CN103923464A - Application of modified cyclosiloxane in preparation of thixotropic additional liquid silicone rubber - Google Patents
Application of modified cyclosiloxane in preparation of thixotropic additional liquid silicone rubber Download PDFInfo
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Abstract
The invention discloses an application of modified cyclosiloxane in preparation of thixotropic additional liquid silicone rubber. The thixotropic additional liquid silicone rubber comprises base polymer, a cross-linking agent, an inhibitor, a catalyst and modified cyclosiloxane. The structural formula of the modified cyclosiloxane is as shown in the description, wherein R is the same or different monovalent alkyl groups, hydrogen or a monovalent functional group; the monovalent functional group is a substituted or non-substituted functional group containing one or more of ether bond, epoxy group and ester group; b is an integer which is not smaller than 3 and not greater than 10; the content of the monovalent functional group in the modified cyclosiloxane is 0.10-0.60mol/100g. The invention further discloses the thixotropic additional liquid silicone rubber which has excellent thixotropism and can be shaped without any molds.
Description
Technical field
The invention belongs to organosilicon material technical field, relate to application and the thixotropy add-on type liquid silicon rubber of modification cyclosiloxane in preparation thixotropy add-on type liquid silicon rubber.
Technical background
Liquid silastic be the linear organopolysiloxane by polymerizable medium degree be base polymer coordinate filler, the preparation of 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 comprised of base polymer, linking agent, catalyzer and inhibitor conventionally, according to practical application and function, need to comprise filler, additive etc., vinyl in base polymer and the Si-H base generation catalytic addition reaction in linking agent, be cross-linked to form the product with network structure, according to packaging means, can be divided into single-component and two-pack.Base polymer is vinyl polysiloxane or vinyl silicone oil containing two or more vinyl, linking agent is mainly the siloxane oligomer that contains 3 above Si-H keys, 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 by the hydrogen bond between surface hydroxyl three dimensional silica network, 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, when 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, simultaneously can be to generation detrimentally affects such as the transmittances of silicon rubber, 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 modification cyclosiloxane 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 modification cyclosiloxane, thixotropy is significantly improved, the base polymer consistency of modification cyclosiloxane 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 modification cyclosiloxane 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, also comprises the modification cyclosiloxane of structural formula as shown in formula I:
In formula I, b is for meeting the integer of 3≤b≤10, R is identical or different monovalence alkyl, hydrogen or monovalence function base, described monovalence function base is substituted or non-substituted one or more the function base containing in ehter bond, epoxy group(ing), ester group, and in described modification cyclosiloxane, the content of monovalence function base is 0.10～0.60mol/100g;
The method of described application is by modification cyclosiloxane 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 the molar weight of the monovalence function base that contains in 100g modification cyclosiloxane.
Preferably, b=4.
Preferably, described monovalence function base is
or
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 3 the integer that is less than or equal to, and x is greater than zero to be less than 20 integer.
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 modification cyclosiloxane is 0.05～0.5%.R represents the substituting group being connected with Siliciumatom, and hydrogen content is the quality percentage composition of hydrogen base, and the quality of modification cyclosiloxane of take is 100%.
Preferably, described monovalence alkyl is phenyl and/or methyl.
In described application, preferably, the quality of described modification cyclosiloxane accounts for 5～10% of thixotropy add-on type liquid silicon rubber quality.
Preferably, in described thixotropy add-on type liquid silicon rubber, also comprise aerosil, the method of application is that modification cyclosiloxane 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 modification cyclosiloxane is (0.01-1): 1.
Preferably, the particle diameter of described aerosil is 20～50nm.
A thixotropy add-on type liquid silicon rubber, comprises base polymer, linking agent, inhibitor, catalyzer, and the modification cyclosiloxane of structural formula as shown in formula I:
In formula I, b is for meeting the integer of 3≤b≤10, R is identical or different monovalence alkyl, hydrogen or monovalence function base, described monovalence function base is substituted or non-substituted one or more the function base containing in ehter bond, epoxy group(ing), ester group, and in described modification cyclosiloxane, the content of monovalence function base is 0.10～0.60mol/100g.
Preferably, in described thixotropy add-on type liquid silicon rubber, also contain aerosil.
More preferably, the mass ratio of described aerosil and modification cyclosiloxane is (0.01-1): 1.
Preferably, the particle diameter of described aerosil is 20～50nm.
Preferably, described base polymer comprises vinyl polysiloxane and vinyl silicone oil, and linking agent comprises containing hydrogen silicone oil.
Beneficial effect of the present invention is: the present invention is by the composition optimizes to modification cyclosiloxane, realize the application of modification cyclosiloxane 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 modification cyclosiloxane 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 modification cyclosiloxane in preparation thixotropy add-on type liquid silicon rubber, thixotropy add-on type liquid silicon rubber comprises base polymer, linking agent, inhibitor and catalyzer, also comprises the modification cyclosiloxane of structural formula as shown in formula I:
In formula I, b is for meeting the integer of 3≤b≤10, R is identical or different monovalence alkyl, hydrogen or monovalence function base, monovalence function base is substituted or non-substituted one or more the function base containing in ehter bond, epoxy group(ing), ester group, and in modification cyclosiloxane, the content of monovalence function base is 0.10～0.60mol/100g;
The method of application is by modification cyclosiloxane and base polymer, linking agent, inhibitor and catalyst mix, obtains thixotropy add-on type liquid silicon rubber.
In modification cyclosiloxane, the content of monovalence function base is preferably 0.10～0.60mol/100g.The content of monovalence function base is the molar weight of the monovalence function base that contains in 100g modification cyclosiloxane.
R is identical or different monovalence alkyl, hydrogen and monovalence function base, be that modification cyclosiloxane of the present invention is the mixing with the modification cyclosiloxane of different R groups, and in modification cyclosiloxane molecule, the R substituting group on same Siliciumatom can be identical or different above-mentioned substituting group.
The invention provides modification cyclosiloxane is applied to prepare the technical scheme in thixotropy add-on type liquid silicon rubber, the modification cyclosiloxane of performance thixotropy improvement effect is the annular siloxane with functional group.The modification cyclosiloxane that is applied to prepare thixotropy add-on type liquid silicon rubber of the present invention has specific 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 the structural formula of modification cyclosiloxane, b represents the number of silica unit in molecular structure, and b is for meeting the integer of 3≤b≤10, and modification cyclosiloxane comprises modification cyclotetrasiloxane, modification D5, modification ring six siloxanes etc.In a preferred embodiment, b=4, is modification cyclotetrasiloxane.
In the molecular structure of modification cyclosiloxane, monovalence function base specifically comprises having the group that forms hydrogen bonding functionality, the group that contains ehter bond, epoxy group(ing), ester group, amino, amide group, hydroxyl, carboxyl etc. all can be used as corresponding function base, when synthetic, by the reactant with function base, cyclosiloxane carried out to modification and introduce, and in same modification cyclosiloxane, can comprise different types of function base, all can be for improving the thixotropic property of liquid silastic in application.
In modification cyclosiloxane of the present invention, monovalence function base is preferably one or more the function base containing in ehter bond, epoxy group(ing), ester group, more preferably
or
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 3 the integer that is less than or equal to, and x is greater than zero to be less than 20 integer.
In monovalence function base,
for polyethers function base, R
3alkylidene group for C2～C5, specifically comprises-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 modification cyclosiloxane 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, there is thixotropy and improve that the modification cyclosiloxane of function can be considered alkyl in cyclosiloxane molecule or silicon hydrogen base substituting group is replaced and obtained by functional group, cyclosiloxane 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 silicone condensation reaction, prepare, and by regulating reaction raw materials ratio to obtain the modification cyclosiloxane with specific function base content, or directly buy and obtain, such as epoxide modified cyclosiloxane etc.
R represents the substituting group being connected with Siliciumatom, and modification cyclosiloxane has certain hydrogen content, and hydrogen content is the quality percentage composition of hydrogen base, by the quality of modification cyclosiloxane, is 100%.Preferably, the hydrogen content of modification cyclosiloxane is 0.05～0.5%, 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, 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 modification cyclosiloxane accounts for 5～10% of thixotropy add-on type liquid silicon rubber quality.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, in existing add-on type liquid silicon rubber product, directly add modification cyclosiloxane, obtain thixotropy add-on type liquid silicon rubber, all can improve its thixotropy, easy to use.
The application of modification cyclosiloxane 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 modification cyclosiloxane and aerosil are added in base polymer, linking agent, inhibitor and catalyzer and mixed, and obtains thixotropy add-on type liquid silicon rubber.
Further preferably, the mass ratio of aerosil and modification cyclosiloxane is (0.01-1): 1, and being used in combination of silicon-dioxide and modification cyclosiloxane 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 modification cyclosiloxane of average composition formula as shown in formula I:
In formula I, b is for meeting the integer of 3≤b≤10, R is identical or different monovalence alkyl, hydrogen or monovalence function base, monovalence function base is substituted or non-substituted one or more the function base containing in ehter bond, epoxy group(ing), ester group, and in modification cyclosiloxane, the content of monovalence function base is 0.10～0.60mol/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, the vinyl polysiloxane that comprises 35-55 weight part, the vinyl silicone oil of 35-55 weight part, the containing hydrogen silicone oil of 2-15 weight part, the structural formula of 4-10 weight part modification cyclosiloxane as shown in the formula (I), and inhibitor and catalyzer.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 thiazolinyl double-seal head platinum complex, and consumption is 5-10ppm.
Further preferably, in thixotropy add-on type liquid silicon rubber, the mol ratio of silicon hydrogen base and vinyl is 1.01～1.3, the molar weight that obtains silicon hydrogen base by hydrogen content and the Mass Calculation of modification cyclosiloxane and containing hydrogen silicone oil, the molar weight that obtains vinyl by contents of ethylene and the Mass Calculation of vinyl polysiloxane and vinyl silicone oil, can obtain both mol ratio.
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 modification cyclosiloxane are brought into play synergistic function, can significantly improve the thixotropy of additive properties liquid silastic.
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 hydrogeneous cyclosiloxane with containing the modified-reaction thing of alkenyl 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 modification cyclosiloxane, modification cyclosiloxane 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 modification cyclosiloxane and the hydrogeneous cyclosiloxane of raw materials thereof can carry out with reference to existing method, containing the modified-reaction thing of alkenyl 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 comprise 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
deng, X wherein
0, X
1, X
2value is without particular restriction, and the alkyl in alkyl acrylate comprises methyl, ethyl, butyl etc.
The monovalence function base of take is example as containing the epoxide modified cyclotetrasiloxane of epoxy group(ing) functional group, and its preparation method can comprise following operation steps:
Passing into dry N
2sherwood oil in add hydrogeneous cyclotetrasiloxane (D
4 h) and Pt/IPA, stir and be warmed up to 70-85 ℃, drip glycidyl allyl ether (AGE), after dropwising, at 70-85 ℃, react 6-12h, after completion of the reaction, underpressure distillation, obtains epoxide modified cyclosiloxane.
Wherein the R in epoxide modified cyclosiloxane is hydrogen, methyl and 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, the hydrogen content of containing hydrogen silicone oil, modification cyclosiloxane 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 modification cyclosiloxane can reference: Liu Jie, Tang Li, and Li Yan, a kind of determination of epoxide number of Fast Practical, leather and chemical industry, 2012,29(1): 26-28.
Embodiment 1
Preparation modification cyclosiloxane:
In four-hole bottle, pass into dry N
2, add 24.00gD
4 h(1,3,5,7-tetramethyl-ring tetrasiloxane, 0.10mol, hydrogen content is 1.6125%), sherwood oil (100.00g) and Pt/IPA(0.15g, 60 μ g/g), stir and be warmed up to 85 ℃, by constant pressure funnel, drip glycidyl allyl ether (AGE) (57.08g, 0.50mol), after dropwising, at 85 ℃, react 6h, after completion of the reaction, underpressure distillation, obtains modification cyclosiloxane.
Measuring respectively the hydrogen content obtain modification cyclosiloxane is 0.1568%, containing the γ-glycidyl ether oxygen propyl of epoxy group(ing)
content is 0.53mol/100g.
Embodiment 2
Preparation modification cyclosiloxane:
In four-hole bottle, pass into dry N
2, add D
4 h(24.00g, 0.10mol, hydrogen content is 1.6125%), sherwood oil (100.00g) and Pt/IPA(0.41g, 60 μ g/g), stir and be warmed up to 85 ℃, by constant pressure funnel, drip the allyl polyethenoxy ether that 200g molecular weight is 500, after dropwising, at 85 ℃, react 10h, after completion of the reaction, underpressure distillation, obtains modification cyclosiloxane.
The hydrogen content that records modification cyclosiloxane is 0.1352%, containing the polyoxyethylene ether oxygen propyl (CH of ether
2cH
2cH
2o (CH
2cH
2o)
10h) content is 0.16mol/100g.
Embodiment 3
Preparation modification cyclosiloxane:
In four-hole bottle, pass into dry N
2, add D
4 h(hydrogen content is 1.6125% for 24.00g, 0.10mol), sherwood oil (100.00g) and Pt/IPA(0.16g, 60 μ g/g), stirring is warmed up to 85 ℃, by constant pressure funnel, drips 1,2-epoxy-4-vinyl cyclohexane (62.07g, 0.5mol), after dropwising, at 85 ℃, react 8h, after completion of the reaction, underpressure distillation, obtains modification cyclosiloxane.
Measuring respectively the hydrogen content obtain modification cyclosiloxane is 0.4726%, containing the HEO ethyl of epoxy group(ing)
content is 0.40mol/100g.
Embodiment 4
Preparation modification cyclosiloxane:
In four-hole bottle, pass into dry N
2, add D
4 h(hydrogen content is 1.6125% for 24.00g, 0.10mol), hydroquinone monomethyl ether (0.07g, 0.00056mol), sherwood oil (100.00g) and Pt/IPA(0.12g, 60 μ g/g), stir and be warmed up to 70 ℃, by constant pressure funnel, drip methyl acrylate (43.05g, 0.5mol), after dropwising, at 70 ℃, react 12h, after completion of the reaction, underpressure distillation, obtains modification cyclosiloxane.
The hydrogen content that records modification cyclosiloxane is 0.2916%, containing the function base of ester group
content is 0.53mol/100g.
Embodiment 5
Preparation modification cyclosiloxane:
In four-hole bottle, pass into dry N
2, add D
4 h(hydrogen content is 1.6125% for 24.00g, 0.10mol), hydroquinone monomethyl ether (0.09g, 0.00072mol), (sherwood oil (100.00g) and Pt/IPA(0.16g, 60 μ g/g), stir and be warmed up to 85 ℃, by constant pressure funnel, drip butyl acrylate (64.08g, 0.5mol), after dropwising, at 85 ℃, react 10h, after completion of the reaction, underpressure distillation, obtains modification cyclosiloxane.
The hydrogen content that records modification cyclosiloxane is 0.2486%, containing the function base of ester group
content is 0.45mol/100g.
Embodiment 6
Prepare dual composition addition type liquid silastic, comprise A, B component, composed as follows:
A component:
25 parts of vinyl polysiloxanes
26.764 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 7.5 parts of the modification cyclosiloxane of embodiment 1～5 preparation add in B component and particle diameter is 40nm is added in A component, obtain A, the B component of 1～5# thixotropy add-on type liquid silicon rubber; Only 7.5 parts of the modification cyclosiloxane of embodiment 1 preparation are added in B component, A component forms constant, obtain A, the B component of 6# thixotropy add-on type liquid silicon rubber, and 1 part of the aerosil that is only 40nm by particle diameter adds in A component, B component forms constant, obtains A, the B component of 7# thixotropy 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, first silicon-dioxide is mixed by Banbury mixer banburying with vinyl silicone oil, then be uniformly mixed with other components.
Test implementation example
1～7# thixotropy add-on type liquid silicon rubber (abbreviation liquid silastic) of embodiment 6 preparations and blank sample are used as to LED packaging plastic, to after A, B component mixing and stirring, use, it is carried out to performance test, investigate the extrudability and thixotropy before liquid silastic solidifies, and the hardness after solidifying,, 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.
By after liquid silastic vacuum defoamation, adopt the mode of pouring into a mould to encapsulate, make liquid silastic form lensing hemisphere, through 100 ℃ * 1 hour+150 ℃ * 3 hours, solidify, 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, add modification cyclosiloxane of the present invention to can significantly improve liquid silastic in add-on type liquid silicon rubber thixotropic property.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 (9)
1. the application of modification cyclosiloxane 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 contain modification cyclosiloxane, the structural formula of described modification cyclosiloxane is as shown in formula I:
In formula I, b is for meeting the integer of 3≤b≤10, R is identical or different monovalence alkyl, hydrogen or monovalence function base, described monovalence function base is substituted or non-substituted one or more the function base containing in ehter bond, epoxy group(ing), ester group, and in described modification cyclosiloxane, the content of monovalence function base is 0.10～0.60mol/100g;
The method of described application is by modification cyclosiloxane 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
or
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 3 the integer that is less than or equal to, and x is greater than zero to be less than 20 integer.
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. application as claimed in claim 1, is characterized in that, the hydrogen content of described modification cyclosiloxane is 0.05～0.5%.
5. the application as described in claim 1-4 any one, is characterized in that, the quality of described modification cyclosiloxane accounts for 5～10% of thixotropy add-on type liquid silicon rubber quality.
6. application as claimed in claim 1, it is characterized in that, in described thixotropy add-on type liquid silicon rubber, also contain aerosil, the method of described application is that modification cyclosiloxane and aerosil are added in base polymer, linking agent, inhibitor and catalyzer and mixed, and obtains thixotropy add-on type liquid silicon rubber.
7. application as claimed in claim 6, is characterized in that, the mass ratio of described aerosil and modification cyclosiloxane is (0.01-1): 1.
8. a thixotropy add-on type liquid silicon rubber, comprises base polymer, linking agent, inhibitor and catalyzer, it is characterized in that, also comprises the modification cyclosiloxane of structural formula as shown in formula I in described thixotropy add-on type liquid silicon rubber:
In formula I, 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;
B is for meeting the integer of 3≤b≤10, and in described modification cyclosiloxane, the content of monovalence function base is 0.10～0.60mol/100g.
9. thixotropy add-on type liquid silicon rubber as claimed in claim 8, is characterized in that, in described thixotropy add-on type liquid silicon rubber, also contains aerosil.
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Denomination of invention: Application of a modified cyclosiloxane in the preparation of thixotropic addition type liquid silicone rubber Effective date of registration: 20220815 Granted publication date: 20170125 Pledgee: Bank of China Limited by Share Ltd. Huizhou branch Pledgor: HUIZHOU ANPIN SILICONE MATERIAL Co.,Ltd. Registration number: Y2022980012666 |
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