无锡贝拉克新材料科技有限公司 | Method for preparing epoxy resin curing agent |
| JP2012122012A (en) * | 2010-12-09 | 2012-06-28 | Showa Denko Kk | Epoxy resin curing agent and epoxy resin composition |
-
2013
- 2013-07-31 CN CN201310328731.4A patent/CN103435781B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012122012A (en) * | 2010-12-09 | 2012-06-28 | Showa Denko Kk | Epoxy resin curing agent and epoxy resin composition |
| CN102040935A (en) * | 2010-12-21 | 2011-05-04 | 同济大学 | Weak-exothermic room temperature curing epoxy adhesive |
| CN102181042A (en) * | 2011-04-06 | 2011-09-14 | 无锡贝拉克新材料科技有限公司 | Method for preparing epoxy resin curing agent |
Non-Patent Citations (2)
| Title |
|---|
| 李楚新等: ""水性环氧树脂固化剂研究进展"", 《热固性树脂》 * |
| 钟震等: "低放热室温固化环氧胶粘剂的制备及其性能研究", 《热固性树脂》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837798A (en) * | 2015-01-14 | 2016-08-10 | 中国科学院宁波材料技术与工程研究所 | Latent polythiol curing agent, and synthetic method and application of latent polythiol curing agent |
| CN105837798B (en) * | 2015-01-14 | 2018-02-13 | 中国科学院宁波材料技术与工程研究所 | Resting form polythiol curing agent, its synthetic method and application |
| CN107383366A (en) * | 2016-09-21 | 2017-11-24 | 东莞市舜天实业有限公司 | Polyamide Epoxy curing agent |
| CN108676148A (en) * | 2018-06-07 | 2018-10-19 | 安徽匠星联创新材料科技有限公司 | A kind of epoxy curing agent and preparation method thereof applied to porous pavement material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103435781B (en) | 2016-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103408726B (en) | A kind of toughened epoxy resin solidifying agent and preparation method thereof and application | |
| CN102875057B (en) | High-strength quick-curing epoxy mortar and preparation method thereof | |
| CN103980463B (en) | A kind of epoxy resin solvent-free low-temperature solidified agent and preparation method thereof and application | |
| CN102307846B (en) | Curable composition based on epoxy resins and hetero-poly-cyclic polyamines | |
| US10017614B2 (en) | Epoxy-resin composition for fiber-matrix semifinished products | |
| AU2014292018A1 (en) | Use of an epoxide amine-based multicomponent mortar composition | |
| CN102105440A (en) | Mixtures of amines having guanidine derivatives | |
| WO2013142750A3 (en) | Crash-durable adhesive with enhanced stress durability | |
| AU2017375406A1 (en) | Epoxy resin adhesive with high compressive strength | |
| US11542363B2 (en) | Multicomponent epoxide resin composition and curing agent component therefor | |
| CN104725604A (en) | Waterborne curing agent and preparation method thereof | |
| Zhou et al. | Epoxy adhesive with high underwater adhesion and stability based on low viscosity modified Mannich bases | |
| CN103435781A (en) | Epoxy resin curing agent, and preparation method and application of epoxy resin curing agent | |
| JP2019525975A (en) | Room temperature ionic liquid curing agent | |
| CN106083607B (en) | A kind of N, N ' are alkylated methyl cyclohexane diamines and preparation method | |
| CN105348492A (en) | Low temperature super fast-drying cardanol modified amine epoxy curing agent and preparation method thereof | |
| CN106995525A (en) | Daiamid epoxy curing agent and preparation method that a kind of thiocarbamide is modified | |
| CN102827351A (en) | Curing agent of epoxy resin and synthesis method thereof | |
| CN103374320B (en) | Method for toughening and curing epoxy resin adhesive by using amino-terminated liquid nitrile rubber | |
| CN102153731A (en) | Room temperature curing heat-resistant epoxy curing agent | |
| CN103764711B (en) | Polymer and polymer composition | |
| CN103524716B (en) | A kind of ketoimine and preparation method thereof | |
| CN104087057B (en) | A kind of low temperature curing agent composition for epoxy anticorrosion coating | |
| CN103911116A (en) | Adhesive for tile or steel brick | |
| CN104031242A (en) | Flexible epoxy curing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU SUBOTE NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: BOTE NEW MATERIAL CO., LTD., JIANGSU Effective date: 20140609 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 211103 NANJING, JIANGSU PROVINCE TO: 210008 NANJING, JIANGSU PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20140609 Address after: 210008 No. 12 West Beijing Road, Jiangsu, Nanjing Applicant after: Jiangsu Subute New Materials Co., Ltd. Applicant after: Nanjing Bote Building Materials Co., Ltd. Address before: 211103 No. 12 West Beijing Road, Jiangsu, Nanjing Applicant before: Jiangsu Bote New Materials Co., Ltd. Applicant before: Jiangsu Subute New Materials Co., Ltd. Applicant before: Jiangsu Provincial Architectural Science Institute Ltd. Applicant before: Nanjing Bote Building Materials Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210707 Address after: No. 118, Liquan Road, Chunhua street, Jiangning District, Nanjing City, Jiangsu Province, 210000 Patentee after: JIANGSU SUBOTE NEW MATERIALS Co.,Ltd. Patentee after: Jiangsu Fengcai building materials (Group) Co.,Ltd. Patentee after: JIANGSU BOTE NEW MATERIALS Co.,Ltd. Address before: 210008 No. 12 West Beijing Road, Jiangsu, Nanjing Patentee before: JIANGSU SUBOTE NEW MATERIALS Co.,Ltd. Patentee before: JIANGSU BOTE NEW MATERIALS Co.,Ltd. |
|
| TR01 | Transfer of patent right |