CN103435781B - A kind of epoxy curing agent and preparation method thereof and application - Google Patents
A kind of epoxy curing agent and preparation method thereof and application Download PDFInfo
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- CN103435781B CN103435781B CN201310328731.4A CN201310328731A CN103435781B CN 103435781 B CN103435781 B CN 103435781B CN 201310328731 A CN201310328731 A CN 201310328731A CN 103435781 B CN103435781 B CN 103435781B
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Abstract
A kind of epoxy curing agent provided by the invention, is made up of polyamine, mercaptan acid compounds and amino-polyether. Preparation method and the application of this epoxy curing agent are also provided. This epoxy curing agent preparation method is simple, with low cost, have low-temperature setting, toughening effect good, prepare the plurality of advantages such as simple and easy and environmental friendliness.
Description
Technical field
The invention belongs to building material field, particularly a kind of low temperature and good epoxy resin of toughening effect of being applicable toCuring agent and preparation method thereof, also relates to this curing agent in the application of preparing in epoxy resin cured product.
Background technology
Epoxy resin cured product have cohesive force strong, can normal temperature cure, cure shrinkage is little, mechanical property is high and corrosion-resistantThe features such as excellent performance, are therefore widely used in building, machinery, electronics as adhesive, coating, grouting material etc.Etc. various fields. But epoxide resin material low-temperature setting is difficult and large these two shortcomings of fragility, becomes restriction epoxy resinThe greatest problem of material application.
Epoxy resin cured product, in existing application, conventionally adopts and adds the method for curing accelerator to realize its low temperatureSolidify, adopt and add flexibilizer or realize the toughness reinforcing of epoxy-resin systems by the method for polyamide-based curing agent. SoAnd epoxy-based material can show all the more fragility under cryogenic conditions, have a strong impact on epoxies material under cryogenic conditionsUse safety and life-span. Therefore, how to realize low-temperature setting and an efficient toughness reinforcing disaster that becomes epoxide resin material researchPoint, current research is only confined to use curing accelerator and flexibilizer to solve this problem simultaneously, has low temperature barThe poor shortcoming of flexibilizer compatibility under part. If therefore can realize low-temperature setting and efficient toughness reinforcing unification, will greatly expandThe range of application of epoxide resin material, solves actual engineering roadblock.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide a kind of low-temperature setting and good epoxy resin of toughening effect of being applicable toCuring agent and preparation method thereof.
What the second object 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 aminoPolyethers is made.
Wherein, described polyamine is selected from one or more in polyethylene polyamine compounds, polynary aliphatic cyclic amine compounds,Excellent ground, described polyamine is selected from diethylenetriamine, triethylene tetramine, TEPA, IPD, Meng alkane twoOne or more in amine and two (4-aminocyclohexyl) methane.
Wherein, one or more in described mercaptan acid compounds selected from mercapto acetic acid and mercaptopropionic acid.
Wherein, to be selected from molecular weight be one or more in 150～5000 amino-polyether to described amino-polyether.
Wherein, described polyamine and mercaptan acid compounds mol ratio are 1:(0.2～0.5), described polyamine and sulfydryl acidsThe mass ratio of compound gross 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, to obtain final product.
Wherein, in step (1), reaction temperature is 160-200 DEG C, and the reaction time is 3-6h.
The present invention also provides above-mentioned epoxy curing agent in the application of preparing in epoxy resin cured product. This epoxy resinCuring agent can be applied to the preparation of the functional form epoxy resin cured products such as epoxy structural rubber, epoxy resin mortar, epoxy protective paintIn. When practical application, calculate the stoichiometric with epoxy resin reaction according to the number of amine reactive hydrogen, then join in theoryTest to determine best proportioning than in ± 10% scope.
Beneficial effect: epoxy curing agent preparation method provided by the invention is simple, with low cost, have low-temperature setting,Toughening effect is good, prepare the plurality of advantages such as simple and easy and environmental friendliness.
Applicant finds by great many of experiments, and sulfhydryl compound has the curing effect of good promotion under cryogenic conditions,Therefore, epoxy curing agent of the present invention utilizes the above-mentioned characteristic of sulfhydryl compound, adopts and contains and can occur anti-with aminoThe group of answering is if the sulfhydryl compound of carboxyl is as epoxy curing agent raw material, realizes it and organic amine carries out chemical bondClose, thereby prepare the modified amine curing agent that contains sulfydryl, realize the low-temperature setting of epoxy resin.
Applicant finds by great many of experiments, and amino-polyether has submissive longer polyether chain, occurs to solidify with epoxy resinAfter reaction, can effectively reduce the crosslink density of curable epoxide thing, and the decline of solidfied material structural rigidity, therefore canCurable epoxide thing is carried out effectively toughness reinforcing.
Detailed description of the invention
Below in conjunction with detailed description of the invention, further set forth the present invention. Should be understood that these embodiment are only for illustrating thisInvention and be not used in and limit the scope of the invention. In addition should be understood that after having read content of the present invention this area skillArt personnel can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims equallyLimited range.
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, be furnished with the flask of stirringThe middle polyamine that first adds, then adds excessive silica-gel desiccant in reaction bulb, is warming up to 100 DEG C, drips mercaptan acidCompounds dripped off in 30 minutes, was warming up to 160～200 DEG C of reactions 3～6 hours after dripping off, and removed after filtration siliconAfter glue drier, 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 condition is in table 1.
The reaction condition of table 1 step (1)
Wherein, in step (2), reaction condition is in table 2.
The reaction condition of table 2 step (2)
Embodiment 2
The preparation of epoxy resin cured product:
Use prepared 7 kinds of curing agent, commercially available phenol aldehyde modified T31 curing agent (the Changsha chemical industry low-temperature setting of embodiment 1Special), diethylenetriamine (DETA) and IPD (IPDA) respectively with E51 epoxy resin according to the bestReaction ratio is mixed with epoxy resin cured product.
Test respectively its surface drying time, tensile strength, percentage elongation, tension elastic modelling quantity and steel-steel under cryogenic conditionsStretching shearing strength.
Method of testing: epoxy resin cured product performance is according to GB50367-2006 " concrete structure reinforcement design specification ",GB/T2567-2008 " casting resin method for testing performance ", GB/T7124-2008 " adhesive tensile shear strengthMensuration " etc. the relevant regulations in standard carry out.
The results are shown in Table 3.
Table 3 uses the performance of curable epoxide thing prepared by curing agent of the present invention
Note: moulding, maintenance and test are all at 5 DEG C.
The performance test results by table 3 can find, 7 kinds of prepared curing agent of the present invention all show excellent lowTemperature is solidified and the toughness reinforcing effect of low temperature. Compare with commercially available low temperature curing agent T31, its hardening time and tensile strength are suitable,But the percentage elongation of the material of use curing agent of the present invention is large, tension elastic modelling quantity is less, the present invention is prepared in this explanationCuring agent compare commercially available low temperature curing agent and there is suitable low-temperature setting performance, but low temperature toughening effect is obviously better thanCommercially available prod; With the unmodified organic amine contrast such as diethylenetriamine and IPD, its low-temperature setting and low temperature are toughness reinforcingRemarkably productive. Owing to being rich in the functional form such as amide groups, hydroxyl group in epoxy curing agent of the present invention, itself and epoxy are setSolidfied material after fat reacts has the adhesive property stronger with inorganic substrate, the low temperature shear strength tables of data of upper tableBright, the present invention is prepared curing agent adhesive property successful to raising curable epoxide thing under cryogenic conditions.
Claims (3)
1. an epoxy curing agent, is characterized in that: be made up of polyamine, mercaptan acid compounds and amino-polyether;
Wherein, described polyamine is selected from one or more in polyethylene polyamine compounds, polynary aliphatic cyclic amine compounds,One or more in described mercaptan acid compounds selected from mercapto acetic acid and mercaptopropionic acid, described amino-polyether is selected fromMolecular weight is one or more in 150～5000 amino-polyether; Described polyamine and mercaptan acid compounds moleThan being 1:(0.2～0.5), the mass ratio of described polyamine and mercaptan acid compounds gross mass and amino-polyether is 1:(0.2～0.5)；
The preparation of described epoxy curing agent, comprises the following steps: 160-200 DEG C of polyamine and mercaptan acid compounds are anti-Answer 3-6h, obtain amidated sulfhydryl modified amines; Amidated sulfhydryl modified amines and amino-polyether are mixedAfter even, to obtain final product.
2. a preparation method for epoxy curing agent claimed in claim 1, is characterized in that: comprise the following steps:
(1) 160-200 DEG C of reaction 3-6h of polyamine and mercaptan acid compounds, obtains amidated sulfhydryl modified amine compoundsThing;
(2) after amidated sulfhydryl modified amines and amino-polyether mix, to obtain final product.
3. epoxy curing agent claimed in claim 1 is in the application of preparing in epoxy resin cured product.
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| 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 |
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| CN102040935A (en) * | 2010-12-21 | 2011-05-04 | 同济大学 | Weak-exothermic room temperature curing epoxy adhesive |
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| JP2012122012A (en) * | 2010-12-09 | 2012-06-28 | Showa Denko Kk | Epoxy resin curing agent and epoxy resin composition |
| 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 |
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| 低放热室温固化环氧胶粘剂的制备及其性能研究;钟震等;《热固性树脂》;20110331;第26卷(第3期);第29-35页 * |
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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. |