CN103897404A - Application of modified polysiloxane in preparation of thixotropic addition type liquid silicone rubber - Google Patents
Application of modified polysiloxane in preparation of thixotropic addition type liquid silicone rubber Download PDFInfo
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- CN103897404A CN103897404A CN201410112178.5A CN201410112178A CN103897404A CN 103897404 A CN103897404 A CN 103897404A CN 201410112178 A CN201410112178 A CN 201410112178A CN 103897404 A CN103897404 A CN 103897404A
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Abstract
The invention discloses an application of modified polysiloxane in the preparation of thixotropic addition type liquid silicone rubber. The thixotropic addition type liquid silicone rubber comprises a basic polymer, a crosslinking agent, an inhibitor, a catalyst and modified polysiloxane, wherein the average composition formula of the modified polysiloxane is RaSiO(4-a)/2, a is a positive number meeting 1.5=<a<=2.8, R can be same or different monovalent hydrocarbon radicals, hydrogen or monovalent functional group, the monovalent functional group is a substituted or non-substituted functional group containing one or more of an ether bond, an epoxy group and ester group, the viscosity of the modified polysilixane is 30-15000 mPa.s, and the content of the monovalent functional group in the modified polysiloxane is 0.01-0.80 mol/100 g. The invention further discloses the trixotropic addition type liquid silicone rubber, which has excellent trixotropy and can realize forming without a mold.
Description
Technical field
The invention belongs to organosilicon material technical field, relate to application and the thixotropy add-on type liquid silicon rubber of modified polyorganosiloxane in preparation thixotropy add-on type liquid silicon rubber.
Technical background
Liquid silastic be by the linear organopolysiloxane of polymerizable medium degree be base polymer coordinate the preparation of filler, various assistants and additives there is self-leveling or thixotropic base-material, can extrude according to kind and purposes, note type, apply after, in atmosphere or under heating, vulcanization forming is elastomerics, comprises condensed room temperature vulcanized silicone rubber, condensed type one-pack RTV silicone rubber, add-on type liquid silicon rubber etc.Wherein, add-on type liquid silicon rubber is made up of base polymer, linking agent, catalyzer and inhibitor conventionally, need generally also to comprise filler, additive etc. according to practical application and function, Si-H base generation catalytic addition reaction in vinyl and linking agent in base polymer, be cross-linked to form the product with network structure, can be divided into single-component and two-pack according to packaging means.Base polymer is vinyl polysiloxane or the vinyl silicone oil containing two or more vinyl, linking agent is mainly the siloxane oligomer that contains more than 3 Si-H key, be low-viscosity line style methyl hydrogen silicone oil, catalyzer is generally platinum group catalyst, as the platinum catalyst of tetrahydrofuran (THF) coordination, platinum-alkynes basigamy compound etc., inhibitor can postpone hydrosilylation addition reaction, extend storage period and the working life of silicon rubber, as the compound containing alkynyl and many vinyl, filler and additive mainly comprise reinforced filling, heat conductive filler, conductive filler material, tinting material, viscosity increaser, fire retardant, releasing agents etc. make silicon rubber have specific function or meet the material of special process requirement, wherein reinforced filling can be MQ type silicone resin, gas-phase silica etc.
Add-on type liquid silicon rubber need to have thixotropy in particular application, thixotropy refers to that when material is subject to shearing, denseness diminishes, while stopping shearing, denseness increases, or denseness becomes large while being subject to shearing, the phenomenon that while stopping shearing, denseness diminishes, liquid silastic has higher requirements to its thixotropy in some special Application Areass, for example, in mould manufacture, electronic module embedding, the fields such as LED lens packages, there is thixotropic liquid silastic straight forming after extruding, keep shape, in the process that is heating and curing and cured glue body do not deform, subside, thereby do not need by mould assistant formation, its application can be simplified silicon rubber construction technology greatly, reduce costs, enhance productivity.At present, the thixotropic agent using in liquid silastic field comprises silicon-dioxide, carbon black, organobentonite and hydrogenated castor oil, polymeric amide etc.Wherein, silicon-dioxide is the most frequently used thixotropic agent, silica dioxide granule aggregate can be connected to form three dimensional silica network by the hydrogen bond between surface hydroxyl, liquid is wrapped in network structure, thereby and cause viscosity to increase moulding, but hydrogen bond between aggregate a little less than, the power that can be sheared is broken, in the time that shearing force removes, hydrogen bond recovers, and makes liquid moulding again.But silicon-dioxide is powder, high with hybrid technique complexity, the cost of liquid silastic, can produce detrimentally affect to the transmittance of silicon rubber etc. simultaneously, the scope of application is restricted, there is defect not good with liquid silastic Miscibility, bad dispersibility in organic molecule thixotropic agent, causes the thixotropic improvement effect of system limited conventionally.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides the application of modified polyorganosiloxane in preparation thixotropy add-on type liquid silicon rubber, and a kind of thixotropy add-on type liquid silicon rubber, in described thixotropy add-on type liquid silicon rubber, contain modified polyorganosiloxane, thixotropy is significantly improved, the base polymer consistency of modified polyorganosiloxane and add-on type liquid silicon rubber is good simultaneously, Effect on Mechanical Properties after extrudability and curing to it is less, is beneficial to the thixotropic liquid silicon rubber that obtains excellent combination property.
Object of the present invention is achieved through the following technical solutions:
The application of modified polyorganosiloxane in preparation thixotropy add-on type liquid silicon rubber, described thixotropy add-on type liquid silicon rubber comprises base polymer, linking agent, inhibitor, catalyzer and modified polyorganosiloxane, and an average group accepted way of doing sth for described modified polyorganosiloxane is suc as formula shown in (I):
R
aSiO
（4-a）/2 (Ⅰ)
In formula I, a meets the positive number of 1.5≤a≤2.8, and R is identical or different monovalence alkyl, hydrogen or monovalence function base, and described monovalence function base is substituted or non-substituted one or more the function base containing in ehter bond, epoxy group(ing), ester group; The viscosity of described modified polyorganosiloxane is 30～15000mPas, and in modified polyorganosiloxane, the content of monovalence function base is 0.01～0.80mol/100g;
The method of described application is by modified polyorganosiloxane and base polymer, linking agent, inhibitor and catalyst mix, obtains thixotropy add-on type liquid silicon rubber.
The content of described monovalence function base is preferably 0.05～0.50mol/100g, and the content of monovalence function base is the molar weight of the monovalence functional group that contains in 100g modified polyorganosiloxane.
Preferably, 2≤a≤2.3.
Preferably, the viscosity of described modified polyorganosiloxane is 30～15000mPas.
Preferably, described monovalence function base is
in one or more, R
0for the alkyl of identical or different C1～C5, R
1, R
2for identical or different H or the alkyl of C1～C5, R
3for the alkylidene group of identical or different C2～C5, n, r are and are greater than zero and are less than or equal to 3 integer, and x is greater than zero integer that is less than 20.
More preferably, described n, r are that 1, x is 10, R
0, R
1, R
2for methyl, R
3for ethylidene.
Preferably, the hydrogen content of described modified polyorganosiloxane is 0.1～0.5%.In the substituent R that hydrogen content represents to be connected with Siliciumatom, the quality percentage composition of hydrogen base.
Preferably, the capping group of described modified polyorganosiloxane comprises described monovalence function base.
Preferably, described monovalence alkyl is phenyl and/or methyl.
In described application, preferably, the quality of described modified polyorganosiloxane accounts for 1～5% of thixotropy add-on type liquid silicon rubber quality.
Preferably, in thixotropy add-on type liquid silicon rubber, also comprise aerosil, the method of described application is, modified polyorganosiloxane and aerosil are added in base polymer, linking agent, inhibitor and catalyzer and mixed, and obtains thixotropy add-on type liquid silicon rubber.
More preferably, the mass ratio of described aerosil and modified polyorganosiloxane is (0.1-5): 1.
Preferably, the particle diameter of described aerosil is 20～50nm.
A kind of thixotropy add-on type liquid silicon rubber, comprises base polymer, linking agent, inhibitor, catalyzer and the modified polyorganosiloxane of average composition formula as shown in formula I:
R
aSiO
（4-a）/2 (Ⅰ)
In formula I, a meets the positive number of 1.5≤a≤2.8, and R is identical or different monovalence alkyl, hydrogen or monovalence function base, and described monovalence function base is substituted or non-substituted one or more the function base containing in ehter bond, epoxy group(ing), ester group;
The viscosity of described modified polyorganosiloxane is 30～15000mPas, and in modified polyorganosiloxane, the content of monovalence function base is 0.01～0.80mol/100g.
Preferably, in described thixotropy add-on type liquid silicon rubber, also contain aerosil.
More preferably, the mass ratio of described aerosil and modified polyorganosiloxane is (0.1-5): 1.
Preferably, the particle diameter of described aerosil is 20～50nm.
Preferably, described base polymer comprises vinyl polysiloxane and vinyl silicone oil, and described linking agent comprises containing hydrogen silicone oil.
Beneficial effect of the present invention is: the present invention is by the composition optimizes to modified polyorganosiloxane, realize the application of modified polyorganosiloxane in preparation thixotropy add-on type liquid silicon rubber, obtain thixotropy and extrusion performance good, and before and after solidifying, can stablize the thixotropy add-on type liquid silicon rubber of moulding, meet the requirement without concrete application scenarios such as die package, and the adaptability of modified polyorganosiloxane is good, preparation method is simple, be beneficial to and promote applying of thixotropy add-on type liquid silicon rubber, and without the improvement of the liquid silastic application art such as die package.
Embodiment
The invention provides the application of modified polyorganosiloxane in preparation thixotropy add-on type liquid silicon rubber, thixotropy add-on type liquid silicon rubber comprises base polymer, linking agent, inhibitor, catalyzer and modified polyorganosiloxane, and an average group accepted way of doing sth for modified polyorganosiloxane is suc as formula shown in (I):
R
aSiO
（4-a）/2 (Ⅰ)
In formula I, a meets the positive number of 1.5≤a≤2.8, and R is identical or different monovalence alkyl, hydrogen or monovalence function base, and monovalence function base is substituted or non-substituted one or more the function base containing in ehter bond, epoxy group(ing), ester group; The viscosity of modified polyorganosiloxane is 30～15000mPas, and in modified polyorganosiloxane, the content of monovalence function base is 0.01～0.80mol/100g;
The method of application is by modified polyorganosiloxane and base polymer, linking agent, inhibitor and catalyst mix, obtains thixotropy add-on type liquid silicon rubber.
In modified polyorganosiloxane, the content of monovalence function base is preferably 0.05～0.50mol/100g.The content of monovalence function base is the molar weight of the monovalence function base that contains in 100g modified polyorganosiloxane.
R is identical or different monovalence alkyl, hydrogen or monovalence function base, be that modified polyorganosiloxane of the present invention is the mixing with the modified polyorganosiloxane of different R groups, and in modified polyorganosiloxane molecule, the R substituting group on same Siliciumatom can be identical or different above-mentioned substituting group.
The invention provides modified polyorganosiloxane is applied to the technical scheme in preparation thixotropy add-on type liquid silicon rubber, the modified polyorganosiloxane of performance thixotropy improvement effect is the polysiloxane through modification introducing functional group that molecular structure is mainly line style, be in molecular structure, to be mainly two functional silicone unit, and by simple function siloxane unit end-blocking.The modified polyorganosiloxane that the present invention is applied to preparation thixotropy add-on type liquid silicon rubber has special molecular weight and functional group relative content, and the thixotropy of add-on type liquid silicon rubber is significantly improved, and is applicable to LED without application scenarios such as die package.
In an average group accepted way of doing sth for modified polyorganosiloxane, a represents the mean number of substituent R in molecular structure, by forming two functional silicone unit of modified polyorganosiloxane molecule, determining for the simple function siloxane unit of end-blocking and the relative consumption of a small amount of trifunctional siloxane unit.In a preferred embodiment, 2≤a≤2.3.
In the molecular structure of modified polyorganosiloxane, monovalence function base specifically comprises having the group that forms hydrogen bonding functionality, the group that contains ether, epoxy group(ing), ester group, amino, amide group, hydroxyl, carboxyl etc. all can be used as corresponding function base, when synthetic, introduce by the siloxanyl monomers with function base, or by the reactant with function base, polysiloxane carried out to modification and introduce, and in same modified polyorganosiloxane, can comprise different types of function base, all can be for improving the thixotropic property of liquid silastic in application.
In modified polyorganosiloxane of the present invention, monovalence function base is preferably one or more the function base containing in ether, epoxy group(ing), ester group, more preferably
in one or more, R
0, R
1, R
2for H, or the alkyl of identical or different C1～C5, R
3for the alkylidene group of C2～C5, n, r are and are greater than zero and are less than or equal to 3 integer, and x is greater than zero integer that is less than 20.
In monovalence function base,
for polyethers function base, R
3for the alkylidene group of C2～C5, specifically comprise-CH
2cH
2-,-CH
2cH (CH
3the mixing of identical or different segment such as)-wait, R
3be preferably as ethylidene (CH
2cH
2-), x is preferably 10, can make the modified polyorganosiloxane and the liquid silastic that contain this group have good consistency, is beneficial to the thixotropic property that improves liquid silastic.
It is to be noted, in the present invention, having thixotropy improves the modified polyorganosiloxane of function and can be considered that alkyl in polysiloxane molecule or silicon hydrogen base substituting group are replaced and obtained by functional group, polysiloxane is carried out to functional modification, to common are machine silicon modification mode, can adopt existing method preparation, for example, by the addition of silicon hydrogen or the preparation of siloxanes hydrolysis-condensation reaction, and by regulating reaction raw materials ratio to obtain the modified polyorganosiloxane with specific function base content and viscosity, or directly buy and obtain, for example epoxide modified containing hydrogen silicone oil, polyether modified silicon oil, acrylate modified silicone oil etc.
Modified polyorganosiloxane has certain hydrogen content, and hydrogen content is in the R substituting group that represents to be connected with Siliciumatom, and the quality percentage composition of hydrogen base, take the quality of modified polyorganosiloxane as 100%.Preferably, the hydrogen content of modified polyorganosiloxane is 0.1～0.5%, makes it in the addition curing of liquid silastic, participate in addition reaction of silicon with hydrogen, is beneficial to the mechanical property improving after liquid silastic solidifies, and obtains the thixotropic liquid silicon rubber of high comprehensive performance.
In a preferred embodiment, the capping group of modified polyorganosiloxane comprises monovalence function base, and modified polyorganosiloxane, by the simple function siloxane unit end-blocking that contains function base, can improve the thixotropic property of liquid silastic unexpectedly.
In a preferred embodiment, n, r are 1.R
0, R
1, R
2for the alkyl of identical or different C1～C5, specifically can be the similarly saturated alkyl such as methyl, ethyl, propyl group, the tertiary butyl, be preferably methyl.
Monovalence alkyl can be enumerated methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl; Cyclopentyl, cyclohexyl or similar cycloalkyl; Phenyl, tolyl, xylyl or similar aryl; Benzyl, styroyl, hydrocinnamyl or similar aralkyl; 3,3,3-trifluoro propyl, 3-chloropropyl or similar haloalkyl; Below most preferably alkyl and aryl, especially methyl and phenyl.
In a preferred embodiment, the quality of modified polyorganosiloxane accounts for 1～5% of thixotropy add-on type liquid silicon rubber quality, and more preferably 1.5～3.5%.Wherein, basic components to add-on type liquid silicon rubbers such as base polymer, linking agent, inhibitor and catalyzer is not particularly limited, base polymer comprises vinyl polysiloxane, vinyl silicone oil etc., linking agent comprises containing hydrogen silicone oil, inhibitor and catalyzer are all without particular restriction, in this thixotropy add-on type liquid silicon rubber, also can contain as required filler and additive, as heat conductive filler, conductive filler material, fire retardant etc. simultaneously.
In reality, can in existing add-on type liquid silicon rubber product, directly add modified polyorganosiloxane, obtain thixotropy add-on type liquid silicon rubber, all can improve its thixotropy, easy to use.
The application of modified polyorganosiloxane provided by the invention in preparation thixotropy add-on type liquid silicon rubber, further preferably in thixotropy add-on type liquid silicon rubber, also contain aerosil, application method is that modified polyorganosiloxane and aerosil are added in base polymer, linking agent, inhibitor and catalyzer and mixed, and obtains thixotropy add-on type liquid silicon rubber.
Further, the mass ratio of aerosil and modified polyorganosiloxane is (0.1-5): 1, and being used in combination of silicon-dioxide and modified polyorganosiloxane presents outstanding synergistic function, can significantly improve the thixotropic property of additive properties liquid silastic.
In a preferred embodiment, the particle diameter of aerosil is 20-50nm.
The embodiment of the present invention further provides a kind of thixotropy add-on type liquid silicon rubber, comprises base polymer, linking agent, inhibitor, catalyzer and the modified polyorganosiloxane of average composition formula as shown in formula I:
R
aSiO
（4-a）/2 (Ⅰ)
In formula I, a meets the positive number of 1.5≤a≤2.8, and R is identical or different monovalence alkyl, hydrogen or monovalence function base, and described monovalence function base is substituted or non-substituted one or more the function base containing in ehter bond, epoxy group(ing), ester group;
The viscosity of described modified polyorganosiloxane is 30～15000mPas, and in modified polyorganosiloxane, the content of monovalence function base is 0.01～0.80mol/100g.
In a preferred embodiment, base polymer comprises vinyl polysiloxane and vinyl silicone oil, and linking agent comprises containing hydrogen silicone oil.
Further preferably, thixotropy add-on type liquid silicon rubber is bi-component addition type liquid silastic, comprise the vinyl polysiloxane of 35-55 weight part, the vinyl silicone oil of 35-55 weight part, the containing hydrogen silicone oil of 2-15 weight part, an above-mentioned average group accepted way of doing sth for 1-5 weight part modified polyorganosiloxane and inhibitor and catalyzer as shown in the formula (I).Provide the composition of preferred thixotropy add-on type liquid silicon rubber herein, but be not particularly limited in application, also can meet tackifier that application request adds etc. containing promising.
In a preferred embodiment, vinyl polysiloxane medium vinyl content is 0.1-2%, comprises that this areas such as vinyl methyl silicon resin, ethenylphenyl silicone resin, vinyl methyl phenyl silicone resin commonly use vinyl polysiloxane; The viscosity of vinyl silicone oil is 5000～10000mPas, and contents of ethylene is 0.5-2%; Silicon Containing Hydrogen oil viscosity is 15～50mPas, and hydrogen content is 0.8-1.6%.Meanwhile, inhibitor and catalyzer are not particularly limited, and can select according to practical situation, and for example inhibitor is ethynylcyclohexanol, and consumption is 0.025-0.035 weight part, and catalyzer is vinyl double-seal head platinum complex, and consumption is 5-10ppm.
Correspondingly, in the preferred thixotropy add-on type liquid silicon rubber that the embodiment of the present invention provides, also contain aerosil.Silicon-dioxide and modified polyorganosiloxane are brought into play synergistic function, can significantly improve the thixotropy of additive properties liquid silastic.More preferably, the mass ratio of aerosil and modified polyorganosiloxane is (0.1-5): 1.The particle diameter of aerosil is preferably 20～50nm.
The embodiment of the present invention further provides the preferred preparation method of thixotropy add-on type liquid silicon rubber, comprises following operation steps:
By containing hydrogen silicone oil and containing holding the modified-reaction thing of thiazolinyl in inert gas environment and organic solvent, at 85-95 ℃ through platinum catalyst catalyzed reaction 6～12h, after completion of the reaction, underpressure distillation, obtain modified polyorganosiloxane, modified polyorganosiloxane is added in base polymer, linking agent, inhibitor and catalyzer and mixed, obtain thixotropy add-on type liquid silicon rubber.
In above preparation method, the synthetic of modified polyorganosiloxane and raw materials containing hydrogen silicone oil thereof can carry out with reference to existing method, containing end thiazolinyl modified-reaction thing be contain the groups such as ether, epoxy group(ing), ester group, amino, amide group, hydroxyl, carboxyl and can with the compound of the unsaturated double-bond of si-h bond generation addition reaction, specifically can enumerate glycidyl allyl ether (AGE), 1,2-epoxy-4-vinyl cyclohexane, alkyl acrylate, allyl polyethenoxy ether (CH
2=CHCH
2o (CH
2cH
2o)
x0h), methacrylic Soxylat A 25-7, ethylene glycol mono vinyl ether (
), vinyl polyether (
) etc., wherein X
0, X
1, X
2value is without particular restriction, and the alkyl in alkyl acrylate comprises methyl, ethyl, butyl etc.
Comprise the modified polyorganosiloxane of monovalence function base in order to obtain capping group, can adopt the preparation method of the art to prepare hydrogen end-blocking containing hydrogen silicone oil, then react and obtain modified polyorganosiloxane with the modified-reaction thing that contains end thiazolinyl.
Take monovalence function base as containing the functional group of epoxy group(ing), and capping group comprises that the epoxy-modified polysiloxane of monovalence function base is example, and its preparation method can comprise following operation steps:
A, prepare hydrogen end-blocking containing hydrogen silicone oil: will octamethylcyclotetrasiloxane, containing hydrogen silicone oil, hydrogeneous double-seal head and resin cation (R.C.) be warming up to 10～50 ℃ after mixing, stirring reaction, after 9～10 hours, filters, remove resin cation (R.C.), underpressure distillation, removes low-boiling-point substance, obtains hydrogen end-blocking containing hydrogen silicone oil;
B, preparation epoxy-modified polysiloxane: the hydrogen end-blocking containing hydrogen silicone oil of preparing in steps A and isopropyl alcohol solution of chloroplatinic acid are added in sherwood oil, pass into dry N
2, stir and be warmed up to 85 ℃, drip while stirring glycidyl allyl ether (AGE), at 85 ℃, react 6～8h, after completion of the reaction, underpressure distillation, obtains epoxy-modified polysiloxane.
Wherein, the R in modified polyorganosiloxane is hydrogen, methyl or γ-glycidyl ether oxygen propyl, and capping group comprises γ-glycidyl ether oxygen propyl.
The present invention can be by following embodiment further instruction, but embodiment is not limiting the scope of the invention.In following embodiment, Me represents methyl, Ph represents phenyl, R ' represents the monovalence function base in modified polyorganosiloxane, the viscosity measurement of modified polyorganosiloxane adopts standard GB/T/T2794-1995 " mensuration of tackiness agent viscosity ", the hydrogen content of containing hydrogen silicone oil, modified polyorganosiloxane etc. is the quality percentage composition of hydrogen in material institute silicon-hydrogen bond containing, testing method can reference: Zhang Donghui, Zhang Songlin, Fan Huijun etc., amino-polyether modified organosilyl synthetic and antifoam performance research, Chemical Engineering and Technology, 2013,3:122-126; The epoxy group content testing method of modified polyorganosiloxane can reference: Liu Jie, Tang Li, Li Yan's, a kind of determination of epoxide number of Fast Practical, leather and chemical industry, 2012,29(1): 26-28.
Embodiment 1
Prepare modified polyorganosiloxane:
A, take 74.16g(0.25mol) octamethylcyclotetrasiloxane (D4), 60g containing hydrogen silicone oil (0.025mol, siloxane unit number is 40, molecular weight is 2400), 13.43g(0.1mol) hydrogeneous double-seal head and 7.38g resin cation (R.C.), is warming up to 50 ℃ after mixing, stirring reaction is after 9 hours, filter, remove resin cation (R.C.), underpressure distillation, removes low-boiling-point substance, obtain hydrogen end-blocking containing hydrogen silicone oil, viscosity is 35mPas;
B, 29.48g hydrogen end-blocking containing hydrogen silicone oil and 0.072g isopropyl alcohol solution of chloroplatinic acid (platinum content is 0.0072g) are added in 50.00g sherwood oil, pass into dry N
2, stir and be warmed up to 85 ℃, drip while stirring 10.26g glycidyl allyl ether (AGE), at 85 ℃, react 6h, after completion of the reaction, underpressure distillation, obtains modified polyorganosiloxane.
According to the raw material consumption of preparing hydrogen end-blocking containing hydrogen silicone oil in steps A, can calculate the mole number of two senses and simple function siloxane unit in hydrogen end-blocking containing hydrogen silicone oil, the composition formula that obtains modified polyorganosiloxane for (R ' Me
2siO
1/2)
0.09(R ' MeSiO)
0.15(Me
2siO)
0.45(HMeSiO)
0.31, R ' be γ-glycidyl ether oxygen propyl (
).Measuring the viscosity that obtains modified polyorganosiloxane is respectively 45mPas, and hydrogen content is 0.3455%, is 0.26mol/100g containing γ-glycidyl ether oxygen propyl content of epoxy group(ing).
Embodiment 2
Prepare modified polyorganosiloxane:
A, take 74.16g octamethylcyclotetrasiloxane (D4), 136g methyl phenyl ring siloxane mixture, 60g containing hydrogen silicone oil (0.025mol, siloxane unit number is 40, and molecular weight is 2400), the hydrogeneous double-seal head of 13.43g and 7.38g resin cation (R.C.), after mixing, be warming up to 30 ℃, after stirring reaction 10 hours, filter, remove resin cation (R.C.), underpressure distillation, remove low-boiling-point substance, obtain the hydrogeneous phenyl silicone oil of hydrogen end-blocking, viscosity is 65mPas;
B, the hydrogeneous phenyl silicone oil of 28.34g hydrogen end-blocking and 0.067g isopropyl alcohol solution of chloroplatinic acid (platinum content is 0.0067g) are added in 45.00g sherwood oil, pass into dry N
2, stir and be warmed up to 85 ℃, drip while stirring 8.56gAGE, at 85 ℃, react 7h, after completion of the reaction, underpressure distillation, obtains modified polyorganosiloxane.
The composition formula of gained modified polyorganosiloxane be (R ' Me
2siO
1/2)
0.06(R ' MeSiO)
0.11(Me
2siO)
0.31(MePhSiO)
0.31(HMeSiO)
0.21, R ' be γ-glycidyl ether oxygen propyl (
).Measuring the viscosity that obtains modified polyorganosiloxane is respectively 80mPas, and hydrogen content is 0.2056%, is 0.19mol/100g containing γ-glycidyl ether oxygen propyl content of epoxy group(ing).
Embodiment 3
Prepare modified polyorganosiloxane:
Hydrogen end-blocking containing hydrogen silicone oil prepared by 29.48g embodiment 1 and 0.073g isopropyl alcohol solution of chloroplatinic acid (platinum content is 0.0073g) add in 50.00g sherwood oil, pass into dry N
2, stir and be warmed up to 85 ℃, drip while stirring 11.18g1,2-epoxy-4-vinyl cyclohexane reacts 6h at 85 ℃, and after completion of the reaction, underpressure distillation, obtains modified polyorganosiloxane.
The composition formula of gained modified polyorganosiloxane be (R ' Me
2siO
1/2)
0.09(R ' MeSiO)
0.11(Me
2siO)
0.45(HMeSiO)
0.35, R ' be HEO ethyl (
), and capping group comprise HEO ethyl (
).Measuring the viscosity that obtains modified polyorganosiloxane is respectively 90mPas, and hydrogen content is 0.3806%, is 0.22mol/100g containing the HEO ethyl content of epoxy group(ing).
Embodiment 4
Prepare modified polyorganosiloxane:
The hydrogeneous phenyl silicone oil of hydrogen end-blocking prepared by 28.34g embodiment 2 and 0.067g isopropyl alcohol solution of chloroplatinic acid (platinum content is 0.0067g) add in 45.00g sherwood oil, pass into dry N
2, stir and be warmed up to 85 ℃, drip while stirring 9.30g1,2-epoxy-4-vinyl cyclohexane reacts 8h at 85 ℃, and after completion of the reaction, underpressure distillation, obtains modified polyorganosiloxane.
The composition formula of gained modified polyorganosiloxane be (R ' Me
2siO
1/2)
0.06(R ' MeSiO)
0.08(Me
2siO)
0.31(MePhSiO)
0.31(HMeSiO)
0.24, R ' be HEO ethyl (
), and capping group comprise HEO ethyl (
).Measuring the viscosity that obtains modified polyorganosiloxane is respectively 80mPas, and hydrogen content is 0.2033%, is 0.16mol/100g containing the HEO ethyl content of epoxy group(ing).
Embodiment 5
Prepare modified polyorganosiloxane:
Hydrogen end-blocking containing hydrogen silicone oil prepared by 29.48g embodiment 1 and 0.073g isopropyl alcohol solution of chloroplatinic acid (platinum content is 0.0073g) add in 60.00g sherwood oil, pass into dry N
2, stir and be warmed up to 85 ℃, drip while stirring 59.76g molecular weight and be 500 allyl polyethenoxy ether (CH
2=CHCH
2o (CH
2cH
2o)
10h), at 85 ℃, react 10h, after completion of the reaction, underpressure distillation, obtains modified polyorganosiloxane.
The composition formula of gained modified polyorganosiloxane be (R ' Me
2siO
1/2)
0.09(R ' MeSiO)
0.13(Me
2siO)
0.45(HMeSiO)
0.33, R ' is polyoxyethylene ether oxygen propyl (CH
2cH
2cH
2o (CH
2cH
2o)
10h), and capping group comprise polyoxyethylene ether oxygen propyl (CH
2cH
2cH
2o (CH
2cH
2o)
10h).Measuring the viscosity that obtains modified polyorganosiloxane is respectively 130mPas, and hydrogen content is 0.2122%, and polyoxyethylene ether oxygen propyl content is 0.12mol/100g.
Embodiment 6
Prepare modified polyorganosiloxane:
The hydrogeneous phenyl silicone oil of hydrogen end-blocking prepared by 28.34g embodiment 2 and 0.067g isopropyl alcohol solution of chloroplatinic acid (platinum content is 0.0067g) add in 45.00g sherwood oil, pass into dry N
2, stir and be warmed up to 85 ℃, drip while stirring 72.39g molecular weight and be 500 allyl polyethenoxy ether (CH
2=CHCH
2o (CH
2cH
2o)
10h), at 85 ℃, react 12h, after completion of the reaction, underpressure distillation, obtains modified polyorganosiloxane.
The composition formula of gained modified polyorganosiloxane be (R ' Me
2siO
1/2)
0.06(R ' MeSiO)
0.08(Me
2siO)
0.31(MePhSiO)
0.31(HMeSiO)
0.24, wherein R ' is polyoxyethylene ether oxygen propyl (CH
2cH
2cH
2o (CH
2cH
2o)
10h), and capping group comprise polyoxyethylene ether oxygen propyl (CH
2cH
2cH
2o (CH
2cH
2o)
10h).Measuring the viscosity that obtains modified polyorganosiloxane is respectively 155mPas, and hydrogen content is 0.15%, and polyoxyethylene ether oxygen propyl content is 0.09mol/100g.
Embodiment 7
Prepare dual composition addition type liquid silastic, comprise A, B component, composed as follows:
A component:
25 parts of vinyl polysiloxanes
24.264 parts of vinyl silicone oils
Catalyzer 6ppm;
B component:
Wherein, the contents of ethylene of vinyl polysiloxane is 1.15%, and the viscosity of vinyl silicone oil is 7000mPas, contents of ethylene is 1.06%, and Silicon Containing Hydrogen oil viscosity is 25mPas, and hydrogen content is 1.37%, inhibitor is ethynylcyclohexanol, and catalyzer is vinyl double-seal head platinum complex.
Respectively 1 part of the aerosil that 2.5 parts of the modified polyorganosiloxanes of embodiment 1～6 preparation add in B component and particle diameter is 40nm is added in A component, obtain A, the B component of 1～6# thixotropy add-on type liquid silicon rubber; 2.5 parts of the modified polyorganosiloxanes only prepared by embodiment 1 add in B component, and A component composition is constant, obtains A, the B component of 7# thixotropy add-on type liquid silicon rubber; And 1 part of the aerosil that is only 40nm by particle diameter adds A component, B component composition is constant, obtains A, the B component of 8# add-on type liquid silicon rubber; The add-on type liquid silicon rubber that does not add thixotropic agent is designated as blank.Wherein, when aerosil is added to A component, after first silicon-dioxide being mixed with vinyl silicone oil, through Banbury mixer banburying, then mix with other components.
Test implementation example
1～8# thixotropy add-on type liquid silicon rubber (abbreviation liquid silastic) prepared by embodiment 7 and blank sample are as LED packaging plastic, to after A, B component mixing and stirring, use, it is carried out to application performance test, investigate the extrudability and thixotropy before liquid silastic solidifies, and solidify after hardness,, observe while adopting this liquid silastic to adopt the mode of cast to encapsulate, whether the formed body shape before and after solidifying subsides or is out of shape meanwhile.
Wherein, NDJ-1 type rotational viscosimeter for thixotropy index, tests by GB7193.1-87, gets same rotor, measures respectively the viscosity of liquid silastic under 6r/min and 60r/min, calculates thixotropy index, thixotropy index K=η
1/ η
2(η
1viscosity number during for 6r/min, η
2viscosity number during for 60r/min).
Extrudability testing method is: by after liquid silastic vacuum defoamation, pack in PE pipe, put same syringe needle, at 20kg/cm
2under air pressure, extrude continuously, the gel quantity of 5s extruded continuously in record.
Hardness adopts LX-A type Shore durometer to measure, three promise instrument company limiteds of Shenzhen.
By after liquid silastic vacuum defoamation, adopt the mode of pouring into a mould to encapsulate, make liquid silastic form lensing hemisphere, solidified through 100 ℃ × 1 hour+150 ℃ × 3 hours, observe and solidify front and back formed body shape and height, be designated as thixotroping stability.
By after liquid silastic vacuum defoamation, adopt the mode of cast to be packaged in the 2835 lamp pearls of 0.2w, under the condition of 25 ℃ of heat sink temperatures and working current 60mA, measure its optical throughput.
Test result is in table 1.
Table 1
From table 1 data, modified polyorganosiloxane of the present invention is added to the thixotropic property that can significantly improve liquid silastic in add-on type liquid silicon rubber.Gained thixotropy silicon rubber is through casting, before solidifying, can form hemispherical lens shape, after solidifying, substantially maintain original shape, thixotroping has good stability, and extrudabilityly can meet service requirements, after application, the optical throughput impact on lamp pearl is very little simultaneously, be that thixotropy add-on type liquid silicon rubber of the present invention can straight forming, without using mould, during for LED encapsulation, can directly replace traditional mould top packaging process, easy handling, simple process, simplified the production of support, makes that application cost is low, production efficiency is high.
Finally it should be noted that above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention.It will be understood by those of skill in the art that and can carry out some deductions or be equal to replacement technical scheme of the present invention, and do not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. the application of modified polyorganosiloxane in preparation thixotropy add-on type liquid silicon rubber, described thixotropy add-on type liquid silicon rubber comprises base polymer, linking agent, inhibitor and catalyzer, it is characterized in that, in described thixotropy add-on type liquid silicon rubber, also comprise modified polyorganosiloxane, an average group accepted way of doing sth for described modified polyorganosiloxane is suc as formula shown in (I):
R
aSiO
（4-a）/2 (Ⅰ)
In formula I, a meets the positive number of 1.5≤a≤2.8, and R is identical or different monovalence alkyl, hydrogen or monovalence function base, and described monovalence function base is substituted or non-substituted one or more the function base containing in ehter bond, epoxy group(ing), ester group; The viscosity of described modified polyorganosiloxane is 30～15000mPas, and in modified polyorganosiloxane, the content of monovalence function base is 0.01～0.80mol/100g;
The method of described application is by modified polyorganosiloxane and base polymer, linking agent, inhibitor and catalyst mix, obtains thixotropy add-on type liquid silicon rubber.
2. application as claimed in claim 1, is characterized in that, described monovalence function base is
3. application as claimed in claim 2, is characterized in that, described n, r are that 1, x is 10, R
0, R
1, R
2for methyl, R
3for ethylidene.
4. the application as described in claim 1～3 any one, is characterized in that, the hydrogen content of described modified polyorganosiloxane is 0.1～0.5%.
5. the application as described in claim 1～4 any one, is characterized in that, the capping group of described modified polyorganosiloxane comprises described monovalence function base.
6. the application as described in claim 1～4 any one, is characterized in that, in described thixotropy add-on type liquid silicon rubber, the quality of modified polyorganosiloxane accounts for 1～5%.
7. application as claimed in claim 1, it is characterized in that, in described thixotropy add-on type liquid silicon rubber, also comprise aerosil, the method of described application is mixed for modified polyorganosiloxane and aerosil are added in base polymer, linking agent, inhibitor and catalyzer, obtains thixotropy add-on type liquid silicon rubber.
8. application as claimed in claim 7, is characterized in that, the mass ratio of described aerosil and modified polyorganosiloxane is (0.1-5): 1.
9. a thixotropy add-on type liquid silicon rubber, comprise base polymer, linking agent, inhibitor and catalyzer, it is characterized in that, in described thixotropy add-on type liquid silicon rubber, also comprise that an average group accepted way of doing sth is suc as formula the modified polyorganosiloxane shown in (I):
R
aSiO
（4-a）/2 (Ⅰ)
In formula I, a meets the positive number of 1.5≤a≤2.8, and R is identical or different monovalence alkyl, hydrogen or monovalence function base, and described monovalence function base is substituted or non-substituted one or more the function base containing in ehter bond, epoxy group(ing), ester group;
The viscosity of described modified polyorganosiloxane is 30～15000mPas, and in modified polyorganosiloxane, the content of monovalence function base is 0.01～0.80mol/100g;
Described add-on type liquid silicon rubber composition contains base polymer, linking agent, inhibitor and catalyzer.
10. thixotropy add-on type liquid silicon rubber as claimed in claim 9, is characterized in that, in described thixotropy add-on type liquid silicon rubber, also comprises aerosil.
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