CN102352025B - 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
- Publication number
- CN102352025B CN102352025B CN 201110193050 CN201110193050A CN102352025B CN 102352025 B CN102352025 B CN 102352025B CN 201110193050 CN201110193050 CN 201110193050 CN 201110193050 A CN201110193050 A CN 201110193050A CN 102352025 B CN102352025 B CN 102352025B
- Authority
- CN
- China
- Prior art keywords
- curing agent
- epoxy
- parts
- epoxy resin
- add
- 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 - Fee Related
Links
Images
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 resisted the destruction of causing because of humidity, radiation, biological degradation, mechanochemistry damage.The matrix that varnish colour is commonly used is Resins, epoxy, and Resins, epoxy this as thermoplastic linear structure, be heated that rear solid resin can soften, melting, become the thickness attitude; The liquid resin reduced viscosity that is heated.After only having the solidifying agent of adding, Resins, epoxy just can obtain practicality.Resins, epoxy 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 low, the easy machine-shaping of shrinking percentage and the advantage such as with low cost, but pure epoxy resin is tridimensional network after solidifying, cross-linking density is high, there are the large and shortcomings such as quality is firmly crisp, resistance to cracking, shock resistance, humidity resistance is poor and stripping strength is low of internal stress, so limited to a great extent its application in some harsh and unforgiving environments.Owing to having special structure, nano-silicon dioxide particle shows peculiar physics and chemistry character, such as 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 again matrix material have more excellent performance, so nanometer SiO
2Can be used to prepare various resins, coating, support of the catalyst etc., is excellent strongthener.
Solidifying agent is indispensable important component part in the Resins, epoxy Application Areas, and it is determining the physicals of cured product with Resins, epoxy.In numerous epoxy curing agents, lower aliphatic amine solidifying agent is most widely used, consumption is maximum.It has the characteristics such as speed of response is fast, ambient temperature curable.But there is following defective in the fatty amines solidifying agent that directly uses: 1. relatively poor with the consistency of Resins, epoxy, the properties 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 occurs under the room temperature, speed of response is wayward; 3. curing shrinkage internal stress is large, so that coating is easy to crack, property is crisp; Above defective is even more serious under the warm condition.This so that epoxy coating be subject to certain restrictions in actual applications.
Summary of the invention
The object of the invention is to the shortcoming for above-mentioned Resins, epoxy, propose that a kind of technique 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 Resins, epoxy as solidifying agent, improved the consistency between solidifying agent and the Resins, epoxy; Through SiO
2Resins, epoxy stretching intensity after modified firming agent solidifies, ageing resistance has had raising to a certain degree, with the solidifying agent after the modification under certain operating procedure condition and the mixing such as Resins, epoxy, solvent, defoamer, softening agent, obtain a kind of thickness transparence, had good water tolerance, the tensile property of excellence and the woodenware epoxy resin varnish coating of high gloss performance.
The technical solution used in the present invention is in order to achieve the above object:
A kind of method of silica modified epoxy curing agent, concrete steps are as follows:
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 reactor, add 5~15 parts of diethylenetriamines, when reaching 60~80 ℃ of preset temps, slowly add while stirring 10~20 parts of SiO
2Ester compound after the modification carries out end-blocking as end-capping reagent to solidifying agent;
3) dropwise the latter stage intensification, increasing extent of temperature 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 gradually 1~5 part of dimethylbenzene and butanols with organic mixed solvent of 7: 3 of mass ratio, the Resins, epoxy after the dissolving carries out chain extending reaction, adds afterreaction 1~3h, and organic solvent mixes with 2: 1 with Resins, epoxy; 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 as follows:
1) with dimethylbenzene and butanols with 1~3 part of organic mixed solvent of 7: 3 of mass ratio, mix with 5~15 parts of Resins, epoxy, add 0.2~0.5 part of defoamer, 1~30 part of softening agent, mechanical stirring is even, obtains the resin system of thickness;
2) get 5~20 parts of SiO that make
2Modified amine curing agent is slowly to add 5~15 parts of steps 1 under the 1000r/min in mechanical stirring speed) resin system;
3) continue to stir 30min, namely obtain epoxy resin varnish.
Described Resins, epoxy is bisphenol A type epoxy resin.Described defoamer is fatty acid alkyl ester, ethylene oxide oligopolymer or methyl-silicone oil.Described softening agent is dibutyl phthalate or dioctyl phthalate (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 Resins, epoxy as solidifying agent, further improved the consistency between solidifying agent and the Resins, epoxy; Through SiO
2Resins, epoxy stretching intensity after modified firming agent solidifies, ageing resistance has had raising to a certain degree, solidifying agent after the modification under certain operating procedure condition and the mixing such as Resins, epoxy, solvent, defoamer, softening agent, a kind of have good water tolerance, excellent tensile property and the woodenware epoxy resin varnish coating of high gloss performance have been obtained.
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 brittle rupture 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 reactor, 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, increasing extent of temperature is 5 ℃/h, and heating up and carrying out the end capping time is 2h;
4) under mechanical stirring at the uniform velocity, add gradually 3 parts of Resins, epoxy with organic solvent dissolution 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 with 10 parts of Resins, epoxy, adds 0.4 part of ethylene oxide oligopolymer, 15 parts of dioctyl phthalate (DOP)s, and mechanical stirring is even, obtains the resin system of thickness;
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, namely 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, without obviously reuniting.
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 reactor, 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, increasing extent of temperature is 5 ℃/h, and heating up and carrying out the end capping time is 2h;
4) under mechanical stirring at the uniform velocity, add gradually 3 parts of Resins, epoxy with organic solvent dissolution 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 with 10 parts of Resins, epoxy, adds 0.4 part of ethylene oxide oligopolymer, 15 parts of dioctyl phthalate (DOP)s, and mechanical stirring is even, obtains the resin system of thickness;
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, namely 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 brittle rupture compare, the matrix of Fig. 2 that embodiment 2 obtains has produced tiny crack, and obvious ductile rupture feature has been arranged, because the specific surface area of nanoparticle is large, active group is many, can produce stronger interface interaction with resin matrix.When matrix is subject to impacting, matrix yielding distortion (comprising cavitation, tiny crack, shear zone effect) around particle causes, produce a large amount of tiny cracks between particle and matrix, and increase 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 reactor, 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, increasing extent of temperature is 5 ℃/h, and heating up and carrying out the end capping time is 2h;
4) under mechanical stirring at the uniform velocity, add gradually 3 parts of Resins, epoxy with organic solvent dissolution 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 with 10 parts of Resins, epoxy, adds 0.4 part of ethylene oxide oligopolymer, 15 parts of dioctyl phthalate (DOP)s, and mechanical stirring is even, obtains the resin system of thickness;
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, namely 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 reactor, 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, increasing extent of temperature is 5 ℃/h, and heating up and carrying out the end capping time is 1h;
4) under mechanical stirring at the uniform velocity, add gradually 1 part of Resins, epoxy with organic solvent dissolution 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 with 5 parts of Resins, epoxy, adds 0.2 part of ethylene oxide oligopolymer, 10 parts of dioctyl phthalate (DOP)s, and mechanical stirring is even, obtains the resin system of thickness;
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, namely 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 reactor, 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, increasing extent of temperature is 5 ℃/h, and heating up and carrying out the end capping time is 2h;
4) under mechanical stirring at the uniform velocity, add gradually 3 parts of Resins, epoxy with organic solvent dissolution 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 with 10 parts of Resins, epoxy, adds 0.5 part of methyl-silicone oil, 30 parts of dioctyl phthalate (DOP)s, and mechanical stirring is even, obtains the resin system of thickness;
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, namely 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 reactor, 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, increasing extent of temperature is 5 ℃/h, and heating up and carrying out the end capping time is 3h;
4) under mechanical stirring at the uniform velocity, add gradually 5 parts of Resins, epoxy with organic solvent dissolution 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 with 15 parts of Resins, epoxy, adds 0.3 part of fatty acid alkyl ester, 20 parts of dibutyl phthalates, and mechanical stirring is even, obtains the resin system of thickness;
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, namely obtain epoxy resin varnish.
Embodiment 4,5, and 6 implementation result shows that the varnish film coated surface is smooth behind the interpolation defoamer, without obviously bubble existence, has reduced the generation of defective, 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 respectively the test of Elongation test and photostabilization.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 as follows:
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 reactor, add 5~15 parts of diethylenetriamines, when reaching 60~80 ℃ of preset temps, slowly add while stirring 10~20 parts of SiO
2Tertiary carbonic acid glycidyl ester after the modification carries out end-blocking as end-capping reagent to the diethylenetriamine solidifying agent;
3) dropwise the latter stage intensification, increasing extent of temperature 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 gradually 1~5 part of dimethylbenzene and the butanols Resins, epoxy after with organic mixed solvent dissolving of mass ratio 7:3 and carry out chain extending reaction, add afterreaction 1~3h, organic mixed solvent mixes with 2:1 with Resins, epoxy; Can obtain silica modified epoxy curing agent after the cooling.
2. method for preparing epoxy resin varnish, step is as follows:
1) with dimethylbenzene and butanols with 1~3 part of organic mixed solvent of mass ratio 7:3, mix with 5~15 parts of Resins, epoxy, add 0.2~0.5 part of defoamer, 1~30 part of softening agent, mechanical stirring is even, obtains the resin system of thickness;
2) getting the silica modified epoxy curing agent that 5~20 parts of the method for claim 1 make, 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, namely obtain epoxy resin varnish.
3. method as claimed in claim 2 is characterized in that described Resins, epoxy is bisphenol A type epoxy resin.
4. method as claimed in claim 2 is characterized in that described defoamer 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 dibutyl phthalate or dioctyl phthalate (DOP).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201110193050 CN102352025B (en) | 2011-07-11 | 2011-07-11 | Preparation method of silica modified epoxy resin curing agent and varnish |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 201110193050 CN102352025B (en) | 2011-07-11 | 2011-07-11 | Preparation method of silica modified epoxy resin curing agent and varnish |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102352025A CN102352025A (en) | 2012-02-15 |
CN102352025B true CN102352025B (en) | 2013-03-06 |
Family
ID=45575687
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 201110193050 Expired - Fee Related CN102352025B (en) | 2011-07-11 | 2011-07-11 | Preparation method of silica modified epoxy resin curing agent and varnish |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102352025B (en) |
Families Citing this family (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 |
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 |
CN112226186B (en) * | 2020-09-27 | 2022-11-29 | 上海牛元工贸有限公司 | Long-service-life seam beautifying agent and preparation method thereof |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1674495A1 (en) * | 2004-12-22 | 2006-06-28 | Huntsman Advanced Materials (Switzerland) GmbH | 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 |
-
2011
- 2011-07-11 CN CN 201110193050 patent/CN102352025B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN102352025A (en) | 2012-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106832262B (en) | With the nano combined nylon material and preparation method thereof for exempting to spray high optical property | |
CN105694790A (en) | Epoxy adhesive capable of being removed quickly and preparing and removing methods thereof | |
CN102250320A (en) | Preparation method of modified epoxy resin curing agent and epoxy varnish paint | |
WO2022206875A1 (en) | Coating composition, preparation method therefor and use thereof | |
CN102352025B (en) | Preparation method of silica modified epoxy resin curing agent and varnish | |
CN102190858B (en) | Epoxy resin material toughened by nanometer silica and preparation method thereof | |
CN104744639A (en) | Preparation method of organic silicon modified normal-temperature multiple self-crosslinked epoxy resin emulsion | |
CN104945875A (en) | Polycarbonate release film | |
CN105885365A (en) | Glass bead modified PBT (polybutylene terephthalate) material with epoxy resin bonding performance and preparation method for glass bead modified PBT material | |
CN105176081A (en) | Preparation method for flame-retardant heat-resistant antenna radome base material | |
CN102911584A (en) | Anti-graffiti anti-sticking nano coating and preparation method thereof | |
CN105885362A (en) | Hyperbranched resin toughened PBT (polybutylene terephthalate) material with epoxy resin bonding performance and preparation method for hyperbranched resin toughened PBT material | |
CN105176374B (en) | Applied to aqueous priming paint on carbon fiber in epoxy composite material and preparation method thereof | |
CN103865010A (en) | Preparation method of functional inorganic/polymer hollow microspheres for polysulfide sealant | |
CN113511832A (en) | Heterogeneous solution method for preparing polymer-coated inorganic particles and application thereof | |
CN105001825A (en) | Low temperature resisting epoxy resin adhesive and preparation method thereof | |
JP2006225521A (en) | Curing agent-containing fine particle, its manufacturing method, and one-pack epoxy resin adhesive composition | |
CN107955443A (en) | A kind of selfreparing anti-corrosion primer | |
CN113502139B (en) | Low-temperature-resistant slow-bonding prestressed tendon | |
CN103666316A (en) | High-temperature-repairable conductive adhesive and preparation method thereof | |
CN103435974A (en) | Preparation method of modified wollastonite used for toughening epoxy resin | |
CN105413980B (en) | A kind of static elimination method in the offline coating of PET basement membranes | |
CN101531809B (en) | Method for preparing PC-PS blend alloy | |
CN104004429A (en) | Normal temperature-curable composite coating based on modified 107 silicone rubber and preparation method thereof | |
CN101838439A (en) | Nanometer carboxylic acrylonitrile butadiene rubber modified epoxy resin and production method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130306 Termination date: 20130711 |