CN101974227A - Low-stress epoxy/organic silicon/POSS nano hybrid material, and preparation method and application thereof - Google Patents
Low-stress epoxy/organic silicon/POSS nano hybrid material, and preparation method and application thereof Download PDFInfo
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Abstract
本发明涉及光电及化工技术领域，涉及一种低应力环氧/有机硅/POSS纳米杂化材料及其制备方法和应用。该环氧/有机硅/POSS纳米杂化材料包含：(a)一种环氧树脂，(b)一种聚有机硅氧烷，(c)一种笼型聚倍半硅氧烷(POSS)，(d)一种环氧固化剂，(e)非必须硅烷氧基化合物，(f)非必须助剂，其中，聚有机硅氧烷带有环氧基团和硅烷氧基团。固化后的纳米杂化体系具有优异的网状交联结构，没有微相分离。本发明制备的环氧/有机硅/POSS纳米杂化材料具有机械强度高、耐热性好、粘结性好、化学稳定性好、耐紫外线老化性好、光学透明性好等优异性能，还具有内应力低和缓冲压力的作用，可用作LED封装材料、光学保护材料、电路保护涂层材料、胶粘剂、涂料等使用。The invention relates to the technical fields of optoelectronics and chemical industry, and relates to a low-stress epoxy/organic silicon/POSS nano-hybrid material and its preparation method and application. The epoxy/silicone/POSS nanohybrid material comprises: (a) an epoxy resin, (b) a polyorganosiloxane, (c) a cage polysilsesquioxane (POSS) , (d) an epoxy curing agent, (e) an optional siloxy compound, (f) an optional auxiliary agent, wherein the polyorganosiloxane has an epoxy group and a siloxy group. The cured nano-hybrid system has an excellent network cross-linked structure without microphase separation. The epoxy/organosilicon/POSS nano-hybrid material prepared by the present invention has excellent properties such as high mechanical strength, good heat resistance, good adhesion, good chemical stability, good ultraviolet aging resistance, good optical transparency, and the like. It has the function of low internal stress and buffering pressure, and can be used as LED packaging material, optical protection material, circuit protection coating material, adhesive, coating, etc.
Description
Technical field
The present invention relates to photoelectricity and chemical technology field, is about a kind of low-strees epoxy/organosilicon/POSS nano-hybrid material and its production and application.More specifically, the present invention relates to a kind of low-strees epoxy/organosilicon/POSS nano-hybrid material, it comprises Resins, epoxy, organopolysiloxane, cage modle polysilsesquioxane (POSS), epoxy hardener, nonessential silane oxycompound and nonessential auxiliary agent; The invention still further relates to the preparation method and the application of low-strees epoxy/organosilicon/POSS nano-hybrid material.Nano-hybrid material of the present invention can be applied to fields such as LED packaged material, optics protecting materials, circuit protection coated material, tackiness agent, coating.
Background technology
The protecting materials of photoelectricity base material mainly is Resins, epoxy and silicone resin at present, and both all can be solidified into the film of colourless high-clarity.Resins, epoxy is owing to its excellent metal sticking power, suitable thermal expansivity, snappiness and cheap cost are widely used, but its lower thermostability has limited its application of epoxy greatly because of its inner a large amount of epoxide group, can good adhesive and snappiness be arranged with metal base; But because epoxy group(ing) easily decomposition at high temperature, so the Resins, epoxy poor heat stability has limited its development.Silicone resin has good thermostability, be usually used in hot environment, owing to can in than the temperature of broad, humidity range, keep good physics and electric property, be not vulnerable to the pollution of environment, and has an effect of compensator or trimmer pressure, the characteristic that also has good anti-ultraviolet aging, and extraordinary chemical stability; But itself and metal base sticking power are bad, and snappiness is poor, soft, the scope of application of having dwindled it greatly.
Chinese patent CN 200910072179.0 discloses a kind of preparation method of heat resistant epoxide resin.This method is by adding a kind of heat resistant epoxide resin that obtains of diatomite modified epoxy.
Chinese patent CN200910011292.8 discloses a kind of with MQ silicone resin TiO
2The method of compound modification of epoxy resin.This method adds methyl MQ silicone resin and nano-TiO in Resins, epoxy
2, utilize the MQ silicone resin to carry out chemical modification, utilize nano-TiO
2The physically modified that the surface effects of particle uniqueness and small-size effect are carried out.
At fluoropolymer resin as sizing agent; the optics protecting materials; when coated materials etc. are used; sometimes need long-time high calorie; use under the high optical condition; and the easy moulding of fluoropolymer resin; good but the thermostability of adhesive property; photostabilization is poor; if use inorganic materials; thermotolerance; photostabilization is good; but be difficult to moulding; poor adhesive force; the inorganic nanometer modified fluoropolymer resin of normal employing is used to improve the problems referred to above; but inorganic nano-particle need be by modifier modification with the consistency of raising with polymkeric substance, and it is good to be difficult to obtain the transparency; the inorganic nanometer modified polymkeric substance that inorganic nano content is high.
The hexahedron that cage shape oligomer silasesquioxanes (POSS) has the Si-O nanostructure does not have the machine frame core, and the periphery is an organic group, and diameter is minimum silicon dioxide granule at 1～3nm, is called as molecular silicas.The inorganic cage structure of POSS has the stable advantage of chemical property under ultraviolet (UV) illumination, and its surperficial organo-functional group has fabulous polymer phase capacitive.Utilization has the one or more functional groups with reactive behavior that have on the cage structure POSS and carries out polymerization, grafting, surface modification etc., POSS is introduced the polymer molecule segment, can be implemented on the nanoscale design and prepare novel Organic.POSS has Heat stability is good, resistance to oxidation, weather-proof, advantages such as low-temperature performance good, surface energy is low, low-k, low-stress, damping low noise, environmental protection hypotoxicity, difficult combustion or uninflammability, can improve the resistance toheat and the optical property of material after compound with Resins, epoxy.As (Journal of Adhesion and Interface such as Huang, 2006,7 (4)) prepare epoxy/cage shape oligomer silasesquioxanes (POSS) by hydrogen containing siloxane and the alkene addition reaction of silicon with hydrogen under the Pt inorganic nano-particle that contains epoxycyclohexyl.Japanese Patent JP 200610429 is by with epoxypropoxy methyl dimethoxysilane and dimethyldimethoxysil,ne hydrolysis condensation prepared epoxy/cage shape oligomer silasesquioxanes (POSS) then under base catalysis.(HybridNanocomposites such as Huang, 2009,1927-1934.) be raw material with eight (glycidyl ether siloxanes) octuple half siloxanes (OG) and bisglycidyl ether bisphenol A epoxide resin, by the synthetic POSS/ epoxy nano composite material of light polymerization process, because the crosslinking reaction of strengthening action, OG and the Resins, epoxy of POSS, the rubbery state storage modulus of nano composite material significantly improves.But adopt the method for simple blend to be separated poor mechanical property easily; Shortcoming by chemical modification method is the process complexity, can use solvent usually and cause purification difficult, and restive level of response.
Summary of the invention
The object of the present invention is to provide the epoxy/organosilicon/POSS nano-hybrid material of a kind of high transparent, high weather-proof, high heat-resisting, low-stress.
Low-strees epoxy/organosilicon provided by the present invention/POSS nano-hybrid material, it comprises Resins, epoxy, organopolysiloxane, cage modle polysilsesquioxane (POSS), epoxy hardener, nonessential silane oxycompound and nonessential auxiliary agent.
The present invention also provides the preparation method and the application of above-mentioned low-strees epoxy/organosilicon/POSS nano-hybrid material.
The present invention also provides a kind of nano-hybrid material with POSS to improve thermotolerance, weathering resistance and sunproof method, is not separated.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, it comprises: (a) at least a Resins, epoxy, (b) at least a organopolysiloxane, (c) at least a cage modle polysilsesquioxane (POSS), (d) at least a epoxy hardener, (e) nonessential silane oxycompound, (f) nonessential auxiliary agent; Wherein, organopolysiloxane has epoxide group and silane oxygen groups.At first, under acidic conditions, make Resins, epoxy part open loop hydroxylation, adopt sol-gel process that Resins, epoxy, organopolysiloxane, cage modle polysilsesquioxane (POSS) and nonessential silane oxycompound are carried out chemical condensation reaction then, obtain homogeneous phase epoxy/organosilicon/POSS composition, add epoxy hardener again, obtain low-strees epoxy/organosilicon/POSS nano-hybrid material; Gross weight in epoxy/organosilicon/POSS nano-hybrid material, each amounts of components is: Resins, epoxy 10-50wt%, organopolysiloxane 30-88wt%, cage modle polysilsesquioxane (POSS) 1-59wt%, epoxy hardener 1-20wt%, silane oxycompound 0-20wt%, nonessential auxiliary agent 0-20wt%.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, described Resins, epoxy are selected from one or more combination of bisphenol A epoxide resin, bisphenol F epoxy resin, glycidyl ester based epoxy resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin, organic-silicon-modified bisphenol A epoxide resin, organic titanium modified bisphenol A epoxy resin.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, the limiting examples of described Resins, epoxy comprises, as: the bisphenol A epoxide resin GY240 that Switzerland Ciba company limited (Ciba) produces, GY250, GY260, GY226 etc. and cycloaliphatic epoxy resin PY284, CY179, the bisphenol A epoxide resin D.E.R.331 that Dow Chemical (DOW) is produced, D.E.R.383, D.E.R.332, D.E.R.337 etc., bisphenol F epoxy resin D.E.R.351, D.E.R.353 and cycloaliphatic epoxy resin ERL 4229, ERL-4221, the bisphenol-A epoxy Epon 825 that U.S. Shell Co. Ltd (Shell) produces, Epon826, Epon828, Epon830, Epon834 etc. and hydrogenated bisphenol A epoxy resin EPONEX 1510, the bisphenol A epoxide resin Epikote162 that U.S. Hexion company produces, Epikote827, Epikote828, Epikote158, the hydrogenated bisphenol A epoxy resin HBGE. that BASF Aktiengesellschaft (BASF) produces, the GY250 of German Hunstman company, GY184, GT7071, GT7072 etc. and bisphenol F epoxy resin GY281 etc.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, described organopolysiloxane is that molecular weight is the (RSiO that has that has epoxide group and silane oxygen groups of 800-8000
1.5) polymkeric substance of n structure, R can be the derivative of alkyl, thiazolinyl, aryl and alkyl, thiazolinyl, aryl, epoxy group(ing), alkoxyl group, selects its one or more combination.
Organopolysiloxane can adopt sol-gel process, is raw material with the silicon alkoxyl group monomer that has machine functional group, and hydrolytie polycondensation obtains under acidity or basic catalyst effect.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, the limiting examples of described organopolysiloxane comprises, as: epoxy group(ing) methoxyl group organopolysiloxane, epoxy group(ing) oxyethyl group organopolysiloxane, vinyl epoxy group(ing) methoxyl group organopolysiloxane, benzyl ring Oxymethoxy organopolysiloxane, phenyl epoxy base oxethyl organopolysiloxane etc.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, (the RSiO of described cage modle polysilsesquioxane (POSS) for having cage structure
1.5)
nPolysilsesquioxane, wherein R can be mutually the same or different, but contain an epoxide group at least, and all the other R groups can be distinguished independent be hydrogen atom, halogen atom, hydroxyl, C
1-20Alkyl, alkenyl, alkynyl, aryl, alicyclic radical or alkoxyl group select its one or more combination.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, the limiting examples of described cage modle polysilsesquioxane (POSS) comprises, as: octa-epoxy POSS, diisobutyl-six epoxy group(ing) POSS, tetraphenyl-four epoxy group(ing) POSS, trivinyl-five epoxy group(ing) POSS, hexamethyl-bicyclic oxygen POSS, phenylbenzene-dimethyl-four epoxy group(ing) POSS, hexahydroxy--bicyclic oxygen POSS, dimethoxy-six epoxy group(ing) POSS etc.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, described epoxy hardener be can with the conventional epoxy hardener of epoxy resin cure, as one or more combination of amine curing agent, amides solidifying agent, acids solidifying agent, acid anhydride type curing agent.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, the limiting examples of described epoxy hardener comprises: as: the Aradur830 that German Hunstman company produces, Aradur3440, Aradur100, Aradur125 etc., the XZ92441.01 that Dow Chemical (DOW) is produced, XZ92415.00, D.E.H.81 etc., the VestaminIPD that Germany Degussa company produces, the Epikure105 that U.S. Hexion company produces, Epikure185, Epikure3055 etc., acid anhydride type curing agent such as Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, the methyl carbic anhydride, dodecyl succinic anhydride, pyromellitic dianhydride, the benzophenone tetracarboxylic dianhydride, methyl cyclic ethylene tetracarboxylic dianhydride, the phenyl ether tetracarboxylic dianhydride, trimellitic acid 1,2-anhydride, poly-nonane diacid acid anhydride etc.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, described nonessential silane oxycompound are that molecular weight is one or more combination of 100～2000 epoxy radicals silicone hydride oxycompound, alkyl silane oxycompound, thiazolinyl silane oxycompound, aromatic base silane oxycompound.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, the limiting examples of described nonessential silane oxycompound comprises: as: epoxy Trimethoxy silane, methyltrimethoxy silane, Union carbide A-162, methyl tripropoxy silane, phenyltrimethoxysila,e, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl dipropoxy silane, the trimethylammonium methoxy silane, trimethylethoxysilane, tetraethoxy, phenyltrimethoxysila,e, the phenyl methyl diethoxy silane, vinyltrimethoxy silane, vinyl propyl group dimethoxy silane, the dodecyl Trimethoxy silane, the dodecyl triethoxyl silane, the hexadecyl Trimethoxy silane, the hexadecyl triethoxyl silane, the 3-methacryloxypropyl trimethoxy silane, 3-glycidyl ether oxygen propyl trimethoxy silicane etc.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, described nonessential auxiliary agent are one or more combination of common solvent in the sizing agent, UV light absorber, curing catalyst, ageing-resistant dose, thermo-stabilizer, toughner, viscosity increaser, thickening material etc.
Low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, each amounts of components is: Resins, epoxy 10-50wt%, organopolysiloxane 30-88wt%, cage modle polysilsesquioxane (POSS) 1-59wt%, epoxy hardener 1-20wt%, silane oxycompound 0-20wt%, nonessential auxiliary agent 0-20wt%.
The preparation method of low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes, concrete steps are as follows:
(1) press set of dispense than weighing Resins, epoxy, under 70-130 ℃ of condition, Resins, epoxy reacted 1-24 hour under acidic conditions, made the Resins, epoxy ring-opening reaction of 10-50%;
(2) add organopolysiloxane, cage modle polysilsesquioxane (POSS) and nonessential silane oxycompound in the product that in step (1), obtains, evenly blend, under 0-90 ℃ of condition, add minor amount of water, be hydrolyzed condensation reaction 1-72 hour, and obtained homogeneous phase epoxy/organosilicon/POSS composition;
(3) add epoxy hardener and nonessential auxiliary agent in the epoxy/organosilicon/POSS composition that obtains in step (2), crosslinking curing under 0～300 ℃ of condition obtains low-strees epoxy/organosilicon/POSS nano-hybrid material.
Among the present invention, described Resins, epoxy is selected from bisphenol A epoxide resin, bisphenol F epoxy resin, glycidyl ester based epoxy resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin, organic-silicon-modified bisphenol A epoxide resin, organic titanium modified bisphenol A epoxy resin.
Among the present invention, described organopolysiloxane is that molecular weight is the polymkeric substance with Si-O-Si backbone structure that has epoxide group and silane oxygen groups of 800-8000.
Among the present invention, (the RSiO of described cage modle polysilsesquioxane (POSS) for having cage structure
1.5)
nPolysilsesquioxane, wherein R can be mutually the same or different, but contain an epoxide group at least, and all the other R groups can be distinguished independent be hydrogen atom, halogen atom, hydroxyl, C
1-20Alkyl, alkenyl, alkynyl, aryl, alicyclic radical, alkoxyl group.
Among the present invention, described epoxy hardener be can with the conventional epoxy hardener of epoxy resin cure, as amine curing agent, amides solidifying agent, acids solidifying agent, acid anhydride type curing agent.
Among the present invention, described nonessential silane oxycompound is that molecular weight is 100～2000 epoxy radicals silicone hydride oxycompound, alkyl silane oxycompound, thiazolinyl silane oxycompound, aromatic base silane oxycompound.
Among the present invention, described nonessential auxiliary agent is one or more the combination of common solvent in the sizing agent, UV light absorber, curing catalyst, ageing-resistant dose, thermo-stabilizer, toughner, viscosity increaser, thickening material etc.
Low-strees epoxy/organosilicon of the present invention/POSS nano-hybrid material is as the application that can be used as LED packaged material, optics protecting materials, circuit protection coated material, tackiness agent, coating etc.
A kind of low-strees epoxy/organosilicon/POSS nano-hybrid material that the present invention proposes has the following advantages:
(1) epoxy/organosilicon of the present invention/POSS nano-hybrid material is made up of organopolysiloxane, POSS, Resins, epoxy and solidifying agent, and the more former Resins, epoxy of thermostability has lifting significantly.
(2) epoxy/organosilicon of the present invention/POSS nano-hybrid material has the characteristics of Resins, epoxy, silicone resin concurrently, utilizes the organo-functional group of POSS to form cross-linked structure, is not separated.
(3) epoxy/organosilicon/POSS nano-hybrid material of the present invention's preparation can be at the lesser temps film-forming, have excellent properties such as excellent thermostability, light transmission rate, snappiness, sticking power, hardness, low-stress, and production cost is low, production technique is simple and easy, can be used for substrate surfaces such as metal, glass, plastics.
(4) low-strees epoxy/organosilicon/POSS nano-hybrid material of obtaining of the present invention can be used as application such as LED packaged material, optics protecting materials, circuit protection coated material, tackiness agent, coating.
The present invention adopts following analysis and characterization method to measure epoxy/organosilicon/POSS nano-hybrid material.Adopt the refractive index of the Britain NKD of AQUILA company film analysis system testing nano-hybrid material; Adopt the thermostability of the Pyris 1TGA thermal gravimetric analyzer mensuration material of Perkin Elmer Instruments company; Guomei's spectrum reaches the light transmission rate of the UV-1800PC type measurement of ultraviolet-visible spectrophotometer film of Instr Ltd. in the employing; Adopt cross-hatching to measure the sticking power of material; Adopt pencil to measure hardness.
Description of drawings
Fig. 1 is the surperficial SEM stereoscan photograph of epoxy/organosilicon/POSS nano-hybrid material, and as can be seen from the figure, the epoxy/organosilicon of preparation/POSS nano-hybrid material surface is even, fine and close.
Fig. 2 is the section S EM stereoscan photograph of epoxy/organosilicon/POSS nano-hybrid material, and as can be seen from the figure, Resins, epoxy and silicone resin are not found phenomenon of phase separation in the epoxy/organosilicon of preparation/POSS nano-hybrid material.
Fig. 3 is the thermal weight loss TGA curve of epoxy/organosilicon/POSS nano-hybrid material, and as can be seen from the figure, the epoxy/organosilicon of preparation/POSS nano-hybrid material resistance toheat is than pure epoxy resin and epoxy/silicone resin height.
Embodiment
Example 1:
In 250ml four neck flasks, add bisphenol A epoxide resin 30 grams, at 80-100 ℃, acidic conditions reacted 5 hours down, make Resins, epoxy part open loop hydroxylation, the epoxy group(ing) methoxyl group organopolysiloxane that adds 60 gram molecular weights 2000 again, 5 gram six isobutyl-s-bicyclic oxygen POSS, 2 gram epoxy group(ing) dimethoxy silane, 20-40 ℃ of stirring, condensation reaction 72 hours, obtain homogeneous phase epoxy/organosilicon/POSS composition, add 10 gram Tetra hydro Phthalic anhydride epoxy hardeners, solidified 3 hours at 100 ℃, obtain low-strees epoxy/organosilicon/POSS nano-hybrid material.The hardness 3H of material, snappiness 1mm, visible light transmissivity 95%.
Example 2:
In 250ml four neck flasks, add cycloaliphatic epoxy resin 10 grams, reaction is 8 hours under 70-80 ℃, acidic conditions, make Resins, epoxy part open loop hydroxylation, the epoxy and phenyl methoxyl group organopolysiloxane, the 45 gram six epoxy group(ing)-dimethoxy POSS that add 40 gram molecular weights 1000 again, 60-70 ℃ of stirring, condensation reaction 24 hours, obtain homogeneous phase epoxy/organosilicon/POSS composition, add 3 gram Aradur830 epoxy hardeners, 2 gram ethanol auxiliary agents, solidified 3 hours at 150 ℃, obtain low-strees epoxy/organosilicon/POSS nano-hybrid material.The hardness 2H of material, snappiness 1mm, visible light transmissivity 99%.
Example 3:
In 250ml four neck flasks, add bisphenol A epoxide resin 5 grams, bisphenol F epoxy resin 5 grams, organosilicon epoxy resin 5 grams, at 100-120 ℃, acidic conditions reacted 5 hours down, make Resins, epoxy part open loop hydroxylation, the epoxy group(ing) oxyethyl group organopolysiloxane that adds 30 gram molecular weights 5000 again, 10 gram epoxy group(ing)-seven methyl POSS, 10 gram diisobutyl-six epoxy group(ing) POSS, add 20 gram methyl alcohol auxiliary agents, 50-60 ℃ of stirring, condensation reaction 48 hours, obtain homogeneous phase epoxy/organosilicon/POSS composition, add 15 gram methyl tetrahydrophthalic anhydride epoxy hardeners, solidified 5 hours at 180 ℃, obtain low-strees epoxy/organosilicon/POSS nano-hybrid material.The hardness 4H of material, snappiness 1mm, visible light transmissivity 97%.
Example 4:
In 250ml four neck flasks, add hydrogenated bisphenol A epoxy resin 40 grams, at 100-120 ℃, acidic conditions reacted 10 hours down, make Resins, epoxy part open loop hydroxylation, the epoxy group(ing) methyl ethoxy organopolysiloxane that adds 30 gram molecular weights 10000 again, 10 gram three epoxy group(ing)-five hexyl POSS, 5 gram tetraethoxys, 5 gram phenyltrimethoxysila,e, 70-90 ℃ of stirring, condensation reaction 48 hours, obtain homogeneous phase epoxy/organosilicon/POSS composition, add 10 gram hexahydrophthalic anhydride epoxy hardeners, solidified 7 hours at 150 ℃, obtain low-strees epoxy/organosilicon/POSS nano-hybrid material.The hardness 4H of material, snappiness 2mm, visible light transmissivity 99%.
Example 5:
In 250ml four neck flasks, add aliphatic glycidyl ether resin 5 grams, organosilicon epoxy resin 5 grams, at 80-100 ℃, acidic conditions reacted 10 hours down, make Resins, epoxy part open loop hydroxylation, the epoxy group(ing) ethyl methoxyl group organopolysiloxane that adds 70 gram molecular weights 5000 again, 3 gram octa-epoxy POSS, add 9 gram acetone auxiliary agents, 50-60 ℃ of stirring, condensation reaction 48 hours, obtain homogeneous phase epoxy/organosilicon/POSS composition, add 5 gram tetraethylenepentamine epoxy hardeners, 1 gram UV absorption agent, 2 gram curing catalysts, solidified 1 hour at 80 ℃, obtain low-strees epoxy/organosilicon/POSS nano-hybrid material.The hardness H of material, snappiness 1mm, visible light transmissivity 90%.
Claims (4)
1. low-strees epoxy/organosilicon/POSS nano-hybrid material, it is characterized in that this hybrid material comprises: (a) at least a Resins, epoxy, (b) at least a organopolysiloxane, (c) at least a cage modle polysilsesquioxane POSS, (d) at least a epoxy hardener, (e) nonessential silane oxycompound reaches (f) nonessential auxiliary agent, wherein, organopolysiloxane has epoxide group and silane oxygen groups; At first, under acidic conditions, make Resins, epoxy part open loop hydroxylation, adopt then sol-gel process with Resins, epoxy, organopolysiloxane, cage modle polysilsesquioxane and nonessential silane oxycompound by chemical condensation reaction, obtain homogeneous phase epoxy/organosilicon/POSS composition, add epoxy hardener, obtain low-strees epoxy/organosilicon/POSS nano-hybrid material; Gross weight in epoxy/organosilicon/POSS nano-hybrid material, each amounts of components is: Resins, epoxy 10-50wt%, organopolysiloxane 30-88wt%, cage modle polysilsesquioxane POSS 1-59wt%, epoxy hardener 1-20wt%, silane oxycompound 0-20wt%, nonessential auxiliary agent 0-20wt%;
Wherein, Resins, epoxy is selected from one or more the combination in bisphenol A epoxide resin, bisphenol F epoxy resin, glycidyl ester based epoxy resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin, organic-silicon-modified bisphenol A epoxide resin, the organic titanium modified bisphenol A epoxy resin;
Organopolysiloxane is that molecular weight is the polymkeric substance with Si-O-Si backbone structure that has epoxide group and silane oxygen groups of 800-8000, selects its one or more combination;
Cage modle polysilsesquioxane POSS is the (RSiO with cage structure
1.5)
nPolysilsesquioxane, wherein R can be mutually the same or different, but contain an epoxide group at least, and all the other R groups can be distinguished independent be hydrogen atom, halogen atom, hydroxyl, C
1-20The combination of one or more in alkyl, alkenyl, alkynyl, aryl, alicyclic radical or the alkoxy base;
Epoxy hardener be can with the conventional epoxy hardener of epoxy resin cure, be one or more combination of amine curing agent, amides solidifying agent, acids solidifying agent or acid anhydride type curing agent;
Nonessential silane oxycompound is that molecular weight is one or more combination of 100～2000 epoxy radicals silicone hydride oxycompound, alkyl silane oxycompound, thiazolinyl silane oxycompound, aromatic base silane oxycompound;
Nonessential auxiliary agent is common solvent in the sizing agent, UV light absorber, curing catalyst, ageing-resistant dose, one or more combination of thermo-stabilizer, toughner, viscosity increaser, thickening material.
2. low-strees epoxy/organosilicon/POSS nano-hybrid material is characterized in that described Resins, epoxy is selected from one or more combination of bisphenol A epoxide resin, bisphenol F epoxy resin, glycidyl ester based epoxy resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin, organic-silicon-modified bisphenol A epoxide resin, organic titanium modified bisphenol A epoxy resin.
3. the preparation method of low-strees epoxy/organosilicon as claimed in claim 1/POSS nano-hybrid material is characterized in that concrete steps are as follows:
(1) press set of dispense than weighing Resins, epoxy, under 70-130 ℃ of condition, Resins, epoxy reacted 1-24 hour under acidic conditions, made the Resins, epoxy ring-opening reaction of 10-50%;
(2) in the product that step (1) obtains, add organopolysiloxane, cage modle polysilsesquioxane POSS and nonessential silane oxycompound, evenly blend, under 0-90 ℃ of condition, add minor amount of water, be hydrolyzed condensation reaction 1-72 hour, obtain homogeneous phase epoxy/organosilicon/POSS composition;
(3) add epoxy hardener and nonessential auxiliary agent in epoxy/organosilicon/POSS composition that step (2) obtains, crosslinking curing under 0～300 ℃ of condition obtains low-strees epoxy/organosilicon/POSS nano-hybrid material.
4. one kind as the application in fields such as LED packaged material, optics protecting materials, circuit protection coated material, tackiness agent, coating of claim 1,2 described low-strees epoxy/organosilicons/POSS nano-hybrid material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101793375A CN101974227A (en) | 2010-05-20 | 2010-05-20 | Low-stress epoxy/organic silicon/POSS nano hybrid material, and preparation method and application thereof |
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| CN2010101793375A CN101974227A (en) | 2010-05-20 | 2010-05-20 | Low-stress epoxy/organic silicon/POSS nano hybrid material, and preparation method and application thereof |
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| CN109735203A (en) * | 2018-12-25 | 2019-05-10 | 陕西科技大学 | A kind of semi-closed cage-like trifunctional epoxy ether-based POSS composite material, coating and preparation method |
| CN109880583A (en) * | 2019-01-10 | 2019-06-14 | 北京康美特科技股份有限公司 | A kind of heat conduction organosilicon adhesive and its solidfied material and LED element |
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| CN106894009B (en) * | 2017-02-24 | 2019-03-15 | 武汉大学 | A kind of epoxy group POSS modified metal surface pretreating reagent and preparation method thereof, application |
| CN110157368A (en) * | 2018-02-13 | 2019-08-23 | 宁德时代新能源科技股份有限公司 | Adhesive and electrochemical device using same |
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| CN109880583B (en) * | 2019-01-10 | 2021-06-22 | 北京康美特科技股份有限公司 | Heat-conducting organic silicon adhesive, cured product thereof and LED element |
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Application publication date: 20110216 |