CN102181043B - latent curing agent with multiple storage stability - Google Patents
latent curing agent with multiple storage stability Download PDFInfo
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- CN102181043B CN102181043B CN201110070328A CN201110070328A CN102181043B CN 102181043 B CN102181043 B CN 102181043B CN 201110070328 A CN201110070328 A CN 201110070328A CN 201110070328 A CN201110070328 A CN 201110070328A CN 102181043 B CN102181043 B CN 102181043B
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- curing agent
- latent curing
- epoxy
- dipping
- amine
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Abstract
The invention discloses a latent curing agent with multiple storage stability. The latent curing agent has the characteristics of being nontoxic and inodorous and belongs to an environment-friendly curing agent. The latent curing agent is characterized by containing organic acids, inorganic compounds, 4,4 '-diamino diphenyl methane and dibutyl phthalate. Aiming at solving the problems that epoxy or epoxy-modified unsaturated polyester has poor usage stability and needs timely replacement or addition when being used for trickle-dipping and roll-dipping solventless varnish, the invention provides an amine complex curing agent, wherein at certain temperature, an epoxy group can be opened by amine, zinc and epoxy can form an alkoxy compound, while the amine can be restrained below 40 DEG C, therefore, the usage stability at room temperature is sustained by multiple times and the latent curing agent has extensive application value in the occasions of trickle-dipping and roll-dipping electrical coils, and the like.
Description
Technical field
The present invention relates to a kind of solidifying agent, particularly relate to a kind of latent curing agent as epoxy resin and epoxide modified unsaturated polyester.
Background technology
Solidifying agent has another name called stiffening agent, ripening agent or set agent, is one type of material or mixture of promoting or controlling curing reaction.Resin solidification is through chemical reactions such as condensation, closed loop, addition or catalysis, makes thermosetting resin that irreversible change procedure take place, and curing is accomplished through adding curing (crosslinked) agent.Present epoxy or epoxide modified unsaturated polyester are used for dripping and soak, roll and soak solvent-free paint, and under the situation that single component is used, 40 ℃ of following life cycles were generally 24 hours, needed in time to change or add, and troublesome poeration is met Holiday, even can cause and scrap or stop work.Simultaneously common amine curing agent exists and causes and swash anxious heat release, and the shortcoming of electrical property and thermal property difference can not satisfy the needs of actual use.
Summary of the invention
Be used for dripping and soak, roll that to soak the solvent-free paint stability in use relatively poor in order to solve in the prior art epoxy or epoxide modified unsaturated polyester; The problem that needs replacing in time or add; The invention provides a kind of amine complex compound solidifying agent, at a certain temperature, amine can be opened epoxy group(ing); Zinc can form alkoxy compound with epoxy; But can restraining effect arranged to amine again below 40 ℃, thereby several times ground prolongs the stability in use under the room temperature, soak dripping of electric coil, roll and occasion such as soak and have use value more widely.
In order to address the above problem, the technical scheme that the present invention taked is:
A kind of latent curing agent with several times package stability is characterized in that: comprise naphthenic acid, zinc oxide, 4.4 ' MDA, Witcizer 300, its molar constituent is:
Naphthenic acid 1.0-2.5
Zinc oxide 1-1.5
4.4 ' MDA 0.2-0.4
Witcizer 300 0.2-0.4
Aforesaid a kind of latent curing agent with several times package stability is characterized in that: comprise naphthenic acid, zinc oxide, 4.4 ' MDA, Witcizer 300, its molar constituent is:
Naphthenic acid 2.5
Zinc oxide 1
4.4 ' MDA 0.2
Witcizer 300 0.4
A kind of latent curing agent with several times package stability is characterized in that: comprise sad, zinc sulfate, 4.4 ' MDA, Witcizer 300, also added sodium hydroxide, its molar constituent is:
Sad 1.0-2.5
Zinc sulfate 1-1.5
Sodium hydroxide 1.0-2.5
4.4 ' MDA 0.2-0.4
Witcizer 300 0.2-0.4
Aforesaid a kind of latent curing agent with several times package stability is characterized in that: comprise sad, zinc sulfate, 4.4 ' MDA, Witcizer 300, also added sodium hydroxide, its molar constituent is:
Sad 2.5
Zinc sulfate 1.5
Sodium hydroxide 2.5
4.4 ' MDA 0.2
Witcizer 300 0.4
The invention has the beneficial effects as follows:
1, solidifying agent of the present invention is a kind of amine complex compound solidifying agent; After solidifying agent decomposes at a certain temperature; To the curing of epoxy resin, solidifying agent plays a major role, and amine hardener plays a driving role; Therefore the sharp anxious heat release that does not have common amine curing agent to cause, the shortcoming of electrical property and thermal property difference.Below 40 ℃, main solidifying agent and amine synthesize the complex compound state, can play stabilization again to amine curing agent, and therefore, life cycle obtains the prolongation of several times ground under the room temperature.
2, solidifying agent of the present invention is a kind of amine complex compound solidifying agent, at a certain temperature, still has amine solidified characteristics, and effect is following:
The temperature gel time
120 ℃＜2 minutes
110 ℃＜5 minutes
100 ℃＜15 minutes
90 ℃＜30 minutes
3, solidifying agent of the present invention is an amine complex compound solidifying agent, and this solidifying agent has stabilization to amine curing agent again in certain temperature range:
Temperature is not coagulated the change time
60 ℃ 2 days
50 ℃ 3 days
40 ℃ >=4 days
30 ℃ >=10 days
25 ℃ >=30 days
Solidifying agent of the present invention is used for dripping when soaking, rolling the epoxy resin dipping solvent-free paint, and the single component life cycle can reach 1 month below 25 ℃, and two components have the package stability of half a year, are very easy to use.
4, remaining hydroxyl and carboxyl has coupling in solidifying agent of the present invention and the unsaturated polyester resin; With unsaturated polyester good consistency is arranged; This solidifying agent is again the good solidifying agent of epoxy resin simultaneously, therefore, and both can be separately as curing agent for epoxy resin; Can be used as the co-cured agent of epoxy and unsaturated polyester again, thereby enlarged the range of application of these two kinds of resins.
5, the nontoxic odorless of solidifying agent of the present invention, with epoxy resin at 120 ℃, 0.5-1 hour is promptly curable, volatile matter during curing≤1% is a kind of epoxy type solidifying agent.
Embodiment
To combine specific embodiment below, specify embodiment of the present invention:
Embodiment 1
Carry out proportioning by following molar constituent:
Naphthenic acid 2.5
Zinc oxide 1
4.4 ' MDA 0.2
Witcizer 300 0.4
Be warming up to 120 ℃-130 ℃, react transparent, left standstill layering 0.5-1 hour to solution; Remove upper water, vacuumize, remove unreacted matters, wash 2-4 time; Detect whether have free zinc oxide, vacuum hydro-extraction again gets brown transparent thick liquid; Zinc content>=14%, acid number≤1mgKOH ∕ g dissolves in acetone entirely.
Embodiment 2
Carry out proportioning by following molar constituent:
Sad 2.5
Zinc sulfate 1.5
Sodium hydroxide 2.5
4.4 ' MDA 0.2
Witcizer 300 0.4
Sodium hydroxide adds with dripping method, after dropwising, rises to 80 ℃ of insulations 1 hour, adds zinc sulfate and 4.4 ' MDA then, rises to 120 ℃-130 ℃; React transparent to solution, layering removes lower layer of water, vacuumizes; Remove educt, wash 4-5 time, detect whether have the free sulfate ion, vacuum is drawn water again; Get brown transparent liquid, zinc content>=14%, acid number≤1mgKOH ∕ g dissolves in acetone entirely.
Embodiment 3
Composition (wt%)
E44 or cyD-128 100
Solidifying agent 8-10
Vinylbenzene (or VT) 40
Stirring below 40 ℃, 100 ℃, coagulate change time≤20 minute, 120 ℃ were cured 0.5 hour, and sample is transparent, toughness solid, compressive strength>=22KV/mm, 96 hours gels not.
Embodiment 4
Composition (wt%)
E44 or cyD-128 50
191 unsaturated polyesters 50
Solidifying agent 8-10
Vinylbenzene (or VT) 50
Stirring below 40 ℃, 100 ℃ of following gel time≤15 minute, 120 ℃ to cure after 0.5 hour sample transparent, toughness solid, compressive strength>=20KV/mm.
More than show and described ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain by appending claims and equivalent circle thereof.
Claims (1)
1. latent curing agent with several times package stability is characterized in that: comprise naphthenic acid, zinc oxide, 4,4 '-MDA, Witcizer 300, its molar constituent is:
Naphthenic acid 1.0-2.5
Zinc oxide 1-1.5
4,4 '-MDA 0.2-0.4
Witcizer 300 0.2-0.4.
2, a kind of latent curing agent with several times package stability according to claim 1 is characterized in that: comprise naphthenic acid, zinc oxide, 4,4 '-MDA, Witcizer 300, its molar constituent is:
Naphthenic acid 2.5
Zinc oxide 1
4,4 '-MDA 0.2
Witcizer 300 0.4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110070328A CN102181043B (en) | 2011-03-23 | 2011-03-23 | latent curing agent with multiple storage stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110070328A CN102181043B (en) | 2011-03-23 | 2011-03-23 | latent curing agent with multiple storage stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102181043A CN102181043A (en) | 2011-09-14 |
| CN102181043B true CN102181043B (en) | 2012-10-24 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110070328A Active CN102181043B (en) | 2011-03-23 | 2011-03-23 | latent curing agent with multiple storage stability |
Country Status (1)
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| CN (1) | CN102181043B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786663A (en) * | 2012-08-28 | 2012-11-21 | 中国船舶重工集团公司第七一二研究所 | Epoxy resin latent curing agent, preparation method thereof and method for preparing insulated paint by using epoxy resin latent curing agent |
| WO2014157175A1 (en) * | 2013-03-29 | 2014-10-02 | ナミックス株式会社 | Resin composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056887A (en) * | 1990-05-28 | 1991-12-11 | 无锡市化工研究设计院 | The preparation of transparent solf seal adhesive with epoxy double component |
-
2011
- 2011-03-23 CN CN201110070328A patent/CN102181043B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056887A (en) * | 1990-05-28 | 1991-12-11 | 无锡市化工研究设计院 | The preparation of transparent solf seal adhesive with epoxy double component |
Non-Patent Citations (1)
| Title |
|---|
| 赵永红等.氟金云母填充环氧树脂复合材料研究.《西安交通大学学报》.2002,(第07期),正文第748-751页. * |
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| CN102181043A (en) | 2011-09-14 |
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Owner name: WUJIANG GOODE EIS SHARE CO., LTD. Free format text: FORMER OWNER: WUJIANG GOODE EIS CO., LTD. Effective date: 20120208 |
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Effective date of registration: 20120208 Address after: 215211, Jiangsu Wujiang Fen Lake Economic Development Zone, Fen Lake Road, 558, science and Technology Pioneer Park Applicant after: Wujiang Goode EIS Share Co., Ltd. Address before: 215211 science and Technology Pioneer Park, 558 Fen Lake Road, Fen Lake Economic Development Zone, Suzhou, Wujiang, Jiangsu Applicant before: Wujiang Goode EIS Share Co., Ltd. |
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Owner name: GUDE ELECTRIC MATERIAL SYSTEM (SUZHOU) CO., LTD. Free format text: FORMER NAME: WUJIANG GOODE EIS CO., LTD. |
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Address after: 215214, No. 88 Fen Yang Road, Fen Hu hi tech Zone, Suzhou, Jiangsu, Wujiang Patentee after: Goode EIS (Suzhou) Corp., Ltd. Address before: 215211, science and Technology Pioneer Park, 558 Fen Lake Road, Fen Lake Economic Development Zone, Jiangsu, Wujiang Patentee before: Wujiang Goode EIS Share Co., Ltd. |