CN101525467A - Epoxy/organosilicon hybrid material, and preparation method and application thereof - Google Patents
Epoxy/organosilicon hybrid material, and preparation method and application thereof Download PDFInfo
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- CN101525467A CN101525467A CN 200910048920 CN200910048920A CN101525467A CN 101525467 A CN101525467 A CN 101525467A CN 200910048920 CN200910048920 CN 200910048920 CN 200910048920 A CN200910048920 A CN 200910048920A CN 101525467 A CN101525467 A CN 101525467A
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Abstract
The invention belongs to the technical field of chemical engineering, more specifically relates to an epoxy/organosilicon hybrid material and the preparation method thereof. The epoxy/organosilicon hybrid material is made from epoxy resin, organosilicon resin, an acidic curing agent, unnecessary organic epoxy silane, an unnecessary adjuvant and the like. The components are hybridized and cured in situ under catalytic action of the acidic curing agent by simple physical mixing to obtain the epoxy/organosilicon hybrid material. The production and preparation processes are environment-friendly, energy-saving, simple and easy for control, and no solvent is used in the processes. The epoxy/organosilicon hybrid material prepared by the method has the characteristics of good bonding property, high mechanical strength, high shear strength and excellent machinability of the epoxy resin, and has the characteristics of strong heat resistance, good insulativity, strong elasticity, strong ageing resistance and good transparence of the organosilicon resin. The epoxy/organosilicon hybrid material can be taken as an adhesive, an insulating material, printing ink, a coating material, a solder mask material of a printed circuit, an optical protection material, an LED encapsulation material, an optoelectronic conversion material and the like.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of epoxy and its production and application.
Background technology
Silicone resin 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, is widely used in sizing agent, coated material, optics, Electronic Protection material etc.But silicone resin is relatively poor to base material sticking power, and organic solvent resistance is poor, hardness is low, and the surface is easy to the adhesion dust when high temperature, cost an arm and a leg etc.Resins, epoxy has good mechanical property, electric property, adhesiveproperties, thermotolerance, solvent resistance and easy-formation processing, advantage such as with low cost, yet because it has the 3 D stereo reticulated structure, lack slip between molecular chain, C-C, carbon-oxygen bond can be less, surface energy is higher, and some hydroxyls that have etc. make that its internal stress is big, easy degradation with aging under the embrittlement, high temperature.Use the epoxy-organic silicon resin, both can reduce the Resins, epoxy internal stress, can increase Resins, epoxy toughness again, improve its thermotolerance and resistance to chemical reagents, have good acid-and base-resisting, salt, performance such as humidity, water-fast, oil resistant and anti-chemical atmosphere corrosion.
At present more to the research of epoxy-organic silicon resin, as strengthen the hardness and the cohesive force of silicone resin with Resins, epoxy; Improve heat-resisting, the anti-UV and the electric property of Resins, epoxy with silicone resin.Adopt the method for simple blend to be separated poor mechanical property easily.Usually the method with epoxy/silicone resin hydridization is by addition or condensation reaction.For example people (Journal of Adhesion and Interface Vol.7, No.4,2006) such as W.Huang prepares by hydrogen containing siloxane and alkene addition reaction of silicon with hydrogen under the Pt solidifying agent of containing epoxycyclohexyl.Be to adopt the organosilicon segment is introduced in the molecular structure of Resins, epoxy in the U.S. Pat 6632892.Among the Japanese Patent JP 200610429 be by with epoxypropoxy methyl dimethoxysilane and dimethyldimethoxysil,ne under base catalysis hydrolysis then condensation prepare epoxy silicone resin.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 that a kind of preparation technology is simple, temperature tolerance good, good weatherability, good insulating, photostabilization is good, antiseptic property is excellent epoxy.
Epoxy provided by the invention, it comprises Resins, epoxy, silicone resin, acid curing agent, nonessential organic epoxy silane, and nonessential auxiliary agent.
The present invention also provides the preparation method and the application of above-mentioned epoxy.
The present invention is made into mixture by the simple physical blending means earlier with Resins, epoxy and silicone resin, utilizing Resins, epoxy and silicone resin that in-situ hybridization takes place under the solidifying agent katalysis again solidifies, obtain epoxy, do not contain any solvent in the hybrid material, can not be separated yet.
The epoxy that the present invention proposes, it comprises: (a) at least a Resins, epoxy, (b) at least a silicone resin, (c) at least a acid curing agent, (d) nonessential organic epoxy silane, (e) nonessential auxiliary agent; Each amounts of components is respectively with the mass fraction note: 100 parts of Resins, epoxy, 1～500 part of silicone resin, 0.01～20 part of acid curing agent, 0～100 part of organic epoxy silane, 0～30 part of auxiliary agent.
The epoxy that the present invention proposes does not contain any organic solvent, and solid content is 100wt%.
The epoxy that the present invention proposes, each amounts of components is preferably: 100 parts of Resins, epoxy, 1～300 part of silicone resin, 0.01～5 part of acid curing agent, 0～50 part of organic epoxy silane, 0～10 part of auxiliary agent.
The epoxy that the present invention proposes, Resins, epoxy is selected from the one or more combination of bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin, cycloaliphatic epoxy resin.
The epoxy 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.331j, D.E.R.383, D.E.R.332, D.E.R.337 etc. 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 hydrogenated bisphenol A epoxy resin HBGE. that BASF Aktiengesellschaft (BASF) produces, the cycloaliphatic epoxy resin JEw-0112 that Changhu Jiafa chemistry Co., Ltd. produces, the cycloaliphatic epoxy resin CER-170 that the gloomy luxuriant Fine Chemical Co., Ltd in Wuhan produces, the hydrogenated bisphenol A epoxy resin GEST3000 of Guangdong HongChang Electronic Materials Co., Ltd etc.
The epoxy that the present invention proposes, silicone resin are molecular weight in 100～20000 hydroxy silicon oil and one or more the combination in the hydroxyl poly organic silicon sesquioxyalkane.
The structure of hydroxy silicon oil is represented by following general formula:
Wherein, R
1=hydroxyl; R
2=methyl or phenyl; The integer of n1=1～100.
The structure of hydroxyl poly organic silicon sesquioxyalkane is represented by following general formula:
(R
3SiO
3/2)
n2(R
3SiO
2/2)
n3(R
3SiO
1/2)
n4(SiO
4/2)
n5
Wherein, n2=1～100, n3=0～100, n4=0～100, n5=0～100; R
3=phenyl, hydroxyl or contain the alkyl of 1～40 carbon atom; At least contain 1 mole oh group in the resin.
It is 100～10000 hydroxyl poly organic silicon sesquioxyalkane at 100～10000 hydroxy silicon oil or molecular weight that the epoxy that the present invention proposes, described silicone resin are preferably molecular weight.
The epoxy that the present invention proposes, the limiting examples of described silicone resin comprises X-21-5841, KF-9701, KR-220, the KR-216 that produces as: Japanese Shin-Etsu Chemial Co., Ltd (Shin Etsu), SILRES 601, SILRES 602, SILRES 604, SILRES 605 that Germany Wa Ke company (Wacker) produces, DC6018, DC217, DC220, DC249, DC233, DC 4-2737, DC 1-9770, DC3563 etc. that Dow corning company (Dow Corning) produces.
The epoxy that the present invention proposes, acid curing agent are one or more combination of acid anhydrides, hydrogenation acid anhydrides, metal carboxylate, the metal acetylacetonate complex compound of molecular weight 100～5000.
The epoxy that the present invention proposes, the metal described in the acid curing agent is selected from second and third main group metal, fourth, fifth, the transition metal in six cycles and lanthanide series metal.
The epoxy that the present invention proposes, the limiting examples of described acid curing agent comprises: the combination of one or more in Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, methyl tetrahydro phthalic anhydride, HHPA, methyl hexahydrophthalic anhydride, zinc naphthenate, zinc octoate, cobalt naphthenate, stannous octoate, methyl ethyl diketone tin, methyl ethyl diketone zirconium, aluminium acetylacetonate, titanium acetylacetone, acetyl acetone, four acetyl acetones and the methyl ethyl diketone platinum.
The epoxy that the present invention proposes, organosilane are that molecular weight is one or more the combination in 100～2000 the band oxygen groups organo-siloxane; Described organosilane has following structure:
(R
4)
nSi(OR
5)
4-n，
Wherein, n=1,2,3;
R
5=contain the alkyl of 1～20 carbon atom, preferentially select the alkyl of 1～10 carbon atom for use.
The epoxy that the present invention proposes, the limiting examples of described organosilane comprises KBM-303, KBM-403, KBE-402, the KBE-403 that produces as: Japanese Shin-Etsu Chemial Co., Ltd (Shin Etsu), DC Z-6040, DC Z-6042 that Dow corning company (Dow Corning) produces, Silquest 187, Silquest 186 that Singapore Momentive performance materials company (mpm) produces, German Wa Ke company (Wacker) produces
GF 80, GF 82, the silane that German goldschmidt chemical corporation (Degussa) is produced
GLYMO, homemade silane KH-560 etc.
The epoxy that the present invention proposes, auxiliary agent are one or more combination of UV light absorber commonly used in the sizing agent, ageing-resistant dose, thermo-stabilizer, toughner, viscosity increaser, thickening material etc.
In epoxy of the present invention, can also comprise other optional component, as long as they and consumption thereof bring adverse influence to epoxy of the present invention indistinctively, optional component comprises tinting material, sterilant, sanitas, weighting agent etc., or combination arbitrarily.
The preparation method of the above-mentioned epoxy that the present invention proposes, its concrete steps are as follows:
(1) by set of dispense than each component of weighing, the Resins, epoxy of 20～70wt% and silicone resin and nonessential organosilane are carried out blend, stirred 0.1～24 hour;
(2) remaining Resins, epoxy and solidifying agent are mixed the thing that is uniformly mixed, 1～24 hour time;
(3) under agitation condition, drip the uniform mixture that obtains in the step (2) in the blend that in step (1), obtains, 0.1～5 hour blend time; Add nonessential auxiliary agent as need, then nonessential auxiliary agent drips the back to be continued to stir 0.1～5 hour; Promptly make described epoxy.
Epoxy of the present invention is as the application of sizing agent, insulating material, printing ink, coated material, printed wiring solder resist material, optics protecting materials, LED packaged material, photoelectric conversion material.
Utilize the present invention, the epoxy in-situ hybridization crosslinking curing under 0～300 ℃ of condition with obtaining after the simple physical blend obtains epoxy.
Utilize the present invention, the epoxy in-situ hybridization crosslinking curing under 20～200 ℃ of conditions with obtaining after the simple physical blend obtains epoxy.
A kind of temperature tolerance that the present invention proposes is good, good weatherability, good insulating, photostabilization is good, antiseptic property is excellent epoxy, has following characteristics:
(1) the present invention passes through simple blend with Resins, epoxy and organic hydroxy silicate resin, utilize the hydroxyl reaction of acid curing agent and silicone resin, again with the Resins, epoxy ring-opening polymerization, epoxy/organosilicon in-situ hybridization, obtain the homogeneous phase hybrid material, phenomenon of phase separation can not take place.
(2) epoxy of the present invention preparation both had that epoxy bond is good, physical strength and slip resistance height, characteristics that workability is good, the characteristics that have heat resistance of organic silicon resin height, good insulating again simultaneously, elasticity are strong, ageing resistance good, the transparency is good.
(3), can regulate and control the cohesive strength of epoxy on different substrate materials, sticking power size, heat resisting temperature, specific inductivity etc. by the ratio of gate ring epoxy resins and silicone resin.
(4) production of the present invention and preparation process simple and be easy to control, production process does not contain any solvent, is a kind of environmental protection, energy-conservation epoxy green synthesis method.
(5) epoxy of the present invention's preparation can be used as sizing agent, insulating material, printing ink, coated material, printed wiring solder resist material, optics protecting materials, LED packaged material, photoelectric conversion material etc.
Description of drawings
Fig. 1 is the surperficial SEM stereoscan photograph of the epoxy of embodiment 2, and as can be seen from the figure, the epoxy surface of preparation is even, fine and close.
Fig. 2 is the section S EM stereoscan photograph of the epoxy of embodiment 2, and as can be seen from the figure, Resins, epoxy and silicone resin are not found phenomenon of phase separation in the epoxy of preparation.
Embodiment
The following example has further described and has proved the preferred embodiment in the scope of the invention.These embodiment that given only are illustrative, and are unintelligible for being limitation of the present invention.
Embodiment 1:
Epoxy prescription 1
Form consumption (part)
Hydrogenated bisphenol A epoxy resin 100
Hydroxyl poly-phenyl silsesquioxane 70
Epoxy radicals silicone hydride 20
Methyl hexahydrophthalic anhydride 2
UV absorption agent 3
In reactor, add the hydroxyl poly-phenyl silsesquioxane of 50 parts of hydrogenated bisphenol A epoxy resins (EPONEX 1510), 70 parts of molecular-weight average 5000, stirred 5 hours, add 20 parts of epoxy radicals silicone hydrides (GF-82), continue to stir 0.5 hour, get the A component, stand-by.
In reactor, add 50 parts of hydrogenated bisphenol A epoxy resins (EPONEX 1510), 2 parts of methyl hexahydrophthalic anhydrides, stirred 2 hours, add the A component, continue to stir 1 hour, add 3 parts of UV absorption agents (Octabenzone) again, stirred 1 hour, obtain epoxy.
150 ℃ of heating 2 hours, in-situ solidifying obtained epoxy with above-mentioned epoxy.
Embodiment 2:
Epoxy prescription 2
Form consumption (part)
Hydrogenated bisphenol A epoxy resin 100
Hydroxyl poly-phenyl silsesquioxane 2
Hydroxy silicon oil 5
Epoxy radicals silicone hydride 2
Stannous octoate 0.6
In reactor, add the hydroxyl poly-phenyl silsesquioxane of 50 parts of hydrogenated bisphenol A epoxy resins (GEST3000), 2 parts of molecular-weight average 3500, the hydroxy silicon oil of 5 parts of molecular-weight average 10000, stirred 1 hour, add 2 parts of epoxy radicals silicone hydrides (GLYMO), continue to stir 1 hour, get the A component, stand-by.
In reactor, add 50 parts of hydrogenated bisphenol A epoxy resins (GEST3000), 0.6 part of stannous octoate, stirred 5 hours, add the A component, continue to stir 5 hours, obtain epoxy.
180 ℃ of heating 0.5 hour, in-situ solidifying obtained epoxy with above-mentioned epoxy.
Embodiment 3:
Epoxy prescription 3
Form consumption (part)
Cycloaliphatic epoxy resin 100
Hydroxy silicon oil 100
Methyl ethyl diketone zirconium 0.01
In reactor, add the hydroxy silicon oil of 70 parts of cycloaliphatic epoxy resins (ERL-4221), 100 parts of molecular-weight average 2000, stirred 15 hours, get the A component, stand-by.
In reactor, add 30 parts of cycloaliphatic epoxy resins (ERL-4221), 0.01 part of methyl ethyl diketone zirconium, stirred 10 hours, get the B component.
Above-mentioned A component, B component are mixed, and 50 ℃ of heating 5 hours, in-situ solidifying obtained epoxy.
Embodiment 4:
Epoxy prescription 4
Form consumption (part)
Cycloaliphatic epoxy resin 100
Hydroxyl poly-phenyl silsesquioxane 100
Epoxy radicals silicone hydride 40
Hexahydrophthalic anhydride 15
In reactor, add the hydroxyl poly-phenyl silsesquioxane of 40 parts of cycloaliphatic epoxy resins (CER-170), 100 parts of molecular-weight average 2500, the hydroxy silicon oil of 200 parts of molecular-weight average 1000, stirred 0.5 hour, add 40 parts of epoxy radicals silicone hydrides (Z-6042) again, continue to stir 2 hours, get the A component, stand-by.
In reactor, add 60 parts of cycloaliphatic epoxy resins (CER-170), 15 parts of hexahydrophthalic anhydrides, stirred 4 hours, get the B component.
Above-mentioned A component, B component are mixed, placed 48 hours in room temperature, in-situ solidifying obtains epoxy.
Embodiment 5:
Epoxy prescription 5
Form consumption (part)
Bisphenol A epoxide resin 100
Hydroxy silicon oil 60
Epoxy radicals silicone hydride 70
Titanium acetylacetone 1
Thermo-stabilizer 3
UV absorption agent 2
In reactor, add hydroxy silicon oil, 70 parts of epoxy radicals silicone hydrides (KH-560) of 50 parts of bisphenol A epoxide resins (D.E.R.337), 60 parts of molecular-weight average 2500, stirred 24 hours, get the A component, stand-by.
In reactor, add 50 parts of bisphenol A epoxide resins (D.E.R.337), 1 part of titanium acetylacetone, stirred 14 hours, add 3 parts of thermo-stabilizers (three fumaric acid list benzene methyl lanthanums), 2 parts of UV absorption agents (benzotriazole), continue to stir 5 hours, add the A component again, continue to stir 2 hours, obtain epoxy.
130 ℃ of heating 20 hours, in-situ solidifying obtained epoxy with above-mentioned epoxy.
Claims (13)
1, a kind of epoxy, it is characterized in that this hybrid material comprises: (a) at least a Resins, epoxy, (b) at least a silicone resin, (c) at least a acid curing agent, (d) nonessential organic epoxy silane, (e) nonessential auxiliary agent; Each amounts of components is respectively with the mass fraction note: 100 parts of Resins, epoxy, 1～500 part of silicone resin, 0.01～20 part of acid curing agent, 0～100 part of organic epoxy silane, 0～20 part of auxiliary agent;
Wherein, Resins, epoxy is selected from bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin, the combination of one or more in the cycloaliphatic epoxy resin; Silicone resin is a molecular weight in 100～20000 hydroxy silicon oil and one or more the combination in the hydroxyl poly organic silicon sesquioxyalkane; Acid curing agent is one or more the combination of molecular weight in 100～10000 acid anhydrides, hydrogenation acid anhydrides, metal carboxylate, metal alkyl complex compound and metal acetylacetonate complex compound; Organic epoxy silane is one or more the combination of molecular weight in 100～2000 band oxygen groups organo-siloxane; Auxiliary agent is one or more the combination in the UV light absorber commonly used in the sizing agent, ageing-resistant dose, thermo-stabilizer, toughner, viscosity increaser, thickening material.
2, it is 100～10000 hydroxyl poly organic silicon sesquioxyalkane at 100～10000 hydroxy silicon oil or molecular weight that epoxy according to claim 1, described silicone resin are preferably molecular weight.
3, epoxy according to claim 1 is characterized in that the structure of described hydroxy silicon oil is:
Wherein, R
1=hydroxyl; R
2=methyl or phenyl; N1=1～100.
4, epoxy according to claim 1 is characterized in that the structure of described hydroxyl poly organic silicon sesquioxyalkane is:
(R
3SiO
3/2)
n2(R
35iO
2/2)
n3(R
3SiO
1/2)
n4(SiO
4/2)
n5，
Wherein, n2=1～100, n3=0～100, n4=0～100, n5=0～100; R
3=phenyl, hydroxyl or contain the alkyl of 1～40 carbon atom; At least contain 1 mole oh group in the resin.
5, epoxy according to claim 1 is characterized in that described acid curing agent is a molecular weight in one or more combination of 100～5000 acid anhydrides, hydrogenation acid anhydrides, metal carboxylate, metal acetylacetonate complex compound.
6, epoxy according to claim 5 is characterized in that the metal in the wherein said acid curing agent is selected from second and third main group metal, fourth, fifth, the transition metal in six cycles and lanthanide series metal.
7, epoxy according to claim 5 is characterized in that described acid curing agent is Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, MALEIC ANHYDRIDE, tung oil acid anhydride, methyl tetrahydro phthalic anhydride, HHPA, methyl hexahydrophthalic anhydride, zinc naphthenate, zinc octoate, cobalt naphthenate, stannous octoate, methyl ethyl diketone tin, methyl ethyl diketone zirconium, aluminium acetylacetonate, titanium acetylacetone, acetyl acetone, four acetyl acetones or methyl ethyl diketone platinum.
8, epoxy according to claim 1 is characterized in that the structure of described organosilane is:
(R
4)
nSi (OR
5)
4-n, wherein, n=1,2,3;
R
5=contain the alkyl of 1～20 carbon atom, preferentially select the alkyl of 1～10 carbon atom for use.
9, epoxy according to claim 1 is characterized in that each amounts of components is: 100 parts of Resins, epoxy, 1～300 part of silicone resin, 0.01～10 part of acid curing agent, 0～50 part of organic epoxy silane, 0～10 part of auxiliary agent.
10, a kind of preparation method of epoxy as claimed in claim 1 is characterized in that concrete steps are as follows:
(1) by set of dispense than each component of weighing, the Resins, epoxy of 20～70wt% and silicone resin and nonessential organosilane are carried out blend, stirred 0.1～24 hour;
(2) remaining Resins, epoxy and solidifying agent are mixed the thing that is uniformly mixed, 1～24 hour blend time;
(3) under agitation condition, drip the uniform mixture that obtains in the step (2) in the blend that in step (1), obtains, 0.1～5 hour blend time; Add nonessential auxiliary agent as need, then nonessential auxiliary agent drips the back to be continued to stir 0.1～5 hour; Promptly make described epoxy.
11, a kind of epoxy as claimed in claim 1 is as the application of sizing agent, insulating material, printing ink, coated material, printed wiring solder resist material, optics protecting materials, LED packaged material, photoelectric conversion material.
12, the application method of epoxy according to claim 1 is characterized in that the epoxy in-situ hybridization crosslinking curing under 0～300 ℃ of condition that will obtain after the blend.
13, application method according to claim 11 is characterized in that the epoxy-organic silicon hybrid material in-situ hybridization crosslinking curing under 20～200 ℃ of conditions that will obtain after the blend.
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