CN103923464B - 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, it is related to modified cyclosiloxane in preparation thixotropy add-on type liquid silicon
Application in rubber and thixotropy add-on type liquid silicon rubber.
Technical background
Liquid silastic is by polymer complex filler based on the linear polysiloxane of intermediate degree of polymerisation, various helps
What agent and additive were prepared has self-leveling or thixotropic base material, can according to kind and purposes extrusion, note type, coat after,
In an atmosphere or the lower vulcanization forming of heating is elastomer, including condensed room temperature vulcanized silicone rubber, condensed type one pack system rtv silicon rubber
Glue, add-on type liquid silicon rubber etc..Wherein, add-on type liquid silicon rubber is generally by base polymer, cross-linking agent, catalyst and suppression
Preparation forms, and needs to may include filler, additive etc. according to practical application and function, the vinyl in base polymer with crosslinked
There is catalytic addition reaction in the si-h base in agent, be cross-linked to form the product with network structure, can be divided into list according to manner of packing
Component and bi-component.Base polymer is the vinyl polysiloxane or vinyl silicone oil containing two or more vinyls, hands over
Connection agent is mainly the siloxane oligomer containing more than 3 si-h keys, i.e. low viscosity linear methyl silicone oil, and catalyst is usually
Platinum group catalyst, the such as platinum catalyst of oxolane coordination, platinum-alkynes basigamy compound etc., inhibitor can postpone silicon hydrogenation addition
Reaction, extends storage period and the working life of silicone rubber, the such as compound containing alkynyl and many vinyls, and filler and additive mainly wrap
Including reinforced filling, heat filling, conductive filler, coloring agent, tackifier, fire retardant, releasing agent etc. makes silicone rubber have special work(
The material of special process requirement or can be met, wherein reinforced filling can be mq type silicones, gas-phase silica etc..
Add-on type liquid silicon rubber needs with thixotropy in particular application, when thixotropy refers to that material is sheared
Denseness diminishes, and stopping denseness during shearing increases, or when being sheared, denseness becomes big, stops the phenomenon that during shearing, denseness diminishes, liquid
Body silicone rubber has higher requirements to its thixotropy in some special applications, for example Making mold, electronic module embedding,
The fields such as led lens packages, have the extruded rear straight forming of thixotropic liquid silastic, keep shape, are heating and curing
In journey and cured glue body does not deform, subsides, from without by mould assistant formation, its application can greatly simplify
Silicone rubber construction technology, reduces cost, improve production efficiency.At present, the thixotropic agent using in field of liquid silicone rubber includes two
Silicon oxide, white carbon black, organobentonite and castor oil hydrogenated, polyamide etc..Wherein, silicon dioxide is the most frequently used thixotropic agent, two
Silicon oxide particle aggregation can connect formation three dimensional silica network by the hydrogen bond between surface hydroxyl, so that liquid is wrapped in
In network structure, and lead to viscosity to increase thus molding, but the hydrogen bond between aggregation is weaker, the power that can be sheared is broken, and works as shearing
When power removes, hydrogen bond recovers, and makes liquid molding again.But silicon dioxide is powder body, complicated with the hybrid technique of liquid silastic,
High cost, can produce harmful effect to light transmittance of silicone rubber etc., the scope of application is restricted simultaneously, and organic molecule thixotroping
Agent is then usually present not good with liquid silastic Miscibility, bad dispersibility defect, leads to thixotropic improvement to system
Limited use.
Content of the invention
For above-mentioned the deficiencies in the prior art, the present invention provides modified cyclosiloxane in preparation thixotropy add-on type liquid silicon
Application in rubber, and a kind of thixotropy add-on type liquid silicon rubber, contain in described thixotropy add-on type liquid silicon rubber and change
Property cyclosiloxane, so that thixotropy is significantly improved, simultaneously the base polymer of modified cyclosiloxane and add-on type liquid silicon rubber
The thing compatibility is good, to its extrudability and solidification after Effect on Mechanical Properties less, beneficial to obtain excellent combination property thixotropy
Liquid silastic.
The purpose of the present invention is achieved through the following technical solutions:
Application in preparation thixotropy add-on type liquid silicon rubber for the modified cyclosiloxane, described thixotropy add-on type liquid
Silicone rubber includes base polymer, cross-linking agent, inhibitor and catalyst, also includes modified ring silicon as shown in formula () for the structural formula
Oxygen alkane:
In formula (), b is the integer of satisfaction 3≤b≤10, and r is identical or different monovalent hydrocarbon, hydrogen or monovalence function base,
Described monovalence function base is the substituted or non-substituted function base containing one or more of ehter bond, epoxy radicals, ester group, described
In modified cyclosiloxane, the content of monovalence function base is 0.10～0.60mol/100g；
The method of described application is to mix modified cyclosiloxane with base polymer, cross-linking agent, inhibitor and catalyst,
Obtain thixotropy add-on type liquid silicon rubber.
The content of described monovalence function base is the mole of the monovalence function base containing in 100g modification cyclosiloxane.
Preferably, b=4.
Preferably, described monovalence function base is
OrOne or more of, r0For the alkyl of identical or different c1～c5, r1、r2
For the alkyl of identical or different h or c1～c5, r3For the alkylidene of identical or different c2～c5, n, r are little more than zero
In the integer equal to 3, x is the integer more than zero less than 20.
It is highly preferred that described n, r are 1, x is 10, r0、r1、r2For methyl, r3For ethylidene.
Preferably, the hydrogen content of described modification cyclosiloxane is 0.05～0.5%.R represents the replacement being connected with silicon atom
Base, hydrogen content is the weight/mass percentage composition of hydrogen-based, is counted with the quality of modified cyclosiloxane for 100%.
Preferably, described monovalent hydrocarbon is phenyl and/or methyl.
It is preferable that the quality of described modification cyclosiloxane accounts for thixotropy add-on type liquid silicon rubber quality in described application
5～10%.
Preferably, also include aerosil in described thixotropy add-on type liquid silicon rubber, the method for application be by
Modified cyclosiloxane is added in base polymer, cross-linking agent, inhibitor and catalyst with aerosil and mixes, and obtains thixotroping
Property add-on type liquid silicon rubber.
It is highly preferred that described aerosil is (0.01-1) with the mass ratio of modified cyclosiloxane: 1.
Preferably, the particle diameter of described aerosil is 20～50nm.
A kind of thixotropy add-on type liquid silicon rubber, including base polymer, cross-linking agent, inhibitor, catalyst, Yi Jijie
Modified cyclosiloxane as shown in formula () for the structure formula:
In formula (), b is the integer of satisfaction 3≤b≤10, and r is identical or different monovalent hydrocarbon, hydrogen or monovalence function base,
Described monovalence function base is the substituted or non-substituted function base containing one or more of ehter bond, epoxy radicals, ester group, described
In modified cyclosiloxane, the content of monovalence function base is 0.10～0.60mol/100g.
Preferably, also contain aerosil in described thixotropy add-on type liquid silicon rubber.
It is highly preferred that described aerosil is (0.01-1) with the mass ratio of modified cyclosiloxane: 1.
Preferably, the particle diameter of described aerosil is 20～50nm.
Preferably, described base polymer includes vinyl polysiloxane and vinyl silicone oil, and cross-linking agent includes containing hydrogen silicone oil.
The invention has the benefit that the present invention is by the structure optimization to modified cyclosiloxane, realize modified ring silica
Application in preparation thixotropy add-on type liquid silicon rubber for the alkane, obtains thixotropy and extrusion performance is good, and can before and after solidification
Stablize the thixotropy add-on type liquid silicon rubber of molding, meet the requirement of the no concrete application occasion such as die package, and modified ring
The adaptability of siloxanes is good, and preparation method is simple, beneficial to the popularization and application promoting thixotropy add-on type liquid silicon rubber, Yi Jiwu
The improvement of the liquid silastic technique for applying such as die package.
Specific embodiment
The present invention provides application in preparation thixotropy add-on type liquid silicon rubber for the modified cyclosiloxane, thixotropy addition
Type liquid silastic includes base polymer, cross-linking agent, inhibitor and catalyst, also includes structural formula changing as shown in formula ()
Property cyclosiloxane:
In formula (), b is the integer of satisfaction 3≤b≤10, and r is identical or different monovalent hydrocarbon, hydrogen or monovalence function base,
Monovalence function base is the substituted or non-substituted function base containing one or more of ehter bond, epoxy radicals, ester group, modified ring silicon
In oxygen alkane, the content of monovalence function base is 0.10～0.60mol/100g；
The method of application is to mix modified cyclosiloxane with base polymer, cross-linking agent, inhibitor and catalyst, obtains
Thixotropy add-on type liquid silicon rubber.
In modified cyclosiloxane, the content of monovalence function base is preferably 0.10～0.60mol/100g.The containing of monovalence function base
Measure the mole for the monovalence function base containing in 100g modification cyclosiloxane.
R is identical or different monovalent hydrocarbon, hydrogen and monovalence function base, and that is, the modified cyclosiloxane of the present invention is to have not
With the r substituent group on same silicon atom in the mixing of the modified cyclosiloxane of r group, and modified cyclic siloxane molecules can be
Identical or different above-mentioned substituent group.
The present invention provides and is applied to prepare the technical scheme in thixotropy add-on type liquid silicon rubber by modified cyclosiloxane,
The modified cyclosiloxane playing thixotropy improvement result is the annular siloxane with functional group.The preparation that is applied to of the present invention is touched
The modified cyclosiloxane of degeneration add-on type liquid silicon rubber has specific functional group relative amount, makes add-on type liquid silicon rubber
The thixotropy of glue significantly improves it is adaptable to the application scenario such as led no die package.
In the structural formula of modified cyclosiloxane, b represents the number of silica unit in molecular structure, b be satisfaction 3≤b≤
10 integer, that is, modified cyclosiloxane include modified cyclotetrasiloxane, modified D5, modified ring six siloxanes etc..?
In preferred embodiment, b=4, as modified cyclotetrasiloxane.
In the molecular structure of modified cyclosiloxane, monovalence function base specifically includes has the group forming hydrogen bonding functionality, contains
Have the group of ehter bond, epoxy radicals, ester group, amino, amide groups, hydroxyl, carboxyl etc. all can as corresponding function base, during synthesis by
Reactant with function base is modified to cyclosiloxane and introduces, and can comprise variety classes with modified cyclosiloxane
Function base, may be incorporated in application improving the thixotropic property of liquid silastic.
In the modified cyclosiloxane of the present invention, monovalence function base be preferably contain one of ehter bond, epoxy radicals, ester group or
Several function bases, more preferably
OrOne or more of, r0、r1、r2For h, or identical or different c1～c5
Alkyl, r3Alkylidene for c2～c5, n, r are the integer being less than or equal to 3 more than zero, and x is the integer more than zero less than 20.
In monovalence function base,For polyethers function base, r3Alkylene for c2～c5
Base, specifically includes-ch2ch2-、-ch2ch(ch3The mixing of the identical or different segment of)-wait, r3Be preferably be ethylidene (-
ch2ch2-), x is preferably 10, the modified cyclosiloxane containing this group and liquid silastic can be made to have the preferable compatibility, profit
In the thixotropic property improving liquid silastic.
Can be considered that cyclosiloxane divides it is pointed out that there is in the present invention thixotropy and improving the modified cyclosiloxane of function
Alkyl in son or silicon hydrogen-based substituent group are replaced by functional group and are obtained, and carry out functional modification to cyclosiloxane, are common
Organic-silicon-modified mode, can for example pass through Si-H addition reaction or silicone condensation reaction preparation, and lead to using existing method preparation
Overregulate reaction raw materials ratio and obtain the modified cyclosiloxane with specific function base content, or be directly commercially available, such as ring
Oxygen modification cyclosiloxane etc..
R represents the substituent group being connected with silicon atom, and modified cyclosiloxane has certain hydrogen content, and hydrogen content is hydrogen-based
Weight/mass percentage composition, is based on 100% by the quality of modified cyclosiloxane.Preferably, the hydrogen content of modified cyclosiloxane be 0.05～
0.5% so as to participate in hydrosilylation in the addition curing of liquid silastic, after raising liquid silastic solidification
Mechanical performance, obtains the thixotropic liquid silicone rubber of high comprehensive performance.
In a preferred embodiment, n, r are 1.r0、r1、r2For the alkyl of identical or different c1～c5, concretely methyl,
The saturated alkyl that ethyl, propyl group, tert-butyl group etc. are similar to, preferably methyl.
Monovalent hydrocarbon can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or similar alkyl；Ring penta
Base, cyclohexyl or similar cycloalkyl；Phenyl, tolyl, xylyl or similar aryl；Benzyl, phenethyl, phenylpropyl or
Similar aralkyl；3,3,3- trifluoro propyl, 3- chloropropyl or similar haloalkyl；Below most preferably alkyl and virtue
Base, especially methyl and phenyl.
In a preferred embodiment, the quality of modified cyclosiloxane account for thixotropy add-on type liquid silicon rubber quality 5～
10%.Wherein, there is no spy to the basic components of the add-on type liquid silicon rubbers such as base polymer, cross-linking agent, inhibitor and catalyst
Different limit, base polymer includes vinyl polysiloxane, vinyl silicone oil etc., and cross-linking agent includes containing hydrogen silicone oil, inhibitor and urging
Agent all no particular restriction, also can contain filler and additive in this thixotropy add-on type liquid silicon rubber simultaneously as needed,
As heat filling, conductive filler, fire retardant etc..
In practice, directly add modified cyclosiloxane in existing add-on type liquid silicon rubber product, obtain thixotropy and add
Molding liquid silicone rubber, all can improve its thixotropy, easy to use.
Application in preparation thixotropy add-on type liquid silicon rubber for the modified cyclosiloxane that the present invention provides, excellent further
Selection of land, also contains aerosil in thixotropy add-on type liquid silicon rubber, application process is by modified cyclosiloxane and gas
Aerosil adds in base polymer, cross-linking agent, inhibitor and catalyst and mixes, and obtains thixotropy add-on type liquid silicon rubber
Glue.
It is further preferred that aerosil is (0.01-1) with the mass ratio of modified cyclosiloxane: 1, silicon dioxide
Present prominent synergistic function with being applied in combination of modified cyclosiloxane, be remarkably improved additivity liquid silastic
Thixotropic property.
In a preferred embodiment, the particle diameter of aerosil is 20-50nm.
The embodiment of the present invention further provides for a kind of thixotropy add-on type liquid silicon rubber, including base polymer, crosslinking
Agent, inhibitor, the catalyst and average composition formula modified cyclosiloxane as shown in formula ():
In formula (), b is the integer of satisfaction 3≤b≤10, and r is identical or different monovalent hydrocarbon, hydrogen or monovalence function base,
Monovalence function base is the substituted or non-substituted function base containing one or more of ehter bond, epoxy radicals, ester group, modified ring silicon
In oxygen alkane, the content of monovalence function base is 0.10～0.60mol/100g.
In a preferred embodiment, base polymer includes vinyl polysiloxane and vinyl silicone oil, and cross-linking agent includes hydrogeneous
Silicone oil.
It is further preferred that thixotropy add-on type liquid silicon rubber is bi-component addition type liquid silastic, including 35-55
The vinyl polysiloxane of weight portion, the vinyl silicone oil of 35-55 weight portion, the containing hydrogen silicone oil of 2-15 weight portion, 4-10 weight portion
The (i) shown modified cyclosiloxane of structural formula such as formula, and inhibitor and catalyst.Give preferred thixotropy to add herein
The composition of molding liquid silicone rubber, but be not particularly limited in application, also can contain the promising increasing meeting application request addition
Stick etc..
In a preferred embodiment, vinyl polysiloxane medium vinyl content be 0.1-2%, including vinyl methyl silicones,
The vinyl polysiloxanes commonly used in the art such as Vinylphenyl silicon resin, vinyl methyl phenyl polysiloxane；Vinyl silicone oil viscous
Spend for 5000～10000mpa s, contents of ethylene is 0.5-2%；The viscosity of containing hydrogen silicone oil is 15～50mpa s, hydrogen content
For 0.8-1.6%.Meanwhile, inhibitor and catalyst are not particularly limited, and can be selected according to practical situation, and such as inhibitor is second
Alkynyl Hexalin, consumption is 0.025-0.035 weight portion, and catalyst is thiazolinyl double-seal head platinum complex, and consumption is 5-10ppm.
It is further preferred that in thixotropy add-on type liquid silicon rubber, silicon hydrogen-based is 1.01 with the mol ratio of vinyl
～1.3, obtained the mole of silicon hydrogen-based by the hydrogen content of modified cyclosiloxane and containing hydrogen silicone oil and Mass Calculation, by vinyl silicon
The contents of ethylene of resin and vinyl silicone oil and Mass Calculation obtain the mole of vinyl, you can obtain both mole
Than.
Correspondingly, also contain gas phase titanium dioxide in preferred thixotropy add-on type liquid silicon rubber provided in an embodiment of the present invention
Silicon.Silicon dioxide plays synergistic function with modified cyclosiloxane, is remarkably improved the thixotropy of additivity liquid silastic.
The embodiment of the present invention further provides for the preferred preparation method of thixotropy add-on type liquid silicon rubber, grasps including following
Make step:
By hydrogeneous cyclosiloxane with modified-reaction thing containing alkenyl in inert gas environment and organic solvent, in 85-
Through platinum catalyst catalytic reaction 6～12h at 95 DEG C, after completion of the reaction, vacuum distillation, that is, obtain modified cyclosiloxane, by modification
Cyclosiloxane adds mix homogeneously in base polymer, cross-linking agent, inhibitor and catalyst, obtains thixotropy add-on type liquid silicon
Rubber.
In method made above, the synthesis of modified cyclosiloxane and its hydrogeneous cyclosiloxane of preparing raw material is referred to existing
Method is carried out, and the modified-reaction thing containing alkenyl is containing bases such as ether, epoxy radicals, ester group, amino, amide groups, hydroxyl, carboxyls
Roll into a ball and can occur with si-h bond the compound of the unsaturated double-bond of additive reaction, specifically may include allyl glycidyl ether
(age), 1,2- epoxy -4- vinyl cyclohexane, alkyl acrylate, allyl polyethenoxy ether (ch2=chch2o
(ch2ch2o)x0H), methyl allyl polyoxyethylene ether, ethylene glycol monovinyl ether
Vinyl polyether Deng wherein x0、
x1、x2Value no particular restriction, the alkyl in alkyl acrylate includes methyl, ethyl, butyl etc..
So that monovalence function base is the epoxide modified cyclotetrasiloxane containing epoxy radicals functional group as a example, its preparation method is permissible
Including following operating procedure:
N is dried being passed through2Petroleum ether in add hydrogeneous cyclotetrasiloxane (d4 h) and pt/ipa, stir and be warmed up to 70-85
DEG C, Deca allyl glycidyl ether (age), after completion of dropping, reacts 6-12h, after completion of the reaction, decompression at 70-85 DEG C
Distillation, obtains epoxide modified cyclosiloxane.
R in wherein epoxide modified cyclosiloxane is hydrogen, methyl and γ-glycidyl ether oxygen propyl.
The present invention can pass through examples below further instruction, but embodiment is not the limit to the scope of the present invention
System.In following embodiments, the hydrogen content of containing hydrogen silicone oil, modified cyclosiloxane etc. is the percent mass of hydrogen in material institute silicon-hydrogen bond containing
Content, method of testing refers to document: Zhang Donghui, Zhang Songlin, Fan Hui army etc., the synthesis of amino-polyether modified organosilicon and froth breaking
Performance study, Chemical Engineering and Technology, 2013,3:122-126；The epoxy group content method of testing of modified cyclosiloxane refers to
Document: Liu Jie, Tang Li, Li Yan, a kind of determination of epoxide number of Fast Practical, leather and chemical industry, 2012,29(1): 26-28.
Embodiment 1
The modified cyclosiloxane of preparation:
In four-hole bottle, it is passed through dry n2, add 24.00gd4 h(1,3,5,7- tetramethyl-ring tetrasiloxane,
0.10mol, hydrogen content is 1.6125%), petroleum ether (100.00g) and pt/ipa(0.15g, 60 μ g/g), stirring is warmed up to 85
DEG C, with constant pressure funnel Deca allyl glycidyl ether (age) (57.08g, 0.50mol), after completion of dropping, anti-at 85 DEG C
Answer 6h, after completion of the reaction, vacuum distillation, obtain modified cyclosiloxane.
The hydrogen content that mensure obtains modified cyclosiloxane respectively is 0.1568%, the γ-glycidyl ether oxygen third containing epoxy radicals
BaseContent is 0.53mol/100g.
Embodiment 2
The modified cyclosiloxane of preparation:
In four-hole bottle, it is passed through dry n2, add d4 h(24.00g, 0.10mol, hydrogen content is 1.6125%), petroleum ether
(100.00g) and pt/ipa(0.41g, 60 μ g/g), stirring be warmed up to 85 DEG C, with constant pressure funnel Deca 200g molecular weight be 500
Allyl polyethenoxy ether, after completion of dropping, at 85 DEG C react 10h, after completion of the reaction, vacuum distillation, obtain modified ring
Siloxanes.
The hydrogen content recording modified cyclosiloxane is 0.1352%, polyoxyethylene the ether oxygen propyl (- ch containing ether2ch2ch2o
(ch2ch2o)10H) content is 0.16mol/100g.
Embodiment 3
The modified cyclosiloxane of preparation:
In four-hole bottle, it is passed through dry n2, add d4 h(24.00g, 0.10mol, hydrogen content is 1.6125%), petroleum ether
(100.00g) and pt/ipa(0.16g, 60 μ g/g), stirring be warmed up to 85 DEG C, with constant pressure funnel Deca 1,2- epoxy -4- ethylene
Butylcyclohexane (62.07g, 0.5mol), after completion of dropping, reacts 8h at 85 DEG C, after completion of the reaction, vacuum distillation, changed
Property cyclosiloxane.
The hydrogen content that mensure obtains modified cyclosiloxane respectively is 0.4726%, the HEO second containing epoxy radicals
BaseContent is 0.40mol/100g.
Embodiment 4
The modified cyclosiloxane of preparation:
In four-hole bottle, it is passed through dry n2, add d4 h(24.00g, 0.10mol, hydrogen content is 1.6125%), to benzene two
Phenol monomethyl ether (0.07g, 0.00056mol), petroleum ether (100.00g) and pt/ipa(0.12g, 60 μ g/g), stirring is warmed up to 70
DEG C, with constant pressure funnel Deca acrylic acid methyl ester. (43.05g, 0.5mol), after completion of dropping, react 12h at 70 DEG C, reacted
Bi Hou, vacuum distillation, obtain modified cyclosiloxane.
The hydrogen content recording modified cyclosiloxane is 0.2916%, the function base containing ester group Contain
Measure as 0.53mol/100g.
Embodiment 5
The modified cyclosiloxane of preparation:
In four-hole bottle, it is passed through dry n2, add d4 h(24.00g, 0.10mol, hydrogen content is 1.6125%), to benzene two
Phenol monomethyl ether (0.09g, 0.00072mol), (petroleum ether (100.00g) and pt/ipa(0.16g, 60 μ g/g), stirring is warmed up to
85 DEG C, with constant pressure funnel Deca butyl acrylate (64.08g, 0.5mol), after completion of dropping, react 10h, reaction at 85 DEG C
After finishing, vacuum distillation, obtain modified cyclosiloxane.
The hydrogen content recording modified cyclosiloxane is 0.2486%, the function base containing ester group
Content is 0.45mol/100g.
Embodiment 6
Prepare dual composition addition type liquid silastic, including a, b component, form as follows:
A component:
25 parts of vinyl polysiloxane
26.764 parts of vinyl silicone oil
Catalyst 6ppm；
B component:
Wherein, the contents of ethylene of vinyl polysiloxane is 1.15%, and the viscosity of vinyl silicone oil is 7000mpa s, second
Amount vinyl content is 1.06%, and the viscosity of containing hydrogen silicone oil is 25mpa s, and hydrogen content is 1.37%, and inhibitor is ethynylcyclohexanol,
Catalyst is vinyl double-seal head platinum complex.
Respectively 7.5 parts of the modified cyclosiloxane of embodiment 1～5 preparation is added in b component and particle diameter is the gas phase of 40nm
Silica 1 part adds in a component, obtains a, b component of 1～5# thixotropy add-on type liquid silicon rubber；Only embodiment 1 is made
7.5 parts of standby modified cyclosiloxane adds in b components, and a group is grouped into constant, obtains 6# thixotropy add-on type liquid silicon rubber
A, b component, and only 1 part of the aerosil for 40nm adds in a component by particle diameter, b group is grouped into constant, obtains 7# thixotroping
A, b component of property add-on type liquid silicon rubber；The add-on type liquid silicon rubber being not added with thixotropic agent is designated as blank.Wherein, by gas
Aerosil add a group timesharing, through banbury banburying after first silicon dioxide being mixed with vinyl silicone oil, then with other components
It is uniformly mixed.
Testing example
1～7# thixotropy add-on type liquid silicon rubber (abbreviation liquid silastic) that prepare embodiment 6 and blank sample are used
Make led packaging plastic, will use after a, b component mixing and stirring, it is carried out with performance test, before investigating liquid silastic solidification
Extrudability and thixotropy, and solidification after hardness, meanwhile, observe using this liquid silastic using cast by the way of encapsulate
When, whether the formed bodies before and after solidification subside or deform.
Wherein, thixotropic index ndj-1 type rotating cylinder viscometer, is tested by gb7193.1-87, is taken same rotor,
Measure the viscosity of liquid silastic under 6r/min and 60r/min respectively, be calculated thixotropic index, thixotropic index k=η1/η2(η1
For viscosity number during 6r/min, η2Viscosity number for during 60r/min).
Extrudability method of testing is: after liquid silastic vacuum defoamation, loads in pe pipe, puts same syringe needle,
20kg/cm2Continuously extrude under air pressure, the continuous gel quantity extruding 5s of record.
After liquid silastic vacuum defoamation, encapsulated by the way of cast, make liquid silastic form lenticular hemisphere
Body, solidified through 100 DEG C × 1 hour+150 DEG C × 3 hours, observes formed bodies and height before and after solidification, is designated as thixotroping stable
Property.
After liquid silastic vacuum defoamation, in encapsulating to 2835 lamp bead of 0.2w by the way of cast, in heat sink temperature
Under conditions of 25 DEG C and operating current 60ma of degree, measure its luminous flux.
Test result is shown in Table 1.
Table 1
From the data in table 1, it can be seen that the modified cyclosiloxane of the present invention is added in add-on type liquid silicon rubber can be notable
Improve the thixotropic property of liquid silastic.Gained thixotropy silicone rubber, through moulding by casting, can form hemispherical lens shape before solidification,
Substantially maintain original shape after solidification, thixotroping has good stability, and extrudability disclosure satisfy that use requirement, to lamp simultaneously after applying
The luminous flux impact very little of pearl, that is, the thixotropy add-on type liquid silicon rubber of the present invention can straight forming, without using mould, use
Traditional mould top package technique can directly be replaced it is easy to operation, simple process when led encapsulates, simplify the production of support, make
Application cost is low, production efficiency is high.
Finally it should be noted that above example only in order to illustrate technical scheme rather than to the present invention protect
The restriction of scope.It will be understood by those of skill in the art that can carry out to technical scheme some deducing or waiting
With replacing, without deviating from the spirit and scope of technical solution of the present invention.
Claims (7)
1. application in preparation thixotropy add-on type liquid silicon rubber for the modified cyclosiloxane, described thixotropy add-on type liquid silicon
Rubber includes base polymer, cross-linking agent, inhibitor and catalyst it is characterised in that described thixotropy add-on type liquid silicon rubber
Modified cyclosiloxane is also contained in glue, shown in the structural formula such as formula () of described modification cyclosiloxane:
In formula (), b is the integer of satisfaction 3≤b≤10, and r is identical or different monovalent hydrocarbon, hydrogen or monovalence function base, described
Monovalence function base is the substituted or non-substituted function base containing one or more of ehter bond, epoxy radicals, ester group, described modification
In cyclosiloxane, the content of monovalence function base is 0.10～0.60mol/100g；
Aerosil is also contained, the method for described application is by modified ring silicon in described thixotropy add-on type liquid silicon rubber
Oxygen alkane is added in base polymer, cross-linking agent, inhibitor and catalyst with aerosil and mixes, and obtains thixotropy add-on type
Liquid silastic.
2. application as claimed in claim 1 is it is characterised in that described monovalence function base is
One or more of, r0For
The alkyl of identical or different c1～c5, r1、r2For the alkyl of identical or different h or c1～c5, r3For identical or different c2
The alkylidene of～c5, n, r are the integer being less than or equal to 3 more than zero, and x is the integer more than zero less than 20.
3. application as claimed in claim 2 is it is characterised in that described n, r are 1, x is 10, r0、r1、r2For methyl, r3For sub- second
Base.
4. application as claimed in claim 1 is it is characterised in that the hydrogen content of described modification cyclosiloxane is 0.05～0.5%.
5. the application as described in any one of claim 1-4 is it is characterised in that the quality of described modification cyclosiloxane accounts for thixotropy
The 5～10% of add-on type liquid silicon rubber quality.
6. application as claimed in claim 1 is it is characterised in that the mass ratio of described aerosil and modified cyclosiloxane
For (0.01-1): 1.
7. a kind of thixotropy add-on type liquid silicon rubber, including base polymer, cross-linking agent, inhibitor and catalyst, its feature
It is, in described thixotropy add-on type liquid silicon rubber, also include modified cyclosiloxane as shown in formula () for the structural formula:
In formula (), r is identical or different monovalent hydrocarbon, hydrogen or monovalence function base, and described monovalence function base is to replace or non-take
The function base containing one or more of ehter bond, epoxy radicals, ester group in generation；
B is the integer of satisfaction 3≤b≤10, and in described modification cyclosiloxane, the content of monovalence function base is 0.10～0.60mol/
100g, also contains aerosil in described thixotropy add-on type liquid silicon rubber.
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| CN113950511B (en) | 2019-06-21 | 2024-01-16 | 美国陶氏有机硅公司 | Method for preparing thixotropic curable silicone compositions |
| CN112979963B (en) * | 2020-12-30 | 2022-04-15 | 北京康美特科技股份有限公司 | Reactive silicone thixotropic agent, silicone packaging adhesive and LED element |
| JP2023026788A (en) * | 2021-08-16 | 2023-03-01 | 信越化学工業株式会社 | Heat-conductive silicone composition |
| CN113773499A (en) * | 2021-09-29 | 2021-12-10 | 安徽硅宝有机硅新材料有限公司 | Functional silane macromolecular polymer, preparation method, additive and application |
| CN115678497A (en) * | 2023-01-04 | 2023-02-03 | 北京康美特科技股份有限公司 | Organic silicon packaging adhesive for micro LED element and packaging method and application thereof |
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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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