CN102352025A - Preparation method of silica modified epoxy resin curing agent and varnish - Google Patents
Preparation method of silica modified epoxy resin curing agent and varnish Download PDFInfo
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- CN102352025A CN102352025A CN2011101930502A CN201110193050A CN102352025A CN 102352025 A CN102352025 A CN 102352025A CN 2011101930502 A CN2011101930502 A CN 2011101930502A CN 201110193050 A CN201110193050 A CN 201110193050A CN 102352025 A CN102352025 A CN 102352025A
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Abstract
The invention relates to a preparation method of a silica modified epoxy resin curing agent and a varnish, and provides a preparation method of a SiO2 modified epoxy resin curing agent and an epoxy varnish paint which has simple process and excellent performance. An end capping reaction carried out for the curing agent by a terminated compound is capable of minimizing the number of the contained active hydrogen bond, reducing the reactive activity of the curing agent, achieving the purpose of controlling the solidification speed and reducing the solidification contraction stress; the epoxy resin is taken as a chain extender of the curing agent so that the compatibility between the curing agent and epoxy resin is enhanced; the tensile strength, aging resistance of the epoxy resin solidified by the SiO2 modification curing agent are improved to a certain extent. The modified curing agent is mixed with epoxy resin, a solvent, an antifoaming agent, a plasticizer and the like under certain operation technological condition to obtain the viscous and transparent epoxy varnish paint with good water resistance, excellent stretching performance and high luster performance used for woodenware.
Description
Technical field
The present invention relates to top coat and application techniques field, particularly a kind of SiO
2Modified epoxy resin curing agent and varnish preparation method.
Background technology
Varnish colour is absolutely necessary for timber and metal.It can make it be able to resist the destruction of being caused because of humidity, radiation, biological degradation, mechanochemistry damage.The matrix that varnish colour is commonly used is an epoxy resin, and epoxy resin this as thermoplastic linear structure, be heated that the back solid resin can soften, fusion, become the thickness attitude; The viscosity of being heated liquid resin reduces.After having only the solidifying agent of adding, epoxy resin just can obtain practicality.Epoxy resin has good cohesiveness, wear resistance, electrical insulating property, resistant of high or low temperature, chemical proofing; Have simultaneously that sticking power is good, good mechanical performance and shrinking percentage is low, be prone to machine-shaping and advantage such as with low cost; But pure epoxy resin is tridimensional network after solidifying; Cross-linking density is high; Exist internal stress big with shortcomings such as quality is crisp firmly, resistance to cracking, shock resistance, humidity resistance difference and stripping strength are low, so to a great extent limit its application in some harsh and unforgiving environments.Owing to having particular structural, nano-silicon dioxide particle shows peculiar physics and chemical property; Like performances such as the mechanics of excellence, optics, electromagnetism, absorption; Nano silicon in the matrix material had both been inherited the good fillibility of general silica; Make matrix material have excellent more performance again, so nanometer SiO
2Can be used to prepare various resins, coating, support of the catalyst etc., is excellent strongthener.
Solidifying agent is an indispensable important component part in the epoxy resin Application Areas, and it is determining the physicals of cured product with epoxy resin.In numerous epoxy curing agents, lower aliphatic amine solidifying agent is used the most extensively, consumption is maximum.It has characteristics such as speed of response is fast, ambient temperature curable.But there is following defective in the fatty amine curing agent that directly uses: 1. relatively poor with the consistency of epoxy resin, each item performance that causes filming all descends to some extent; 2. in the lower aliphatic amine molecule, because of reactive hydrogen more, very fast with the epoxy resin cure speed of response, intense reaction just takes place under the room temperature, speed of response is wayward; 3. curing shrinkage internal stress is big, makes that coating is easy to crack, property is crisp; Above defective is even more serious under the warm condition.This makes epoxy coating be subjected to certain restriction in actual applications.
Summary of the invention
The objective of the invention is to the shortcoming to above-mentioned epoxy resin, propose that a kind of technology is simple, a kind of SiO of excellent property
2Modified epoxy resin curing agent and epoxy resin varnish preparation method for coating.
In the present invention, adopt end-caps that solidifying agent is carried out end capping, reduced the quantity of its contained active hydrogen bond, reduced the reactive behavior of solidifying agent, thereby reach the purpose of its curing speed of control, reduce curing shrinkage internal stress; With the chainextender of epoxy resin, improved the consistency between solidifying agent and the epoxy resin as solidifying agent; Through SiO
2Epoxy resin stretching intensity after modified firming agent solidifies; Stability to aging has all had raising to a certain degree; With the solidifying agent after the modification under certain operating procedure condition with mixing such as epoxy resin, solvent, skimmer, softening agent; Obtained a kind of thickness transparence, the woodenware with excellent water tolerance, excellent tensile properties and high gloss performance is used epoxy resin varnish coating.
The technical scheme of the present invention's employing is in order to achieve the above object:
A kind of method of silica modified epoxy curing agent, concrete steps are following:
1) in 10～20 parts of end-caps tertiary carbonic acid glycidyl esters, stirs 0.2～0.8 part of SiO of adding
2Ultrasonic 0.5～1h behind the powder;
2) in reaction kettle, add 5～15 parts of diethylenetriamines, when reaching 60～80 ℃ of preset temps, slowly add 10～20 parts of SiO while stirring
2Ester compound after the modification carries out end-blocking as end-capping reagent to solidifying agent;
3) dropwise the intensification of latter stage property, the intensification amplitude is 5 ℃/h, and heating up and carrying out the end capping time is 1～3h;
4) under mechanical stirring at the uniform velocity, add 1～5 part of YLENE and butanols gradually with organic mixed solvent of 7: 3 of mass ratio, the epoxy resin after the dissolving carries out chain extending reaction, adds afterreaction 1～3h, and organic solvent mixes with 2: 1 with epoxy resin; Can obtain the solidifying agent of modification after the cooling.
The solidifying agent of employing claim 1 prepares the method for epoxy resin varnish, and step is following:
1) with YLENE and butanols with 1～3 part of organic mixed solvent of 7: 3 of mass ratio, mix for 5～15 parts with epoxy resin, add 0.2～0.5 part of skimmer, 1～30 part of softening agent, mechanical stirring is even, obtains the heavy-gravity resin system;
2) get 5～20 parts of SiO that make
2Modified amine curing agent is the resin system that slowly adds 5～15 parts of step 1) under the 1000r/min in mechanical stirring speed;
3) continue to stir 30min, promptly obtain epoxy resin varnish.
Described epoxy resin is bisphenol A type epoxy resin.Described skimmer is fatty acid alkyl ester, ethylene oxide oligopolymer or methyl-silicone oil.Described softening agent is Witcizer 300 or DOP.
Described SiO
2Powder is: the nano-scale particle about particle diameter 50nm, and through the silane coupling agent processing.
Owing among the present invention, adopt end-caps that solidifying agent is carried out end capping, reduced the quantity of its contained active hydrogen bond, and then reached its curing speed of control; With the chainextender of epoxy resin, further improved the consistency between solidifying agent and the epoxy resin as solidifying agent; Through SiO
2Epoxy resin stretching intensity after modified firming agent solidifies; Stability to aging has all had raising to a certain degree; With the solidifying agent after the modification under certain operating procedure condition with mixing such as epoxy resin, solvent, skimmer, softening agent, obtained a kind of woodenware and used epoxy resin varnish coating with excellent water tolerance, excellent tensile properties and high gloss performance.
In Fig. 3, curve 1 is not for adding SiO
2Resin matrix to the transmittance of UV-light, curve 2 is for adding SiO
2After resin matrix to the transmittance of UV-light.Very significantly find out and add SiO
2After, the transmittance of UV-light has obviously and reduces, and nanometer SiO is described
2Particle has bridging effect to UV-light in modification is filmed, so just improved the photostabilization of paint film.
Description of drawings
Fig. 1: do not contain SiO
2Matrix show obvious feature of brittle Electronic Speculum figure;
Fig. 2: SiO
2Matrix after the modification has produced tiny crack Electronic Speculum figure;
Fig. 3: resin matrix is to the light transmittance curve of UV-light.
Embodiment
Embodiment 1:
(1) modification of epoxy hardener and preparation
1) in 15 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P), adds 0.2 part of nanometer SiO under the stirring
2Powder, and ultrasonic 30min;
2) in reaction kettle, add 10 parts of diethylenetriamines, when reaching 65 ℃ of preset temps, stirs slow adding 15 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P) on one side;
3) dropwise, carry out stage and heat up, the intensification amplitude is 5 ℃/h, and heating up and carrying out the end capping time is 2h;
4) under mechanical stirring at the uniform velocity, add 3 parts of epoxy resin with organic solvent dissolution gradually and carry out chain extending reaction, add afterreaction 2h, cooling can obtain the solidifying agent of blocking modification.
(2) preparation of epoxy resin varnish
1) organic solvent is 2 parts, mixes for 10 parts with epoxy resin, adds 0.4 part of ethylene oxide oligopolymer, 15 parts of DOPs, and mechanical stirring is even, obtains the heavy-gravity resin system;
2) getting 15 parts of modified amine curing agents that make, is slowly to add 10 parts of above-mentioned resin systems that make under the 1000r/min in mechanical stirring speed;
3) continue to stir 30min, promptly obtain epoxy resin varnish.
Result of implementation shows: add 0.2 part of nanometer SiO
2Powder, dispersion effect is better, and particle is particulate state and disperses in resin matrix, do not have obviously and reunite.
Embodiment 2:
(1) modification of epoxy hardener and preparation
1) in 15 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P), adds 0.4 part of nanometer SiO under the stirring
2Powder, and ultrasonic 30min;
2) in reaction kettle, add 10 parts of diethylenetriamines, when reaching 65 ℃ of preset temps, stirs slow adding 15 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P) on one side;
3) dropwise, carry out stage and heat up, the intensification amplitude is 5 ℃/h, and heating up and carrying out the end capping time is 2h;
4) under mechanical stirring at the uniform velocity, add 3 parts of epoxy resin with organic solvent dissolution gradually and carry out chain extending reaction, add afterreaction 2h, cooling can obtain the solidifying agent of blocking modification.
(2) preparation of epoxy resin varnish
1) organic solvent is 2 parts, mixes for 10 parts with epoxy resin, adds 0.4 part of ethylene oxide oligopolymer, 15 parts of DOPs, and mechanical stirring is even, obtains the heavy-gravity resin system;
2) getting 15 parts of modified amine curing agents that make, is slowly to add 10 parts of above-mentioned resin systems that make under the 1000r/min in mechanical stirring speed;
3) continue to stir 30min, promptly obtain epoxy resin varnish.
Result of implementation shows, adds 0.4 part of nanometer SiO
2Powder, dispersion effect is better, and stretching SEM figure presents very many tiny cracks, and intensity obviously improves, and the ultraviolet transparence declines to a great extent.
With do not contain SiO
2Matrix Fig. 1 of showing obvious feature of brittle compare; The matrix of Fig. 2 that embodiment 2 obtains has produced tiny crack, and tangible ductile rupture characteristic has been arranged, because the specific surface area of nanoparticle is big; Reactive group is many, can produce stronger interface interaction with resin matrix.When matrix receives when impacting; Matrix yield deformation (comprising cavitation, tiny crackization, shear zone effect) around particle causes produces a large amount of tiny cracks between particle and matrix, and increases matrix cracking expansion resistance; Passivation crack propagation effect; Make interparticle matrix generation viscous deformation, absorb more striking energy, can reach enhancing, toughening effect.
Embodiment 3:
(1) modification of epoxy hardener and preparation
1) in 15 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P), adds 0.8 part of nanometer SiO under the stirring
2Powder, and ultrasonic 30min;
2) in reaction kettle, add 10 parts of diethylenetriamines, when reaching 65 ℃ of preset temps, stirs slow adding 15 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P) on one side;
3) dropwise, carry out stage and heat up, the intensification amplitude is 5 ℃/h, and heating up and carrying out the end capping time is 2h;
4) under mechanical stirring at the uniform velocity, add 3 parts of epoxy resin with organic solvent dissolution gradually and carry out chain extending reaction, add afterreaction 2h, cooling can obtain the solidifying agent of blocking modification.
(2) preparation of epoxy resin varnish
1) organic solvent is 2 parts, mixes for 10 parts with epoxy resin, adds 0.4 part of ethylene oxide oligopolymer, 15 parts of DOPs, and mechanical stirring is even, obtains the heavy-gravity resin system;
2) getting 15 parts of modified amine curing agents that make, is slowly to add 10 parts of above-mentioned resin systems that make under the 1000r/min in mechanical stirring speed;
3) continue to stir 30min, promptly obtain epoxy resin varnish.
Result of implementation shows: add 0.8 part of nanometer SiO
2Powder, the ultraviolet transparence has obvious decline, and light fastness is outstanding.
Embodiment 4:
(1) modification of epoxy hardener and preparation
1) in 10 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P), adds 0.4 part of nanometer SiO under the stirring
2Powder, and ultrasonic 30min;
2) in reaction kettle, add 5 parts of diethylenetriamines, when reaching 60 ℃ of preset temps, stirs slow adding 10 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P) on one side;
3) dropwise, carry out stage and heat up, the intensification amplitude is 5 ℃/h, and heating up and carrying out the end capping time is 1h;
4) under mechanical stirring at the uniform velocity, add 1 part of epoxy resin with organic solvent dissolution gradually and carry out chain extending reaction, add afterreaction 1h, cooling can obtain the solidifying agent of blocking modification.
(2) preparation of epoxy resin varnish
1) organic solvent is 1 part, mixes for 5 parts with epoxy resin, adds 0.2 part of ethylene oxide oligopolymer, 10 parts of DOPs, and mechanical stirring is even, obtains the heavy-gravity resin system;
2) getting 5 parts of modified amine curing agents that make, is slowly to add 5 parts of above-mentioned resin systems that make under the 1000r/min in mechanical stirring speed;
3) continue to stir 30min, promptly obtain epoxy resin varnish.
Embodiment 5:
(1) modification of epoxy hardener and preparation
1) in 15 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P), adds 0.4 part of nanometer SiO under the stirring
2Powder, and ultrasonic 30min;
2) in reaction kettle, add 10 parts of diethylenetriamines, when reaching 70 ℃ of preset temps, stirs slow adding 15 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P) on one side;
3) dropwise, carry out stage and heat up, the intensification amplitude is 5 ℃/h, and heating up and carrying out the end capping time is 2h;
4) under mechanical stirring at the uniform velocity, add 3 parts of epoxy resin with organic solvent dissolution gradually and carry out chain extending reaction, add afterreaction 2h, cooling can obtain the solidifying agent of blocking modification.
(2) preparation of epoxy resin varnish
1) organic solvent is 2 parts, mixes for 10 parts with epoxy resin, adds 0.5 part of methyl-silicone oil, 30 parts of DOPs, and mechanical stirring is even, obtains the heavy-gravity resin system;
2) getting 15 parts of modified amine curing agents that make, is slowly to add 20 parts of above-mentioned resin systems that make under the 1000r/min in mechanical stirring speed;
3) continue to stir 30min, promptly obtain epoxy resin varnish.
Embodiment 6:
(1) modification of epoxy hardener and preparation
1) in 20 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P), adds 0.4 part of nanometer SiO under the stirring
2Powder, and ultrasonic 30min;
2) in reaction kettle, add 15 parts of diethylenetriamines, when reaching 80 ℃ of preset temps, stirs slow adding 20 parts of end-caps tertiary carbonic acid glycidyl esters (E10-P) on one side;
3) dropwise, carry out stage and heat up, the intensification amplitude is 5 ℃/h, and heating up and carrying out the end capping time is 3h;
4) under mechanical stirring at the uniform velocity, add 5 parts of epoxy resin with organic solvent dissolution gradually and carry out chain extending reaction, add afterreaction 3h, cooling can obtain the solidifying agent of blocking modification.
(2) preparation of epoxy resin varnish
1) organic solvent is 3 parts, mixes for 15 parts with epoxy resin, adds 0.3 part of fatty acid alkyl ester, 20 parts of Witcizer 300s, and mechanical stirring is even, obtains the heavy-gravity resin system;
2) getting 11 parts of modified amine curing agents that make, is slowly to add 12 parts of above-mentioned resin systems that make under the 1000r/min in mechanical stirring speed;
3) continue to stir 30min, promptly obtain epoxy resin varnish.
Embodiment 4,5, and 6 implementation result shows that the varnish film coated surface is smooth behind the interpolation skimmer, does not have obvious bubble and exists, and has reduced generation of defects, makes the raising to a certain degree of paint film mechanical property.
The epoxy resin varnish coating that embodiment is made is loaded in the blackwash sprayer, is sprayed at the polytetrafluoroethylplastic plastic surface, after the curing, does the test of Elongation test and photostabilization respectively.Test finds that the varnish transparency of the present invention is optimum, and curing speed is slower at normal temperatures; The Elongation test better performances, photostabilization is good.
Claims (5)
1. the method for a silica modified epoxy curing agent is characterized in that concrete steps are following:
1) in 10～20 parts of end-caps tertiary carbonic acid glycidyl esters, stirs 0.2～0.8 part of SiO of adding
2Ultrasonic 0.5～1h behind the powder;
2) in reaction kettle, add 5～15 parts of diethylenetriamines, when reaching 60～80 ℃ of preset temps, slowly add 10～20 parts of SiO while stirring
2Ester compound after the modification carries out end-blocking as end-capping reagent to solidifying agent;
3) dropwise the intensification of latter stage property, the intensification amplitude is 5 ℃/h, and heating up and carrying out the end capping time is 1～3h;
4) under mechanical stirring at the uniform velocity, add 1～5 part of YLENE and butanols gradually with organic mixed solvent of 7: 3 of mass ratio, the epoxy resin after the dissolving carries out chain extending reaction, adds afterreaction 1～3h, and organic solvent mixes with 2: 1 with epoxy resin; Can obtain the solidifying agent of modification after the cooling.
2. the solidifying agent of employing claim 1 prepares the method for epoxy resin varnish, and step is following:
1) with YLENE and butanols with 1～3 part of organic mixed solvent of 7: 3 of mass ratio, mix for 5～15 parts with epoxy resin, add 0.2～0.5 part of skimmer, 1～30 part of softening agent, mechanical stirring is even, obtains the heavy-gravity resin system;
2) get 5～20 parts of SiO that make
2Modified amine curing agent is the resin system that slowly adds 5～15 parts of step 1) under the 1000r/min in mechanical stirring speed;
3) continue to stir 30min, promptly obtain epoxy resin varnish.
3. method as claimed in claim 2 is characterized in that described epoxy resin is bisphenol A type epoxy resin.
4. method as claimed in claim 2 is characterized in that described skimmer is fatty acid alkyl ester, ethylene oxide oligopolymer or methyl-silicone oil.
5. method as claimed in claim 2 is characterized in that described softening agent is Witcizer 300 or DOP.
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623474A (en) * | 2016-03-25 | 2016-06-01 | 大庆庆鲁朗润科技有限公司 | Anti-H2S anti-C02 and high-temperature-corrosion-resistant polymer coating |
| CN110739092A (en) * | 2019-10-25 | 2020-01-31 | 洛阳市琦安科技有限公司 | nuclear radiation curing pressing decontamination functional material |
| CN112226186A (en) * | 2020-09-27 | 2021-01-15 | 上海牛元工贸有限公司 | Long-service-life seam beautifying agent and preparation method thereof |
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| CN1752163A (en) * | 2005-10-20 | 2006-03-29 | 同济大学 | A kind of aqueous epoxide resin paint and preparation method thereof |
| JP2007099956A (en) * | 2005-10-06 | 2007-04-19 | Tamura Kaken Co Ltd | Thermosetting resin composition, resin film and structure |
| CN101128504A (en) * | 2004-12-22 | 2008-02-20 | 亨斯迈先进材料（瑞士）有限公司 | Coating system |
| CN101386700A (en) * | 2007-09-12 | 2009-03-18 | 德古萨有限责任公司 | Curing composition containing fumed silica |
-
2011
- 2011-07-11 CN CN 201110193050 patent/CN102352025B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101128504A (en) * | 2004-12-22 | 2008-02-20 | 亨斯迈先进材料（瑞士）有限公司 | Coating system |
| JP2007099956A (en) * | 2005-10-06 | 2007-04-19 | Tamura Kaken Co Ltd | Thermosetting resin composition, resin film and structure |
| CN1752163A (en) * | 2005-10-20 | 2006-03-29 | 同济大学 | A kind of aqueous epoxide resin paint and preparation method thereof |
| CN101386700A (en) * | 2007-09-12 | 2009-03-18 | 德古萨有限责任公司 | Curing composition containing fumed silica |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105623474A (en) * | 2016-03-25 | 2016-06-01 | 大庆庆鲁朗润科技有限公司 | Anti-H2S anti-C02 and high-temperature-corrosion-resistant polymer coating |
| CN110739092A (en) * | 2019-10-25 | 2020-01-31 | 洛阳市琦安科技有限公司 | nuclear radiation curing pressing decontamination functional material |
| CN110739092B (en) * | 2019-10-25 | 2023-07-14 | 洛阳市琦安科技有限公司 | Nuclear radiation curing pressing decontamination functional material |
| CN112226186A (en) * | 2020-09-27 | 2021-01-15 | 上海牛元工贸有限公司 | Long-service-life seam beautifying agent and preparation method thereof |
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| CN102352025B (en) | 2013-03-06 |
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