CN1111186C - Single-component thermosetting epoxy resin system - Google Patents
Single-component thermosetting epoxy resin system Download PDFInfo
- Publication number
- CN1111186C CN1111186C CN99100591A CN99100591A CN1111186C CN 1111186 C CN1111186 C CN 1111186C CN 99100591 A CN99100591 A CN 99100591A CN 99100591 A CN99100591 A CN 99100591A CN 1111186 C CN1111186 C CN 1111186C
- Authority
- CN
- China
- Prior art keywords
- onium
- resin system
- iodine
- catalyst
- 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.)
- Expired - Lifetime
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Abstract
The present invention relates to single-component thermosetting epoxy resin system which can be stored at room temperature for a long time and is expressed as the following chemical formulas: R1-I<1+>-R. A<1->, R'1-onium-R'3. A<1-> and R1-onium-CH2-onium-R2 which are disclosed in the specification. A catalyst mainly containing onium salts is added to epoxy resin, and an active hydrogen supplier is used as a synergistic catalyst, wherein the onium salts are mainly iodine onium salts or sulphur onium salts, and the structure of the iodine onium salt is expressed as a general formula of R1-I<1+>-R. A<1->. The structure of the sulphur onium salts is expressed as a general formula (1), the structure of the synergistic catalyst is expressed as a general formula (2), a main catalyst accounts for 1 to 10 wt% of the total weight, and the ratio of the main catalyst to the synergistic catalyst is (1:2) to (2:1). The present invention can be stored at room temperature for more than one year and is suitable for technologies, such as composite material fluid forming prepreg laminating, electronic material embedding, etc. due to the single component.
Description
The present invention relates to the single-component thermosetting epoxy resin system that a class at room temperature can be long time stored.
Epoxy-resin systems is made up of Resins, epoxy and solidifying agent usually.Solidifying agent comprises amine, anhydrides and latent curing agent etc., though conventional its cured article of epoxy-resin systems has good adhesive property and chemical resistance, but the applicable craft cycle of resin system is shorter, have only a few hours storage period at room temperature, thereby can not satisfy its transportation and requirements such as technological operation preferably, have only the requirement of they being taked could satisfy after some refrigeration measures its technological operation.If add an amount of promotor in resin after, though its curing cycle shortens to some extent, solidification value decreases, the also further thereupon variation of its room temperature storage.If adopt two component forms to store, use more inconvenient, in addition some product is the Resins, epoxy of material prepreg (as be used to prepare) that can not store with two component forms.Therefore, done number of research projects at the reactive behavior of shelf characteric that improves resin and raising resin both at home and abroad, Japanese Patent JP57-192428 has provided the compound system catalytic amine cured epoxy with three alkane acid amide boron and pyrocatechol; United States Patent (USP) U.S.P4101459 uses methylene fluoride sulfonate catalytic amine cured epoxy; U.S.P4447586 then makes catalyzer with cupric fluoborate; And U.S.P5134239 adopted a class the compound of πDian Zi receptor as catalyzer, though the technology that these patents provide can make the room temperature storage performance of resin system increase, its also only at 20～30 days room temperature storage phase.
The objective of the invention is, the room temperature storage performance that solve the heat reactive resin system is to satisfy the requirement to epoxy-resin single-component technology of matrix material, tackiness agent and electronics embedding and packaged material.
Technical solution of the present invention is to add the Primary Catalysts salt (salt compounded of iodine or sulfosalt) of 1～10% (wt) of resin system gross weight in Resins, epoxy, 0.5～5% synergistic catalyst active hydrogen supply body; Wherein Resins, epoxy can be following type:
(1) glycidyl ether epoxy;
(2) glycidyl ester epoxy;
(3) alicyclic ring epoxy;
(4) aliphatic epoxy.
Primary Catalysts salt is mainly salt compounded of iodine or sulfosalt; The general structure of salt compounded of iodine is: R
3-I
+-R
4A
R
3Be one of following group:
R
4Be one of following group:
The general structure of sulfosalt is:
R '
1, R '
2, R '
3Be respectively one of following group:
Negative ion A
-Be one of following structure: S
bF
6 -, A
3F
6 -, PF
6 -, BF
4 -The general structure that synergistic catalyst---active hydrogen is supplied with body is:
R
1Be one of following group :-CH
3,-CH
2CH
3,-CH
2CH
2CH
3Deng
R
2Be one of following group :-CH
3, OCH
3, OCH
2CH
3Deng
The proportional range of Primary Catalysts and synergistic catalyst is: 1: 2～2: 1.
Advantage of the present invention is, owing in Resins, epoxy, use Primary Catalysts to be salt, synergistic catalyst is that active hydrogen is supplied with body, make resin at room temperature reach storage period more than 1 year, and owing to be single-component, so its transportation and technological operation are all convenient and simple, saved production cost, simplified production technique, and this resinoid can make the resin of single-component low viscosity long storage, thereby be convenient to be used for the composite liquid forming technique.
Embodiment:
1. choose 97 parts of E54 epoxies, 2 parts of phenylbenzene iodine hexafluoro antimonates and 1.5 parts of methyl ethyl diketones mix, and are heated to 50～70 ℃ of stirrings and promptly get the homogeneous resin system in 5 minutes.
2. choose 97 parts of TDE85 Resins, epoxy, 2 parts of phenylbenzene iodine hexafluoro antimonates and 1.5 parts of methyl ethyl diketones mix, and are heated to 50～70 ℃ of stirrings and promptly get the homogeneous resin system in 5 minutes.
3. poly-97 part 400
#Epoxy, 2 parts of phenylbenzene iodine hexafluoro antimonates, 1.5 parts of methyl ethyl diketones mix post-heating to 50～70 a ℃ stirring and promptly got the homogeneous resin system in 5 minutes.
4. be equipped with Primary Catalysts and the synergistic catalyst with amount, epoxy is replaced into 97 parts of aliphatic epoxy B-63 and obtains the homogeneous resin system to operate with last identical operations method with embodiment 3.
5. get 97 parts of E54 epoxies, 2 parts of triphenyl sulphur hexafluoro antimonates, 1.5 parts of methyl ethyl diketones mix and are heated to 50～70 ℃, stir 5 minutes, promptly get the homogeneous resin system.
6. get 97 parts of E54 epoxies, 2 parts of 2-hydroxyl-tetradecyl phenylate base phenyl-iodide hexafluoro hydrochlorates
, 1.5 parts of methyl ethyl diketones are mixed and heated to 50～70 ℃ and stirred 5 minutes, promptly get the homogeneous resin system.
7. the synergistic catalyst methyl ethyl diketone among the embodiment 1 is replaced to methyl aceto acetate, other is constant, promptly gets the resin system of same quality.
Claims (2)
1. the single-component thermosetting epoxy resin system of being made up of Resins, epoxy and catalyzer is characterized in that, catalyzer comprises Primary Catalysts salt compounded of iodine or sulfosalt and synergistic catalyst active hydrogen supply body:
R
1Be one of following group :-CH
3,-CH
2CH
3,-CH
2CH
2CH
3R
2Be one of following group :-CH
3,-OCH
3,-OCH
2CH
3The content of Primary Catalysts accounts for 1～10% (wt) of resin system gross weight, and the ratio of Primary Catalysts and synergistic catalyst is 1: 2～2: 1.
2. single-component thermosetting epoxy resin system according to claim 1 is characterized in that, Primary Catalysts is salt compounded of iodine or sulfosalt; The general structure of salt compounded of iodine is: R
3-I
+-R
4A
-, R
3And R
4Be one of following group:
The general structure of sulfosalt is:
R
1, R
2And R
3Be one of following group:
In salt compounded of iodine and the sulfosalt, negative ion A
-Be one of following structure: S
bF
6 -, A
SF
6 -, PF
6 -, BF
4 -
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99100591A CN1111186C (en) | 1999-02-05 | 1999-02-05 | Single-component thermosetting epoxy resin system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99100591A CN1111186C (en) | 1999-02-05 | 1999-02-05 | Single-component thermosetting epoxy resin system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1262289A CN1262289A (en) | 2000-08-09 |
| CN1111186C true CN1111186C (en) | 2003-06-11 |
Family
ID=5270086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99100591A Expired - Lifetime CN1111186C (en) | 1999-02-05 | 1999-02-05 | Single-component thermosetting epoxy resin system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1111186C (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4404355A (en) * | 1980-10-08 | 1983-09-13 | Ciba-Geigy Corporation | Heat curable epoxy resin compositions |
| US4842800A (en) * | 1987-10-01 | 1989-06-27 | General Electric Company | Method of encapsulating electronic devices |
| US5037861A (en) * | 1989-08-09 | 1991-08-06 | General Electric Company | Novel highly reactive silicon-containing epoxides |
| US5086124A (en) * | 1990-07-05 | 1992-02-04 | General Electric Company | High heat distortion temperature epoxy siloxane/organic epoxy compositions |
| US5319024A (en) * | 1990-04-19 | 1994-06-07 | Nippon Oil And Fats Company, Limited | Thermosetting compositions, thermal latent hydroxyl compounds, thermal latent thiol compounds and methods of preparation thereof |
| DE19612746A1 (en) * | 1995-03-31 | 1996-10-02 | Mazda Motor | Single component coating compsn. for automobile finishes |
-
1999
- 1999-02-05 CN CN99100591A patent/CN1111186C/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4404355A (en) * | 1980-10-08 | 1983-09-13 | Ciba-Geigy Corporation | Heat curable epoxy resin compositions |
| US4842800A (en) * | 1987-10-01 | 1989-06-27 | General Electric Company | Method of encapsulating electronic devices |
| US5037861A (en) * | 1989-08-09 | 1991-08-06 | General Electric Company | Novel highly reactive silicon-containing epoxides |
| US5319024A (en) * | 1990-04-19 | 1994-06-07 | Nippon Oil And Fats Company, Limited | Thermosetting compositions, thermal latent hydroxyl compounds, thermal latent thiol compounds and methods of preparation thereof |
| US5086124A (en) * | 1990-07-05 | 1992-02-04 | General Electric Company | High heat distortion temperature epoxy siloxane/organic epoxy compositions |
| DE19612746A1 (en) * | 1995-03-31 | 1996-10-02 | Mazda Motor | Single component coating compsn. for automobile finishes |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1262289A (en) | 2000-08-09 |
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Legal Events
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|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: BEIJING AVIATION MATERIAL INST., CHINA AVIATION IN Free format text: FORMER NAME: BEIJING AVIATION MATERIAL INST. Owner name: BEIJING INSTITUTE OF AERONAUTICAL MATERIALS, CHINA Free format text: FORMER NAME: BEIJING AVIATION MATERIAL INST., CHINA AVIATION INDUSTRY NO.1 GROUP CORP. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 100095 mailbox 81, Beijing City Patentee after: AVIC BEIJING INSTITUTE OF AERONAUTICAL MATERIALS Address before: 100095 mailbox 81, Beijing City Patentee before: Beijing Institute of aeronautical materials, China aviation industry first Group Corporation Address after: 100095 mailbox 81, Beijing City Patentee after: Beijing Institute of aeronautical materials, China aviation industry first Group Corporation Address before: 100095 mailbox 81, Beijing City Patentee before: Beijing Institute of Aeronautical Materials |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20030611 |