CN1103349C - Epoxy resin composition flexibilized with liquid and hydroxyl rubber - Google Patents
Epoxy resin composition flexibilized with liquid and hydroxyl rubber Download PDFInfo
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- CN1103349C CN1103349C CN 99108080 CN99108080A CN1103349C CN 1103349 C CN1103349 C CN 1103349C CN 99108080 CN99108080 CN 99108080 CN 99108080 A CN99108080 A CN 99108080A CN 1103349 C CN1103349 C CN 1103349C
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- epoxy resin
- phosphoric acid
- acid ester
- organotin
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Abstract
The present invention relates to an epoxy resin composition toughened by liquid hydroxyl-terminated rubber, which comprises bisphenol A epoxy resin, organic tin-phosphoester condensate, liquid hydroxyl-terminated rubber and a solidifying agent, wherein the raw materials are mixed and solidified at 140 DEG C to be prepared into the epoxy resin composition. The solidified epoxy resin composition toughened by liquid hydroxyl-terminated rubber has the breaking energy of 689 j/m<2>, the bending strength of 137.4MPa and the bending modulus of 2.35 GPa; the vitrification temperature measured by DSC is 143.1 DEG C, and the toughening effect is obvious.
Description
The present invention relates to a kind of rubber toughened epoxy-resin systems of terminal hydroxy liquid that adopts.
Resins, epoxy is the thermosetting polymer with premium properties, is widely used in aspects such as coating, packaged material, sqtructural adhesive and matrices of composite material.But because they have very high cross-linking density, performance is more crisp usually, and toughness reinforcing is crucial.Epoxy resin toughened common method is to introduce rubber-like elastomerics, thermoplastics or rigid inorganic filler second phase.Nbr carboxyl terminal (CTBN) is the most frequently used toughner.
Terminal hydroxy liquid rubber has fabulous low temperature flexibility and good thermotolerance as end hydroxy polyether, the soft segment of doing polyurethane elastomer commonly used.End hydroxy polyether is mass-produced Industrial products, but the reactive behavior of hydroxyl is very low, can't be directly used in toughness reinforcing amine solidified Resins, epoxy.Therefore usually with polyethers do toughner must be earlier by react with hydroxyl be converted into carboxyl, amino isoreactivity group (Journalof Applied Polymer Science, 1999,72,427-434).
This breadboard patent application 98101525.5 discloses with the promotor of class organotin-phosphoric acid ester condenses as Resins, epoxy/polyamine system.We discover that further the above-mentioned condenses of different molecular weight can both promote the hydroxyl of polyethers and the reaction of epoxy group(ing) effectively.
The present invention has overcome in the prior art can't use terminal hydroxy liquid rubber, shortcoming as the direct toughness reinforcing amine solidified epoxy-resin systems of polyethers, a kind of direct use side liquid hydroxyl rubber is provided, and is the composition epoxy resin of promotor as toughner with organotin-phosphoric acid ester condenses as polyethers.
Epoxy resin toughened composition of the present invention comprises Resins, epoxy, amine curing agent, promotor organotin-phosphoric acid ester condenses and terminal hydroxy liquid rubber, its component and content following (weight part): Resins, epoxy: 100 organotins-phosphoric acid ester condenses: 0.1-10, be preferably 1-3 terminal hydroxy liquid rubber: 1-20, be preferably 2-10 solidifying agent: 1-60
Above-mentioned Resins, epoxy is the resin that contains two above epoxy group(ing) in the molecule, comprises bisphenol A type epoxy resin (as E51), novolac epoxy, polyprotonic acid glycidyl ester, amino polyfunctional epoxy resin and cycloaliphatic epoxy resin.They can use separately, also can several mixed with resin use.
The structural representation of above-mentioned organotin-phosphoric acid ester condenses is as follows:
Wherein, R
1, R
2Be respectively the alkyl that contains 1 to 18 carbon atom.This class condenses can pass through dialkyltin R
1 2SnO and alkyl phosphate (R
2O)
3The P=O reaction obtains.Tin content changes in 5% to 35% scope in condenses, is preferably 15% to 30%, is preferably 23% to 28%; Phosphorus content changes in 5% to 25% scope, and is better in 7% to 13% scope.The condenses molecular weight changes in 500 to 20000 scopes, and is better in 1000 to 10000 scopes.This class organotin-phosphoric acid ester condenses also can obtain by other organo-tin compound and phosphate compound reaction, some existing in the literature concrete report.As at Organometallics 1984,3, introduced the preparation method of a kind of organotin-phosphoric acid ester condenses in 426.
Above-mentioned terminal hydroxy liquid rubber comprises that molecular weight is end hydroxy polyether, hydroxyl telechelic polyester, terminal hydroxy group divinyl below 10000 etc.End hydroxy polyether is a molecular weight for the 300-3000 preferred molecular weight is hydroxy-terminated polytetrahydrofuran, terminal hydroxy group polypropylene glycol, terminal hydroxy group tetrahydrofuran (THF)-propylene oxide copolyether of 700-2000 etc.
Above-mentioned solidifying agent is an aromatic polyamine, as 4, and 4 '-two amido sulfobenzides (DDS), 4,4 '-two amido ditanes etc.The consumption of solidifying agent is usually by stoichiometry, also is amino in the solidifying agent and the epoxy group(ing) equimolar amount in the Resins, epoxy; According to requirement to condensate performance, but also nonstoichiometry of the amount of solidifying agent.
The adding of end hydroxy polyether significantly improves the fracture toughness property of system among the present invention, and less for other performance impact.See Table 1 for example.
Table 1
| The embodiment numbering | Energy-to-break (J/m 2) | Flexural strength (MPa) | Modulus in flexure (GPa) | Second-order transition temperature (DSC method) (℃) |
| 234 (contrasts) | 514 689 262 | 147.5 137.4 145.1 | 2.41 2.35 2.43 | 152.8 143.1 157.1 |
| 67 (contrasts) | 311 178 | 174.2 174.0 | 2.55 2.68 | 147.1 142.7 |
Further characteristics of the present invention are described below by embodiment.
Embodiment 1
Reaction under 240-260 ℃ obtains organotin-phosphoric acid ester condenses 1# with 50.0g Dibutyltin oxide and 107g tributyl phosphate, and its number-average molecular weight is 6400, and tin content is 23.9%, and phosphorus content is 10.9%.
With 100 parts of E51 Resins, epoxy, 1 part of organotin-phosphoric acid ester condenses 1#, 5 parts of molecular weight is that 1000 hydroxy-terminated polytetrahydrofuran mixes, add an amount of toluene as solvent, react 1h down at 100-120 ℃, the centrifugal a small amount of insolubles that generates in the solution of removing, drain after the toluene, add 32 parts of DDS again and mix, be cast in the mould after the deaeration under the vacuum.Solidify 4.5h down at 140 ℃.The energy-to-break of cured article is 371J/m
2, bending strength is 158.9MPa, and composite bending modulus is 2.58GPa, and the second-order transition temperature Tg that DSC records is 149.1 ℃.
Embodiment 2
With 100 parts of E51 Resins, epoxy, 1 part of organotin-phosphoric acid ester condenses 1#, 5 parts of molecular weight is that 2000 hydroxy-terminated polytetrahydrofuran mixes, add an amount of toluene as solvent, react 1h down at 100-120 ℃, the centrifugal a small amount of insolubles that generates in the solution of removing, drain after the toluene, add 32 parts of DDS again and mix, be cast in the mould after the deaeration under the vacuum.Solidify 4.5h down at 140 ℃.The energy-to-break of cured article is 514J/m
2, bending strength is 147.5MPa, and composite bending modulus is 2.41GPa, and the second-order transition temperature Tg that DSC records is 152.8 ℃.
Embodiment 3
With 100 parts of E51 Resins, epoxy, 1 part of organotin-phosphoric acid ester condenses 1#, 10 parts of molecular weight is that 700 hydroxy-terminated polytetrahydrofuran mixes, add an amount of toluene as solvent, react 1h down at 100-120 ℃, the centrifugal a small amount of insolubles that generates in the solution of removing, drain after the toluene, add 32 parts of DDS again and mix, be cast in the mould after the deaeration under the vacuum.Solidify 4.5h down at 140 ℃.The energy-to-break of cured article is 689J/m
2, bending strength is 137.4MPa, and composite bending modulus is 2.35GPa, and the second-order transition temperature Tg that DSC records is 143.1 ℃.
Embodiment 4 (contrast)
100 parts of E51 Resins, epoxy, 1 part of organotin-phosphoric acid ester condenses 1# are mixed, add an amount of toluene as solvent, stir 1h down at 100-120 ℃, the centrifugal a small amount of insolubles that generates in the solution of removing, drain after the toluene, add 32 parts of DDS again and mix, be cast in the mould after the deaeration under the vacuum.Solidify 4.5h down at 140 ℃.The energy-to-break of cured article is 262J/m
2, bending strength is 145.1MPa, and composite bending modulus is 2.43GPa, and the second-order transition temperature Tg that DSC records is 157.1 ℃.
Embodiment 5
Reaction under 140-220 ℃ obtains organotin-phosphoric acid ester condenses with 50.0g Dibutyltin oxide and 37.2g tributyl phosphate, be called organotin-phosphoric acid ester condenses 2# through behind the acetone recrystallization, its number-average molecular weight is 1400, and tin content is 27.2%, and phosphorus content is 7.24%.
With 100 parts of E51 Resins, epoxy, 2 parts of organotin-phosphoric acid ester condenses 2#, 2 parts of molecular weight is that 700 hydroxy-terminated polytetrahydrofuran mixes, and at 100-120 ℃ of reaction 1h down, adds 32 parts of DDS again to mix, and is cast in the mould after the deaeration under the vacuum.Solidify 4.5h down at 140 ℃.The energy-to-break of cured article is 287J/m
2, bending strength is 178.9MPa, and composite bending modulus is 2.65GPa, and the second-order transition temperature Tg that DSC records is 148.4 ℃.
Embodiment 6
With 100 parts of E51 Resins, epoxy, 2 parts of organotin-phosphoric acid ester condenses 2#, 2 parts of molecular weight is that 2000 hydroxy-terminated polytetrahydrofuran mixes, and at 100-120 ℃ of reaction 1h down, adds 32 parts of DDS again to mix, and is cast in the mould after the deaeration under the vacuum.Solidify 4.5h down at 140 ℃.The energy-to-break of cured article is 311J/m
2, bending strength is 174.2MPa, and composite bending modulus is 2.55GPa, and the second-order transition temperature Tg that DSC records is 147.1 ℃.
Embodiment 7 (contrast)
With 100 parts of E51 Resins, epoxy, 2 parts of organotin-phosphoric acid ester condenses 2#, 32 parts of DDS mix, and are cast in the mould after the deaeration under the vacuum.Solidify 4.5h down at 140 ℃.The energy-to-break of cured article is 178J/m
2, bending strength is 174.0MPa, and composite bending modulus is 2.68GPa, and the second-order transition temperature Tg that DSC records is 142.7 ℃.
Claims (3)
1. one kind is adopted the rubber toughened composition epoxy resin of terminal hydroxy liquid, it is characterized in that described composition epoxy resin comprises following component and content by weight: the molecular weight of bisphenol A type epoxy resin 100 organotins-phosphoric acid ester condenses 1-3 end hydroxy polyether 2-10 solidifying agent 32 described organotin-phosphoric acid ester condensess is 1400-6400, described terminal hydroxy liquid rubber is that molecular weight is the hydroxy-terminated polytetrahydrofuran of 700-2000, described solidifying agent is 4,4 '-two amido sulfobenzides.
2. composition epoxy resin according to claim 1 is characterized in that tin content is 23% to 28% in organotin-phosphoric acid ester condenses.
3. composition epoxy resin according to claim 1 is characterized in that phosphorus content is 7% to 13% in organotin-phosphoric acid ester condenses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99108080 CN1103349C (en) | 1999-06-11 | 1999-06-11 | Epoxy resin composition flexibilized with liquid and hydroxyl rubber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99108080 CN1103349C (en) | 1999-06-11 | 1999-06-11 | Epoxy resin composition flexibilized with liquid and hydroxyl rubber |
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|---|---|
| CN1277225A CN1277225A (en) | 2000-12-20 |
| CN1103349C true CN1103349C (en) | 2003-03-19 |
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| CN 99108080 Expired - Fee Related CN1103349C (en) | 1999-06-11 | 1999-06-11 | Epoxy resin composition flexibilized with liquid and hydroxyl rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| ATE421984T1 (en) * | 2004-04-02 | 2009-02-15 | Dow Global Technologies Inc | HEAT CURRENT RESINS TUGANGIZED WITH AMPHIPHILIC BLOCK COPOLYMER |
| US8796360B2 (en) | 2010-11-24 | 2014-08-05 | Malaxit | Epoxy-rubber composition for cured materials |
| CN102746615B (en) * | 2011-04-21 | 2016-10-05 | 咸阳天华电子科技有限公司 | High heat resistant type height insulating heat-conductive aluminum-based copper-clad plate glue composition and preparation technology |
| CN103666330B (en) * | 2013-11-22 | 2015-12-09 | 东营中一橡胶有限公司 | A kind ofly utilize the synthesis of fluid rubber and utilize it to prepare the method for tackiness agent |
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