CN105331314A - Weather-resistant epoxy glue as well as preparation method and applications thereof - Google Patents
Weather-resistant epoxy glue as well as preparation method and applications thereof Download PDFInfo
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- CN105331314A CN105331314A CN201510790535.8A CN201510790535A CN105331314A CN 105331314 A CN105331314 A CN 105331314A CN 201510790535 A CN201510790535 A CN 201510790535A CN 105331314 A CN105331314 A CN 105331314A
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Abstract
The invention discloses weather-resistant epoxy glue. The epoxy glue is prepared by mixing an epoxy resin main agent A and a curing agent B. The piperidylamine structure of a weather-resistant piperidylamine type light stabilizer is introduced into the epoxy structure of the main agent A with a chemical grafting method, the component A and the component B are mixed and cured, and an epoxy resin system with permanent weather resistance is formed. The manner that the light stabilizer is linked with the chemical method is more stable, migration of the micromolecular light stabilizer in the epoxy system can be substantially reduced, so that the weather resistance of a product can be improved, and the service life can be prolonged; in particular, the epoxy glue is applied to the food packaging field with higher requirements for weather resistance and micromolecule migration, the migration of the light stabilizer in the product is substantially reduced by the aid of the chemical grafting scheme, thus, the safety of food is improved, and human health is better guaranteed.
Description
Technical field
The present invention relates to a kind of weather resistant epoxy glue and its preparation method and application, belong to epoxy resin field.
Background technology
Epoxy resin has the performance such as machinery, mechanics, electricity of higher internal cohesive energy, acid-proof alkaline and excellence, make its by widely be used in the fields such as coating, sizing agent, electron pouring sealant and matrix material.
Require in the application in higher field in high-end coating, ornaments and electronics embedding etc. to color and luster, the transparency and weathering resistance etc., the bisphenol A-based resins (as E54, E51 and E44 etc.) used in conventional epoxies, its weather resisteant is poor, particularly in the process of outdoor application, be easy to xanthochromia even efflorescence occurs, this greatly reduces the aesthetic property of goods, then can reduce machinery and mechanical property, thus shorten the work-ing life of epoxy glue.
In order to solve the weathering resistance problem of epoxy resin, researchist has carried out large quantifier elimination.In general, three kinds of methods are mainly contained:
One is develop the alicyclic solidifying agent containing saturated structures, and result confirms that this method has certain effect, but due to the primary structure of epoxy be dihydroxyphenyl propane, therefore its weathering resistance still cannot meet service requirements;
Two is use to replace traditional bisphenol-A epoxy containing the alicyclic epoxy of saturated structures, but due to the former cost higher and limit its application in conventional epoxy field with the low reaction activity of amido;
Last method, be also most simple effective method, in epoxy formulations system, namely add weather-proof auxiliary agent as photostabilizer etc., this method is easy to operate, and cost is lower, successful, is the method for the raising epoxy weathering resistance of main flow in current formula system.
CN103382378A joins piperidinamines photostabilizer in epoxy adhesive system by the mode of physical mixed, result display light stablizer add the weathering resistance that can significantly improve epoxy adhesive system, extend work-ing life of goods.
CN101314704A describes the application of epoxy glue in stone skin patching, based on the high durable requirement of stone surface coating, optimize except having done some on formula composition, in its system, add the photostabilizer of about 1wt% simultaneously, make system have good light fastness aging, thus meet the application demand of downstream client.
Equally, also mention in CN10477777A and requiring high LED epoxy glue encapsulation field to weather-proof, greatly extended the work-ing life of LED by the method for physics interpolation photostabilizer, ensure that the LED transparency and colour stability for a long time.Also be all adopt similar method in CN101970568A and CN103013047A, achieve good weathering resistance requirement.
It should be noted that above-mentioned technology is all by weathering resistance auxiliary agent such as photostabilizer etc. is joined in epoxy systems by the mode of physical mixed, and realize its requirement to weathering resistance.But because small molecules photostabilizer is present in the three-dimensional crosslinking structure of epoxy with physics free state, therefore inevitably from epoxy systems to surface transport, then reduce weathering resistance and the work-ing life of epoxy glue, also there is the problem of migration toxicity simultaneously.Problems has more in the fields such as urethane to be mentioned, as all disclosed in CN200880020758 and CN200880020950 in polyurethane structural network, small molecules amines catalyst is the indispensable additive of system, but due to it for physics adds, be easy to move to polyurethane material surface, cause product to have larger irritating smell, have a strong impact on the use of human consumer.
For the problems referred to above, need to find a kind of effective means and move the problems such as the smell that brings and toxicity to solve additive in prior art etc., thus guarantee the weathering resistance of epoxy glue and longer work-ing life.
Summary of the invention
The object of the present invention is to provide a kind of Weather-resistant epoxy glue.By the method for chemical graft, piperidinamines photostabilizer is incorporated in epoxy cross-linking structure, achieve the even introducing of piperidine structure, the existence due to chemical bond avoids the migration of piperidinamines stablizer, thus improves the performance of the light aging resisting of epoxy glue.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of weather resistant epoxy glue, is prepared from by the raw material comprising following component:
Component A is epoxy resin host,
B component is solidifying agent;
Add piperidinamines photostabilizer in the preparation process of described component A, described piperidinamines photostabilizer is the piperidines containing primary amine groups, and its structure is as follows:
Wherein, described substituent R
1, R
2, R
3, R
4, R
5, R
6, R
7and R
8identical or different, be separately H, the alkyl of C1-C10, C atomicity are the alkoxyl group of 1-10, the cycloalkyl of C3-C6, the aromatic base/aralkyl of C6-C12, the amide group of C1-C10, the alkyl amine group of C1-C10, C atomicity are 1-10 alkoxyl group amido or amido, and described substituent R
1, R
2, R
3, R
4, R
5, R
6, R
7and R
8in have that a substituting group is the amide group of C1-C10, C1-C10 alkyl amine group, C atomicity are 1-10 alkoxyl group amido or amido at least;
Described piperidinamines photostabilizer be preferably in 4-amino piperidine amine, 4-amino-1-methyl piperidine amine, 4-amino-1-benzyl piepridine amine, 4-aminomethyl-1-(normal-butyl) piperylhydrazine and 2,2,6,6-tetramethyl piperidine amine one or more; Be more preferably in 4-aminomethyl-1-(normal-butyl) piperylhydrazine, 4-amino-1-benzyl piepridine amine and 2,2,6,6-tetramethyl piperidine amine one or more, more preferably 2,2,6,6-tetramethyl piperidine amine.
In the present invention, the mass ratio of described component A and B component is (0.5 ~ 10): 1, preferably (1 ~ 4): 1.
In the present invention, described component A is prepared from by the raw material comprising following component, based on following composition weight sum:
In the present invention, need in described component A preparation process to add and the piperidinamines photostabilizer of response type can carry out modification to epoxy resin, the modified epoxy of color inhibition can be obtained.
In the present invention, the epoxy resin in described component A epoxy resin host is the one or two or more in bisphenol A-type and bisphenol f type epoxy resin; Preferred oxirane value is 0.1 ~ 0.65, be the one or two or more in the epoxy resin bisphenol A-type of liquid and bisphenol f type epoxy resin under room temperature; Preferred bisphenol A type epoxy resin includes but not limited to the one or two or more in E-44, E-51 and E-54 etc., and preferred bisphenol f type epoxy resin includes but not limited to the one or two or more in CYDF-170, GEFR170, NPE-170, CYDF-180 and YDF190 etc.
In the present invention, the thinner in described component A epoxy resin host is one or more in reactive thinner and non-activated thinner; Preferred thinner is including but not limited to C12-C14 alkyl glycidyl ether, butylglycidyl ether, benzyl glycidyl ether, butanediol diglycidyl ether, 1, the one or two or more of 6-hexanediol diglycidyl ether, 1,2-cylohexanediol diglycidyl ether, polyethyleneglycol diglycidylether, trihydroxymethylpropanyltri diglycidyl ether, phenylcarbinol, phenylethyl alcohol, nonyl phenol, propylene carbonate, Viscoat 295, diisopropanol methyl ether, toluene and dimethylbenzene etc.
In the present invention, the oxidation inhibitor in described component A epoxy resin host is the one or two or more in hindered phenol and phosphorous acid ester, be preferably 168,626, PEPQ, 3019 and the one or two or more of TNPP.
In the present invention, the flow agent in described component A epoxy resin host is one or more in polyacrylic ester and modified organic silicon, be preferably 388,320, one or two or more in 358N and 392.
In the present invention, the defoamer in described component A epoxy resin host is one or more in polyacrylic ester and modified organic silicon, is preferably the one or two or more in BYK066N, BYKA530,6800,141 and 354.
The preparation method of the component A of weather resistant epoxy glue of the present invention, step is as follows:
1) respectively epoxy resin and thinner are added reactor, be warmed up to 70-80 DEG C, the add-on of epoxy resin and thinner is respectively the 10-50wt% of its total add-on;
2) add piperidinamines photostabilizer, reaction 1-2 hour, is cooled to 40-50 DEG C, adds remaining epoxy resin and thinner;
3) add oxidation inhibitor, flow agent and defoamer, continue reaction 1-2 hour, after leaving standstill, obtain component A.
In the present invention, described B component is modified amine curing agent, adopt containing the molecule of epoxy-functional, as bisphenol A epoxide resin and/or benzyl glycidyl ether etc. carry out modification to raw material amine, described raw material amine includes but not limited to one or more of polyetheramine and aliphatic cyclic amine; Described polyetheramine is preferably D230; Described aliphatic cyclic amine is preferably 1,3-cyclohexyldimethylamine, isophorone diamine, 4, one or two or more in 4 '-diamino-dicyclohexyl methane, diamino cyclohexane, diaminomethyl cyclohexyl methane and aminoethyl piperazine, be more preferably 1,3-cyclohexyldimethylamine, isophorone diamine and 4, one or two or more in 4 '-diamino-dicyclohexyl methane, more preferably isophorone diamine and/or 4,4 '-diamino-dicyclohexyl methane.The concrete preparation method of modified amine curing agent described in the present invention can refer to method disclosed in CN104151530A.
In the present invention, as preferred scheme, piperidinamines photostabilizer with 2,2,6,6-tetramethyl piperidine amine (being called for short tetramethyl piperidine amine) is example, be specially, the primary amine groups in described tetramethyl piperidine amine is can reactive group, reacted by the primary amine groups functional group of described piperylhydrazine and the epoxy-functional of epoxy resin, piperidine structure is introduced in epoxy molecule structure by the method for chemical graft; Then utilize amine curing agent and other epoxy-functionals to react and form cross-linked network structure, in the curable epoxide thing obtained, because chemical bond between epoxy resin and piperylhydrazine effectively can suppress the migration of piperylhydrazine, thus achieve the long-time light aging resisting property of epoxy glue resin system.
Given this, the present invention proposes the reactive behavior utilizing primary amine in piperidinamines photostabilizer structure and epoxy resin, by the graft reaction of primary amine groups and epoxy, piperylhydrazine structure in being reacted by chemical graft by piperidinamines photostabilizer is incorporated in epoxy construction, prepare the modified epoxy with light stability, all the other solidifying agent reaction subsequently forms cross-linked epoxy, achieves and has permanent weathering resistance and the cross-linked epoxy resin moved without small molecules photostabilizer piperidinamines compound.
In the present invention, in described preferred scheme, the reaction mechanism of tetramethyl piperidine amine and epoxy resin is as follows:
The present invention also provides the preparation method of described weather resistant epoxy glue goods:
Be (0.5 ~ 10) by mass ratio: 1, preferably (1 ~ 4): the component A of 1 and B component, mixing and stirring, deaeration, solidifies in carrier or mould.
In the present invention, adopt in the preparation process of described weather resistant epoxy glue goods and vacuumize or standing 5-50min deaeration, described solidification value is generally room temperature-120 DEG C
The present invention still further provides above-mentioned weather resistant epoxy glue sticks with glue the field such as agent, transparent composite purposes at high-end epoxide terrace, ornaments, transparent electron embedding, food.As high-end epoxide terrace, food stick with glue agent and requires higher to weathering resistance and molecular migration etc., ornaments, transparent electron embedding, transparent composite etc. require higher field to color inhibition, weathering resistance, the transparency etc.
Beneficial effect of the present invention is:
Using in the present invention can response type photostabilizer piperylhydrazine, is grafted in epoxy cross-linking system by the method for chemical graft, with traditional by compared with physical mixed addition manner method,
(1) effectively improve the weathering resistance of epoxy adhesive, extend the duration of service of epoxy resin product.
(2) structure of chemical graft access photostabilizer is more stable, effectively can suppress the migration of small molecules photostabilizer in epoxy systems, thus the weathering resistance of goods can be improved and its life-span, be especially applied to when needing the technique of heating or its goods to be in for a long time in middle hot environment.
(3) field in the food product pack being applied to weathering resistance, the method for chemical graft significantly can reduce the migration of photostabilizer, thus improves the security of food, better ensure that HUMAN HEALTH.
Embodiment
By specific embodiment, the present invention will be further described, and embodiment of the present invention just as to explanation of the present invention, is not used in and limits the scope of the invention.
Raw material information refers to table 1
Table 1 raw material information table
Hardness test standard is ASTMD2240
Embodiment 1
The preparation of color inhibition type epoxy ornaments:
Component A is prepared from by following component, and the weight part of each component is respectively:
In B component, each feed composition weight part is respectively:
1. the preparation of component A: 20 parts of epoxy resin E51 are dropped into after in reactor, add 2.5 parts of phenylcarbinol thinners, being warmed up to 70 DEG C stirs after 1 hour, add 4-aminomethyl-1-(normal-butyl) piperylhydrazine 0.1 part, reaction 1.5h, is cooled to 50 DEG C subsequently, adds each component of residue, stir after 1-2 hour, cooling discharge is packed;
2. the preparation of B component: by polyetheramine 230, isophorone diamine is put in reactor, and stir (5-10 minute), the mixed solution of slow dropping epoxy resin E51 and phenylcarbinol composition, after dropwising half an hour, mix and blend 2 hours, leaves standstill cooling discharge packaging;
3. get 3 parts of component A, 1 part of B component, mixing and stirring under room temperature, then plane coating or add in forming mould, 80 degrees Celsius of solidifications 2 ~ 4 hours, can obtain the epoxy adhesive goods that weathering resistance is good.
Gained epoxy glue ornaments Article Stiffness Determination 80 ~ 85D, UV-irradiation 24 hours is without obvious xanthochromia.
Embodiment 2
The preparation of the epoxy resin adhesive that low photostabilizer dissociates:
Component A is prepared from by following component, and the weight part of each component is respectively:
In B component, each feed composition weight part is respectively:
1. the preparation of component A: 34 parts of epoxy resin E51 are dropped in reactor, add 10 parts of CYDF-170,4 parts of phenylcarbinols more successively, be warmed up to 75 DEG C, add 2 parts of tetramethyl piperidine amine, stir after 1 hour, be cooled to 40 DEG C, add remaining E51 epoxy resin and benzyl glycidyl ether, oxidation inhibitor, defoamer, stir after 1-2 hour, cooling discharge is packed;
2. the preparation of B component: polyetheramine 230,1,3-cyclohexyldimethylamine is put in reactor, stir (5-10 minute), slowly drips the mixed solution of epoxy resin E51 and phenylcarbinol composition, after dropwising half an hour, mix and blend 2 hours, leaves standstill cooling discharge packaging;
3. get 2 parts of component A, 1 part of B component, mixing and stirring under room temperature, then froth in vacuum, pour into mould, ambient temperature curable 24 hours, can obtain the epoxy resin adhesive that low photostabilizer is free.
Through soxhlet extraction and gas chromatography test, proves without the piperylhydrazine small molecules dissociated in tackiness agent, and goods UV-irradiation 108 hours is without obvious xanthochromia.
Embodiment 3
The preparation of weather resistant transparent epoxy resin potting compound:
Component A is prepared from by following component, and the weight part of each component is respectively:
In B component, each feed composition weight part is respectively:
1. the preparation of component A: 8.3 parts of epoxy resin E51 are dropped in reactor, add 6 parts of phenylcarbinols and 1.0 parts of 4-amino-1-benzyl piepridine amine again, being warmed up to 70 DEG C stirs after 1 hour, be cooled to 50 DEG C, add remaining epoxy resin, phenylcarbinol and all the other benzyl glycidyl ethers, oxidation inhibitor, defoamers etc., stirred after 1-2 hour, and cooling discharge is packed;
2. the preparation of B component: by 4,4 '-diamino-dicyclohexyl methane, 1,3-cyclohexyldimethylamine is put in reactor, stir (5-10 minute), slowly drips the mixed solution of epoxy resin E51 and phenylcarbinol composition, after being added dropwise to complete half an hour, mix and blend, after 2 hours, leaves standstill cooling discharge packaging;
3. get 2 parts of component A, 1 part of B component, mixing and stirring under room temperature, then froth in vacuum, pour in the device needing embedding, self-vulcanizing 24 hours, the transparent potting compound that weathering resistance is good can be obtained.Resulting product hardness 80 ~ 85D, without obvious xanthochromia, 80 degrees Centigrade 108 hours were also without obvious xanthochromia in 76 hours for UV-irradiation.
Embodiment 4
The preparation of weather resistant transparent epoxy resin terrace
Component A is prepared from by following component, and the weight part of each component is respectively
In B component, the weight part of each feed composition is respectively:
4，4′-diaminodicyclohexylmethane 50 parts
Phenylcarbinol 45 parts
Epoxy resin E515 part
1. the preparation of component A: 30 parts of epoxy resin E51 are dropped in reactor, add phenylcarbinol 5 parts and tetramethyl piperidine amine 1.5 parts again, being warmed up to 70 DEG C stirs after 1 hour, be cooled to 50 DEG C, add remaining epoxy resin, phenylcarbinol, and oxidation inhibitor, defoamer etc., stir after 1-2 hour, cooling discharge is packed;
2. the preparation of B component: 4，4′-diaminodicyclohexylmethane is put in reactor, stir (5-10 minute), the mixed solution of slow dropping epoxy resin E51 and phenylcarbinol composition, after being added dropwise to complete half an hour, mix and blend, after 2 hours, leaves standstill cooling discharge packaging;
3. get 2 parts of component A, 1 part of B component, mixing and stirring under room temperature, then froth in vacuum, on the base materials such as coating and cement, room temperature or heating cure, can obtain the transparent epoxy terrace that weathering resistance is good.
Gained epoxide terrace hardness 80 ~ 85D, there is not efflorescence in 760 hours without obvious xanthochromia in 76 hours in the high and UV-irradiation of surfacing, glossiness.
Comparative example 1
Do not add piperidinamines photostabilizer in component A preparation process, other conditions are consistent with embodiment 4, and namely its goods occur obvious xanthochromia in 24 hours in UV-irradiation, within 240 hours, namely occur powder phenomenon-tion.
Comparative example 2
In component A preparation process, piperidinamines photostabilizer is replaced by two-2,2,6, the 6-tetramethyl piperidine alcohol esters of sebacic acid, other conditions are consistent with embodiment 4, and namely its goods occur obvious xanthochromia in 48 hours in UV-irradiation, within 400 hours, namely occur powder phenomenon-tion.
Claims (10)
1. a weather resistant epoxy glue, is prepared from by the raw material comprising following component:
Component A epoxy resin host,
B component solidifying agent;
Add piperidinamines photostabilizer in the preparation process of described component A, described piperidinamines photostabilizer is the piperidines containing primary amine groups, and its structure is as follows:
Wherein, described substituent R
1, R
2, R
3, R
4, R
5, R
6, R
7and R
8identical or different, be separately H, the alkyl of C1-C10, C atomicity are the alkoxyl group of 1-10, the cycloalkyl of C3-C6, the aromatic base/aralkyl of C6-C12, the amide group of C1-C10, the alkyl amine group of C1-C10, C atomicity are 1-10 alkoxyl group amido or amido, and described substituent R
1, R
2, R
3, R
4, R
5, R
6, R
7and R
8in have that a substituting group is the amide group of C1-C10, C1-C10 alkyl amine group, C atomicity are 1-10 alkoxyl group amido or amido at least;
Described piperidinamines photostabilizer be preferably in 4-amino piperidine amine, 4-amino-1-methyl piperidine amine, 4-amino-1-benzyl piepridine amine, 4-aminomethyl-1-(normal-butyl) piperylhydrazine and 2,2,6,6-tetramethyl piperidine amine one or more; Be more preferably in 4-aminomethyl-1-(normal-butyl) piperylhydrazine, 4-amino-1-benzyl piepridine amine and 2,2,6,6-tetramethyl piperidine amine one or more, more preferably 2,2,6,6-tetramethyl piperidine amine.
2. weather resistant epoxy glue as claimed in claim 1, it is characterized in that, described component A is prepared from by the raw material comprising following component, based on following composition weight sum:
3. weather resistant epoxy glue as claimed in claim 1 or 2, it is characterized in that, the preparation method of described component A, comprises following steps:
1) add in reactor by epoxy resin and thinner respectively, be warmed up to 70-80 DEG C, the add-on of epoxy resin and thinner is respectively the 10-50wt% of its total add-on;
2) add piperidinamines photostabilizer, reaction 1-2 hour, is cooled to 40-50 DEG C, adds remaining epoxy resin and thinner;
3) add oxidation inhibitor, flow agent and defoamer, continue reaction 1-2 hour, after leaving standstill, obtain component A.
4. weather resistant epoxy glue as claimed in claim 1, it is characterized in that, the mass ratio of described component A and B component is (0.5 ~ 10): 1, preferably (1 ~ 4): 1.
5. as claimed in claim 2 or claim 3 weather resistant epoxy glue, is characterized in that, described epoxy resin is one or more in bisphenol A type epoxy resin and bisphenol f type epoxy resin; Described bisphenol A type epoxy resin is preferably the one or two or more in E-44, E-51 and E-54; Bisphenol f type epoxy resin is preferably CYDF-170, GEFR170, one or two or more in NPEF-170 and CYDF-180.
6. weather resistant epoxy glue as claimed in claim 2 or claim 3, it is characterized in that, described thinner is the one or two or more in reactive thinner and non-activated thinner, described thinner is preferably C12-C14 alkyl glycidyl ether, butylglycidyl ether, benzyl glycidyl ether, butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, 1, 2-cylohexanediol diglycidyl ether, polyethyleneglycol diglycidylether, trihydroxymethylpropanyltri diglycidyl ether, phenylcarbinol, phenylethyl alcohol, nonyl phenol, propylene carbonate, Viscoat 295, diisopropanol methyl ether, the one or two or more of toluene and dimethylbenzene.
7. as claimed in claim 2 or claim 3 weather resistant epoxy, is characterized in that, described oxidation inhibitor is the one or two or more in hindered phenol and phosphite ester compound, be preferably 168,626, PEPQ, 3019 and TNPP in one or two or more; Described flow agent is the one or two or more in polyacrylic ester and modified organic silicon, preferably 388,320, one or two or more in 358N and 392; Described defoamer is the one or two or more in polyacrylic ester and modified organic silicon, the one or two or more in preferred BYK066N, BYKA530,6800,141 and 354.
8. weather resistant epoxy glue as claimed in claim 1, it is characterized in that, described B component is modified amine curing agent, and adopt the molecule containing epoxy-functional, preferred bisphenol A epoxide resin and/or benzyl glycidyl ether carry out modification to amine raw material; Described amine raw material is one or more of polyetheramine and aliphatic cyclic amine, and described polyetheramine is preferably D230; Described aliphatic cyclic amine is preferably 1,3-cyclohexyldimethylamine, isophorone diamine, 4, one or two or more in 4 '-diamino-dicyclohexyl methane, diamino cyclohexane, diaminomethyl cyclohexyl methane and aminoethyl piperazine, be more preferably 1,3-cyclohexyldimethylamine, isophorone diamine and 4, one or two or more in 4 '-diamino-dicyclohexyl methane, more preferably isophorone diamine and/or 4,4 '-diamino-dicyclohexyl methane.
9. the preparation method of the weather resistant epoxy glue goods according to any one of claim 1-8, step is as follows: be (0.5 ~ 10) by mass ratio: 1, preferably (1 ~ 4): the component A of 1 and B component, mixing and stirring, deaeration, solidifies in carrier or mould.
10. the weather resistant epoxy glue according to any one of claim 1-8 sticks with glue the purposes in agent and transparent composite at high-end epoxide terrace, ornaments, transparent electron embedding, food.
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