CN105384912A - Itaconic-acid-based cyclic silicon framework epoxy resin, preparation method and application to preparing paint with epoxy resin as matrix resin - Google Patents
Itaconic-acid-based cyclic silicon framework epoxy resin, preparation method and application to preparing paint with epoxy resin as matrix resin Download PDFInfo
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- CN105384912A CN105384912A CN201510732163.3A CN201510732163A CN105384912A CN 105384912 A CN105384912 A CN 105384912A CN 201510732163 A CN201510732163 A CN 201510732163A CN 105384912 A CN105384912 A CN 105384912A
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Abstract
The invention discloses itaconic-acid-based cyclic silicon framework epoxy resin, a preparation method and application to preparing paint with the epoxy resin as matrix resin. The epoxy resin is itaconic acid methylene (a functional group in the formula 2) mono-substituted or polysubstituted polybasic cyclosiloxane and is an addition product obtained by itaconic acid bis-oxiranylmethyl ester and cyclosiloxane under catalysis of a platinum catalyst. The epoxy resin has excellent flexibility. Rigidity of a material can not be greatly reduced and even can be kept. Itaconic acid bis-oxiranylmethyl ester serves as a biological renewable resource, and product performance can be regulated and controlled through the charge ratio. The paint good in performance can be prepared with the epoxy resin as the matrix resin.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of methylene-succinic acid basic ring shape silicon skeletal epoxy resin, preparation method and prepare the application of coating as matrix resin.
Background technology
Epoxy resin has excellent mechanical property, resistance to elevated temperatures, erosion resistance, and cementability and electrical insulating property, be widely used in automobile, building, electronics, the fields such as aviation.But because epoxy resin defines highly cross-linked 3 D stereo reticulated structure in the curing process, between molecular chain, lack slip; Add C-C key, C-O key bond energy less, surface energy is higher; Cause that cured resin internal stress is comparatively large, property is crisp, easily crack, thus limit its application in some technical field.In order to improve toughness and the over-all properties of epoxy resin, expand its Application Areas further, Chinese scholars has carried out a large amount of research work.
What Recent study was more is polysiloxane toughening epoxy resin.Polysiloxane has well flexible and thermostability, and large quantity research proves, polysiloxane really can be epoxy resin toughened, but due to consistency be not fine, toughening effect is not very remarkable.In order to improve the consistency of polysiloxane and epoxy resin, do large quantifier elimination both at home and abroad, comprising: introduce silane coupling agent, polar group (as: hydroxyl, amino, epoxy group(ing) in polysiloxane chain termination, carboxyl, isocyano etc.), in polysiloxane chain, introduce the segment of close epoxy resin, and by chemical bonding, polysiloxane is received in epoxy resin.
Publication number is the preparation method that the Chinese patent literature of CN101787132A discloses a kind of organic-silicon hybridization epoxy resin, obtained by the silicone oil of silicone-containing structure and epoxyalkylsilane coupling agent hydrolysis-condensation reaction, comprise following steps: by the silicone oil of 100 mass parts silicone-containing structures, 50 ~ 500 mass parts epoxyalkylsilane coupling agents, 50 ~ 600 mass parts organic solvents, 5 ~ 120 mass parts deionized waters and 0.5 ~ 6 mass parts of catalyst mix, then in 50 ~ 100 DEG C of reactions 2 ~ 8 hours, except organic solvent and the deionized water of dereaction, obtain organic-silicon hybridization epoxy resin.The method preparation process is complicated, make use of a large amount of silane coupling agents, and the hybrid meeting residual hydroxyl that hydrolytie polycondensation obtains, be easily cross-linked with each other.
Publication number is that the Chinese patent literature of CN102977554A discloses a kind of LED epoxy/organosilicon co-curing matrix material and preparation method thereof, comprises following component according to the mass fraction: the hydrogeneous cyclosiloxane of epoxy group(ing) 50 ~ 500 parts, 0 ~ 10 part, oxidation inhibitor, UV light absorber 0 ~ 10 part, light scattering agent 0 ~ 15 part, phenyl vinyl polysiloxane 100 parts, epoxy hardener 0.5 ~ 15.0 part and Si―H addition reaction curing catalysts 0.01 ~ 1.0 part.
Publication number is that the Chinese patent literature of CN104356361A discloses a kind of bio-based epoxy such as itaconic acid diglycidyl ester, maleic acid 2-glycidyl ester, fumaroyl 2-glycidyl ester utilizing bio-based source abundant and end hydrogen siloxane addition reaction of silicon with hydrogen, the bio-based silicon skeletal epoxy resin obtained.The process employs chain end hydrogen polysilicone, cost is very high, and the toughness of modified epoxy of preparation particularly resistance toheat, intensity, hardness etc. are very responsive to the length of chain.
The most synthetic method of epoxy resin of existing modification is complicated, and the raw material of employing can not Sustainable development.And the intensity of the coating adopting existing modified epoxy to prepare and toughness aspect are difficult to reach desirable effect simultaneously.
Summary of the invention
The invention provides a kind of polyfunctionality ring-type silicon skeletal epoxy resin based on methylene-succinic acid, wherein ring silicon skeleton structure can give the toughness of epoxy resin cured product excellence and the polyfunctionality of modified epoxy; Thus make epoxy resin cured product have excellent resistance toheat.
A kind of methylene-succinic acid basic ring shape silicon skeletal epoxy resin is one or more of formula 1 structural compounds:
R is-H or formula 2 functional group;
N is the integer of 3-8; Wherein in n R, has one at least for formula 2 functional group.
The present invention adopts the hydrogen of the Si-H of methylene-succinic acid methylene radical (formula 2 functional group) monosubstituted or polysubstituted cyclosiloxane, thus is embedded in epoxy molecule by ring-type silicon skeleton.More epoxy-functional can be introduced in described epoxy molecule structure; And there is in molecule Si-O-Si flexible chain, when being subject to external impacts, the energy of absorption can be converted to heat energy by molecular motion; Contribute to the toughness increasing described epoxy resin.The silicon skeleton structure of this epoxy resin is ring texture, not only there is general organosilyl excellent flexibility, simultaneously because cyclic molecules volume ratio is larger, to whole molecule segment motion, there is certain inhibition, the problem that existing epoxy resin significantly may reduce epoxy resin rigidity in toughing ways can be solved.
Through type 1 is known, the ring-type silicon skeleton of described epoxy resin (referring to methylene-succinic acid basic ring shape silicon skeletal epoxy resin provided by the invention) be hexa-atomic, eight yuan, ten yuan, ten binary, ten quaternarys or sixteen-ring siloxane structure.In cyclosiloxane structure, each Siliciumatom is containing a methyl; And having at least a Siliciumatom to be replaced by formula 2 functional group, other Siliciumatoms are replaced by hydrogen or formula 2 functional group.
As preferably, the ring-type silicon skeleton of described epoxy resin is hexa-atomic or octatomic ring siloxane structure.
Structure size that is hexa-atomic or octatomic ring shape silicon skeletal epoxy resin is moderate, intermolecular formula 2 functional group not quite sterically hindered, and it is good that formula 2 functional group replaces number Modulatory character, and the range of application of this based epoxy resin is wider.
Further preferably, described methylene-succinic acid basic ring shape silicon skeletal epoxy resin is one or more of formula 3 structural compounds:
R
1, R
2, R
3, R
4for-H or formula 2 functional group; Wherein, R
1, R
2, R
3, R
4has one at least for formula 2 functional group.
The epoxy resin structural of this octatomic ring siloxane structure is stable, raw materials is simple and easy to get, can load 2-8 Ge Shi 2 functional group in molecular structure, and this epoxy resin has excellent performance in flexibility.
Further preferred, in formula 3 structural compounds, R
1, R
2, R
3, R
4for formula 2 functional group.
The epoxy functionalities of described epoxy resin is many, not only shows excellent self toughening performance after solidification, has excellent heat, mechanical property simultaneously.
The present invention also comprises the preparation method of a kind of above-mentioned methylene-succinic acid Quito functionality silicon skeletal epoxy resin, comprises the following steps:
By the platinum catalyst of the organic solvent of the itaconic acid diglycidyl ester of 100 mass parts, 20 ~ 500 mass parts, the cyclosiloxane of 25 ~ 100 mass parts and the total mass relative to itaconic acid diglycidyl ester and cyclosiloxane, reaction 0.5 ~ 50 hour under 60 ~ 140 DEG C of heating, obtains described methylene-succinic acid Quito functionality silicon skeletal epoxy resin through revolving to steam except after desolventizing.
Itaconic acid diglycidyl ester carries out addition reaction with the Si-H key of cyclosiloxane under the catalysis of described platinum catalyst, and due to sterically hindered effect, the adduct of generation is mainly the mixture of formula 1 structural compounds.In the present invention, can regulate and control relative to the ingredient proportion of cyclosiloxane the product assay that polyfunctional group (formula 2 functional group) replaces by regulation and control itaconic acid diglycidyl ester, as increased the ingredient proportion of itaconic acid diglycidyl ester relative to cyclosiloxane, the content of the epoxy resin of the polyfunctional group replacement of prepared epoxy resin can be higher.Therefore, the performance of product can be controlled by the proportioning regulating and controlling material, thus meet the preparation demand of the epoxy resin of industrial different demand.
In the present invention, cyclosiloxane provides multiple reaction site, adds the diversity of product.
In addition reaction, the mass fraction of catalyzer is for the total mass of itaconic acid diglycidyl ester and cyclosiloxane.
Under described temperature of reaction, the catalytic efficiency of the catalyzer of described charging capacity is high, and reaction can complete within a short period of time.Under this reaction system, by extending the reaction times, can increase the ratio of polyfunctional group substitution product, the toughness of the epoxy resin prepared thus can be better, thus, and also can in the to a certain degree lower performance regulating product by the regulation and control reaction times.
As preferably, described platinum catalyst is Platinic chloride or 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0).
As preferably, described cyclosiloxane is formula 4 structural compounds,
Wherein, m is the integer of 3-8.
Described cyclosiloxane be hexa-atomic, eight yuan, ten yuan, ten binary, ten quaternarys or sixteen-ring siloxanes, and each Siliciumatom is connected with respectively a methyl and a hydrogen.Wherein, Si-H carries out addition reaction with itaconic acid diglycidyl ester under catalyzer.
Further preferably, described cyclosiloxane is 1,3,5-trimethylammonium three hydrogen cyclotrisiloxane or 1,3,5,7-tetramethyl-tetrahydrochysene cyclotetrasiloxane.
Further preferred, described cyclosiloxane is 1,3,5,7-tetramethyl-tetrahydrochysene cyclotetrasiloxane.
Described itaconic acid diglycidyl ester structural formula is such as formula 5:
The present invention adopts reproducible itaconic acid diglycidyl ester as epoxy donor, and this epoxy donor has higher consistency with cyclosiloxane under described solvent, and the transformation efficiency of raw material is high.In addition reaction process, the product (anti-Markonikov's rule product) of main production 1 structure under the sterically hindered effect of cyclosiloxane, this kind of product imparts the good verticity of Si-C key, sterically hindered between adjacent formula 2 functional group effectively reducing prepared product.In the building-up process of described epoxy resin, the introducing quantity (being namely equal to the introducing quantity of epoxy group(ing)) of formula 2 functional group can not be restricted because of sterically hindered, thus can the performance of manual control product, contribute to the industrial applicability of the epoxy resin prepared by expanding.
Described organic solvent is tetrahydrofuran (THF), dioxane, butylacetate, toluene, benzene, dimethylbenzene, N, one or more in N '-dimethyl methane amide, dimethyl sulfoxide (DMSO).
Organic solvent plays the effect of dissolving and diluting reaction thing, and above-mentioned non-protonic solvent contributes to the carrying out of addition reaction, and moderate boiling point, the solvent recuperation being conducive to aftertreatment is applied mechanically.
The present invention also comprises a kind of application described methylene-succinic acid Quito functionality silicon skeletal epoxy resin being prepared coating as matrix resin.
The present invention is applied to the preparation field of coating, contributes to preparing the coating with the feature such as high strength, high tenacity.
The methylene-succinic acid basic ring shape silicon skeletal epoxy resin of above-mentioned synthesis and commercial solidifying agent are heating and curing and form.
As preferably, described coating comprises the described methylene-succinic acid Quito functionality silicon skeletal epoxy resin and solidifying agent that weight ratio is 1:0.1-0.4.
Above-mentioned solidifying agent is the Common curing agents of existing commercialization, and as preferably, described solidifying agent is IPDA, DDM, polyetheramine, polymeric amide.
In the present invention, the methylene-succinic acid basic ring shape silicon skeletal epoxy resin of formula 1 structure can be used for preparing thermosetting resin; The existence of ring-type silicon skeleton, makes thermosetting resin possess self toughening characteristic, can also increase the toughness of other epoxy resin as flexibilizer additive.Minimumly in the epoxy resin structural provided in the present invention contain 2 epoxide groups, 16 can be reached at most, simultaneously due to molecular volume that ring-type silicon skeleton is large, the motion of molecule segment can be hindered to a certain extent, therefore can make cured article (prepared coating) good heat resistance after solidification, add the resistance toheat that can not reduce system in other epoxy-resin systems equally as toughner to.
Epoxy resin provided by the invention has excellent snappiness; And can not significantly reduce the rigidity that even can keep material.The itaconic acid diglycidyl ester adopted is bio-renewables, and product property can be regulated and controled by charge ratio.Adopt epoxy resin provided by the invention can prepare the coating of excellent property as substrate resin.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of methylene-succinic acid basic ring shape silicon skeletal epoxy resin prepared by embodiment 1.
Embodiment
Following examples are pressed aforesaid operations method and are implemented:
Embodiment 1
By itaconic acid diglycidyl ester 10g, dioxane 2g, 1,3,5,7-tetramethyl-tetrahydrochysene cyclotetrasiloxane 2.5g and 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0) (platinum content is 2%) 0.0001g, reacts 20 hours at 100 DEG C of conventional heatings, obtains methylene-succinic acid basic ring shape silicon skeletal epoxy resin through underpressure distillation except after desolventizing.According to this methylene-succinic acid Quito functionality silicon skeletal epoxy resin
1hNMR spectrogram as shown in Figure 1,
1occur in HNMR spectrogram that 2.5-3.18ppm represents the peak of epoxide group, about 1.25ppm represents Si―H addition reaction is formed and Si-CH
2-on hydrogen, add that other peak conforms to the H proton displacement of methylene-succinic acid Quito functionality silicon skeletal epoxy resin, utilize hydrochloric acid-acetone method to record oxirane value is 0.66 simultaneously.The provable material obtained is the methylene-succinic acid basic ring shape silicon skeletal epoxy resin shown in formula I.
By the epoxy resin 10g of above-mentioned synthesis, with 4,4 '-diaminodiphenyl-methane 3.3g mixes, first 80 DEG C of solidifications 3 hours, then 150 DEG C of solidifications 2 hours, last 180 DEG C of solidifications 2 hours, obtain epoxy resin cured product, the resistance to impact shock of cured article is 64kJ/m
2, second-order transition temperature is 181 DEG C, and tensile strength is 97MPa.Relative to the epoxy resin (oxirane value is 0.68) of the bio-based straight chain silicon skeleton of existing publication (CN104356361A) embodiment 5 preparation, the cured article prepared under identical solidifying agent and condition of cure, performance is more excellent.
Embodiment 2
By itaconic acid diglycidyl ester 10g, tetrahydrofuran (THF) 6g, 1,3,5,7-tetramethyl-tetrahydrochysene cyclotetrasiloxane 5g and 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0) (platinum content is 2%) 0.001g, reacts 50 hours at 60 DEG C of conventional heatings, obtains methylene-succinic acid basic ring shape silicon skeletal epoxy resin through underpressure distillation except after desolventizing.Utilizing hydrochloric acid-acetone method to record oxirane value is 0.55.
By the epoxy resin 10g of above-mentioned synthesis, with 4,4 '-diaminodiphenyl-methane 2.7g mixes, first 80 DEG C of solidifications 3 hours, then 150 DEG C of solidifications 2 hours, last 180 DEG C of solidifications 2 hours, obtain epoxy resin cured product, the resistance to impact shock of cured article is 70kJ/m
2, second-order transition temperature is 175 DEG C, and tensile strength is 90MPa.
Embodiment 3
By itaconic acid diglycidyl ester 10g, dimethyl sulfoxide (DMSO) 20g, dimethylbenzene 30g, 1,3,5,7-tetramethyl-tetrahydrochysene cyclotetrasiloxane 10g and Platinic chloride 0.01g, react 0.5 hour at 140 DEG C of conventional heatings, obtain methylene-succinic acid basic ring shape silicon skeletal epoxy resin through underpressure distillation except after desolventizing.Utilizing hydrochloric acid-acetone method to record oxirane value is 0.41.
By the epoxy resin 10g of above-mentioned synthesis, with 4,4 '-diaminodiphenyl-methane 2g mixes, first 80 DEG C of solidifications 3 hours, then 150 DEG C of solidifications 2 hours, last 180 DEG C of solidifications 2 hours, obtain epoxy resin cured product, the resistance to impact shock of cured article is 76kJ/m
2, second-order transition temperature is 166 DEG C, and tensile strength is 85MPa.
Embodiment 4
By itaconic acid diglycidyl ester 10g, ethyl acetate 6g, benzene 6g, 1,3,5,7,9-pentamethyl-pentahydro-D5 4g and Platinic chloride 0.003g, reacts 40 hours at 80 DEG C of conventional heatings, obtains methylene-succinic acid basic ring shape silicon skeletal epoxy resin through underpressure distillation except after desolventizing.Utilizing hydrochloric acid-acetone method to record oxirane value is 0.58.
By the epoxy resin 10g of above-mentioned synthesis, with 4,4 '-diaminodiphenyl-methane 2.9g mixes, first 80 DEG C of solidifications 3 hours, then 150 DEG C of solidifications 2 hours, last 180 DEG C of solidifications 2 hours, obtain epoxy resin cured product, the resistance to impact shock of cured article is 72kJ/m
2, second-order transition temperature is 177 DEG C, and tensile strength is 92MPa.
Embodiment 5
By itaconic acid diglycidyl ester 10g, 10g toluene, 20gN, dinethylformamide, 1,3,5-trimethylammonium three hydrogen cyclotrisiloxane 7.5g and 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0) (platinum content is 2%) 0.006g, reacts 10 hours at 120 DEG C of conventional heatings, obtains methylene-succinic acid basic ring shape silicon skeletal epoxy resin through underpressure distillation except after desolventizing.Utilizing hydrochloric acid-acetone method to record oxirane value is 0.48.
By the epoxy resin 10g of above-mentioned synthesis, with 4,4 '-diaminodiphenyl-methane 2g mixes, first 80 DEG C of solidifications 3 hours, then 150 DEG C of solidifications 2 hours, last 180 DEG C of solidifications 2 hours, obtain epoxy resin cured product, the resistance to impact shock of cured article is 72kJ/m
2, second-order transition temperature is 169 DEG C, and tensile strength is 88MPa.
Application examples 1
Methylene-succinic acid Quito functionality silicon skeletal epoxy resin (oxirane value 0.66) of 3g embodiment 1 being prepared and 0.84g isophorone diamine mix, it is applied on clean sheet tin with spreader, first 80 DEG C of solidifications 3 hours, then 130 DEG C solidify 2 hours, finally 180 DEG C of solidifications 3 hours, the coating thickness obtained about 30 μm, records inverse impact strength according to ASTMD2794 and is greater than 172, record pencil hardness 5H according to ASTMD3363, ASTMD4366 records
pendulum-rocker hardness 210s.
Comparative example 1
By the bio-based straight chain silicon skeletal epoxy resin (oxirane value is 0.68) that 3g is prepared by existing publication (CN104356361A) embodiment 5, mix with 0.86g isophorone diamine, first 80 DEG C of solidifications 3 hours, then 130 DEG C solidify 2 hours, finally 180 DEG C of solidifications 3 hours, the coating thickness obtained about 30 μm, records inverse impact strength 160 according to ASTMD2794, record pencil hardness 4H according to ASTMD3363, ASTMD4366 records
pendulum-rocker hardness 185s.
Claims (10)
1. a methylene-succinic acid basic ring shape silicon skeletal epoxy resin, is characterized in that, is one or more of formula 1 structural compounds:
R is-H or formula 2 functional group;
N is the integer of 3-8; Wherein in n R, has one at least for formula 2 functional group.
2. methylene-succinic acid basic ring shape silicon skeletal epoxy resin according to claim 1, is characterized in that, is one or more of formula 3 structural compounds:
R
1, R
2, R
3, R
4for-H or formula 2 functional group; Wherein, R
1, R
2, R
3, R
4has one at least for formula 2 functional group.
3. methylene-succinic acid basic ring shape silicon skeletal epoxy resin according to claim 2, is characterized in that, in formula 3 structural compounds, and R
1, R
2, R
3, R
4for formula 2 functional group.
4. the preparation method of the methylene-succinic acid basic ring shape silicon skeletal epoxy resin according to any one of claim 1-3, is characterized in that, comprise the following steps:
By the platinum catalyst of the organic solvent of the itaconic acid diglycidyl ester of 100 mass parts, 20 ~ 500 mass parts, the cyclosiloxane of 25 ~ 100 mass parts and 0.001 ~ 0.1 mass parts, reaction 0.5 ~ 50 hour under 60 ~ 140 DEG C of heating, obtains described methylene-succinic acid Quito functionality silicon skeletal epoxy resin through revolving to steam except after desolventizing.
5. the preparation method of methylene-succinic acid basic ring shape silicon skeletal epoxy resin according to claim 4, is characterized in that, described platinum catalyst is Platinic chloride or 1,3-divinyl-1,1,3,3-tetramethyl disiloxane platinum (0).
6. the preparation method of methylene-succinic acid basic ring shape silicon skeletal epoxy resin according to claim 4, it is characterized in that, described organic solvent is one or more in tetrahydrofuran (THF), dioxane, butylacetate, toluene, benzene, dimethylbenzene, DMF, dimethyl sulfoxide (DMSO).
7. the preparation method of methylene-succinic acid basic ring shape silicon skeletal epoxy resin according to claim 4, it is characterized in that, described cyclosiloxane is formula 4 structural compounds,
Wherein, m is the integer of 3-8.
8. the preparation method of methylene-succinic acid basic ring shape silicon skeletal epoxy resin according to claim 7, is characterized in that, described cyclosiloxane is 1,3,5,7-tetramethyl-tetrahydrochysene cyclotetrasiloxane.
9. the methylene-succinic acid basic ring shape silicon skeletal epoxy resin according to any one of claim 1-3 prepares the application of coating as matrix resin.
10. application according to claim 9, is characterized in that, comprises the following steps: described coating comprises the described methylene-succinic acid Quito functionality silicon skeletal epoxy resin and solidifying agent that weight ratio is 1:0.1-0.4.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106146804A (en) * | 2016-07-29 | 2016-11-23 | 广东工业大学 | A kind of photo-curable silicone/epoxy resin composite material and its preparation method and application |
| CN109054632A (en) * | 2018-06-13 | 2018-12-21 | 宁波双人新材料有限公司 | A kind of water-fast weather-proof composite powder coatings and preparation method thereof |
| CN115011219A (en) * | 2022-07-07 | 2022-09-06 | 浙江伟星实业发展股份有限公司 | Button coating, preparation method and application thereof |
| WO2023208180A1 (en) * | 2022-04-29 | 2023-11-02 | 华为技术有限公司 | Epoxy resin, method for preparing same, and resin composition thereof |
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| CN103781814A (en) * | 2011-10-25 | 2014-05-07 | 株式会社艾迪科 | Photocurable resin composition and novel siloxane compound |
| CN104356361A (en) * | 2014-10-15 | 2015-02-18 | 中国科学院宁波材料技术与工程研究所 | Bio-based multifunctional silicon-framework epoxy resin as well as preparing method and application thereof |
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| CN101223181A (en) * | 2006-03-02 | 2008-07-16 | 设计分子有限公司 | Adhesive composition containing cyclosiloxane |
| CN103781814A (en) * | 2011-10-25 | 2014-05-07 | 株式会社艾迪科 | Photocurable resin composition and novel siloxane compound |
| CN104356361A (en) * | 2014-10-15 | 2015-02-18 | 中国科学院宁波材料技术与工程研究所 | Bio-based multifunctional silicon-framework epoxy resin as well as preparing method and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146804A (en) * | 2016-07-29 | 2016-11-23 | 广东工业大学 | A kind of photo-curable silicone/epoxy resin composite material and its preparation method and application |
| CN106146804B (en) * | 2016-07-29 | 2018-10-19 | 广东工业大学 | A kind of photo-curable silicone/epoxy resin composite material and its preparation method and application |
| CN109054632A (en) * | 2018-06-13 | 2018-12-21 | 宁波双人新材料有限公司 | A kind of water-fast weather-proof composite powder coatings and preparation method thereof |
| CN109054632B (en) * | 2018-06-13 | 2020-11-27 | 宁波双人新材料有限公司 | Water-resistant weather-resistant composite powder coating and preparation method thereof |
| WO2023208180A1 (en) * | 2022-04-29 | 2023-11-02 | 华为技术有限公司 | Epoxy resin, method for preparing same, and resin composition thereof |
| CN115011219A (en) * | 2022-07-07 | 2022-09-06 | 浙江伟星实业发展股份有限公司 | Button coating, preparation method and application thereof |
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