CN103319692A - High performance organosilicon epoxy material, preparation method and applications thereof - Google Patents
High performance organosilicon epoxy material, preparation method and applications thereof Download PDFInfo
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Abstract
The invention belongs to the field of light emitting semiconductor packaging, and discloses a high performance organosilicon epoxy material, a preparation method and applications thereof. According to the present invention, a vinyl epoxy monomer and methylhydrosiloxane are subjected to a catalysis reaction for 2-24 h, an end capping agent and a catalyst are added to continuously carry out the reaction to obtain end capped epoxy cyclosiloxane, 0.1-5.0 parts of a cyclosiloxane ring opening agent, 0.01-80 parts of an epoxy curing agent and 0.01-5.0 parts of a curing catalyst are added to 100 parts of the end capped epoxy cyclosiloxane in batches, stirring is performed for 0.5-12.0 h under a nitrogen condition during the addition, an auxiliary agent is added, stirring is continuously performed for 0.5-3.0 h, and curing is performed to obtain the organosilicon epoxy material; and the material has characteristics of the epoxy resin and the organosilicon material, further has characteristics of excellent light transmittance, excellent adhesion, excellent mechanical strength, excellent heat resistance and excellent UV performance, and can be adopted as a LED packaging material, an optical lens material, a photoelectric conversion material, an integrated circuit packaging material, an insulation material, a coating material and an adhesive.
Description
Technical field
The invention belongs to the emitting semiconductor encapsulation field, relate to a kind of packaged material for sealed light emitting diode (LED) and optical lens, be specifically related to a kind of high performance organo-silicon epoxy material and preparation method thereof and application.
Technical background
Since 21 century, energy problem is day by day serious, and under the background that the worry of global energy shortage rises once again, save energy will be the important problem that will face future.At present, illumination accounts for about 20% of world's total energy consumption, if the light source of, life-span length low with energy consumption, safety, environmental protection replaces the conventional light source of poor efficiency, high current consumption, will have to the Sustainable development in the whole world strategic meaning.Photodiode (LED) as a new generation the green solid lighting source, the electric energy of consumption only be incandescent light 1/10, power saving fluorescent lamp 1/3, its life-span then is 100 times of incandescent light.Compare with conventional light source, LED has the advantages such as the mercury, the volume that do not use serious environment pollution are little, use voltage is low, switching time is short, the life-span is long, thereby is widely used among the various lighting installations.LED is one of the hi-tech of tool development prospect of 21 century, and it replaces the conventional light source such as incandescent light also will be the inexorable trend of following lighting field development.
The LED encapsulation mainly is the encapsulation to luminescence chip, not only requires to play the effect of protection luminescence chip, requires to have simultaneously the transparence of height, thereby packaged material is had special requirement.As: the packaged material requirement specific refractory power that the power-type LED device uses is higher than 1.5 (25 ℃), transmittance is not less than 98% (wavelength 400～800nm, thickness of sample 1mm); The development of white light LEDs, especially based on the appearance of the white light LEDs of UV-light, require packaged material when keeping the visible region high transmission rate, can have stronger absorption to leak to prevent UV-light to UV-light, thereby packaged material need to have stronger anti-ultraviolet ageing performance.At present, fast development along with the LED technology, especially the progressively raising of luminous efficiency, packaged material require to have the demand that high transmission rate, refractive index and thermal conductivity, anti-ultraviolet and the characteristics such as thermal ageing, low-stress, water-intake rate, ion content and low thermal coefficient of expansion satisfy the LED development.
Resins, epoxy has good cementability, electrical insulation capability, stopping property, erosion resistance and dielectric properties etc., occupies domestic more than 65% of market of LED encapsulation, is the packaged material that cost is minimum and consumption is maximum in the LED encapsulation; But Resins, epoxy exists thermotolerance not high, humidity resistance and weathering resistance are relatively poor, and the problems such as matter is crisp, fatiguability, toughness is low and heat dispersion is poor, xanthochromia easily occurs under ultraviolet lighting and hot conditions, and be difficult for heat radiation, can cause the chip junction temperature to rise rapidly, the stress that causes rapid thermal expansion to produce causes open circuit and lost efficacy, thereby accelerate the device light decay, affect the work-ing life of LED device.In addition, organosilicon material also is one of the most promising LED packaged material in the market, and it has excellent heat, light stability, at UV-light and blue light, even in high light intensity, under high humidity and the high temperature, can both keep its optical property; But the relative Resins, epoxy of its refractive index is lower, and bonding force is poor, mechanical strength is not high, and easy and chip comes off, and greatly reduces light emission rate and the work-ing life of LED.At present, more to modifying epoxy resin by organosilicon or the organosilyl research of Resins, epoxy reinforcement, adopt the polydimethylsiloxane--modified cycloaliphatic epoxy resin such as (Macromol Mater and Eng DOI:10.1002/mame.201100143) such as Marco Sangermano, its addition is hydrophobicity and the surface property that 0.3wt% can effectively improve Resins, epoxy, simultaneously the cementability of retaining ring epoxy resins excellence.Yasumasa Morita (J Appl Polym Sci Vol.100, No.3,2006) etc. then take the siloxanes of Si-H end-blocking and with the Resins, epoxy of vinyl as raw material, the organosilicon epoxy resin that has synthesized different chain length, the introducing of epoxy has improved bonding force and the mechanical property of material, with the growth of dimethyl siloxane segment, the thermostability of material and toughness improve significantly and improve simultaneously.But the modifying epoxy resin by organosilicon of above-mentioned employing or epoxy reinforcement organosilicon material, the mode that dependence adds organosilicon or single-phase curable epoxide prepares, organosilicon and epoxy two-phase interface overtension in the material, consistency are relatively poor, fail to take into account other performances such as transparence of material.
Summary of the invention
In order to overcome the deficiencies in the prior art part, primary and foremost purpose of the present invention is to provide a kind of organosilicon epoxy material, is a kind of have high transmission rate, good bonding force and organosilicon epoxy packages material of mechanical strength and heat-resisting/ultraviolet performance.
Another object of the present invention provides the preparation method of above-mentioned organosilicon epoxy material.
The present invention also aims to provide the application of above-mentioned organosilicon epoxy material.
Purpose of the present invention is achieved through the following technical solutions:
A kind of organosilicon epoxy material, this material is prepared from by the following by weight raw material of meter:
100 parts of end-blocking oxirane ring siloxanes, 0.1～5.0 part of cyclosiloxane ring opening agent, 0.01～80 part of epoxy hardener, 0.01～5.0 part of curing catalysts, 0～20 part of auxiliary agent.
In order to realize better the present invention, organosilicon epoxy material of the present invention is prepared from by the following by weight raw material of meter: 100 parts of end-blocking oxirane ring siloxanes, 0.3～2.0 part of cyclosiloxane ring opening agent, 0.1～60 part of epoxy hardener, 0.5～3.0 part of curing catalysts, 0～10 part of auxiliary agent.
The chemical general formula of described end-blocking oxirane ring siloxanes is:
Wherein, 0＜b≤6,0≤c＜6, b, c are integer, and 3≤(b+c)≤6;
Described R is
In more than one, wherein m is 2～6 integer; Described R ' is more than one in saturated alkoxyl group, alkyl oxygen ethyl, saturated alkyl or the alkoxyl group propyl group, and is preferred-OC
2H
5,-OCH
2CH
2CH
3,-OCH
2CH
2CH
2CH
3,-CH
2CH
2OCH
2CH
2CH
3,-CH
2CH
2OCH
2CH
2CH
2CH
3,-CH
2CH
2OCH
2CH
2CH
2CH
3,-CH
2CH
2CH
2OCH
2CH
3,-CH
2CH
3,-CH
2CH
2CH
3,-CH
2CH
2CH
2CH
3,-CH
2CH
2CH
2CH
2CH
2CH
3,-CH
2CH
2CH
2OCH
2CH
2CHCH
3In more than one.
The preparation method of described end-blocking oxirane ring siloxanes is as follows:
(1) vinyl epoxy monomer and methyl hydrogen siloxane are dissolved in solvent, pass into high pure nitrogen, stir, then be warming up to gradually 60～100 ℃, after homo(io)thermism, add catalyst solution, reaction 2～24h;
(2) add excessive end-capping reagent and catalyst solution, unreacted Si-H in the methyl hydrogen siloxane is carried out end-blocking, continue reaction 2～12h, after reaction finishes, revolve to steam and remove unreacted raw material, comprise solvent, unreacted end-capping reagent or vinyl epoxy monomer, obtain water white end-blocking oxirane ring siloxanes.
Reaction process is as follows:
Described vinyl epoxy monomer is
In more than one, wherein m is 2～6 integer, and is preferred
In more than one.
Described methylhydracyclosiloxane is 1,3,5-trimethylammonium cyclotrisiloxane (C
3H
12O
3Si
3), 1,3,5,7-tetramethyl-ring tetrasiloxane (C
4H
16O
4Si
4), 1,3,5,7,9-pentamethyl-D5 (C
5H
20O
5Si
5), 1,3,5,7,9,11-pregnancy basic ring six siloxanes (C
6H
24O
6Si
6) in more than one, namely a is 3～6 integer.
The mol ratio of described vinyl epoxy monomer and described methyl hydrogen siloxane is n, 1≤n≤7.
Temperature described in the step (1) is preferably 70～80 ℃; The time of the reaction described in the step (1) is preferably 4～16h.
The adding mode of the catalyst solution described in step (1) and the step (2) is the dropping mode.
Catalyst solution described in step (1) and the step (2) obtains in the organic solvent for catalyzer is dissolved in; Described catalyzer is more than one in platinum chloride, Platinic chloride, dicyclopentadiene platinum dichloride, allyl group silicon (oxygen) alkane platinum or the monocyclopentadienyl nickel; Described organic solvent is more than one in tetrahydrofuran (THF), toluene, acetone or the monohydroxy-alcohol, the preferred Virahol of described monohydroxy-alcohol, ethanol or butanols, and the consumption of solvent only need to get final product catalyst dissolution.
The quality of catalyzer is 1.0 * 10 of reactant methyl hydrogen siloxane and vinyl epoxy monomer quality sum in the described catalyst solution of step (1)
-6～100 * 10
-6In the described catalyst solution of step (1) in the quality of catalyzer and the described catalyst solution of step (2) the quality sum of catalyzer be 1.0 * 10 of total reactant methyl hydrogen siloxane, vinyl epoxy monomer and end-capping reagent quality sum
-6～100 * 10
-6
The described end-capping reagent of step (2) is more than one in saturated alcohol, alkyl vinyl ether, allyl group alkyl oxide or the alkene, preferred C
2H
5OH, CH
3CH
2CH
2OH, CH
3CH
2CH
2CH
2OH, CH
2=CHOCH
2CH
2CH
3, CH
2=CH
2OCH
2CH
2CH
2CH
3, CH
2=CHCH
2OCH
2CH
3, CH
2=CHCH
2OCH
2CH
2CH
2CH
3, CH
2=CH
2, CH
2=CHCH
3, CH
2=CHCH
2CH
3, CH
2=CHCH
2CH
2CH
3Or CH
2=CHCH
2CH
2CH
2CH
2CH
2In more than one.The computation process of the consumption of end-capping reagent is: the amount of substance of supposing methyl hydrogen siloxane is x, the amount of substance of vinyl epoxy monomer is y, z=((x * a)-y), when z≤0, the Si-H key in the methyl hydrogen siloxane all with the reaction of vinyl epoxy monomer, end-blocking is finished, need not add end-capping reagent this moment, if adding then is excessive end-capping reagent, the vinyl epoxy monomer may be excessive simultaneously, boils off except excessive unreacted end-capping reagent and vinyl epoxy monomer by revolving; And when z＞0, the amount of substance of the end-capping reagent of adding is greater than z, makes that end-capping reagent is excessive to be got final product, and namely the consumption of end-capping reagent is excessive getting final product.
The described solvent of step (1) is toluene, dimethylbenzene, hexanaphthene, sherwood oil, butanone, 4-methyl-2 pentanone, pimelinketone, glycol dimethyl ether, 1, in 4-dioxy six alkane or the ethyl acetate more than one, the consumption of solvent is that reactants dissolved is got final product, without particular requirement.
In order to realize better the present invention, described cyclosiloxane ring opening agent is an acidic catalyst or basic catalyst; Described an acidic catalyst is more than one in organic acid, mineral acid or the Lewis acid, and described organic acid is preferably trifluoromethanesulfonic acid (CF
3SO
3H), described mineral acid is preferably H
2SO
4Or HClO
4, described Lewis acid is preferably BF
3, SbF
5Or AlCl
3Described basic catalyst be alkali metal hydroxide, alkali metal alcoholates, quaternary ammonium hydroxide, season phosphine alkali or silicon alkoxide in more than one, in the preferred sodium hydroxide of described alkali metal hydroxide, potassium hydroxide or the lithium hydroxide more than one, the preferred KOC of described alkali metal alcoholates
2H
5Or NaOC
2H
5In more than one, the preferred (CH of described quaternary ammonium hydroxide
3)
4NOH, the preferred (CH of described season phosphine alkali
3CH
2CH
2CH
2)
4POH, the preferred KOH of described silicon alkoxide or (CH
3)
4The silicon alkoxide of NOH.
Secondly, the molecular weight of described epoxy hardener is 100～10000, be in acid anhydrides, hydrogenation acid anhydrides or the metal acetylacetonate complex compound more than one, more than one in preferred Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, methyl carbic anhydride, MALEIC ANHYDRIDE, Pyroglutaric acid, poly-nonane diacid acid anhydride, aluminium acetylacetonate, methyl ethyl diketone zirconium or the titanium acetylacetone.
Described curing catalysts is more than one in quaternary ammonium salt or the silanol, more than one in preferred cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide, Tetrabutyl amonium bromide, triphenyl silanol, Diphenylsilanediol or the dimethyl phonyl silanol.
Described auxiliary agent is more than one in photostabilizer, uv-absorbing agent, antiager, thermo-stabilizer, toughner or the strengthening agent.
The preparation method of above-mentioned organosilicon epoxy material, concrete steps are as follows: 0.1～5.0 part of cyclosiloxane ring opening agent, 0.01～80 portion of epoxy hardener and 0.01～5.0 part of curing catalysts are joined in 100 parts of end-blocking oxirane ring siloxanes in batches, stir 0.5～12.0h under the condition of nitrogen gas during this time, add 0～20 part of auxiliary agent, add rear continuation and stir 0.5～3.0h, Procuring 0.5～2h under 80～110 ℃ and vacuum condition, solidify 2～10h in 120～140 ℃, in 150～180 ℃ of curing 2～6h, make the organosilicon epoxy material of homogeneous phase transparent again.
Described vacuum condition is that vacuum tightness is 267～(2 * 10
4) Pa.
Above-mentioned organosilicon epoxy material not only can be used as the LED packaged material, also can be used as optical lens package material, photoelectric conversion material, integrated circuit packaging material, insulating material, coated material or sizing agent.
Principle of the present invention is:
The present invention carries out the addition of silicon hydrogen by methylhydracyclosiloxane and vinyl epoxy and prepares the oxirane ring siloxanes, utilizes end-capping reagent that excessive Si-H is carried out end-blocking, and then synthetic end-blocking oxirane ring siloxanes; The co-curing mode that curable epoxide by end-blocking oxirane ring siloxanes and the ring-opening polymerization of cyclosiloxane are solidified, solve organosilicon and epoxy generation problem of phase separation, the LED for preparing the excellent combination properties such as a kind of cementability, mechanical strength, heat-resisting and ultraviolet encapsulates and uses the organosilicon epoxy material.This material has Resins, epoxy and organosilyl advantage concurrently, such as characteristics such as the cementability of excellence, toughness, physical strength, high transmission rate, heat-resisting and ultraviolet performances, traditional modifying epoxy resin by organosilicon or the poor easy problem that is separated of epoxy reinforcement organosilicon material two-phase consistency have been solved.
Compared with the prior art, the present invention has the following advantages and beneficial effect:
The organosilicon epoxy material of the LED encapsulation usefulness that a kind of transmittance provided by the invention is high, cementability good, weathering resistance is strong, mechanical strength is excellent has following characteristics:
(1) low power LED packaged material is bisphenol A epoxide resin in the market, the high power LED package material is organosilicon material, from structural analysis, the organosilicon epoxy material does not contain benzene ring structure, thereby has better heat-resisting/ultraviolet ageing ability than bisphenol A epoxide resin, bisphenol A epoxide resin has the epoxy group(ing) six-ring, make it have better mechanical property than organosilicon, and the organosilicon epoxy material of the present invention's preparation has organosilicon unit and epoxy group(ing) concurrently, make it possess the organosilicon transmittance high, good weatherability, water-intake rate is low, the characteristics of snappiness excellence possess again the adhesiveproperties of Resins, epoxy excellence, the characteristics such as mechanical strength and insulating property.
(2) the present invention prepares organosilicon epoxy packages material by the curable epoxide of end-blocking oxirane ring siloxanes and the co-curing mode of cyclosiloxane ring-opening polymerization curing, can improve material mechanical performance and keep simultaneously material transmittance (＞90%, 800nm), and solve the problem that traditional blending method organosilicon epoxy systems is separated.
(3) the present invention is by the ratio of control vinyl epoxy monomer and methylhydracyclosiloxane, can regulate the surface bonding power, mechanical strength, water-intake rate, thermotolerance of organosilicon epoxy material etc.
(4) organosilicon epoxy material of the present invention not only can be used as the LED packaged material, also can be used as optical lens material, photoelectric conversion material, integrated circuit packaging material, insulating material, coated material, sizing agent etc.
Embodiment
By the following examples the present invention is described in further detail, but embodiments of the present invention are not limited to this.
In the material testing partial performances, UV 8000 ultraviolet-visible pectrophotometers that transmittance adopts Shanghai unit to analyse Instr Ltd. are tested, thickness of sample is 3mm, and the scope of scanning wavelength is 280～800nm, and the absorbancy of choosing 800nm and 400nm place compares;
Water-intake rate is tested with reference to method shown in the GB1034-86, and before the test, sample elder generation, soaks 24h and measures relative water-intake rate to constant mass at 50 ℃ of dry 24h in the boiling water;
Thermal weight loss adopts German NETZSCH TG209 thermal gravimetric analyzer to test under nitrogen protection, temperature rise rate is 10 ℃/min, weightless 5% temperature is the temperature of material breakdown when being original quality 95% to quality, and weightless 50% temperature is the temperature of material breakdown when being original quality 50% to quality;
Surface bonding power records according to the testing method of standard A STM C3359-B;
Hardness reference standard JB 6148-92 adopts Shore durometer D to test.
Embodiment 1
The preparation method of organosilicon epoxy material is as follows:
(1) preparation of end-blocking oxirane ring siloxanes: in the round-bottomed flask that agitator, reflux exchanger, thermometer, nitrogen interface are housed, add 0.5mol (90.1g) 1,3,5-trimethylammonium cyclotrisiloxane C
3H
12O
3Si
3(chemical industry company limited of Beijing Hua Weirui section provides), 1.0mol (114.1g) glycidyl allyl ether (CH
2=CHCH
2OCH
2CHCH
2O, An Naiji chemistry (Energy Chemical) provides) and the 100ml hexanaphthene, room temperature downhill reaction device passes into high pure nitrogen and stirs, then be warming up to gradually 70 ℃, the Platinic chloride tetrahydrofuran solution that slow dropping 0.4ml concentration is 1g/160ml after homo(io)thermism is as catalyzer, dropwise afterreaction 8h, in reactor, add 59.3g end-capping reagent propyl carbinol and the above-mentioned Platinic chloride tetrahydrofuran solution of 0.15ml, continue again reaction 6h, after reaction finishes, steam desolventizing hexanaphthene and excessive propyl carbinol by revolving, obtain water white end-blocking oxirane ring siloxanes.Wherein, the computation process of the consumption of end-capping reagent is: the amount of substance of methyl hydrogen siloxane is x=0.5mol, a=3, the amount of substance of vinyl epoxy monomer is y=1.0mol, z=((x * a)-y)=0.5＞0, the amount of substance of the end-capping reagent that then adds makes end-capping reagent excessive greater than 0.5mol.
(2) preparation of organosilicon epoxy material: cyclosiloxane ring opening agent trifluoromethanesulfonic acid, epoxy hardener methyl hexahydrophthalic anhydride and curing catalysts dimethyl phonyl silanol are added in batches in the end-blocking oxirane ring siloxanes of step (1) preparation by prescription 1, mechanical stirring 0.5h under the condition of nitrogen gas during this time, add auxiliary agent uv-absorbing agent benzotriazole, after continuing to stir 2h, be Procuring 2h under the 267Pa in 80 ℃ in vacuum tightness, then solidify 4h in 120 ℃, solidify 6h in 150 ℃ again, obtain water white cured product, i.e. the organosilicon epoxy material.
Prescription 1
Embodiment 2
The preparation method of organosilicon epoxy material is as follows:
(1) preparation of end-blocking oxirane ring siloxanes: in the round-bottomed flask that agitator, reflux exchanger, thermometer, nitrogen interface are housed, add 0.5mol (120.2g) 1,3,5,7-tetramethyl-ring tetrasiloxane C
4H
16O
4Si
4(Quzhou Rui Lijie chemical industry company limited provides), 0.5mol (62.1g) 1,2-epoxy-4 vinyl epoxy cyclohexane (
CH
2=CHC
6H
9O, Sigma Aldrich provides) and 150ml dimethylbenzene, room temperature downhill reaction device passes into high pure nitrogen and stirs, then be warming up to gradually 60 ℃, after homo(io)thermism, the isopropyl alcohol solution of chloroplatinic acid that slow dropping 3.22ml concentration is 1g/160ml is as catalyzer, after dropwising afterreaction 2h, in reactor, add 176.7g end-capping reagent 1-heptene and the above-mentioned isopropyl alcohol solution of chloroplatinic acid of 2.52ml, continue again reaction 6h, after reaction finishes, steam desolventizing dimethylbenzene and unreacted 1-heptene by revolving, obtain water white end-blocking oxirane ring siloxanes.
(2) preparation of organosilicon epoxy material
Cyclosiloxane ring opening agent Tetramethylammonium hydroxide silicon alkoxide, epoxy hardener aluminium acetylacetonate and curing catalysts Diphenylsilanediol are added in batches in the end-blocking oxirane ring siloxanes of step (1) preparation by prescription 2, mechanical stirring 2h under the condition of nitrogen gas is 1 * 10 in 90 ℃ in vacuum tightness during this time
4Behind the Procuring 1h, in 140 ℃ of curing 2h, in 180 ℃ of curing 4h, obtain the water white transparency cured product, i.e. the organosilicon epoxy material again under the Pa.Wherein, preparation method's reference Se-Young Jung and Byung-Kyu Kim.Electrical Properties of Siicone Rubber Filled With Surface Treated Alumina Trihydrate[J of Tetramethylammonium hydroxide silicon alkoxide] .Transactions on Electrical and Electronic Materials, 2006,7 (3): 134-140.
Prescription 2
Embodiment 3
The preparation method of organosilicon epoxy material is as follows:
(1) preparation of end-blocking oxirane ring siloxanes: in the round-bottomed flask that agitator, reflux exchanger, thermometer, nitrogen interface are housed, add 0.5mol (180.4g) 1,3,5,7,9,11-pregnancy basic ring six siloxanes C
6H
24O
6Si
6(Kingston Chemistry provides), 3.5mol (434.63g) 1,2-epoxy-4-vinyl cyclohexane (CH
2=CHC
6H
9O,
Sigma Aldrich provides) and 100ml toluene, room temperature downhill reaction device passes into high pure nitrogen and stirs, then be warming up to gradually 100 ℃, after homo(io)thermism, drip 0.10ml concentration and be the dicyclopentadiene platinum dichloride ethanolic soln of 1g/160ml as catalyzer, behind the reaction 24h, in reactor, add 20.0g end-capping reagent ethanol and the above-mentioned dicyclopentadiene platinum dichloride of 0.01ml ethanolic soln, reaction 2h steams desolventizing toluene and excessive unreacted 1 by revolving, 2-epoxy-4-vinyl cyclohexane and ethanol obtains water white transparency oxirane ring siloxanes.
(2) preparation of organosilicon oxirane ring silica: the cyclosiloxane ring opening agent vitriol oil, epoxy hardener methyl carbic anhydride and curing catalysts Trimethyllaurylammonium bromide are added in batches in the end-blocking oxirane ring siloxanes of step (1) preparation by prescription 3, mechanical stirring 12h under the condition of nitrogen gas during this time, add auxiliary agent uv-absorbing agent benzophenone and photostabilizer hindered amine, continuing to stir 0.5h, is 2 * 10 in 110 ℃ in vacuum tightness
4Procuring 0.5h under the Pa then in 120 ℃ of curing 6h, in 180 ℃ of curing 3h, obtains the water white transparency cured product, i.e. the organosilicon epoxy material again.
Prescription 3
Embodiment 4
(1) preparation of end-blocking oxirane ring siloxanes
In the round-bottomed flask that agitator, reflux exchanger, thermometer, nitrogen interface are housed, add 84.18g1,3,5,7-tetramethyl-ring tetrasiloxane C
4H
16O
4Si
4(Quzhou Rui Lijie chemical industry company limited provides) and 45.1g1,3,5,7,9-pentamethyl-D5 C
5H
20O
5Si
4(J﹠amp; K Scientific provides) mixture, the amount of substance sum of tetramethyl-ring tetrasiloxane and pentamethyl-D5 is 0.5mol, mol ratio is 7: 3, and adds 0.8mol (123.4g) 1,2-epoxy-9-certain herbaceous plants with big flowers alkene CH
2=CH (CH
2)
6CHCH
2O (Chemical Reagent Co., Ltd., Sinopharm Group provides) and 200ml dimethylbenzene, room temperature downhill reaction device passes into high pure nitrogen and stirs, then be warming up to gradually 70 ℃, after homo(io)thermism, drip 1.72ml concentration and be the Platinic chloride butanol solution of 1g/160ml as catalyzer, behind the reaction 4h, in reactor, add 153.3g end-capping reagent allyl ethyl ether and the above-mentioned Platinic chloride butanol solution of 1.20ml, continue again reaction 12h, after reaction finishes, steam desolventizing dimethylbenzene and unreacted allyl ethyl ether by revolving, obtain water white end-blocking oxirane ring siloxanes.
(2) preparation of organosilicon epoxy material: cyclosiloxane ring opening agent potassium hydroxide, epoxy hardener methyl ethyl diketone zirconium and curing catalysts triphenyl silanol are added in batches in the end-blocking oxirane ring siloxanes of step (1) preparation by prescription 4, mechanical stirring 4h under the condition of nitrogen gas during this time, be Procuring 1h under the 267Pa in 90 ℃ in vacuum tightness, then solidify 4h in 130 ℃, solidify 4h in 170 ℃ again, obtain the water white transparency cured product, i.e. the organosilicon epoxy material.
Prescription 4
Embodiment 5
(1) preparation of end-blocking epoxysilicone: in the round-bottomed flask that agitator, reflux exchanger, thermometer, nitrogen interface are housed, add 0.5mol (120.2g) 1,3,5,7-tetramethyl-ring tetrasiloxane C
4H
16O
4Si
4(Quzhou Rui Lijie chemical industry company limited provides), 1.5mol (147.2g) 1,2-epoxy-5-hexene CH
2=CH (CH
2)
2CHCH
2O (An Naiji chemistry (Energy Chemical) provides) and 200ml 1,4-dioxy six alkane, room temperature downhill reaction device passes into high pure nitrogen and stirs, then be warming up to gradually 80 ℃, after homo(io)thermism, drip 0.3ml concentration and be the isopropyl alcohol solution of chloroplatinic acid of 1g/160ml as catalyzer, behind the reaction 8h, in reactor, add 68.9g end-capping reagent vinyl propyl ether and the above-mentioned isopropyl alcohol solution of chloroplatinic acid of 0.2ml, continue again reaction 8h, after reaction finishes, steam desolventizing Isosorbide-5-Nitrae-dioxy six alkane and unreacted vinyl propyl ether by revolving, obtain water white end-blocking oxirane ring siloxanes.
(2) preparation of organosilicon epoxy material: cyclosiloxane ring opening agent Tetramethylammonium hydroxide, epoxy hardener methyl tetrahydrophthalic anhydride and curing catalysts Tetrabutyl amonium bromide are added in batches in the end-blocking oxirane ring siloxanes of preparation in the step (1) by prescription 5, mechanical stirring 7h under the condition of nitrogen gas during this time, be Procuring 2h under the 267Pa in 80 ℃ in vacuum tightness, then solidify 6h in 120 ℃, solidify 2h in 180 ℃ again, obtain the water white transparency cured product, i.e. the organosilicon epoxy material.
Prescription 5
Effect embodiment
The performance test results of the organosilicon epoxy material of embodiment 1～5 preparation sees Table 1, the organosilicon epoxy material of embodiment 1 expression embodiment 1 preparation in the table, by that analogy.
The LED encapsulation of each embodiment preparation of table 1 performance of organosilicon epoxy material
By as seen from Table 1, with the increase of reactant medium vinyl epoxy monomer ratio, hardness and the surface bonding power of the organosilicon epoxy material of preparation are greatly improved; And material has preferably transmittance, and the variation of water-intake rate and TGA decomposition temperature is little, shows that material had both had the mechanical property of epoxy excellence, had the characteristics of organosilicon material concurrently.The shore hardness of prepared material＞40, the weightless temperature of TGA test 5%＞330 ℃, 400nm place transmittance＞90%, in the application aspect the LED encapsulation good development prospect is arranged, also can be used as optical lens package material, photoelectric conversion material, integrated circuit packaging material, insulating material, coated material, sizing agent etc. simultaneously.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. organosilicon epoxy material, it is characterized in that: this material is prepared from by the following by weight raw material of meter: 100 parts of end-blocking oxirane ring siloxanes, 0.1～5.0 part of cyclosiloxane ring opening agent, 0.01～80 part of epoxy hardener, 0.01～5.0 part of curing catalysts, and 0～20 part of auxiliary agent;
The chemical general formula of described end-blocking oxirane ring siloxanes is:
Wherein, b, c are natural number, and 3≤(b+c)≤6;
Described R is
In more than one, wherein m is 2～6 integer; R ' is saturated alkoxyl group, alkyl oxygen ethyl, more than one in saturated alkyl or the alkoxyl group propyl group.
2. a kind of organosilicon epoxy material according to claim 1, it is characterized in that: described organosilicon epoxy material is prepared from by the following by weight raw material of meter: 100 parts of end-blocking oxirane ring siloxanes, 0.3～2.0 part of cyclosiloxane ring opening agent, 0.1～60 part of epoxy hardener, 0～10 part of 0.5～3.0 part of curing catalysts and auxiliary agent;
Described R ' is-OC
2H
5,-OCH
2CH
2CH
3,-OCH
2CH
2CH
2CH
3,-CH
2CH
2OCH
2CH
2CH
3,-CH
2CH
2OCH
2CH
2CH
2CH
3,-CH
2CH
2OCH
2CH
2CH
2CH
3,-CH
2CH
2CH
2OCH
2CH
3,-CH
2CH
3,-CH
2CH
2CH
3,-CH
2CH
2CH
2CH
3,-CH
2CH
2CH
2CH
2CH
2CH
3Or-CH
2CH
2CH
2OCH
2CH
2CH
2CH
3In more than one.
3. a kind of organosilicon epoxy material according to claim 1 and 2, it is characterized in that: the preparation method of described end-blocking oxirane ring siloxanes is as follows:
(1) vinyl epoxy monomer and methyl hydrogen siloxane are dissolved in solvent, pass into high pure nitrogen, stir, then be warming up to 60～100 ℃, add catalyst solution, reaction 2～24h;
(2) continue reaction 2～12h behind the excessive end-capping reagent of adding and the catalyst solution, then revolve to steam and remove unreacted raw material, obtain end-blocking oxirane ring siloxanes.
4. a kind of organosilicon epoxy material according to claim 3, it is characterized in that: the temperature described in the step (1) is 70～80 ℃; The time of the reaction described in the step (1) is 4～16h;
The adding mode of the catalyst solution described in step (1) and the step (2) is the dropping mode;
Catalyst solution described in step (1) and the step (2) obtains in the organic solvent for catalyzer is dissolved in; Described organic solvent is more than one in tetrahydrofuran (THF), toluene, acetone or the monohydroxy-alcohol, and described monohydroxy-alcohol is Virahol, ethanol or butanols.
5. a kind of organosilicon epoxy material according to claim 3, it is characterized in that: described vinyl epoxy monomer is
In more than one, wherein m is 2～6 integer;
Described methylhydracyclosiloxane is C
3H
12O
3Si
3, C
4H
16O
4Si
4, C
5H
20O
5Si
5, C
6H
24O
6Si
6In more than one;
The mol ratio of described vinyl epoxy monomer and described methyl hydrogen siloxane is n, 1≤n≤7.
6. a kind of organosilicon epoxy material according to claim 3 is characterized in that:
Catalyzer in the catalyst solution described in step (1) and the step (2) is more than one in platinum chloride, Platinic chloride, dicyclopentadiene platinum dichloride, allyl group silicon (oxygen) alkane platinum or the monocyclopentadienyl nickel;
The quality of catalyzer is 1.0 * 10 of reactant methyl hydrogen siloxane and vinyl epoxy monomer quality sum in the described catalyst solution of step (1)
-6～100 * 10
-6
In the described catalyst solution of step (1) in the quality of catalyzer and the described catalyst solution of step (2) the quality sum of catalyzer be 1.0 * 10 of total reactant methyl hydrogen siloxane, vinyl epoxy monomer and end-capping reagent quality sum
-6～100 * 10
-6
End-capping reagent described in the step (2) is more than one in saturated alcohol, alkyl vinyl ether, allyl group alkyl oxide or the alkene.
7. a kind of organosilicon epoxy material according to claim 3 is characterized in that:
Solvent described in the step (1) is more than one in toluene, dimethylbenzene, hexanaphthene, sherwood oil, butanone, 4-methyl-2 pentanone, pimelinketone, glycol dimethyl ether, Isosorbide-5-Nitrae-dioxy six alkane or the ethyl acetate;
End-capping reagent described in the step (2) is C
2H
5OH, CH
3CH
2CH
2OH, CH
3CH
2CH
2CH
2OH, CH
2=CHOCH
2CH
2CH
3, CH
2=CH
2OCH
2CH
2CH
2CH
3, CH
2=CHCH
2OCH
2CH
3, CH
2=CHCH
2OCH
2CH
2CH
2CH
3, CH
2=CH
2, CH
2=CHCH
3, CH
2=CHCH
2CH
3, CH
2=CHCH
2CH
2CH
3Or CH
2=CHCH
2CH
2CH
2CH
2CH
2In more than one.
8. a kind of organosilicon epoxy material according to claim 1, it is characterized in that: described cyclosiloxane ring opening agent is H
2SO
4, HClO
4, CF
3SO
3H, BF
3, SbF
5, AlCl
3, KOH, NaOH, KOC
2H
5, NaOC
2H
5, (CH
3)
4NOH, (CH
3CH
2CH
2CH
2)
4In POH or the silicon alkoxide more than one; Described silicon alkoxide is KOH or (CH
3)
4The silicon alkoxide of NOH.
Described epoxy hardener is more than one in Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, carbic anhydride, methyl carbic anhydride, MALEIC ANHYDRIDE, Pyroglutaric acid, poly-nonane diacid acid anhydride, aluminium acetylacetonate, methyl ethyl diketone zirconium or the titanium acetylacetone;
Described curing catalysts is more than one in cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide, Tetrabutyl amonium bromide, triphenyl silanol, Diphenylsilanediol or the dimethyl phonyl silanol;
Described auxiliary agent is more than one in photostabilizer, uv-absorbing agent, antiager, thermo-stabilizer, toughner or the strengthening agent.
9. the preparation method of a kind of organosilicon epoxy material according to claim 1, it is characterized in that: concrete preparation method is as follows: with 0.1～5.0 part of cyclosiloxane ring opening agent, 0.01～80 portions of epoxy hardeners and 0.01～5.0 part of curing catalysts join in 100 parts of end-blocking oxirane ring siloxanes in batches, stir 0.5～12.0h under the condition of nitrogen gas during this time, add 0～20 part of auxiliary agent, add rear continuation and stir 0.5～3.0h, Procuring 0.5～2h under 80～110 ℃ and vacuum condition, solidify 2～10h in 120～140 ℃, in 150～180 ℃ of curing 2～6h, make the organosilicon epoxy material again.
10. according to claim 1～8 each described organosilicon epoxy material application in packaged material, it is characterized in that: this material is used as the LED packaged material, or is used as optical lens package material, photoelectric conversion material, integrated circuit packaging material, insulating material, coated material or sizing agent.
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| CN103897644A (en) * | 2014-03-27 | 2014-07-02 | 中科院广州化学有限公司南雄材料生产基地 | Preparation method of silicone-modified epoxy resin packaging adhesive |
| CN105315468A (en) * | 2015-11-26 | 2016-02-10 | 上海应用技术学院 | Epoxy polysiloxane and epoxidation preparation method thereof |
| CN107936890A (en) * | 2017-11-27 | 2018-04-20 | 嘉兴联合化学有限公司 | A kind of epoxy resin adhesive for the oxygen aging of resistance to atom and preparation method thereof |
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| CN103897644A (en) * | 2014-03-27 | 2014-07-02 | 中科院广州化学有限公司南雄材料生产基地 | Preparation method of silicone-modified epoxy resin packaging adhesive |
| CN105315468A (en) * | 2015-11-26 | 2016-02-10 | 上海应用技术学院 | Epoxy polysiloxane and epoxidation preparation method thereof |
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