CN101098911A - Ultraviolet transmissive polyhedral silsequioxane polymers - Google Patents

Ultraviolet transmissive polyhedral silsequioxane polymers Download PDF

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Publication number
CN101098911A
CN101098911A CNA2005800464217A CN200580046421A CN101098911A CN 101098911 A CN101098911 A CN 101098911A CN A2005800464217 A CNA2005800464217 A CN A2005800464217A CN 200580046421 A CN200580046421 A CN 200580046421A CN 101098911 A CN101098911 A CN 101098911A
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China
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multiaspect
group
silicious sesquioxane
reactive
functionalized
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高村德宏
篠谷贤一
理查德·M·莱恩
丽萨·维库利斯
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Panasonic Holdings Corp
University of Michigan
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Matsushita Electric Works Ltd
University of Michigan
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Abstract

Inorganic/organic hybrid polymers containing silsesquioxane cages are robust and exhibit desirable physical properties such as strength, hardness, and optical transparency at infrared and ultraviolet wavelengths. The polymers are prepared by polymerizing functionalized polyhedral silsesquioxane monomers such as polyhedral silsesquioxanes bearing two complementarily reactive functional groups bonded to cage silicon atoms by means of spacer moieties. The spacer moieties allow for steric mobility and more complete cure than polyhedral silsesquioxanes bearing reactive functional groups bound directly to cage silicon atoms.

Description

Ultraviolet transmissive polyhedral silsequioxane polymers
Technical field
The present invention relates to new silsesquioxane (silsesquioxanes) polymer precursor, prepare their method and from the polymkeric substance of the transmitting UV of its preparation.
Background technology
Transparent polymer is widely used.With respect to transparent medium glass for example, comprise for example calcium fluorite of vitreosil or vitreous silica and xln, polymkeric substance shows significant processing advantage.Polymkeric substance can be a thermoplasticity, and promptly melt-processable maybe can be heat cured, promptly by crosslinking curing to the non-thermal plasticity state.Can also obtain hybridized polymer, but for example be thermoplastic at first at heating, when exposure or further crosslinked in time those.
By the processing viewpoint, the organism sill is desirable, and this is because they are suitable for subzero treatment.Therefore, the development that has the transparent material of organic and inorganic materials advantage simultaneously becomes most important.In other words, need have high-clarity and anti-short wavelength light (advantage of inorganic materials) and be easy to material in machining at low temperature (advantage of organic materials).
The polymkeric substance that many application needs are firm, it is attrition resistant and has low thermal expansivity and specific refractory power, and is transmissive in the required part of spectrographic.For example, simple glass is a transmissive in the visible region, and in infrared (IR) and ultraviolet (UV) but be the part transmission in the spectral region.Yet,, must use quartz or fused silica for radiation of further in IR or UV, operating or responding device.These materials are difficult to produce.
Because its chemical bond and existence absorb group, are used for the polymkeric substance of this application before, for example transparent epoxy resin, polyester, polyacrylic ester and organopolysiloxane may have undesirable absorption peak in the SPECTRAL REGION of being concerned about.The transmission well in spectrographic IR and/or UV zone of many these materials.Importantly, these polymkeric substance also have the shortage resistance to abrasion, and have undesirable high thermal expansion coefficient and high refractive index.Therefore, though considerably can process, its optics and physicals are poorer than needed.
Silicious sesquioxane as polyhedral structure is normally known.Silicious sesquioxane can be by hydrolysis trifunctional silane A for example 3The SiB preparation, wherein A is an alkoxy or halogen, B is functional group or non-functional group, for example alkyl, vinyl or hydrogen.
Though can obtain the multiaspect molecule with traditional synthetic method, the resin that main products is normally highly cross-linked, it dissolves in non-polar solvent for example in the toluene.Can be by reacting cured resin, to produce multiple product with reacting to each other property functional monomer.For example can solidify the Si-H functionalized resins with divinyl compound.Yet product is high molecular weight elastomer or solid normally, and comprises a large amount of unreacted functional groups usually, even when reacting in solution.
According to United States Patent (USP) 5,047,492, the resin silicious sesquioxane is known, and has quoted with academic significance.Some products can comprise the multiaspect silicious sesquioxane.Yet when directly at the functionalized silicious sesquioxane of cage Siliciumatom, promptly when the R of functional group was vinyl base or H among Fig. 1, the spatial disposition of functional group and its made its reaction not exclusively to the closely approaching of inflexibility cage.Particularly under the situation of complete functionalized silicious sesquioxane before, promptly in comprising the silicious sesquioxane cage of eight Siliciumatoms, each silicon has identical reactive functional groups for this.Unreacted radical can change the performance of product with afterreaction, maybe may participate in multiple DeR, and for example oxidation generation coloring matter, or hydrolysis produces the hydrolysate as inclusion, and it reduces transparency.
The desirable polymkeric substance that is easy to process that provides, it does not have above-mentioned all or part of defective.
Summary of the invention
Find surprisingly now that polymkeric substance based on the multiaspect silicious sesquioxane is a transmissive highly in spectrographic UV district, and show for example resistance to abrasion and be easy to processing characteristics of desirable performance, wherein by spacer part functionalized described multiaspect silicious sesquioxane on the cage Siliciumatom.The easy preferred functionalized silicious sesquioxane fully of preparation, and when purifying suitably, provide the long storage time.
Description of drawings
Fig. 1 has illustrated the not preferred embodiment of functionalized fully multiaspect silsesquioxane polymer precursor.
Fig. 2 illustrates the polymkeric substance by not functionalized fully precursor preparation.
Fig. 3 has illustrated the UV transmission spectrum of the different materials that comprises preferred polymers of the present invention.
Fig. 4 has illustrated the curing that use is undertaken by the amount of the multiple catalyst passivating agent of dsc measurement.
Embodiment
The present invention relates to the multiaspect silicious sesquioxane, it has the functional group that partly is connected to the cage Siliciumatom by spacer, and described spacer part provides three-dimensional reactivity for functional group, makes and can react than the functional group of many parts.As more abundant detailed description hereinafter, preferred multiaspect silicious sesquioxane is not functionalized fully, makes each molecule on average have about 20 to 80mol% functionalized cage Siliciumatom, and more preferably 30 to 70mol%, most preferably 40 to 60mol% functionalized cage Siliciumatom.For example, at Si 8In the silicious sesquioxane cage, preferably use functionalized preferred average 2 to 6 Siliciumatoms of the reactive functional groups of specified type that partly are connected to cage Si atom by spacer, more preferably 3 to 5,4 Si atoms most preferably from about.
The invention still further relates to novel UV transmission polymkeric substance, it can be by the functionalized multiaspect silicious sesquioxane of part according to the present invention, or functionalized silicious sesquioxane prepares this polymkeric substance fully, and wherein at least a portion reactive functional groups is bonded to the cage Siliciumatom by spacer molecule.The multiaspect silicious sesquioxane has general formula Si nO 1.5n, wherein n is 6～12, most preferably is 8.Owing to have unavoidable impurities, or on purpose have SiO 2/2Or SiO 4/2The unit, actual Si/O stoichiometry can a little change from the ratio of specifying general formula at 1: 3.In addition, because incomplete reaction, cracking or exist inevitable or the monofunctional group SiO of intentional introducing is arranged 1/2, cage may be incomplete (promptly having open side).At SiO 2/2, SiO 4/2And SiO 1/2In the part, satisfy the remaining valency of tetravalence silicon by organic group, hydrogen, halogen etc.
When on purpose adding SiO 4/2During group, for example be prepared as for example SiCl of four functional silanes 4(MeO) 4During the silicious sesquioxane of Si form, with respect to trifunctional SiO 3/2The content of part, its amount will be more preferably less than 10mol% less than 20mol%, most preferably less than 5mol%.Preferably, except since unavoidable impurities or side reaction introduce those, do not have SiO 4/2Part.
Also can there be considerably less SiO 2/2Part is for example also based on SiO 3/2The content of part, less than 5mol%, preferably less than 3mol%, 2mol% or still less most preferably.Preferably, there is not SiO basically 2/2Group.These groups that come from inevitable impurity are acceptable.There is SiO 2/2Group can have two different influences.Under first kind of situation, these groups can prolong the length on one or more " limits " of multiaspect silicious sesquioxane structure.In the case, cage " side " can be pentagon or sexangle (about Si), SiO 2/2Group in polygonal non-three-dimensional in conjunction with the summit.This product is acceptable fully, as long as SiO 2/2The amount of group is not excessive.This product can allow the SiO greater than 5mol% 2/2The unit.Yet, if SiO 2/2Group and himself reaction form oligomeric chain (SiO 2/2) mM＞3 wherein, or when they are used for two or more multiaspect silicious sesquioxanes are linked together, its rigidity of polymerisate possible loss and hardness, and may be created in the zone of scattered beam in the polymkeric substance, particularly short wavelength light, reduce transmitance under these conditions.Therefore, can produce this product if synthesize the pattern of silicious sesquioxane cage, then the SiO of Cun Zaiing 2/2The unit is desirably quite low, and does not preferably have this unit to exist basically.
The SiO of above-mentioned discussion 4/2The amount of group is with respect to four functional monomers, promptly synthesizing four halogenated silanes or the tetraalkoxysilane of introducing during the silicious sesquioxane cage structure, be not complete reaction, promptly when for example having a SiO during preparation silicious sesquioxane such as precipitation or pyrogenic silica, flying dust, rice hull ash from silica source 2The unit.In these sources, SiO 4/2The unit is (as SiO 2) may Already in all or part of polyhedral structure in.
Must with reactive, be the functionalized multiaspect silicious sesquioxane that is used to prepare polymkeric substance of the present invention of polymerizable groups, at least a portion of this polymerizable groups must partly be bonded to the Si atom of multiaspect silicious sesquioxane by spacer.Reactive functional groups can change widely, comprises in principle can being used for chainpropagation or crosslinked silicon-containing monomer or oligopolymer to produce the total overall reaction group of organopolysiloxane or organic carbon siloxanes product.For example, still non-exclusively, addition, hydrosilylation or condensation reaction can easily take place in these groups.Limiting examples comprises Si-H group, unsaturated alkyl, can Michael (Michael) be added to the group of two keys, hydrolyzable group for example Si-OH, SiX wherein X be the preferred chlorine of halogen or Si-OR wherein R be the alkyl preferred alkyl.
The multiaspect silicious sesquioxane can comprise the reactive group of single type or surpass one type reactive group.When having the reactive group of more than one types, preferably the type of reactive group is a complementary interaction, promptly reacts to each other.In the case, a kind of reactive group can be chosen the Siliciumatom of Direct Bonding to multiaspect silicious sesquioxane molecule wantonly, does not promptly have the spacer part.
The example of reactive group comprises for example vinyl of olefinic and acetylene series unsaturated hydrocarbons, allyl group, 2-propenyl, pseudoallyl, the 3-butenyl, crotyl, 5-hexenyl, cycloalkenyl group be cyclopentenyl, cyclohexenyl, norbornene for example, ethynyl, 3-hexin base, acryloxy, methacryloxy etc.When having vinyl, these necessarily can not be directly connected on the cage Si atom, unless polymerizable mixture also contains the complementary interaction group that partly is connected to cage Si atom on identical or different molecule by spacer.
When existing the complementary interaction group for example when unsaturated alkyl, Si alkoxyl group, silanol (Si-OH) base, oximido, acetoxyl group etc., the hydrogen of bonded silica (Si-H) also is suitable reactive group.When having the complementary interaction group and partly being connected to the cage Siliciumatom by spacer whole or in part, the hydrogen of Si-H group can Direct Bonding to the cage Siliciumatom.Alternately, the hydrogen atom of preferred Si-H group can be connected to the cage Siliciumatom by means of spacer.Can be bonded to the SiH group of cage Siliciumatom and the example of spacer part and include, but are not limited to-O-SiR 2H ,-O-R 1-SiR 2H ,-R 1-(SiR 2O) 2H etc.When the SiH base that exists siloxanes to connect, the preferred interval base comprises no more than 4 two organic siloxyies, preferably on average less than 3 two organic siloxyies, and 1 or 2 two organic siloxy-most preferably.In the above-mentioned general formula, R is an organic radical, preferred alkyl, cycloalkyl, aryl, alkaryl or aralkyl, preferable methyl, R 1Be the bivalent hydrocarbon radical except that vinyl or phenyl, preferred alkyl or cycloalkyl.
But reactive functional groups can be the condensation group, for example silanol, alkoxyl group, acetoxyl group, silazane, the functionalized silyl of oximido, or other reaction produces the group of molecule side product species.But preferred condensation functional group, unless can carry out polymerization in a vacuum, or when the by product molecule from polymer diffusion or when being present in the zonule, the wavelength place minimum that scattering of light that wherein should the zone is being concerned about.Silanol, alkoxyl group and acetoxyl group all can with the condensation of Si-H group.During the condensation, by product is respectively molecular hydrogen, alkanol and acetate.
The spacer part can be the to a certain degree three-dimensional reorientation of any permission reactive functional groups, makes to obtain high relatively reactivity.Most preferably spacer partly comprises two organic siloxy-(OSiR 2) and hydrocarbon double-basis spacer, although also can use other spacer part for example alkoxyl group, polyalkylene oxide, ester etc.Phenyl and other aromatic group also can be used as the spacer part, particularly when also having other more on identical or different molecule " flexibility " partly for example when aliphatic hydrocarbon double-basis or dialkyl group silicomethane oxygen double-basis.
Can polymerization two or more different functionalized multiaspect silicious sesquioxanes, or multiaspect silicious sesquioxane that can the polymerization single type.The multiaspect silicious sesquioxane of special preferred polymeric single type, for example " not functionalized fully " silicious sesquioxane or complementary interaction silicious sesquioxane.
" fully functionalized " is meant the multiaspect silicious sesquioxane is modified as and comprises the particular functional group or be different from the functional group that has the type of group in the initial multiaspect silicious sesquioxane, or from the synthetic multiaspect silicious sesquioxane of monomer, this synthesizes and causes the average functional group that has a type on the cage Siliciumatom of 20mol% to 80mol%.For example, the synthetic monomeric convenient starting material of the present invention are eight [hydrogenation] silicious sesquioxanes, H 8Si 8O 12(" OHS ").OHS self is not good especially monomer, even is like this in the mixture of the multiaspect silicious sesquioxane of thiazolinyl siloxy-for example comprising complementary interaction molecule that spacer is connected with other yet.Because the reactivity of silicious sesquioxane cage reduces and the three-dimensional unavailability of the Si-H/ thiazolinyl reaction site of generation, the H-H reaction of whole eight Si-H bondings is along with reaction is restricted.Yet, OHS can be in hydrosilylation reactions and 2 to 6 moles of silane that dialkylene is functionalized allyl dimethyl basic ring hexenyl silane reaction for example, with the incomplete functionalized multiaspect silicious sesquioxane of preparation, it comprises SiH group and 1-propyl group-(cyclohexenyl) dimetylsilyl simultaneously.Preferably, use about 4 moles of hydrogenation sillylation reagents, therefore the multiaspect silicious sesquioxane of preparation on average has about 4 every type complementary interaction group.
Preferred reactive multiaspect silicious sesquioxane has the reactive functional groups that all partly is connected to cage Si atom by spacer, most preferably the type multiaspect silicious sesquioxane also comprises at least two types reactive functional groups, or one or more reactive functional groups and the non-reacted group mixture of methyl or trimethylsiloxy for example.Pass through Si 8O 8- 12With suitably functionalized for example chlorine hydrogenation dimethylsilane reaction (with the Si-H functional group that provides spacer to be connected) or chlorine cycloalkenyl group dimethylsilane reaction (with the cycloalkenyl group functional group that provides spacer to connect) of chlorine two organosilanes, can be easily from eight negatively charged ion Si 8O 8- 12Prepare this preferred reactive multiaspect silicious sesquioxane.In fact, these two reactive parts can be reacted simultaneously or successively, comprise the SiH of spacer connection and the multiaspect silicious sesquioxane of cycloalkenyl group functional group with generation.In this case by in the presence of hydrosilylation catalysts, from single monomer four [hydrogenation dimethylsilane oxygen bases]-four [(cycloalkenyl group) dimethylsilane oxygen base] silicious sesquioxane for example, or from the mixture of the functionalized silicious sesquioxane of difference, the for example hydrosilylation of six [hydrogenation dimethylsilane oxygen bases]-two [(cyclohexenyl) dimethylsilane oxygen base] silicious sesquioxane and two [hydrogenation dimethylsilane oxygen base]-six [(cyclohexenyl) dimethylsilane oxygen base] silicious sesquioxanes can easily be regulated the ratio of functional group and can prepare polymkeric substance.Though usually for any certain monomers system, the complementary interaction functional group of mol ratios such as needs, except equimolar ratio, can preference as 1: 2 to 2: 1, preferred 2: 3 to 3: 2 ratio.Optimum proportion is determined in a series of polymerizations by in varing proportions easily, and the institute of selecting the to offer the best ratio of considering that performance or performance make up, and described performance is for example for being easy to processibility, color, transparency, hardness, tensile strength etc.
The length of spacer part can be considered to the insertion atomicity of all types in the continuous chain between cage Siliciumatom and the reactive functional groups.For example in comprising the dimethylsilane oxygen base of 3-cyclohexenyl reactive functional groups, the insertion atomicity between cage Siliciumatom and the olefinic unsaturates site is 7 atoms (1 O, 1 Si, 5 C).Spacer part preferred length is less than 10 atoms, and more preferably length is less than 8 atoms.When polymer product began to become rubber-like or snappiness rather than rigid solid, spacer was on average oversize.
Especially surprisingly can be by for example eight [hydrogenation dimethylsilane oxygen base] silicious sesquioxane and the two for example reactions such as allyl group cyclohexenyl dimethylsilane, vinyl cyclohexene, cyclohexadiene, cyclopentadiene, norbornadiene of [thiazolinyl] molecule of multiaspect silicious sesquioxane that functionalized multiaspect silicious sesquioxane of SiH (hydrogen bonding is to cage Si) or hydrogenation siloxy-are replaced, with the thiazolinyl or the cycloalkenyl group functional group of preparation spacer connection.In the case, primary product is the ethylenically unsaturated group that corresponding alkylidene group connects.If any, only there is a spot of dipolymer molecule that comprises the silicious sesquioxane cage of alkylidene group connection, and can easily removes.For example cyclohexadiene, cyclopentadiene, 1 of conjugate system particularly, in the 3-hexadiene etc., the single adduct that still comprises reactive unsaturated site is main product.
The diolefine of mentioning before can comprising with the example of the how unsaturated molecule of the functionalized multiaspect silicious sesquioxane of Si-H reaction, and furans, pyrroles, thiophene, thiophene-1,1-dioxide, Dicyclopentadiene (DCPD), vinyl allyl ethers, 5-hexyl allyl ethers, divinyl ether, Vinylstyrene etc.Suitable in addition is for example hexanediol diacrylate, glycerol diacrylate etc. of unsaturated alkanol ester.When the total amount of wishing unsaturated functional group is higher than the total amount that can obtain from the compound that comprises two unsaturated sites of olefinic, can use for example three vinylformic acid glyceryl ester and trimethyol propane triacrylates of multifunctional unsaturated molecule.
Prepare the polymkeric substance from the functionalized multiaspect silicious sesquioxane of the present invention, need the preparation transparent products usually.Need to be provided at the monomer that has the long storage time before using in addition, for example 25 ℃ one month, preferred two months or longer.Find surprisingly and unexpectedly to come purification of samples by precipitation in inconsistent solvent, and preferred by wash filtrate in other inconsistent solvent, help these targets." inconsistent solvent " is meant that product is soluble or sl. sol. solvent therein, for example when being added to first kind of product solution in the solvent, will cause the sedimentary solvent of product.When relating to the functionalized multiaspect silicious sesquioxane of thiazolinyl siloxy-and hydrogenation siloxy-, the example of suitable " compatible " solvent is a toluene, and the example of suitable " incompatible " solvent comprises methyl alcohol, ethanol and acetonitrile.Be passivated after hydrosilylation because be used to prepare the hydrosilylation catalysts of this product, estimate not to be further purified to have any influence.Yet, the unexpected ground level limit that extends storage period.
If desired, can repeat twice or repeatedly be somebody's turn to do sedimentary step from solvent or solvent mixture.Can use identical solvent or solvent mixture, or alternately can change.In addition, the solvent of washing or solvent mixture can be identical with the solvent or the solvent mixture of precipitated product, maybe can be different solvent or solvent mixtures.Preferred solvent and solvent mixture for or comprise and be selected from for example acetonitrile, ether diethyl ether, sulfoxide dimethyl sulfoxide (DMSO) and the acid amides solvent of dimethyl formamide and N,N-DIMETHYLACETAMIDE for example for example for example of alcohol, nitrile.
More surprisingly the monomer of purifying is easier to form transparent polymer product.Again because unpurified monomer solution is transparent and common colourless, show do not have can scattered light oligomeric or polymeric material, be muddy or translucent rather than transparent sometimes by the polymkeric substance of its generation.Very surprisingly purifying begins monomer and can produce the more product of highly transparent usually.
Find surprisingly in addition can help by the synthetic multiaspect silsesquioxane monomers of hydrosilylation reactions with solid (heterogeneous) hydrosilylation catalysts, with the preparation monomer, this produces the polymkeric substance with excellent properties again.Heterogeneous catalyzer can be any solid hydride silylation catalyst, and it is insoluble basically under reaction conditions, and comprises metal for example Pt, Pd, Rh, itself or be particle form or on carrier for example aluminum oxide or silicon-dioxide.Other insoluble metallic compound and complex compound also are suitable, for example preferred PtO 2Can particle form or the use of the form on carrier PtO 2After the hydrosilylation, with ordinary method for example the product of distillation monomer or by pour into, centrifugal, or filter solid catalyst from product and remove solid catalyst, wherein preferably filter.Therefore relatively costly catalyzer is easier to reclaim and/or utilize.The most surprisingly, compare with the monomer that uses solvable hydrosilylation catalysts preparation, the monomer for preparing with this technology shows excellent performance, comprises lower thermal expansivity and the transparency of sometimes improving.
Can use multiple synthetic technology to produce monomer of the present invention, and other method is conspicuous for the organic chemist of this area.Two kinds of preferred method are to make halogenated silanes and multiaspect silicious sesquioxane anionic reactive and the hydrosilylation functionalized multiaspect silicious sesquioxane of described Si-H before.The product of these reactions also can be as synthetic other monomeric intermediate.For example, by making Chlorodimethyl silicomethane and Si 8O 12Eight anionic reactives, can easily synthesize eight [hydrogenation dimethylsilane oxygen base] silicious sesquioxane.Can be by making Si-H functional group and for example vinyl cyclohexene reaction of unsaturated molecule, the further functionalized product that obtains that in the latter reaction, obtains.If use the unsaturated compound that is lower than equimolar amount, will obtain having hydrogenation dimethylsilane oxygen base and dimethyl [ethyl-cyclohexene base] siloxy-functional group, the two all is connected to the silicious sesquioxane cage by spacer.
Si 8O 12The negatively charged ion of eight negatively charged ion and similar other multiaspect silicious sesquioxane also can be in the presence of alkali and reactive halogen for example chlorosilane and chlorine organic compound reaction, produces other functional group.Can introduce non-functional group for example methyl and phenyl with these methods in addition.Monomer of the present invention can comprise this non-functional group and functional group.Preferably,, be less than 70% cage Siliciumatom and connect non-functionalized base base directly or indirectly, more preferably from about 50% or still less, most preferably 30% or still less based on mol/mol.
Find that in addition monomer of the present invention can distil.Consider these monomeric character, this is surprising especially, because its these monomers of silicious sesquioxane cage can be considered to have high inorganic content.These monomeric performances that distil not only cause the additional possibility of monomer purifying, and obtain the novel method of monomer deposition is polymer coated to prepare to the base material, encapsulants etc.Exist under the synthetic situation of oligomerization product, for example, can be used for from dipolymer and oligopolymer separating monomer molecule at low pressure biochemistry.
In order to form polymkeric substance, deposited monomer or monomeric mixture promptly deposit on the suitable substrates from solution or melts by distillation, and wherein base material can for example be to be coated or packaged device, surface to be coated, mould etc., when having solvent, with any solvent of pressure evaporating easily.Heating monomer then is enough to provide required reactivity, i.e. the polymeric time.If desired, polymerizable mixture can comprise catalyzer, to quicken curing.If solidifying (polymerization) reaction is hydrosilylation, can add for example platinum hydrosilylation catalysts of hydrosilylation catalysts.If reaction is condensation reaction, can add condensation catalyst for example tin catalyst, amine catalyst etc.Can not add the many monomers of catalyzer ground thermopolymerization, or only have possibility and from monomer preparation, be retained in relict catalyst in the monomeric products with unsaturated reactive functional groups.
By in the different time of different temperature polymerizations, easily determine suitable polymerization temperature.Temperature and time depends on the type of reaction usually, i.e. addition, hydrosilylation, polycondensation etc., and concrete monomeric reactivity.Can determine the thermopolymerization parameter greatly simplifiedly with DSC, and write down the temperature that polymerization begins by exothermic heat of reaction.In case establish suitable reaction temperature with DSC, can be under the various times a series of samples of polymerization, to determine necessary minimum polymerization time.In some cases, particularly when using active hydrosilylation catalysts not have inhibitor or sulphur compound respectively, polymerization can at room temperature take place.
Under the situation of addition polymerization, can also carry out polymerization photochemically.It is only enough to be exposed to UV in some cases separately, maybe can add light-cured catalyst known in the art, for example from the Darocur  of Ciba Specialty Chemicals and Irgacure  catalyzer with from the Sartomer  light trigger of Sartomer Company.Can also use the radical initiator precursor, or carry out addition polymerization from for example organo-peroxide of thermal source, hydroperoxide, peroxyester, ketone peroxide etc.
Therefore, in the aspect, the present invention relates to monomer and comprise multiple monomeric monomer system, these monomers comprise by spacer molecule and are connected to the reactive functional groups kind of Siliciumatom of multiaspect silicious sesquioxane as their reactivity or at least a portion of complementary interaction group.Preferably, monomer comprises two kinds of complementary interaction groups on identical molecule, and wherein at least a or two parts partly is connected in the cage Siliciumatom by spacer.Preferred monomer comprise direct key be connected to the cage Siliciumatom bonded silica hydrogen and partly be connected in the olefinic or the acetylene series site of cage Siliciumatom by spacer.When only having olefinic or acetylene series site, single type or polytype these at least a portion must partly be connected in the cage Siliciumatom by spacer.Comprise Direct Bonding to the H of each cage Siliciumatom and eight [hydrogenation] silicious sesquioxanes and eight [vinyl] silicious sesquioxane of vinyl be not monomer of the present invention, although these can be with a small amount of as the comonomer in the polymkeric substance of the present invention, promptly preferably be less than 30mol%, most preferably be less than 10mol% based on whole monomers.
In another aspect, the present invention relates to a kind of method for preparing hybrid inorganic-organic polymkeric substance UV protecting materials, plant multiaspect silicious sesquioxane [SiO by one or more are provided 1.5] n, n=6 wherein, 8,10 or 12; With multiple-SiMe 2The described multiaspect silicious sesquioxane of R group functionalization, wherein average at least some R are R 1Base, on average at least some R are R 2Base, wherein R 1And R 2Be the R base of interreaction, residue R base is non-reactive group, to form multiaspect silicious sesquioxane macromonomer; And by making the reactive R radical reaction on Different Silicon sesquioxyalkane macromonomer, solidify described multiaspect silicious sesquioxane macromonomer to produce the hybrid inorganic-organic polymkeric substance, wherein said hybrid inorganic-organic polymkeric substance has at least 60% transmissivity at 215nm.In this embodiment, reactive R base R 1And R 2Can be selected from the H of bonded silica individually, halogen, OR 3R wherein 3Be the preferred C of H or alkyl 1-4Alkyl, the preferred C of thiazolinyl 2-18Thiazolinyl, more preferably C 2-8Thiazolinyl, the preferred C of alkynyl 2-8The preferred C of alkynyl and cycloalkenyl group 4-18Cycloalkenyl group, more preferably C 4-12Cycloalkenyl group, C most preferably 6-10Cycloalkenyl group, non-reacted R are preferably selected from alkyl, cycloalkyl, trialkylsilkl and ω-trialkylsilkl end capped (gathering) siloxy-, and the alkyl in the non-reacted R base is methyl preferably.Reactive group R 1With reactive group R 2Ratio desirably be 0.25: 1 to 1: 1.
On the other hand, the present invention relates to a kind of method for preparing hybrid inorganic-organic polymkeric substance UV transmission material, by with the functionalized multiaspect silicious sesquioxane of first functional group, to form approximate general formula [R 1Me 2SiOSiO 1.5] nMultiaspect silicious sesquioxane or its mixture of first reactive functionalization, wherein n is 6,8,10 or 12 and with the functionalized multiaspect silicious sesquioxane of second functional group, to form approximate general formula [R 2Me 2SiOSiO 1-5] nMultiaspect silicious sesquioxane or its mixture of second reactive functionalization, wherein n is 6,8,10 or 12, wherein R 1And R 2Being interreaction connects the reactive functional groups of described first reactive functional multiaspect silicious sesquioxane and the described second reactive silicon sesquioxyalkane, some of them R with covalent linkage 1And R 2Can by with R 1And R 2Non-reacted R base is replaced and the functionalized silicious sesquioxane of solidification reactivity.Preferably, the first reactive functional multiaspect silicious sesquioxane on average has at least 2 R 1Group, more preferably at least 4 R 1Group, most preferably at least 6 R 1Group, the multiaspect silicious sesquioxane of second reactive functionalization on average has at least 2 R 2Group, more preferably at least 4 R 2Group, most preferably at least 6 R 2Group.
Reactive functional groups R 1Can comprise two kinds of different reactive functional groups R 1' and R 1", reactive functional groups R 2Can comprise two kinds of different reactive functional groups R 2' and R 2", R 1' and R 2' can react R mutually 1" and R 2" can react mutually.Reactive group can with other embodiment in disclosed identical, and needn't repeat.R 1With R 2Mol ratio be preferably 0.20: 1 to 1: 1, more preferably 0.25: 1 to 1: 1, R 1" and R 2" mol ratio be preferably 0.20: 1 to 1: 1, more preferably 0.25: 1 to 1: 1.
Preferably by making approximate general formula [H-Si (Me) 2-O-SiO 1.5] nSilicious sesquioxane or its mixture, wherein n is 6,8,10 or 12, with at least a reaction of dimethyl vinyl methoxy silane and dimethyl vinyl Ethoxysilane, prepares the preferred first and described second functionalized silicious sesquioxane.
In another aspect, the present invention relates to a kind of method for preparing hybrid inorganic-organic polymer encapsulated material, by the multiaspect silicious sesquioxane is provided; Reactive functional groups R with one or more types 1Functionalized multiaspect silicious sesquioxane is to produce general formula [RMe 2SiOSiO 1.5] nFunctionalized multiaspect silicious sesquioxane or its mixture, wherein n is 6,8,10,12, wherein R is reactive or non-reacted organic group, condition is that at least one R is reactive functional groups R 1, to form macromonomer; Add and reactive functional groups R 1The linking agent of reaction is to form curable mixtures; Solidify this curable mixtures, with the hydridization organic and inorganic encapsulants of the optical transmittance at least 60% that is formed on 215nm, wherein R and R 1Can be for aforesaid.
In another embodiment, the present invention relates to a kind of method of synthetic UV transmission hybrid inorganic-organic macromonomer, by the multiaspect that has reactive site on it silicious sesquioxane is provided; Make the described reactive site of at least a portion and one or more functionalized reagents reaction, to produce general formula [RMe 2SiOSiO 1.5] nMacromonomer or its mixture, wherein n is 6,8,10,12, R is non-reacted or reactive group, condition is that at least one R is R 1Reactive group, and at least one R is R 2Reactive group, wherein R 1And R 2For what react to each other, wherein select whole radicals R, make described macromonomer have at least 60% optical transmittance, wherein R, R at 215nm 1And R 2Can be for disclosed before.In particularly preferred this embodiment variant, the multiaspect silicious sesquioxane has general formula [HMe 2SiOSiO 1.5] nAnd carrying out functionalizedly with one or more functionalized reagents, this functionalized reagent is selected from 4-vinyl-1-tetrahydrobenzene, dimethyl vinyl chlorosilane, dimethyl vinyl methoxy silane, dimethyl vinyl Ethoxysilane, dicyclopentadiene, two [trimethyl silyl] acetylene and trimethyl silyl acetylene.
Other preferred functionalized agent can independently be selected from following compounds, although this inventory is an illustrative and nonrestrictive: dimethyl-allyl silane, 1,1,3,3-tetramethyl--1-allyl group sily oxide, 1,1,3,3-tetramethyl--1-vinyl sily oxide, the dimethyl-octa base silane, dimethylsilane, 1,1,3,3-tetramethyl--1, the 3-sily oxide, 1,1,3,3,5, the 5-hexam ethylcyclotrisiloxane, 1,1,3,3,5,5,7,7-prestox tetrasiloxane, 1,2-dimetylsilyl ethane, the divinyl dimethylsilane, 1,3-diallyl tetramethyl disiloxane, 1,3-diallyl tetraphenyl sily oxide, 1,1,3,3-tetramethyl--1, the 3-divinyl disiloxane, 1, two (dimetylsilyl) ethane of 2-, dimethylchlorosilane, the dimethyl methyl TMOS, dimethylethoxysilane, 1,1,3,3-tetramethyl vinyl chlorosilane, 1,1,3,3-tetramethyl-ethylene methoxylsilane, 1,1,3,3-tetramethyl-ethylene base oxethyl silane, [(bicycloheptenyl) ethyl] dimethylchlorosilane, [(bicycloheptenyl) ethyl] dimethyl methyl TMOS, [(bicycloheptenyl) ethyl] dimethylethoxysilane, allyldimethylcholrosilane, the allyl dimethyl methoxylsilane, allyl dimethyl base oxethyl silane, 6-hexenyl dimethylchlorosilane, 6-hexenyl dimethyl methyl TMOS, 6-hexenyl dimethylethoxysilane, 10-undecenyl dimethylchlorosilane, 10-undecenyl dimethyl methyl TMOS, 10-undecenyl dimethylethoxysilane, [2-(3-cyclohexenyl) ethyl] dimethylchlorosilane, [2-(3-cyclohexenyl) ethyl] dimethyl methyl TMOS, [2-(3-cyclohexenyl) ethyl] dimethylethoxysilane, 1,5-dichloro hexam ethylcyclotrisiloxane, 1,5-dimethoxy hexam ethylcyclotrisiloxane, 1,5-diethoxy hexam ethylcyclotrisiloxane, 1,3-dichloro tetramethyl disiloxane, 1,3-dimethoxy tetramethyl disiloxane, 1,3-diethoxy tetramethyl disiloxane, 1,3-dichloro tetraphenyl sily oxide, 1,3-dimethoxy tetraphenyl sily oxide, 1,3-diethoxy tetraphenyl sily oxide, the diallyl diphenyl silane, 1, two (hydroxyl dimetylsilyl) benzene of 4-, the di-isopropyl chlorosilane, the di-isopropyl methoxy silane, the di-isopropyl Ethoxysilane, the di-isopropyl dichlorosilane, diisopropyl dimethoxy silane, the di-isopropyl diethoxy silane, two (2,4, the 6-trimethylphenyl) dichlorosilane, diphenyl chlorosilane, the diphenylacetylene chlorosilane, the diphenylethlene methoxylsilane, the diphenylacetylene Ethoxysilane, diphenyl dichlorosilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, Diphenylsilanediol, diphenyl silane, two (p-methylphenyl) dichlorosilane, two (p-methylphenyl) dimethoxy silane, two (p-methylphenyl) diethoxy silane, 1,5-divinyl-1,3-phenylbenzene-1,3-dimethyl sily oxide, 1,5-divinyl-3-phenyl pentamethyl-trisiloxanes, divinyl tetraphenyl sily oxide, dimethyl dichlorosilane (DMCS), methyl dimethoxysilane, methyldiethoxysilane, the phenylethyl dichlorosilane, phenylethyl dimethoxy silane, the phenylethyl diethoxy silane, phenylmethyldichloroislane, phenyl methyl dimethoxy silane, the phenyl methyl diethoxy silane, phenyl methyl silane, 3-phenyl-1,1,3,5,5-pentamethyl-trisiloxanes, 1,1,3,3-tetra isopropyl-1,3-dichloro sily oxide, 1,1,3,3-tetra isopropyl-1,3-dimethoxy sily oxide, 1,1,3,3-tetra isopropyl-1,3-diethoxy sily oxide, 1,1,3, the 3-tetra isopropyl disiloxane, the ethenylphenyl methyl chlorosilane, ethenylphenyl methyl methoxy base silane, ethenylphenyl methyl ethoxy silane, the ethenylphenyl methyl-monosilane, cyclohexadiene, the dimethyl-allyl chlorosilane, dimethyl hexenyl chlorosilane, with 5-vinyl-2-norbornylene.
The invention still further relates to the polymkeric substance of producing with described method.In this embodiment, the hybrid inorganic-organic polymer materials comprises general formula
[A 0.5Me 2SiOSiO 1.5] n[RMe 2SiOSiO 1.5] n’
The part that comes from covalently bound a plurality of identical or different multiaspect silicious sesquioxane macromonomer, wherein n is a positive integer, n ' is 0 or positive integer, and n+n ' is 6,8,10 or 12, R is non-reacted organic group or unreacted reactive functional groups R 1Or R 2, A connects the bridge linkage group of two multiaspect silicious sesquioxanes parts and comes from two different radicals R that react to each other mutually 1And R 2Reaction, each macromonomer on average has R simultaneously 1And R 2Group, wherein selective reaction and non-reacted radicals R and bridge linkage group A make polymer materials have at least 60% optical transmittance at 215nm.
In another embodiment, the present invention relates to a kind of hybrid inorganic-organic polymer materials, wherein comprise general formula
[A 0.5Me 2SiOSiO 1.5] n[RMe 2SiOSiO 1.5] n’
The part that comes from covalently bound a plurality of identical or different multiaspect silicious sesquioxane macromonomer, wherein n and n ' are described before being, R is non-reacted organic group or unreacted reactive functional groups R 1Or R 2, A connects the divalence bridge linkage group of two multiaspect silicious sesquioxanes parts and comes from two different radicals R that react to each other 1And R 2Reaction, each macromonomer has at least two R 1Or R 2Group, but do not have R simultaneously 1And R 2Group, wherein selective reaction and non-reacted radicals R and bridge linkage group A make polymer materials have at least 60% optical transmittance at 215nm.
In another embodiment, the present invention relates to a kind of hybrid inorganic-organic polymer materials, it comprises general formula
[A 0.5Me 2SiOSiO 1.5] n[B 0.5Me 2SiOSiO 1.5] n”[RMe 2SiOSiO 1.5] n’
The part that comes from covalently bound a plurality of identical or different multiaspect silicious sesquioxane macromonomer, wherein n and n ' are described before being, n's " being 0 or positive integer, n, n ' and n " and be 6,8,10 or 12, R is non-reacted organic group or unreacted reactive functional groups R 1, R 2, R 3Or R 4, A connects the divalence bridge linkage group of two multiaspect silicious sesquioxanes parts and comes from two radicals R that react to each other 1And R 2Reaction, B is for the divalence bridge linkage group that connects two multiaspect silicious sesquioxanes parts and come from two radicals R that react to each other 3And R 4Reaction, wherein the first multiaspect silicious sesquioxane macromonomer has R 1And R 3Group, the second multiaspect silicious sesquioxane macromonomer has R 2And R 4Group, and wherein non-reacted radicals R, unreacted radical R, bridge linkage group A and bridge linkage group B make described polymer materials have at least 60% optical transmittance at 215nm.
The present invention also further relates to organic-inorganic hybrid polymer material, wherein comprises general formula
[A 0.5Me 2SiOSiO 1.5] n[RMe 2SiOSiO 1.5] n’
The a plurality of identical or different multiaspect silicious sesquioxane macromonomer that connects of covalent linkage, wherein n and n ' are as described above; R is non-reacted organic group or unreacted reactive group R 1, R 1For identical or different; A is for connecting the bridge linkage group of two multiaspect silicious sesquioxane parts, by two R 1Reaction form wherein R, R 1Make polymer materials have at least 60% optical transmittance at 215nm with A, and the present invention relates to a kind of organic-inorganic polymer material, it comprises general formula
[A 0.5Me 2SiOSiO 1.5] n[RMe 2SiOSiO 1.5] n’
The part of the silicious sesquioxane macromonomer that comes from a plurality of identical or different covalent bonds, wherein n and n ' are as previously mentioned; R is non-reacted organic group or unreacted reactive functional groups R 1R 1Be identical or different reactive functional groups, its with have at least two R 5Reactive functional groups R on the cross-linker molecules of group 5For what react to each other, R 5For identical or different; A is a divalent linker, comes from the reactive R of multiaspect silicious sesquioxane macromonomer 1The reactive R of group and cross-linker molecules 5The reaction of group; Wherein R, R 1, R 5Make polymkeric substance have at least 60% optical transmittance at 215nm with A.
Except monomer of the present invention, polymkeric substance of the present invention can also comprise the highly cross-linked functionalized silicone resin of non-basically cage shape of as many as 50mol%, preferably less than 20mol%, most preferably less than 10mol%, condition is to keep required optics of polymkeric substance and physicals.Polymkeric substance can also comprise a spot of linearity or branching organopolysiloxane, and it is at least trifunctional, and preferably has a higher functionality.Example comprises poly-(dimethylsilane oxygen base) (hydrogenated methyl siloxy-) oligopolymer and polymkeric substance that Si-H is functionalized.The amount that the latter exists makes that final product is not a snappiness or elastomeric, and its amount is more preferably less than 10mol% less than 20mol% usually.Most preferably said composition does not contain this material.
Can add minimum difunctionality organopolysiloxane or oligopolymer, a for example, ω-Si (CH 3) 2End capped siloxanes of H-or a, the end capped siloxanes of ω-divinyl, for example its amount is more preferably less than 5mol% less than 10mol%, as long as obtain firm, rigid polymer and be not rubber-like elastic body.Equally, also can have same restrictions ground and use polyalkenyl compound for example 1,5-hexadiene and isoprene.Can also use other more monomer for example trimethyol propane triacrylate, three vinylformic acid glyceryl ester, trivinylbenzene, trivinyl hexanaphthenes etc. of highly functionalization.Usually, the monomeric functionality of these non-the present invention is high more, and its admissible amount is just high more.Preferably, the monomer of adding does not have the chemical group at care wavelength absorption light.Can use liquid and low melting point monomer, reducing the viscosity of polymerizable mixture, and sometimes increase oligomeric and the polymerisate and the consistency of polymerization or the less polymeric part of matrix not.If under polymerization temperature, the solubleness of polymerisate in polymerizable mixture is lower, polymkeric substance and/or oligomer particles phase may occur, and its opposite with transparent material can produce muddy or opaque material.
Novel monomeric of the present invention preferably has the multiaspect silicious sesquioxane of complementary interaction functional group on each molecule.Preferred complementary functional groups is hydrogen and the hydrogen of olefinic or acetylene series unsaturates and bonded silica and the alkoxyl group of bonded silica of bonded silica.Novel monomeric is corresponding to general formula
[Si nO 1.5n][R 3] a[R 4] b[R 5] c
Wherein b and c are 1 or bigger, and at least one b or c＞2, a+b+c=n, and n is 6 to 12 integer, most preferably is 8.[Si nO 1.5n] unit is the multiaspect silicious sesquioxane.R 3Be non-functional group, preferred C 1-18Alkyl, more preferably C 1-4Alkyl or C 6-10Aryl, most preferable; R 4For H ,-L-SiR 3 2H or-L-SiR 3H 2, R wherein 3Be non-functionalized hydrocarbon R for example 3, L is the non-reacted spacer part of divalence, it can be C 2-C 18Hydrocarbon, preferred C 2-8Alkylidene group, C 5-8Cycloalkylidene or C 7-10Alkarylene, siloxy--SiR 3 2-O-or polysiloxane group-[SiR 3 2O] m-, wherein m is 2 to 10 integer, preferred 2 to 4; R 5Be the alkenyl-functional groups except vinyl, preferred C 3-18Olefinic or acetylene series unsaturated hydrocarbons, it is not connected to the Siliciumatom of multiaspect silicious sesquioxane at unsaturated carbon atom, preferred thiazolinyl or cycloalkenyl group, or group-[SiR 3 2O-]- o-[SiR 3 2]- pY, wherein o is 0 to 4 integer, and p is 0 or 1, and wherein o and p cannot be 0, and wherein Y is olefinic or acetylene series unsaturated group.R 5Can also have alkoxysilyl and replace unsaturated group, for example in other words dimethyl methoxy base siloxy-etc. has the alkoxyl group of reactive bonding key, preferred C 1-4The group of alkoxyl group.Can also there be multiple alkoxyl group.
Preferred monomer is that wherein a is 0,1 or 2, preferably 0, and b and c average out to 2 to 6, more preferably 3 to 5, and b+c's and on average be 8 those.In preferred monomer, R 4Be-L-SiR 3 2H or-L-SiR 3H 2, preferred radicals R 5Be olefinic unsaturated aliphatic and cycloaliphatic hydrocarbon with 4 to 10 carbon atoms.Cyclic aliphatic on this meaning comprises the cycloaliphatic compounds that is connected to silicon by alkylidene group, for example comes from those of vinyl cyclohexene.Preferred in addition R 5Be general formula SiR 3 2Those of-Y, wherein Y is thiazolinyl, alkynyl or cycloalkenyl group.
Monomeric synthesizing of preferred complementary interaction of the present invention is partial hydrogenation silanization multiaspect silicious sesquioxane, and described multiaspect silicious sesquioxane mainly has, preferably all has the SiR that key connects cage silicon 3 2The H part.Preferably carry out hydrosilylation in suitable, preferred non-polar organic solvent or preferred aromatic solvent, described nonpolar organic solvent for example is a for example hexane of alkane, and described aromatic solvent for example is toluene or dimethylbenzene (individual isomer or mixture).Can also use other solvent for example tetrahydrofuran (THF), diethyl ether, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) etc., as long as during reaction raw material is soluble or becomes dissolved.
As for hydrosilylation catalysts, can use Pt, the Pd, Rh and other precious metal chemical complex that are used as hydrosilylation catalysts usually, comprise the platinum alkene complex that is commonly called the Karstedt catalyzer.Also can use precious metal itself.Preferred hydrosilylation catalysts is those that use among the embodiment, particularly platinum (divinylsiloxanes) complex compound, platinum (dicyclopentadiene) complex compound, most preferred metal Pt and PtO 2
Supported catalyst and solid catalyst are specially suitable, are used for reclaiming or utilizing because can take out these from reaction mixture, and do not need to occur catalyst deactivation.Find surprisingly and unexpectedly, for example, can will use the solid catalyst PtO by removing by filter subsequently 2The TCHS polymerization of preparation becomes transparent polymer, and this The thermal expansion of polymer coefficient is lower than the TCHS of the similar composition of the soluble catalyst preparation that use deactivates subsequently.
The amount of hydrosilylation catalysts is the normally used amounts of these catalyzer, and the weight based on the initial multiaspect silicious sesquioxane with Si-H functional group can be changed to 1000ppm from 0.01ppm, preferred 0.01ppm to 200ppm, more preferably 0.01 to 50ppm, and most preferably 0.02 to 2pm.When using heterogeneous (solid or load) catalyzer, reasonable in order to keep the reaction times, use bigger a little amount.For 100g eight [hydrogenation dimethylsilane oxygen base] silicious sesquioxane, have been found that 0.05 to 0.2g PtO 2Work satisfactorily.
When using soluble catalyst and not using product at once, deactivation catalyst usually, so that the monomeric products of enough storage periods to be provided, this be because product itself comprise simultaneously can interreaction by hydrosilylation Si-H and ethylenically unsaturated group.Can use conventional catalyst deactivation method, comprise adding for example triphenylphosphine of phosphine, add for example mercaptan of sulphur compound, and any method generally known in the art.If the hydrosilylation catalysts that uses is that effectively catalyst deactivation is optional so in high relatively temperature only.In addition, also can use the known alkynol inhibitor of hydrosilylation field those of skill in the art and other inhibitor.These inhibitor in relative low temperature room temperature and be effectively under the high temperature a little for example, still can not suppress catalyzer at higher temperature usually.When the passivation platinum catalyst, the preferred triphenylphosphine that is less than 0.09 weight % with respect to the monomeric weight of complementary interaction that uses.Yet, also can use other passivator, comprise arsine, antimony hydride, alkali metal cyanide etc.
Use with respect to TCHS be less than 0.09mol% passivator, TCHS is cured as stiffener when being higher than 80 ℃, although even use with respect to TCHS greater than the passivator of 0.2mol%, hybrid does not have completely solidified yet when spending the night for 200 ℃.When adding triphenylphosphine, preferably be less than the passivator of 0.09mol%.The consumption of other passivator changes with type and required condition of cure.Based on these results, the amount of passivator plays important effect in preparation completely solidified material.In addition, passivator is also controlled required temperature of these materials of completely solidified or required time.Equally, it will influence and exist or do not have a solidification rate under the oxygen.
The alternative method that can be used for synthetic novel monomeric of the present invention is disclosed in United States Patent (USP) 5,047, in 492, is incorporated herein by reference herein.Yet, must change reaction sequence and raw material, with preparation multiaspect silicious sesquioxane, and must synthesize the multiaspect silicious sesquioxane to comprise the complementary interaction functional group that spacer connects.
New polymers of the present invention comprises from the polymkeric substance of the multiaspect silsesquioxane monomers preparation of the unsaturated group with spacer connection, optional combination comprises silicone resin or siloxane oligomer or polymkeric substance that surpasses three corresponding or complementary interaction groups and difunctional siloxane oligopolymer or the polymkeric substance that preferably is no more than 5mol%, preferred all or basically all the multiaspect silicious sesquioxane comprise the ethylenically unsaturated group of spacer connection; Maybe can comprise the novel monomeric with complementary interaction group of the present invention, at least a Siliciumatom that is connected to the multiaspect silicious sesquioxane by spacer of described complementary interaction functional group, optional have other molecule or siloxane oligomer or a polymkeric substance that other has at least two kinds and preferred three kinds or more kinds of corresponding functional group (promptly identical with a type of complementary interaction group) or complementary interaction group (promptly dissimilar, but can be with the reaction-ity group reaction of at least a type on the multiaspect silicious sesquioxane).Preferably, only the multiaspect silicious sesquioxane by same type prepares polymkeric substance, although the ratio of complementary interaction group can be different.In each case, the ratio of low functionality polymkeric substance, promptly each molecule has low " density " functional group, makes that product is solid rather than rubber-like elastic body.
Describe the present invention according to the following example now, these embodiment should not be construed as and limit the present invention by any way.Unless otherwise indicated, whole synthetic at room temperature or under the temperature that reaches behind the mix reagent, under environment atmospheric pressure, carry out.
Embodiment
Embodiment 1
Fig. 3 has compared bulk synthetic quartz (blueness), vitreosil (pink), KE-106, Shinetsu silicone resin (light blue, as not have aromatic component), low melt glass (red), transparent epoxy resin (purple) and TCHS (blue-greenish colour curve).
According to Fig. 3, the transparency of TCHS (blue-greenish colour) is more much better than the Resins, epoxy (purple) of the organic transparent encapsulation material that is used as infrared LED now, and has and silicone resin (light blue) and low melt glass (red) transparency much at one.Yet different with silicone resin, this material provides firmer mechanical property.The data of Fig. 3 show that TCHS hybridized nanometer mixture has the excellent feasibility that is used for Clear coating and film, particularly those of necessary transmission UV light.In addition, TCHS solidifies in low relatively temperature (150 to 200 ℃), and at 400 ℃ of air-stables, this is the performance that does not have discovery usually at silicone resin.
Transparency is meant the transmissivity at 〉=215nm place 〉=60% herein, preferred＞70%, most preferably＞85%.Preferably, the minimum wavelength＜380nm of transmitted light, most preferably＜300nm.Solidified TCHS material satisfies these all requirements.
Embodiment 2
Four (cyclohexenyl ethyl dimethylsilane oxygen base) four (dimethylsilane oxygen base) silicious sesquioxane, TCHS
Figure A20058004642100331
In the 250ml Schlenk flask that is equipped with reflux exchanger, and adding eight [hydrogenation dimethylsilane oxygen base] silicious sesquioxane " OHSS " (20g, 20mmol).Under vacuum, heat flask,, use nitrogen purging then to remove remaining air and moisture.(8.7g, 80mmol) and as 2mMPt (the dcp)-toluene solution of catalyzer (1ml Pt:2ppm) adds flask with toluene (50ml), 5-vinyl-1-tetrahydrobenzene then.
Stirred the mixture 5 hours at 90 ℃.Add triphenylphosphine [5mg 0.45mol%)] then,, and remove and desolvate, to produce the white powder product with catalyst deactivation.Output is 27.5g (0.019mol) 94%.Powder is TCHS.
Analytical data
DTA-TGA:Tg 5: 367 ℃ (in air), ceramic yield: 66.9% (in the air 1000 ℃, calculating: 65.2%)
DSC:Mp:76.3 ℃, solidification value: 180 ℃
1H?NMR：Si-CH 3，0.15ppm，26H，s
H-SiCH 3，0.26ppm，23H，s
Si-CH 2，0.65ppm，9.4H，d
Cyclohexenyl, 1.1-2.1ppm, 42H, m
Si-H，4.74ppm，4H，s
C＝C-H，5.66ppm，8.8H，s
13C?NMR：Si-CH 3，0.18ppm，s
H-Si-CH 3，0.73ppm，s
Si-CH 2，15.3ppm，s
Cyclohexenyl, 29.1,30.2,32.2,37.0ppm, s
C＝C，127.5ppm，d
FTIR：ν?C-H，3020cm -1
v?Si-H，2200cm -1
v?Si-O-Si，1095cm -1
According to 1H NMR spectrum and TGA-DTA data, the average structure of measuring TCHS is as follows.
Figure A20058004642100341
Embodiment 3
Synthetic and the purifying of four (cyclohexenyl ethyl dimethylsilane oxygen base) four (dimethylsilane oxygen base) eight-silicious sesquioxane (TCHS)
Figure A20058004642100351
Except adding passivator, according to the synthetic method of embodiment 2.By the TCHS toluene solution being added dropwise to solvent for example in methyl alcohol and the acetonitrile (400ml), so that (OHSS:10g 10mmol) realizes purifying, to obtain white TCHS powder on a small scale.Leach this powder, in beaker, wash then, and filtration obtains white powder with solvent (50ml).Repeat this process three times.The vacuum-drying white powder.The output of the TCHS of purifying is 3.5g (2.4mmol, 24.5%)
The storage period significant prolongation of sample.Although not having the storage period of the not purification of samples of passivator is fortnight, the storage period of purification of samples (no matter which kind of purification solvent) is two months.
Analytical data
1H?NMR：Si-CH 3，0.15ppm，28H，s
H-SiCH 3，0.26ppm，20H，s
Si-CH 2，0.65ppm，10H，d
Cyclohexenyl, 1.1-2.1ppm, 49H, m
Si-H，4.74ppm，3.2H，s
C＝C-H，5.66ppm，9.4H，s
According to 1H NMR spectrum, the integration ratio between tetrahydrobenzene and the Si-H is 4.7 to 3.3, shows following average structure.With unpurified sample as mentioned above 1H NMR spectrum is compared, and this ratio is from 4.2/3.8 (tetrahydrobenzene/Si-H) change.This explanation has been removed the composition that has than low degree of substitution from system.
Figure A20058004642100361
Can also be by making respective anionic and the organochlorosilane for example synthetic OHSS of dimethylchlorosilane reaction and its Q 6, Q 10And Q 12Analogue, and can by with dimethyl vinyl chlorosilane prepared in reaction unsaturated compound eight [vinyl] silicious sesquioxane for example.For example by with the reaction of dimethylsilane or cyclohexenyl dimethylchlorosilane, can the hydrosilylation latter, to produce the silicious sesquioxane that spacer connects.
Embodiment 4
Two (cyclohexenyl ethyl dimethylsilane oxygen base)-six (dimethylsilane oxygen base)-silicious sesquioxanes, BCHS's is synthetic
In the 100ml Schlenk flask that is equipped with reflux exchanger, and adding octahydro silicious sesquioxane OHS (2.5g, 2.5mmol).Under vacuum, heat flask,, use nitrogen purging then to remove remaining air and moisture.(0.26g, 5mmol) and as 2mM Pt (the dcp)-toluene solution of catalyzer (0.1ml Pt:0.2ppm) adds in the flask with toluene (20ml), 5-vinyl-1-tetrahydrobenzene then.
Stirred the mixture 5 hours at 90 ℃.After the reaction, remove and desolvate to obtain white powder.Carry out purifying with the methanol rinse powder, and dry, to produce white powder.Output is 2.33g (1.9mmol) 76%.
Analytical data
DTA-TGA:Tg 5: 452 ℃, ceramic yield: 75.8% (in the air 1000 ℃ calculate: 79.9%).
TGA in the nitrogen also shows because of some complex compound literization and loses some weight.
DSC:Mp:82 ℃, solidification value: 102,167 ℃
1H?NMR：Si-CH 3，0.15ppm，11H，s
H-SiCH 3，0.26ppm，37H，d
Si-CH 2，0.65ppm，4H，d
Cyclohexenyl, 1.1-2.1ppm, 18H, m
Si-H，4.74ppm，6H，s
C＝C-H，5.66ppm，3H，s
13C?NMR：Si-CH 3，0.15ppm，s
H-Si-CH 3，0.70ppm.s
Si-CH 2，15.2ppm.s
Cyclohexenyl, 29.1,30.2,32.2,37.0ppm.s
C＝C，127.5ppm，d
FTIR：v?C-H，3020cm -1
v?Si-H，2200cm -1
v?Si-O-Si，1095cm -1
According to 1H NMR spectrum and TGA-DTA data, the structure of determining BCHS is as follows.
Figure A20058004642100371
Embodiment 5
Eight (cyclohexenyl ethyl dimethylsilane oxygen base) silicious sesquioxane, OCHS's is synthetic
In the 250ml Schlenk flask that is equipped with reflux exchanger, and adding octahydro silicious sesquioxane OHS (21.4g, 21mmol).Under vacuum, heat flask,, use nitrogen purging then to remove remaining air and moisture.(18.2g, 170mmol) and as 2mM Pt (the dcp)-toluene solution of catalyzer (0.1ml Pt:0.02ppm) adds in the flask with 5-vinyl-1-tetrahydrobenzene then.
Stirred the mixture 4 hours at 90 ℃.After the reaction, remove and desolvate, obtain white powder.Carry out purifying with the methanol rinse powder, dry then, produce white powder.Output is 38.5g (20mmol) 97%.
Analytical data
DTA-TGA:Tg 5: 348 ℃, ceramic yield: 46.8% (in the air 1000 ℃ calculate: 51.0%).
Ceramic yield 36st.% only shows some material literization under a normal atmosphere in the nitrogen.Show in addition that if desired this material can be used for liter change (CVD) coating.
DSC：Mp：73℃
1H?NMR：Si-CH 3，0.14ppm，48H，s
Si-CH 2，0.65ppm，17H，d
Cyclohexenyl, 1.1-2.1ppm, 77H, m
C＝C-H，5.67ppm，16H，s
13C?NMR：Si-CH 3，-0.20ppm，s
Si-CH 2，14.8ppm，s
Cyclohexenyl, 25.6,28.7,29.8,31.8,36.6ppm, s
C＝C，127.0ppm，d
FTIR：v?C-H，3020cm -1
v?Si-O-Si，1095cm -1
Figure A20058004642100381
According to 1H NMR spectrum and TGA-DTA data, the structure of determining OCHS is as implied above.
Embodiment 6
Solidify TCHS
TCHS (≈ 1g) is added 10ml Teflon[23.3 * 18.3mm ID] or aluminium cup (25.2 * 39.6mm ID) in.This glass is placed on temperature to be set in 85 ℃ the vacuum drying oven.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Temperature increases to 200 ℃ with 30 ℃/hour then, keeps spending the night in 10 to 24 hours, produces the transparent disk of thickness 2.0-4.0mm.
When adding passivator as embodiment 2, be difficult to curing mixture, obtain elastomeric material.When passivation dosage 〉=0.09mol% (mol ratio of reagent and TCHS), obtain incomplete solidified rubber-like and muddy disk.When use was less than the reagent of 0.09mol%, the completely solidified product that obtains was rigidity and transparent disk.
Analytical data
DTA-TGA:Tg 5: 317 ℃; Ceramic yield: 67.1% (in the air 1000 ℃ calculate: 65.2%)
FTIR：n?Si-H，2140cm -1
d＝C-H，1408cm -1
v?Si-O-Si，1088cm -1
TMA：
142ppm (50-100 ℃): for the resin of purifying TCHS preparation never
160ppm (50-100 ℃): for the resin for preparing from TCHS with the methyl alcohol purifying
133ppm (50-100 ℃): for the resin for preparing from TCHS with the acetonitrile purifying
The TMA data show the effect of purge process.From with the CTE (thermal expansivity) of the resin of the TCHS preparation of acetonitrile purifying less than unpurified TCHS or with the CTE of the TCHS of methyl alcohol purifying.The CTE that this explanation is low if desired improves resin property preferably with the acetonitrile purifying so.
According to FT-IR, the peak intensity of residue Si-H is added the influence of passivator.For example, although derive from the Si-H (2140cm of the resin of TCHS and 5mg (0.45mol%) passivation agents -1) and Si-O-Si (1088cm -1) strength ratio be 0.11 (the Si-H/Si-O-Si strength ratio of initial TCHS is 0.32); When at the same terms (air heating to 200 ℃/24 hours) down during these resins of preparation, the resin ratio that derives from the TCHS that does not have passivator is 0.06.This data declaration does not have the curing ratio of the TCHS of passivator to have the more complete of passivator.
Embodiment 7
Solidify BCHS
BCHS (≈ 1g) is added 10ml Teflon[23.3 * 18.3mm ID] or aluminium cup (25.2 * 39.6mm ID) in.This glass is placed on temperature to be set in 85 ℃ the vacuum drying oven.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures to 200 ℃, and keep spending the night in 10 to 24 hours, produce white powder.Because lack crosslinking functionality, BCHS does not have completely solidified.Therefore, do not produce uniform resin.
Embodiment 8
Solidify the trial of OCHS
OCHS (≈ 1g) is added 10ml Teflon[23.3 * 18.3mm ID] or aluminium cup (25.2 * 39.6mm ID) in.Place temperature to be set in 85 ℃ vacuum drying oven this glass.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures to 200 ℃, and keep spending the night in 10 to 24 hours, produce white powder.The OCHS fusion, but do not have because solidify by the thermopolymerization of vinyl.
Embodiment 9 solidifies OCHS/OHSS
With OCHS (1g, 0.5mmoD/OHSS (0.5g 0.5mmol) adds 10mlTeflon[23.3 * 18.3mm ID] or aluminium cup (25.2 * 39.6mm ID) in.This glass is placed on temperature to be set in 85 ℃ the vacuum drying oven.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures to 200 ℃, and kept 10 to 24 hours, produce the disk of White-opalescent.
Embodiment 10 solidifies OCHS/BCHS
With OCHS (0.08g, 0.04mmol)/BCHS (0.1g 0.08mmol) adds 10mlTeflon[23.3 * 18.3mm ID] or aluminium cup (25.2 * 39.6mm ID) in.This glass is placed on temperature to be set in 85 ℃ the vacuum drying oven.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures to 200 ℃, and kept 10 to 24 hours, produce the disk of White-opalescent.
According to embodiment 6-10, the mol ratio of functional moiety and Si-H functional group is 0.25 to 1 on the preferred functionalized multiaspect silicious sesquioxane, most preferably 0.5, and for example in aforesaid TCHS.Because substitution value influences the physicals of compound, comprise solvability, fusing point etc., mixture such as OCHS/BCHS with the substituent compound of different numbers are always not mixable, the feasible resin that does not always form homogeneous transparent.In addition, a large amount of excessive a kind of reactive groups will cause incomplete curing and heterogeneity, and this will reduce transparency.
Embodiment 11
Eight (dicyclopentadienyl dimethylsilane oxygen base) eight silicious sesquioxanes (ODCPDS)
In the 100ml Schlenk flask that is equipped with reflux exchanger, and adding OHSS (5.1g, 5mmol).Heating unit lenitively under vacuum to remove remaining air and moisture, is used nitrogen purging then.(0.1ml Pt:0.2ppm) adds in the flask with Dicyclopentadiene (DCPD) [10.6g or 13.2g (being respectively 80mmol or 100mmol)] with as 2mM Pt (the dvs)-toluene solution of catalyzer then.
Under 90 ℃ of nitrogen, stirred the mixture 15 hours.Although begin opaquely, solution becomes uniformly after 10 minutes.Output is quantitative.
Analytical data
1H?NMR：Si-CH 3，0.098ppm，32?H，d
HSi-CH 3，0.27ppm，16H，s
Si-H，4.76ppm，2.6H，s
C=C-H, 5.5-5.6ppm, 51H, septet
13C?NMR：Si-CH 3，-1.5，-1.3，-1.2ppm，t
Si-H，0.29ppm，s
C＝C，132.2ppm，m
According to 1H NMR spectrum, the structure of ODCPDS is as follows.Dicyclopentadiene (DCPD) be difficult for OHS on whole Si-H reactions, part is because possible steric hindrance in addition because it is the good part of catalyst substance, thereby slows down reaction.Other catalyzer is Pt or PtO for example 2Can produce excellent result.
Figure A20058004642100421
Embodiment 12
Four (dicyclopentadienyl dimethylsilane oxygen bases) four (hydrogenation dimethylsilane oxygen base), eight silicious sesquioxanes, TDCPDS
Figure A20058004642100422
In the 100ml Schlenk flask that is equipped with reflux exchanger, and adding OHSS (19.0g, 19mmol).Heating unit lenitively under vacuum to remove remaining air and moisture, is used nitrogen purging then.Add toluene (100ml), Dicyclopentadiene (DCPD) (9.9g, 75mmol) and as 2mM Pt (the dvs)-toluene solution of catalyzer (0.2ml, Pt:0.4ppm).Stirred the mixture 6 hours at 90 ℃.After the reaction, evaporating solvent obtains colorless viscous liquid, TDCPS.Output is 28.2g (18mmol), 98%.
Analytical data:
DTA-TGA:Td 5, 458 ℃, ceramic yield: 63.5% (in the air 1000 ℃ calculate: 62.1%)
DSC: solidification value: 180 ℃
1H?NMR：Si-CH 3，0.09ppm，22H，d
H-Si-CH 3，0.26ppm，23H，s
Si-CH 2，0.67ppm，4H，d
Dicyclopentadienyl, 1.2ppm-3.2ppm, 40H, m
Si-H，4.75ppm，4H，s
C＝C-H，5.4-5.8ppm，8H，q
13C?NMR：Si-CH 3，0.28ppm，d
Dicyclopentadienyl, 14.8,25.6,28.7,29.8,31.8,36.6ppm, m
C＝C，127.0ppm，d
According to 1H NMR spectrum and TGA-DTA data, the structure of DCPDS is as follows.
Figure A20058004642100431
Embodiment 13
Prepare resin by TDCPDS
TDCPDS (1g) is added in 10ml Teflon (23.3 * 18.3mm ID) or the aluminium cup (25.2 * 39.6mm (ID)).Place temperature to be set in 85 ℃ vacuum drying oven this glass.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures to 200 ℃, and kept 10 to 24 hours, produce White-opalescent (translucent) disk of thickness 2 to 4mm.
Analytical data
DTA-TGA:Td 5: 414 ℃, ceramic yield: 63.2% (in the air 1000 ℃ calculate: 62.1%)
DMA：Tg：170℃
TMA:106ppm (50 ℃ to 100 ℃)
Embodiment 14
Eight (two dimetylsilyl ethanoyl dimethylsilane oxygen base)-silicious sesquioxanes, OBTMSAS's is synthetic
Figure A20058004642100441
In the 100ml Schlenk flask that is equipped with reflux exchanger, and adding OHSS (1g, 1mmol).Heating unit lenitively under vacuum to remove remaining air and moisture, is used nitrogen purging then.Add THF or toluene (25ml), two trimethyl silyl acetylene (1.7g, 10mmol) and as 2mMPt (the dvs)-toluene solution of catalyzer (0.1ml, Pt:0.2ppm).
Stirred this mixture 6 hours to 2 days at 60 or 90 ℃.After the reaction, triphenylphosphine and gac are added in the solution,, leach by diatomite then with catalyst deactivation.From the filtrate evaporating solvent, produce the viscous liquid of White-opalescent.Output is 1.4g (0.6mmol), 58%.
Analytical data
DTA-TGA:Td 5: 113 ℃, ceramic yield: 76.0% (in the air 1000 ℃ calculate: 85.6%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
1H?NMR：Si-CH 3，0.098ppm，61H，s
HSi-CH 3，0.27ppm，38H，s
Si-H，4.76ppm，5.8H，s
13C?NMR：Si-CH 3，0.13ppm，s
HSi-CH 3，0.24ppm，s
C＝C，114.0ppm，s
FTIR：v?Si-H，2148cm -1
v?C-H，1411cm -1
v?Si-O-Si，1141cm -1
According to 1H NMR spectrum and TGA-DTA data, the structure of OBTMSAS is as follows.Two trimethyl silyl acetylene are by the reaction of the total overall reaction site (Si-H group) on stoichiometry and the OHS, even when the excessive two trimethyl silyl acetylene of adding.This result is steric hindrance and reduces the catalytic active substance of catalytic perfomance and the combination of the vinyl bonded fact.
Figure A20058004642100451
Embodiment 15
Four (two dimetylsilyl ethynyl dimethylsilane oxygen bases)-four (hydrogenation dimethylsilane oxygen bases), eight silicious sesquioxanes, TBTMSAS's is synthetic
Figure A20058004642100461
In the 100ml Schlenk flask that is equipped with reflux exchanger, and adding OHSS (1g, 1mmol).Heating unit lenitively under vacuum to remove remaining air and moisture, is used nitrogen purging then.Add CH then 2Cl 2, THF or toluene (25ml), two trimethyl silyl acetylene (0.68g, 4mmol) and as 2mM Pt (the dvs)-toluene solution of catalyzer (0.1ml, Pt:0.2ppm).
Stirred this mixture 4 hours to 5 days at 60 or 90 ℃.After the reaction, add triphenylphosphine and gac, and leach by diatomite.Then in a vacuum at RT from the filtrate evaporating solvent, produce white powder.Productive rate is respectively 40,68 and 68%.
Analytical data
DTA-TGA:Td 5: 233 ℃, ceramic yield: 74.1% (in the air 1000 ℃ calculate: 81.1%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
DSC: solidification value, 138 ℃
1H?NMR：Si-CH 3，0.162ppm，58H，d
HSi-CH 3，0.225ppm，49H，m
Si-H，4.72ppm，5.2H，s
＝-Si，7.41ppm，3.1H，s
13C?NMR：Si-CH 3，1.03ppm，m
＝-Si，164.7ppm，s
FTIR：v?Si-H，2140cm -1
v?C-H，1420cm -1
v?Si-O-Si，1100cm -1
According to 1H NMR spectrum and TGA-DTA data, the structure of determining TBTMSAS is as follows.According to these data, be less than the Si-H radical reaction on four normal pair of trimethyl silyl acetylene and the OHS, promptly when taking place, reaction adds four equivalents.
Figure A20058004642100471
Embodiment 16
Solidify TBTMSAS
TBTMSAS (1g) is added in 10ml Teflon (23.3 * 18.3mm ID) or the aluminium cup (25.2 * 39.6mm ID).Place temperature to be set in 85 ℃ vacuum drying oven this glass.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures until 200 ℃, and kept 10 to 24 hours, produce White-opalescent (translucent) disk of thickness 2 to 4mm.
Analytical data
DTA-TGA:Td 5: 238 ℃, ceramic yield: 65.3% (in the air 1000 ℃ calculate: 81.1%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
Embodiment 17
Eight (trimethyl silyl ethynyl dimethylsilane oxygen base) eight silicious sesquioxanes or OTMSAS
In the 100ml Schlenk flask that is equipped with reflux exchanger, and adding OHSS (1g, 1mmol).Heating unit lenitively under vacuum to remove remaining air and moisture, is used nitrogen purging then.Add then THF (25ml), trimethyl silyl acetylene (0.98g, 10mmol) and as 2mM Pt (the dvs)-toluene solution of catalyzer (0.1ml, Pt:0.2ppm).
Stirred the mixture 3 hours at 60 ℃.After the reaction, triphenylphosphine (5mg) and gac (0.08g) are added in the solution,, leach by diatomite thereafter with catalyst deactivation.Evaporating solvent produces white powder.Output is 1.67g (0.93mmol), 93%.
Analytical data
DTA-TGA:Td 5: 285 ℃, ceramic yield: 58.8% (in the air 1000 ℃ calculate: 79.8%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
1H?NMR：Si-CH 3，0.07，0.21ppm，8H，d
H-C＝C，6.60ppm，1H，q
According to 1H NMR spectrum and TGA-DTA data, the structure of measuring OTMSAS is as follows.
Figure A20058004642100482
Embodiment 18
Synthesizing of four (trimethyl silyl ethynyl dimethylsilane oxygen bases) four (hydrogenation dimethylsilane oxygen base), eight silicious sesquioxanes
Figure A20058004642100491
In the 100ml Schlenk flask that is equipped with reflux exchanger, and adding OHSS (10g, 10mmol).Heating unit lenitively under vacuum to remove remaining air and moisture, is used nitrogen purging then.Add then THF (50ml), trimethyl silyl acetylene (3.86g, 40mmol) and as 2mM Pt (the dvs)-toluene solution of catalyzer (0.1ml, Pt:0.2ppm).
Stirred the mixture 2 hours at 60 ℃.After the reaction, evaporating solvent under RT produces white powder in a vacuum.Output is 12.5g (89mmol), 88%.
Analytical data
DTA-TGA:Td 5: 281 ℃, ceramic yield: 75.6% (in the air 1000 ℃ calculate: 84.7%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
DSC:Mp:87.2 ℃, solidification value: 130.1 ℃
1H?NMR：Si(CH 3) 3，0.073ppm，35H，d
Si(CH 3) 2，0.21ppm，26H，s
HSi-CH 3，0.25ppm，23H，s
Si-H，4.75ppm，3.6H，s
C＝C-H，6.53ppm，8.1H，q
13C?NMR：Si(CH 3) 3，-1.43ppm，s
H-Si-CH 3，0.39ppm，d
C＝C，148.1，152.7ppm，d
FTIR：v?Si-H，2140cm -1
d＝C-H，1412cm -1
v?Si-O-Si，1095cm -1
According to 1H NMR spectrum and TGA-DTA data, the structure of determining TTMSAS is as follows.
Figure A20058004642100501
Embodiment 19
Solidify TTMSAS
TTMSAS (1g) is added in 10ml Teflon (23.3 * 18.3mm ID) or the aluminium cup (25.2 * 39.6mm ID).Place temperature to be set in 85 ℃ vacuum drying oven this glass.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures to 200 ℃, and kept 10 to 24 hours, produce White-opalescent (translucent) disk of thickness 2 to 4mm.
Analytical data
TMA:CTE=212ppm (50 ℃ to 100 ℃)
Embodiment 20
Four (hydrogenation dimethylsilane oxygen bases), eight silicious sesquioxanes, NorbTHS's is synthetic
Figure A20058004642100511
In the 100ml Schlenk flask that is equipped with reflux exchanger, and adding OHS (1g, 1mmol).Heating unit lenitively under vacuum to remove remaining air and moisture, is used nitrogen purging then.Add then THF (10ml), 5-vinyl-2-norbornylene (0.47g, 3.9mmol) and as 2mM Pt (the dcp)-toluene solution of catalyzer (0.1ml, Pt:0.2ppm).
Stirred the mixture 5 hours at 60 ℃.After the reaction, evaporating solvent under RT produces white powder in a vacuum.Output is 1.6g (1mmol), and it is quantitative.
Analytical data
DTA-TGA:Td 5: 302 ℃, ceramic yield: 55.7% (1000 ℃ in the air, are calculated: 64.1%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
1H NMR: be difficult to ownership
13C?NMR：N/A
FTIR：v＝C-H：3060cm -1
v?Si-H：2140cm -1
d＝C-H：1450cm -1
v?Si-O-Si：1080cm -1
Embodiment 21
Solidify norbTHS
NorbTHS (1g) is added 10ml Teflon (23.3 * 18.3m ID) or aluminium cup (25.2 * 39.6mm ID).Place temperature to be set in 85 ℃ vacuum drying oven this glass.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures to 200 ℃, and kept 10 to 24 hours, produce white solid.
Embodiment 22
Eight (cyclohexenyl dimethylsilane oxygen bases), eight silicious sesquioxanes, OCHDS's is synthetic
Figure A20058004642100521
In the 100ml Schlenk flask that is equipped with reflux exchanger, and adding OHSS (1g, 1mmol).Heating unit lenitively under vacuum to remove remaining air and moisture, is used nitrogen purging then.Add then THF (10ml), 1 (0.79g, 10mmol) and as 2mM Pt (the dcp)-toluene solution of catalyzer (0.1ml, Pt:0.2ppm).
Stirred the mixture 3 hours at 60 ℃.After the reaction, under RT, remove in a vacuum and desolvate, produce the White-opalescent viscous liquid.Output is quantitative 1.80g (1.13mmol).
Analytical data
DTA-TGA:Td 5: 270 ℃, ceramic yield: 52.7% (1000 ℃ in the air, are calculated: 57.9%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
1H?NMR：Si-CH 3，0.141ppm，48H，s
Hexanaphthene: 1.3-1.9ppm 51H, m
H-C＝C，5.67ppm，16H，s
13C?NMR：Si-CH 3，-1.4ppm，s
Hexanaphthene: 23.0,23.4,25.6,27.9ppm, s
C＝C，126.6，127.2ppm，d
FTIR：v?C＝C-H，3016cm -1
v?C＝C-H，1442cm -1
v?Si-O-Si，1145cm -1
According to 1H NMR and FTIR, the structure of OCHDS is as described below.
Figure A20058004642100531
Embodiment 23
Four (cyclohexenyl dimethylsilane oxygen bases) four (hydrogenation dimethylsilane oxygen base), eight silicious sesquioxanes, TCHDS's is synthetic
Figure A20058004642100532
In the 100ml Schlenk flask that is equipped with reflux exchanger, and adding OHSS (1g, 1mmol).Heating unit lenitively under vacuum to remove remaining air and moisture, is used nitrogen purging then.Add then THF (10ml), 1 (0.32g, 4mmol) and as 2mM Pt (the dcp)-toluene solution of catalyzer (0.1ml, Pt:0.2ppm).
Stirred the mixture 3 hours at 60 ℃.After the reaction, under RT, remove in a vacuum and desolvate, produce the White-opalescent viscous liquid.Output is quantitative basically 1.40g (1mmol).
Analytical data
DTA-TGA:Td 5: 238 ℃, ceramic yield: 63.4% (1000 ℃ in the air, are calculated: 65.8%)
1H?NMR：Si-CH 3，0.141ppm，32H，s
HSi-CH 3，0.252ppm，14H，s
Hexanaphthene: 1.3-1.9ppm, 57H, m
Si-H，4.74ppm，2.6H，s
H-C＝C，5.67ppm，11H，s
13C?NMR：Si-CH 3，-1.4ppm，s
HSi-CH 3，0.73ppm，s
Hexanaphthene: 23.0,23.4,25.6,27.9ppm, s
C＝C，126.6，127.2ppm，d
FTIR：v?C＝C-H，3016cm -1
v?Si-H，2152cm -1
v?C＝C-H，1438cm -1
v?Si-O-Si，1146cm -1
According to 1H NMR spectrum determines that the structure of TCHDS is as follows.
Figure A20058004642100541
Embodiment 24
Solidify TCHDS
TCHDS (1g) is added 10ml Teflon (23.3 * 18.3m ID) or aluminium cup (25.2 * 39.6mm ID).Place temperature to be set in 85 ℃ vacuum drying oven this glass.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures to 200 ℃, and kept 10 to 24 hours, produce White-opalescent (translucent) disk of thickness 2 to 4mm.
Analytical data
DTA-TGA:Td 5: 349 ℃, ceramic yield: 66.7% (in the air 1000 ℃ calculate: 65.8%)
TMA：CTE＝180ppm
Embodiment 25
Four (vinyl-dimethyl base siloxyies) four (hydrogenation dimethylsilane oxygen base) silicious sesquioxane, TViTHS's is synthetic
Figure A20058004642100551
In the 500ml Schlenk flask that is equipped with feed hopper, add hexane (130ml), dimethylchlorosilane (3.74g, 31mmol) and the dimethyl vinyl chlorosilane (2.93g, 31mmol).
Cool off this mixture to 0 ℃.Dripped at 40 minutes then eight negatively charged ion/methanol solution (50ml, 6.2mmol).After finishing adding,, stirred 5 hours at RT then in 0 ℃ of restir mixture 30 minutes.
Separate hexane layer, and use Na 2SO 4Drying is removed via rotatory evaporator then, produces white TViTHS powder.Output is 4.46g (3.8mmol) 64%.
Enjoyably, the mol ratio of dimethylchlorosilane and dimethyl vinyl chlorosilane directly influences the replacement ratio on the synthetic compound.For example, as mentioned above when ratio=5/5/1 of dimethylchlorosilane/dimethyl vinyl chlorosilane/eight anion silicon sesquioxyalkanes, according to 1H NMR spectrum, the ratio of dimetylsilyl on the compound that obtains/dimethyl vinyl silyl is 4.02/3.98.Determine that structure is as follows.On the other hand, if ratio is changed to dimethylchlorosilane/dimethylchlorosilane/eight negatively charged ion=4/5/1, dimethyl vinyl silyl is 3.26/4.74 with the ratio of dimetylsilyl so.This means the group composition that is very easy to change on the cubes.
Analytical data
DTA-TGA:Td 5: 132 ℃, ceramic yield: 79.2% (in the air 1000 ℃ calculate: 85.6%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
DSC: solidification value: 207 ℃
1H?NMR：＝Si-CH 3，0.16ppm，25H，s
H-Si-CH 3，0.20ppm，23H，s
Si-H，4.75ppm，4H，s
C＝C-H，5.7-6.2ppm，11H，m
13C?NMR：SiCH 3，-0.07ppm，0.28ppm，d
C＝C，132.7ppm，138.1ppm，d
FTIR：v＝C-H，3050cm -1
v?Si-H，2140cm -1
d＝C-H，1412cm -1
v?Si-O-Si，1191cm -1
According to 1H NMR spectrum and TGA-DTA data, the structure of determining TViTHS is as follows.
Figure A20058004642100561
Embodiment 26
Solidify TViTHS
TViTHS (1g) is added in 10ml Teflon (23.3 * 18.3mm ID) or the aluminium cup (25.2 * 39.6mm ID).Place temperature to be set in 60 ℃ vacuum drying oven this glass.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures to 200 ℃, and kept 10 to 24 hours, produce White-opalescent (translucent) disk of thickness 2 to 4mm.
Analytical data
DTA-TGA:Td 5: 395 ℃, ceramic yield: 71.8% (in the air 1000 ℃ calculate: 85.6%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
Embodiment 27
Four (allyl dimethyl base siloxyies) four (hydrogenation dimethylsilane oxygen base) silicious sesquioxane, TallylTHS's is synthetic
Figure A20058004642100571
In the 250ml Schlenk flask that is equipped with feed hopper, add hexane (65ml), dimethylchlorosilane (1.47g, 16mmol) and the dimethyl-allyl chlorosilane (2.09g, 16mmol).At 0 ℃ of cooling mixture, dripped at 20 minutes then eight negatively charged ion/methanol solution (25ml, 3.1mmol).After finishing adding,, stirred 24 hours at RT then in 0 ℃ of restir mixture 30 minutes.
Separate hexane layer, and use Na 2SO 4Drying is removed via rotatory evaporator then, produces transparent TallylTHS liquid.Output is 2.84g (2.4mmol), 78%.
Analytical data
DTA-TGA:Td 5: 174 ℃, ceramic yield: 78.0% (in the air 1000 ℃ calculate: 80.4%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
DSC: solidification value: 208 ℃
1H?NMR：-Si-CH 3，0.085，0.17ppm，28H，d
H-Si-CH 3，0.26ppm，20H，s
-CH 2-SiCH 3，1.65ppm，8H，dd
Si-H，4.76ppm，4H，s
＝CH 2，4.85ppm，8H，m
＝CH，5.80ppm，4H，m
13C?NMR：SiCH 3，-0.35ppm，0.62ppm，d
Si-CH 2-，26.1ppm，d
C＝C，114.1ppm，134.5ppm，dd
FTIR：v?O-H，3700cm -1
V＝C-H，3075cm -1
v?Si-H，2145cm -1
d＝C-H，1412cm -1
v?Si-O-Si，1150cm -1
As mentioned above, according to 1H NMR and FTIR data, when the anionic ratio of dimethyl-allyl chlorosilane/dimethylchlorosilane/eight is 5/5/1, dimethyl-allyl silyl that replaces on eight negatively charged ion and dimetylsilyl are 3.7/3.7, and rest position can be for deriving from the OH group in unreacted site on eight negatively charged ion.Determine that structure is as follows.On the other hand, 1H NMR and FTIR data show, when this when becoming 6/5/1 (dimethyl-allyl chlorosilane/dimethylchlorosilane/eight negatively charged ion), the dimethyl-allyl silyl is 4.2/3.1 with the ratio of dimetylsilyl, has some remaining OH groups.In this system, change the ratio and the type of reagent organic group easily.Not attempting to optimize should be synthetic.
According to 1H NMR spectrum and TGA-DTA data, the structure of determining AllylTHS is as follows.Under the selected here condition, but all organic group not with eight negatively charged ion on whole reaction site react.
Figure A20058004642100591
Embodiment 28
Solidify TAllylTHS
TAllylTHS (1g) is added in 10ml Teflon (23.3 * 18.3mm ID) or the aluminium cup (25.2 * 39.6mm ID).Place temperature to be set in 85 ℃ vacuum drying oven this glass.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures to 200 ℃, and kept 10 to 24 hours, produce the opaque disk of brown of thickness 2 to 4mm.
Analytical data
DTA-TGA:Td 5: 345 ℃, ceramic yield: 82.5% (in the air 1000 ℃ calculate: 81.5%)
TMA:CTE=227ppm (at 50 to 100 ℃)
Embodiment 29
Four (hexenyl dimethylsilane oxygen base) four (hydrogenation dimethylsilane oxygen base) silicious sesquioxanes, THexenylTHS's is synthetic
Figure A20058004642100592
In the 250ml Schlenk flask that is equipped with feed hopper, add hexane (65ml), dimethylchlorosilane (1.84g, 0.019mol) and dimethyl hexenyl chlorosilane (3.42g, 0.019mol).At 0 ℃ of cooling mixture, dripped at 20 minutes then eight negatively charged ion/methanol solution (25ml, 0.0031mol).After finishing adding, stirred the mixture in addition 30 minutes, stirred 24 hours at RT then at 0 ℃.
Separate hexane layer, and use Na 2SO 4Drying is removed via rotatory evaporator then, produces transparent ThexenylTHS liquid.By washing this liquid of purifying, obtain the output of 4.68g (3.5mmol) 90% with methyl alcohol/acetonitrile (1: 1 volume).
Analytical data
DTA-TGA:Td 5: 95 ℃, ceramic yield: 51.9% (in the air 1000 ℃ calculate: 71.3%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
DSC: solidification value, 224 ℃
1H?NMR：-Si-CH 3，0.085，0.11，0.14，0.18ppm，32H，dd
H-Si-CH 3，0.26ppm，16H，s
-CH 2-SiCH 3，0.55ppm，8H，m
-CH 2-CH 2, 1.40ppm, 17H, wide
-CH 2-CH=CH 2, 2.06ppm, 8H, wide
-Si-H，4.75ppm，3.4H，d
＝CH 2-，4.96ppm，7H，m
＝CH-，5.82?ppm，3.6H，m
13C?NMR：Si-CH 3，-0.47ppm，-0.02ppm，d
-CH 2-，17.4ppm，22.4ppm，32.5ppm，33.4ppm，d
＝CH 2-，114.1ppm，s
＝CH-，138.9ppm，s
FTIR：v＝C-H，3074cm -1
v?Si-H，2140cm -1
d＝C-H，1412cm -1
v?Si-O-Si，1150cm -1
Figure A20058004642100611
According to 1H NMR spectrum determines that the structure of ThexenylTHS is as implied above.
When dimethyl hexenyl chlorosilane/dimethylchlorosilane/when eight anionic ratios are 5/5/1, obtain that the ratio of dimethyl hexenyl silyl and dimetylsilyl is 3.6/3.4 on the product.According to 1H NMR and FTIR data, remaining OH group constitutes remaining reactive site.Determine that structure is as implied above.When dimethyl hexenyl chlorosilane/dimethylchlorosilane/when eight anionic ratios were 6/5/1, dimethyl hexenyl silyl was 4.1/2.9 with the ratio of dimetylsilyl on the product.The residue group is SiOH.Therefore, initial ratio influences the substitute proportion of final product.Aforesaid TAllylTHS system, this system changes the substitute proportion among the TViTHS easily.
Embodiment 30
Solidify ThexenylTHS
ThexenylTHS (1g) is added in 10ml Teflon (23.3 * 18.3mm ID) or the aluminium cup (25.2 * 39.6mm ID).Place temperature to be set in 85 ℃ vacuum drying oven this glass.Behind 85 ℃ of degassing 2h, use the nitrogen purging baking oven., and kept 10 to 24 hours until 200 ℃ with 30 ℃ of/hour elevated temperatures, produce the water white transparency disk of thickness about 2 to 4mm.
Analytical data
DTA-TGA:Td 5: 468 ℃, ceramic yield: 76.5% (in the air 1000 ℃ calculate: 71.3%).
TMA:CTE=277ppm (50 ℃ to 100 ℃)
Embodiment 31
Melting and solidification OVS/OHS mixture
With mortar and pestle mix eight (vinyl-dimethyl base siloxy-) silicious sesquioxane (OVS, 1.5g, 1.2mmol) and eight (hydrogenation dimethylsilane oxygen bases), eight silicious sesquioxanes (OHS, 1.25g, 1.2mol).This mixture is placed 10ml aluminium cup (25.2 * 39.6mm ID).In this glass placement vacuum drying oven at room temperature.Use the nitrogen purging baking oven then, and with 30 ℃ of/hour elevated temperatures until 360 ℃, and kept 10 to 24 hours, produce the water white transparency disk of thickness 2 to 4mm.
Analytical data
DTA-TGA:Td 5: 450 ℃, ceramic yield: 78.3% (in the air 1000 ℃ calculate: 85.6%)
TMA:CTE=180ppm (50 ℃ to 100 ℃)
Embodiment 32
Three (dimethyl (ethoxymethyl) silylation ethyl dimethylsilane oxygen base) five (hydrogenation dimethylsilane oxygen base) silicious sesquioxane, TrisViMe 2SiOEtS's is synthetic
In the 250ml Schlenk flask that is equipped with reflux exchanger, and adding OHSS (10g, 10mmol).Heating unit lenitively under vacuum to remove remaining air and moisture, is used nitrogen purging then.Add then toluene (50ml), dimethyl vinyl Ethoxysilane (3.91g, mmol) and as 2mM Pt (the dvs)-toluene solution of catalyzer (0.1ml, Pt:0.2ppm).Stirred the mixture 2 hours at 90 ℃.After the reaction, evaporating solvent under RT produces transparent viscous liquid in a vacuum, 11.2g (74mmol), 72%.
Analytical data
DTA-TGA:Td 5: 268 ℃, ceramic yield: 67.5% (in the air 1000 ℃ calculate: 74.1%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
DSC: endotherm(ic)peak, 55 ℃, 92 ℃, 127 ℃
1H?NMR：EtOSiCH 3，0.10ppm，21H，s
-SiCH 3，0.14ppm，21H，s
H-Si-CH 3，0.25ppm，24H，s
Si-CH 2-CH 2-Si，0.53ppm，14H，s
OCH 2-CH 3，1.19ppm，10H，t
O-CH 2-，3.66ppm，7H，q
Si-H，4.74ppm，4H，s
13C?NMR：-Si-CH 3，-1.33ppm，-0.87ppm，0.26ppm，t
-CH 2-，9.14ppm，d
CH 3-CH 2-，18.5ppm，s
-OCH 2-，58.3ppm，s
Figure A20058004642100631
According to 1H NMR spectrum is determined TrisViMe 2The structure of SiOEtS is as implied above.
Embodiment 33
Three (dimethyl (ethoxymethyl) silylation ethyl dimethylsilane oxygen base) five (hydrogenation dimethylsilane oxygen base) silicious sesquioxane, (the TrisViMe of partial hydrolysis 2SiOEtS)
Figure A20058004642100641
In the 100ml flask that is equipped with reflux exchanger, add TrisViMe 2SiOEtS (5.6g, 3.6mmol) and THF (20ml).Cooled off this mixture 30 minutes at 0 ℃ then.The 0.1 N HCl aqueous solution (0.43ml) is added in the flask, and stirred this solution 30 minutes, and stirred 30 minutes at RT at 0 ℃.Stirred this mixture 1 day at 60 ℃, to finish hydrolysis.
Analytical data
DTA-TOA:Td 5: 273 ℃, ceramic yield: 78.2% (in the air 1000 ℃ calculate: 77.0%)
1H?NMR：-OSiCH 3，0.10ppm，30H，s
-SiCH 3，0.14ppm，20H，s
H-Si-CH 3，0.25ppm，17H，s
Si-CH 2-CH 2-Si，0.53ppm，14H，s
OCH 2-CH 3，1.19ppm，10H，t
O-CH 2-，3.66ppm，7H，q
Si-H，4.74ppm，3H，s
13C?NMR：N/A
FTIR：v-OH，3340cm -1
v?Si-O-Si，1145cm -1
Figure A20058004642100651
According to 1H NMR spectrum, the TrisViMe of determining section hydrolysis 2The structure of SiOEtS is as implied above.
Embodiment 34
The TrisViMe of cured portion hydrolysis 2SiOEtS
With TrisViMe 2SiOEtS (1g) adds in the 10ml Teflon cup (23.3 * 18.3mm ID).Place temperature to be set in 30 ℃ vacuum drying oven this glass, with evaporating solvent 2 hours.Baking oven recovers environmental stress then.With 30 ℃ of/hour elevated temperatures to 150 ℃, and kept 10 to 24 hours, produce the water white transparency disk of thickness 2 to 4mm.
Analytical data
DTA-TGA:Td 5: 297 ℃, ceramic yield: 80.0% (in the air 1000 ℃ calculate: 74.1%)
FTIR：v-OH，3640，3380cm -1
v?Si-H，2140cm -1
v?Si-O-Si，1072cm -1
TMA:215ppm (50 to 100 ℃)
Embodiment 35
Three (dimethyl (ethoxymethyl) silylation ethyl dimethylsilane oxygen base) five (trimethyl silyl ethyl-dimethylsilane oxygen base) silicious sesquioxane,
(Tris?SiOEtPentakisSiMe 3S)
In the 100ml Schlenk flask that is equipped with reflux exchanger, add TrisViMe 2SiOEtS (2.2g, 0.0015mol).Heating unit lenitively under vacuum to remove remaining air and moisture, is used nitrogen purging then.Add then toluene (10ml), trimethyl-ethylene base silane (0.87g, 0.0087mol) and as 2mM Pt (the dvs)-toluene solution of catalyzer (0.1ml, Pt:0.2ppm).Stirred the mixture 3 hours at 90 ℃.After the reaction, evaporating solvent under RT produces transparent liquid in a vacuum.Output is 3.5g (1.9mmol).
Analytical data
1H?NMR：Si(CH 3) 3，-0.02ppm，38H，s
-SiOEt，0.10ppm，21H，s
-Si(CH 3) 2-，0.13ppm，47H，s
-CH 2-CH 2-，0.52ppm，32H，s
OCH 2-CH 3，1.19ppm，9H，t
O-CH 2-，3.66ppm，6H，q
FTIR：v?CH：2960，2900cm -1
v?Si-O-Si：1145cm -1
Figure A20058004642100662
According to 1H NMR spectrum, the TrisViMe of determining section hydrolysis 2The structure of SiOEtS is as implied above.
Embodiment 36.
Three (dimethyl (ethoxymethyl) silylation ethyl dimethylsilane oxygen base) five (trimethylammonium-silyl ethyl dimethylsilane oxygen base) silicious sesquioxanes, (the TrisSiOEtPentakisSiMe of partial hydrolysis 3S)
Figure A20058004642100671
In the 100ml flask that is equipped with reflux exchanger, add TrisSiOEtPentakisSiMe 3S (5g, 0.0025mol) and THF (15ml).Cooled off this mixture 30 minutes at 0 ℃ then.With the 1 N HCl aqueous solution (0.025ml) and H 2O (0.11g) adds in this flask, and stirs 30 minutes at 0 ℃, and stirs 30 minutes at RT.Then by stirred 1 day further this mixture of hydrolysis at 60 ℃.
Analytical data
DTA-TGA:Td 5: 334 ℃, ceramic yield: 61.0% (in the air 1000 ℃ calculate: 78.9%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
1H?NMR：-Si-(CH 3) 3，-0.02ppm，38H，s
EtOSi-CH 3，0.05ppm，19H，s
CH 2Si-CH 3，0.13ppm，51H，s
CH 2-Si (CH 3), 1.20ppm, 1H, wide
Figure A20058004642100672
According to 1H NMR spectrum, the TrisViMe of determining section hydrolysis 2The structure of SiOEtS is as implied above.
Embodiment 37
Solidify TrisSiOEtPentakisSiMe 3S
With TrisSiOEtPentakisSiMe 3In S solution and 1wt%-dibutyl tin laurate salt adding 10ml Teflon (23.3 * 18.3mm ID) cup as curing catalysts.This glass is placed on temperature to be set in 30 ℃ the vacuum drying oven, with evaporating solvent.Make baking oven pressure return environmental stress then., and kept 10 to 24 hours until 150 ℃ with 30 ℃ of/hour elevated temperatures, produce the opaque disk of thickness 2.0 to 4.0mm.
Analytical data
DTA-TGA:Td 5: 334 ℃, ceramic yield: 61.0% (in the air 1000 ℃ calculate: 80.2%).
As what determine by the test of the TGA in nitrogen, at the TGA duration of test, some material distillations.This material can be used for vapor deposition processes.
FTIR：v-OH，3710cm -1
v?Si-O-Si，1084cm -1
TMA:483ppm (50 ℃ to 100 ℃)
Embodiment 38
Use PtO 2Synthetic TCHS
In the 250ml Schlenk flask that is equipped with reflux exchanger, (10g is 10mg) with as the PtO of catalyzer to add octahydro silicious sesquioxane OHS 2(be respectively 0.02,0.01,0.005g, Pt content: 0.08,0.04,0.02mol).The degassing and heat this device under vacuum to remove air and the moisture of remnants, is used nitrogen purging then.(4.3g 40mg) adds in this flask with toluene (50ml), 5-vinyl-1-tetrahydrobenzene then.
Stirred the mixture 5 hours at 100 ℃.Use diatomite filtration solution then, removing catalyzer, and evaporated filtrate 30 minutes in a vacuum, be deposited in acetonitrile then, obtain white powder.Productive rate is 47%.Powder is TCHS.
Analytical data
DTA-TGA:Tg 5: 454 ℃ (at N 2In)
367 ℃ (in air)
Ceramic yield: 66.9% (in the air 1000 ℃ calculate: 67%)
DSC：Mp：76.3℃
Solidification value: 180 ℃
1H NMR spectrum: Si-CH 3, 0.15ppm, 24H
H-SiCH 3，0.26ppm，23H
Si-CH 2，0.65ppm，9.5H
Cyclohexenyl, 1.2-2.1ppm, 48H
Si-H，4.74ppm，4H
Vinyl in the cyclohexenyl, 5.66ppm, 8H
13C NMR spectrum: Si-CH 3, 0.18ppm
H-Si-CH 3，0.73ppm
Si-CH 2，15.3ppm
Cyclohexenyl 29.1,30.2,32.2,37.0ppm
Vinyl in the cyclohexenyl, 127.5ppm
IR spectrum :=C-H, 3020cm -1
SiH，2200cm -1
Si-O-Si，1095cm -1
Embodiment 39
From PtO 2The TCHS of preparation prepares resin
To add 10ml Teflon[23.3 * 18.3mm ID as the TCHS (≈ 1g) of preparation among the embodiment 28] or aluminium cup (25.2 * 39.6mm ID) in.Place temperature to be set in 85 ℃ vacuum drying oven this glass.After 2 hours, use the nitrogen purging baking oven 85 ℃ of degassings.Then with 30 ℃ of/hour elevated temperatures to 200 ℃, and keep spending the night in 10 to 24 hours, produce the transparent disk of thickness 2.0 to 4.0mm.
CTE(50℃-100℃)：126ppm
Embodiment 40
Can add catalyst passivating agent, to reduce room temperature reaction.Yet, can also maybe can remove catalyzer by reactive in lower temperature storage control by the post of design energy capture catalyst.Scheme as an alternative, the amount of passivator can minimize, and makes will react at comparatively high temps.In some cases, be exposed to the oxidable or decomposition passivator of air or water.In addition, though above use triphenylphosphine, it only is the representative of a large amount of hydrosilylation catalysts passivator that those skilled in the art will know that.For example, other feasible passivator comprises other phosphine, arsine, antimony hydride, alkali metal cyanide etc., and it does not react with cube macromonomer yet, but can the passivation transition metal complex by the permutoid reaction of part.
Fig. 4 shows at 150 ℃ how the amount of passivator (providing triphenylphosphine as an example) controls reaction.According to Fig. 4, represent fusion in the heat absorption of ≈ 70C.The amount that depends on the passivator of adding occurs corresponding to the solidified heat release between 120 ° to 180 ℃.The intensity of heat release is relevant with the inverse of the passivation dosage of use.According to these data, when adding triphenylphosphine, preferred passivator is less than 1mg.The usage quantity of other passivator changes with type and required condition of cure.
With the passivator that is less than 1mg (0.09mol% is with respect to TCHS), TCHS is cured as stiffener when being higher than 80 ℃, although when using greater than 2.5mg (0.2mol% is with respect to TCHS) passivation agents, even spends the night at 200 ℃, and hybrid does not have completely solidified yet.Based on these results, the amount of passivator has important effect in preparation completely solidified material.In addition, passivator is also controlled required temperature of these materials of completely solidified or required time.Equally, it will influence and exist or do not have a solidification rate under the oxygen.
Though illustrated and described embodiment of the present invention, the embodiment of these explanations and description does not constitute all possible forms of the present invention.On the contrary, the wording of using in this specification sheets is illustrative wording rather than limited wording, is to be understood that and can making multiple change without departing from the spirit and scope of the present invention.

Claims (85)

1. method for preparing hybrid inorganic-organic polymkeric substance UV protecting materials comprises:
A) provide one or more to plant multiaspect silicious sesquioxane [SiO 1.5] n, n=6,8,10 or 12 wherein;
B) with multiple-SiMe 2The described multiaspect silicious sesquioxane of R group functionalization, to form multiaspect silicious sesquioxane macromonomer, wherein at least some R are R 1Group, and at least some R are R 2Group, wherein R 1And R 2Be the R group of interreaction, remaining R group is non-reactive group; With
C) by making the reactive R radical reaction on the different silicious sesquioxane macromonomers, solidify described multiaspect silicious sesquioxane macromonomer, with generation hybrid inorganic-organic polymkeric substance,
Wherein said hybrid inorganic-organic polymkeric substance has at least 60% transmissivity at 215nm.
2. the process of claim 1 wherein described reactive R radicals R 1And R 2Be selected from H, halogen and the OR of bonding Si individually 3, R wherein 3Be H, alkyl, thiazolinyl, alkynyl, cycloalkyl or cycloalkenyl group.
3. the process of claim 1 wherein that non-reacted R is selected from alkyl, cycloalkyl, trialkylsilkl and trialkylsilkl end capped (gathering) siloxy-.
4. the method for claim 1, wherein react and introduce reactive functional groups R by making optional deutero-have the multiaspect silicious sesquioxane of Si-H group and functionalized reagent, wherein said functionalized reagent is selected from 4-vinyl-1-tetrahydrobenzene, the dimethyl vinyl chlorosilane, dimethyl vinyl methoxy silane, dimethyl vinyl Ethoxysilane, Dicyclopentadiene (DCPD), two (trimethyl silyl) acetylene, trimethyl silyl acetylene, cyclohexadiene, the dimethyl-allyl chlorosilane, dimethyl hexenyl chlorosilane, 5-vinyl-2-norbornylene and its mixture.
5. the process of claim 1 wherein described reactive group R 1With reactive group R 2Ratio be 0.25: 1 to 1: 1.
6. the process of claim 1 wherein in functionalisation step, to add catalyzer that it quickens multiaspect silicious sesquioxane and functionalized reagent's reaction.
7. the method for claim 6, wherein said catalyzer comprises transition metal.
8. the method for claim 7, wherein at least a catalyzer comprises Pt (dvs) or Pt (dcp) or PtO 2
9. the process of claim 1 wherein and in the presence of catalyzer, carry out described functionalisation step that wherein said catalyzer quickens described multiaspect silicious sesquioxane and reactive R is provided 1And R 2The functionalized reagent's of group reaction, and reaching R 1And R 2After the target proportion of group, do not add catalyst passivating agent ground stopped reaction.
10. the process of claim 1 wherein and in the presence of catalyzer, carry out described functionalisation step that wherein said catalyzer quickens described multiaspect silicious sesquioxane and reactive R is provided 1And R 2The functionalized reagent's of group reaction, and reaching R 1And R 2After the target proportion of group, add a certain amount of catalyst passivating agent, it is the described catalyzer of part passivation only, makes that described macromonomer is a stable storing, and is still crosslinkable.
11. the method for claim 10, wherein catalyzer comprises Pt (dvs) or Pt (dcp), and described catalyst passivating agent comprises triphenylphosphine, and with respect to the silicious sesquioxane macromonomer, the molar weight of triphenylphosphine is greater than 0% and be less than 0.09%.
12. the process of claim 1 wherein after described functionalisation step, the described macromonomer of precipitation from solvent, and with identical or different solvent wash throw out, to obtain solid macromer composition purifying, stable storing.
13. the method for claim 12, wherein at least a solvent is selected from alcohol, nitrile, ether, sulfoxide and acid amides.
14. the method for claim 11, the macromonomer of the described purifying of dissolving in solvent wherein, precipitation, and with other solvent wash throw out, to form more highly purified macromer composition, wherein repeat described dissolving, precipitation and washing step more than twice.
15. the process of claim 1 wherein before the described silsesquioxane monomers step of curing or during solidifying described silsesquioxane monomers step, add at least a effective accelerated reaction R of functional group 1With reactive functional groups R 2Catalyst for reaction.
16. the process of claim 1 wherein and in the melts of silicious sesquioxane macromonomer, carry out described curing.
17. the process of claim 1 wherein and in comprising the solution of silsesquioxane monomers, carry out described curing.
18. the process of claim 1 wherein and in liquid phase, carry out described curing.
19. a method for preparing hybrid inorganic-organic polymkeric substance UV transparent material comprises:
A) with first functionalized group functionalization's multiaspect silicious sesquioxane, to form approximate general formula [R 1Me 2SiOSiO 1.5] nMultiaspect silicious sesquioxane or its mixture of first reactive functionalization, wherein n is 6,8,10 or 12,
B) with second functionalized group functionalization's multiaspect silicious sesquioxane, to form approximate general formula [R 2Me 2SiOSiO 1-5] nMultiaspect silicious sesquioxane or its mixture of second reactive functionalization, wherein n is 6,8,10 or 12,
R wherein 1And R 2Be reactive functional groups, its interreaction connects the multiaspect silicious sesquioxane and the described second reactive silicon sesquioxyalkane of described first reactive functionalization and some of them R with covalent linkage 1And R 2Can by with R 1And R 2Nonreactive R group substitute and
C) solidify the silicious sesquioxane of described first reactive functionalization and the silicious sesquioxane of second reactive functionalization.
20. the method for claim 19, the multiaspect silicious sesquioxane of wherein said first reactive functionalization on average has at least 2 R 1Group, the multiaspect silicious sesquioxane of described second reactive functionalization on average has at least 2 R 2Group.
21. the method for claim 19, the multiaspect silicious sesquioxane of wherein said first reactive functionalization on average has at least 4 R 1Group, the multiaspect silicious sesquioxane of described second reactive functionalization on average has at least 4 R 2Group.
22. the method for claim 19, the multiaspect silicious sesquioxane of wherein said first reactive functionalization on average has at least 6 R 1Group, the multiaspect silicious sesquioxane of described second reactive functionalization on average has at least 6 R 2Group.
23. the method for claim 19, wherein reactive functional groups R 1Comprise two kinds of different reactive functional groups R 1' and R 1", reactive functional groups R wherein 2Comprise two kinds of different reactive functional groups R 2' and R 2", R 1' and R 2' interreaction, R 1" and R 2" interreaction.
24. the method for claim 19, wherein at least a reactive functional groups is selected from hydrogen, thiazolinyl, alkynyl and the cycloalkenyl group of bonded silica.
25. the method for claim 19, wherein non-reacted R group are selected from alkyl, cycloalkyl, trialkylsilkl and trialkylsilkl end capped (gathering) siloxy-.
26. the method for claim 23, wherein at least a reactive functional groups is selected from hydrogen, thiazolinyl, alkynyl and the cycloalkenyl group of bonded silica.
27. the method for claim 19, wherein at least a reactive functional groups comes from multiaspect silicious sesquioxane part and functionalized reagent's reaction, and wherein said functionalized reagent is selected from 4-vinyl-1-tetrahydrobenzene, dimethyl vinyl chlorosilane, dimethyl vinyl methoxy silane, dimethyl vinyl Ethoxysilane, dicyclopentadiene, two [trimethyl silyl] acetylene, trimethyl silyl acetylene and cyclohexadiene, dimethyl-allyl chlorosilane, dimethyl hexenyl chlorosilane and 5-vinyl-2-norbornylene.
28. the method for claim 19, wherein R 1With R 2Mol ratio be 0.20: 1 to 1: 1.
29. the method for claim 23, wherein R 1" and R 2" mol ratio be 0.20: 1 to 1: 1.
30. the method for claim 19 wherein at any or in two functionalisation step, adds the catalyst for reaction of quickening multiaspect silicious sesquioxane and functionalized reagent.
31. the method for claim 30, wherein said catalyzer comprises transition metal.
32. the method for claim 31, wherein said catalyzer comprise at least a Pt (dvs), Pt (dcp) or PtO 2
33. the method for claim 30 is wherein after reaching the target average content of reactive functional groups, at any or do not add catalyst passivating agent ground stop functionalized in two functionalisation step.
34. the method for claim 30, wherein after reaching the target average content of reactive functional groups, stop functionalizedly at any or in two functionalisation step by adding catalyst passivating agent, the add-on of described catalyst passivating agent is less than the required amount of the described catalyzer of passivation fully.
35. the method for claim 34, wherein said catalyst pack contains platinic compound, and described catalyst passivating agent comprises triphenylphosphine, and based on the molar weight of functionalized multiaspect silicious sesquioxane, the passivation amount of described triphenylphosphine is greater than 0mol% and less than 0.09mol%.
36. the method for claim 19, further comprise at any or in two functionalisation step: after step b), from the solution of solvent or solvent mixture, precipitate described functionalized silicious sesquioxane, wash described throw out with identical or different solvent or solvent mixture, to obtain the multiaspect silicious sesquioxane macromonomer of solid purifying, and optional dissolve again, precipitation and more than the washed twice, so that the solid that is further purified macromonomer to be provided.
37. the method for claim 36, wherein at least a solvent is selected from alcohol, nitrile, ether, sulfoxide and acid amides.
38. the method for claim 19 or 23 wherein before solidifying or setting up period, adds the curing catalysts of the reaction of effective accelerated reaction functional group.
39. the method for claim 19 or 23 is wherein carried out described curing in liquid phase.
40. the method for claim 39, wherein said liquid phase are the fusion phase.
41. the method for claim 39, wherein said liquid phase are the solution phase.
42. the method for claim 19, wherein R 1And R 2For identical.
43. the method for claim 42 is wherein by making approximate general formula
[H-Si(Me) 2-O-SiO 1.5] n
Silicious sesquioxane or its mixture, with at least a silane reaction that is selected from dimethyl vinyl methoxy silane and dimethyl vinyl Ethoxysilane, prepare the described first functionalized silicious sesquioxane and the described second functionalized silicious sesquioxane, wherein n is 6,8,10 or 12.
44. a method for preparing hybrid inorganic-organic polymer encapsulated material comprises:
A) provide the multiaspect silicious sesquioxane;
B) with the reactive functional groups R of one or more types 1Functionalized described multiaspect silicious sesquioxane is to produce general formula
[RMe 2SiOSiO 1.5] n
Functionalized multiaspect silicious sesquioxane or its mixture, wherein n be 6,8,10,12 and wherein R be reactive or non-reacted organic group, condition is that at least one R is reactive functional groups R 1, to form macromonomer;
C) add and reactive functional groups R 1The linking agent of reaction is to form curable mixture; With
D) solidify described curable mixture, to be formed on the hydridization organic and inorganic encapsulants of 215nm place optical transmittance at least 60%.
45. the method for claim 44, wherein said multiaspect silicious sesquioxane has HMe 2SiO-functional group, the described functionalized at least a functionalized reagent of hydrosilylation that comprises, described functionalized reagent is selected from 4-vinyl-1-tetrahydrobenzene, the dimethyl vinyl chlorosilane, dimethyl vinyl methoxy silane, dimethyl vinyl Ethoxysilane, dicyclopentadiene, two [trimethyl silyl] acetylene, trimethyl silyl acetylene and dimethyl-allyl silane, 1,1,3,3-tetramethyl--1-allyl group sily oxide, 1,1,3,3-tetramethyl--1-vinyl sily oxide, dimethyl-octa thiazolinyl silane, dimethylsilane, 1,1,3,3-tetramethyl--1, the 3-sily oxide, 1,1,3,3,5, the 5-hexam ethylcyclotrisiloxane, 1,1,3,3,5,5,7,7-prestox tetrasiloxane, 1,2-dimetylsilyl ethane, the divinyl dimethylsilane, 1,3-diallyl tetramethyl disiloxane, 1,3-diallyl tetraphenyl sily oxide, 1,1,3,3-tetramethyl--1, the 3-divinyl disiloxane, 1, two (dimetylsilyl) ethane of 2-, dimethylchlorosilane, the dimethyl methyl TMOS, dimethylethoxysilane, 1,1,3,3-tetramethyl-ethylene base chlorosilane, 1,1,3,3-tetramethyl-ethylene methoxylsilane, 1,1,3,3-tetramethyl-ethylene base oxethyl silane, [(bicycloheptenyl) ethyl] dimethylchlorosilane, [(bicycloheptenyl) ethyl] dimethyl methyl TMOS, [(bicycloheptenyl) ethyl] dimethylethoxysilane, allyldimethylcholrosilane, the allyl dimethyl methoxylsilane, allyl dimethyl base oxethyl silane, 6-hexenyl dimethylchlorosilane, 6-hexenyl dimethyl methyl TMOS, 6-hexenyl dimethylethoxysilane, 10-undecenyl dimethylchlorosilane, 10-undecenyl dimethyl methyl TMOS, 10-undecenyl dimethylethoxysilane, [2-(3-cyclohexenyl) ethyl] dimethylchlorosilane, [2-(3-cyclohexenyl) ethyl] dimethyl methyl TMOS, [2-(3-cyclohexenyl) ethyl] dimethylethoxysilane, 1,5-dichloro hexam ethylcyclotrisiloxane, 1,5-dimethoxy hexam ethylcyclotrisiloxane, 1,5-diethoxy hexam ethylcyclotrisiloxane, 1,3-dichloro tetramethyl disiloxane, 1,3-dimethoxy tetramethyl disiloxane, 1,3-diethoxy tetramethyl disiloxane, 1,3-dichloro tetraphenyl sily oxide, 1,3-dimethoxy tetraphenyl sily oxide, 1,3-diethoxy tetraphenyl sily oxide, the diallyl diphenyl silane, 1, two (hydroxyl dimetylsilyl) benzene of 4-, the di-isopropyl chlorosilane, the di-isopropyl methoxy silane, the di-isopropyl Ethoxysilane, the di-isopropyl dichlorosilane, diisopropyl dimethoxy silane, the di-isopropyl diethoxy silane, two (2,4, the 6-trimethylphenyl) dichlorosilane, diphenyl chlorosilane, the diphenylacetylene chlorosilane, the diphenylethlene methoxylsilane, the diphenylacetylene Ethoxysilane, diphenyl dichlorosilane, dimethoxydiphenylsilane, the phenylbenzene diethoxy silane, diphenyl silanodiol, diphenyl silane, two (p-methylphenyl) dichlorosilane, two (p-methylphenyl) dimethoxy silane, two (p-methylphenyl) diethoxy silane, 1,5-divinyl-1,3-phenylbenzene-1,3-dimethyl sily oxide, 1,5-divinyl-3-phenyl pentamethyl-trisiloxanes, divinyl tetraphenyl sily oxide, dimethyl dichlorosilane (DMCS), methyl dimethoxysilane, methyldiethoxysilane, the phenylethyl dichlorosilane, phenylethyl dimethoxy silane, the phenylethyl diethoxy silane, phenylmethyldichloroislane, phenyl methyl dimethoxy silane, the phenyl methyl diethoxy silane, phenyl methyl silane, 3-phenyl-1,1,3,5,5-pentamethyl-trisiloxanes, 1,1,3,3-tetra isopropyl-1,3-dichloro sily oxide, 1,1,3,3-tetra isopropyl-1,3-dimethoxy sily oxide, 1,1,3,3-tetra isopropyl-1,3-diethoxy sily oxide, 1,1,3, the 3-tetra isopropyl disiloxane, the ethenylphenyl methyl chlorosilane, ethenylphenyl methyl methoxy base silane, ethenylphenyl methyl ethoxy silane, with the ethenylphenyl methyl-monosilane.
46. wherein there is the catalyzer that quickens described functionalisation step in the method for claim 44 or 45 during described functionalisation step.
47. the method for claim 46 wherein when reaching functionalized aim parameter, adds catalyst passivating agent, the add-on of described catalyst passivating agent is less than the required amount of the described catalyzer of passivation fully.
48. the method for claim 44, further comprise by the described macromonomer of precipitation from solvent or solvent mixture, and wash described throw out with identical or different solvent or solvent mixture, come the described macromonomer at least twice of purifying, to obtain the macromonomer of purifying.
49. the method for claim 44 is wherein before solidifying or during curing add curing catalysts, its accelerated reaction radicals R 1And the reaction between the linking agent.
50. the method for claim 44 wherein before solidifying, is planted the described macromonomer of dissolving in the solvent at one or more.
51. the method for the transparent hybrid inorganic-organic macromonomer of synthetic UV comprises:
A) provide the multiaspect silicious sesquioxane that has reactive site thereon;
B) at least a portion of described reactive site and one or more functionalized reagents are reacted, so that general formula to be provided
[RMe 2SiOSiO 1.5] n
Macromonomer or its mixture, wherein n is 6,8,10,12, R is non-reacted group or reactive group, condition is that at least one R is R 1Reactive group, and at least one R is R 2Reactive group, wherein R 1And R 2For react to each other and wherein select whole radicals R, make described macromonomer have at least 60% optical transmittance at the 215nm place.
52. the method for claim 51, wherein R 1And R 2Be selected from hydrogen, thiazolinyl, alkynyl and the cycloalkenyl group of bonded silica individually.
53. the method for claim 51, wherein non-reacted R is selected from alkyl, cycloalkyl, trimethyl silyl and trimethyl silyl end capped (gathering) dimethylsilane oxygen base individually.
54. the method for claim 51, wherein said multiaspect silicious sesquioxane has general formula
[HMe 2SiOSiO 1.5] n
And plant functionalized reagents with one or more and carry out functionalizedly, wherein said functionalized reagent is selected from 4-vinyl-1-tetrahydrobenzene, dimethyl vinyl chlorosilane, dimethyl vinyl methoxy silane, dimethyl vinyl Ethoxysilane, dicyclopentadiene, two [trimethyl silyl] acetylene, trimethyl silyl acetylene, cyclohexadiene, dimethyl-allyl chlorosilane, dimethyl hexenyl chlorosilane and 5-vinyl-2-norbornylene.
55. the method for claim 51, wherein R 1With R 2Mol ratio be 0.20: 1 to 1: 1.
56. the method for claim 51 wherein exists during described functionalisation step and quickens functionalized catalyzer.
57. the method for claim 56, wherein said catalyzer are transistion metal compound.
58. the method for claim 56, wherein said catalyzer are the platiniferous catalyzer.
59. the method for claim 56, wherein at least a catalyzer comprise Pt (dvs) or Pt (dcp) or PtO 2
60. the method for claim 56, wherein when the functionalized targeted degree that realizes with reactive group, the described catalyzer of not passivation ground stops functionalized.
61. the method for claim 56 wherein when the functionalized targeted degree that realizes with reactive group, stops functionalizedly by adding catalyst passivating agent, the amount of described catalyst passivating agent is less than the required amount of the described catalyzer of passivation fully.
62. the method for claim 61, wherein said catalyzer are the platiniferous catalyzer, described catalyst passivating agent is a triphenylphosphine, and with respect to the molar weight of macromonomer, the add-on of described triphenylphosphine is greater than 0mol% and less than 0.09mol%.
63. the method for claim 51, further comprise by from the solution of solvent or solvent mixture, precipitate described macromonomer at every turn, wash described throw out with identical or different solvent or solvent mixture, the described macromonomer at least twice of purifying is to obtain the macromonomer of purifying.
64. the method for claim 63, wherein at least a solvent is selected from alcohol, nitrile, ether, sulfoxide and acid amides.
65. a hybrid inorganic-organic polymer materials comprises general formula
[A 0.5Me 2SiOSiO 1.5] n[RMe 2SiOSiO 1.5] n’
The part that comes from the multiaspect silicious sesquioxane macromonomer that a plurality of identical or different covalent linkage connect, wherein n is a positive integer, n ' is 0 or positive integer, n+n's ' and be 6,8,10 or 12,
R is non-reacted organic group or unreacted reactive functional groups R 1Or R 2And
A comes from two radicals R that react to each other that differ from one another for connecting the divalence bridge linkage group of two multiaspect silicious sesquioxane parts 1And R 2Reaction, each macromonomer on average has R 1And R 2Group,
Wherein selective reaction and non-reacted radicals R and bridge linkage group A make polymer materials have at least 60% optical transmittance at the 215nm place.
66. a hybrid inorganic-organic polymer materials comprises general formula
[A 0.5Me 2SiOSiO 1.5] n[RMe 2SiOSiO 1.5] n’
The part that comes from the multiaspect silicious sesquioxane macromonomer that a plurality of identical or different covalent linkage connect, wherein n is a positive integer, n ' is 0 or positive integer, n+n's ' and be 6,8,10 or 12,
R is non-reacted organic group or unreacted reactive functional groups R 1Or R 2,
A comes from two different radicals R that react to each other for connecting the divalence bridge linkage group of two multiaspect silicious sesquioxane parts 1And R 2Reaction, each macromonomer has at least two R 1Or R 2Group, but R do not had 1And R 2Group both,
Wherein selective reaction and non-reacted radicals R and bridge linkage group A make polymer materials have at least 60% optical transmittance at the 215nm place.
67. a hybrid inorganic-organic polymer materials comprises general formula
[A 0.5Me 2SiOSiO 1.5] n[B 0.5Me 2SiOSiO 1.5] n”[RMe 2SiOSiO 1.5] n’
The part that comes from the multiaspect silicious sesquioxane macromonomer that a plurality of identical or different covalent linkage connect, wherein n ' is 0 or positive integer, n and n " being positive integer, n, n ' and n " and be 6,8,10 or 12,
R is non-reacted organic group or unreacted reactive functional groups R 1, R 2, R 3Or R 4,
A comes from two radicals R that react to each other for connecting the divalence bridge linkage group of two multiaspect silicious sesquioxane parts 1And R 2Reaction,
B comes from two radicals R that react to each other for connecting the divalence bridge linkage group of two multiaspect silicious sesquioxane parts 3And R 4Reaction,
Wherein the first multiaspect silicious sesquioxane macromonomer has R 1And R 3Group, the second multiaspect silicious sesquioxane macromonomer has R 2And R 4Group and
Wherein non-reacted radicals R, unreacted radical R, bridge linkage group A and bridge linkage group B make described polymer materials have at least 60% optical transmittance at the 215nm place.
68. a hybrid inorganic-organic polymer materials comprises general formula
[A 0.5Me 2SiOSiO 1.5] n[RMe 2SiOSiO 1.5] n’
The multiaspect silicious sesquioxane macromonomer that connects of a plurality of identical or different covalent linkage, wherein n is a positive integer, n ' is 0 or positive integer, n+n's ' and be 6,8,10 or 12,
R is non-reacted organic group or unreacted reactive group R 1, R 1For identical or different;
A is for connecting the bridge linkage group of two multiaspect silicious sesquioxane parts, by two R 1Reaction form,
Wherein R, R 1Make described polymer materials have at least 60% optical transmittance at the 215nm place with A.
69. an organic-inorganic polymer material comprises general formula
[A 0.5Me 2SiOSiO 1.5] n[RMe 2SiOSiO 1.5] n’
The part that comes from the silicious sesquioxane macromonomer that a plurality of identical or different covalent linkage connect, wherein n is a positive integer, n ' is 0 or positive integer, n and n's ' and be 6,8,10 or 12,
R is non-reacted organic group or unreacted reactive functional groups R 1,
R 1Be identical or different reactive functional groups, its with have at least two R 5The reactive functional groups R that has on the cross-linker molecules of group 5React to each other R 5For identical or different,
A is a divalent linker, comes from the reactive R of multiaspect silicious sesquioxane macromonomer 1The reactive R of group and cross-linker molecules 5The reaction of group, wherein R, R 1, R 5, and A make described polymkeric substance have at least 60% optical transmittance at the 215nm place.
70. the polymer materials of claim 65 to 69, wherein reactive functional groups is selected from hydrogen, thiazolinyl, alkynyl and the cycloalkenyl group of bonded silica, and composition thereof.
71. the polymer materials of claim 65 to 69, wherein said reactive functional groups derives from the hydrogen of bonded silica and one or more functionalized reagents' reaction, and described functionalized reagent is selected from 4-vinyl-1-tetrahydrobenzene, dimethyl vinyl chlorosilane, dimethyl vinyl methoxy silane, dimethyl vinyl Ethoxysilane, dicyclopentadiene, two [trimethyl silyl] acetylene, trimethyl silyl acetylene, cyclohexadiene, dimethyl-allyl chlorosilane, dimethyl hexenyl chlorosilane and 5-vinyl-2-norbornylene.
72. the polymer materials of claim 65 to 69, wherein at least two kinds of functional groups that react to each other react, and before forming bridged portion A or B, the mol ratio of these the two kinds functional group's existence that react to each other is 0.25: 1 to 1: 1.
73. the polymer materials of claim 68, wherein said reactive functional groups R 1For identical.
74. the polymer materials of claim 68, wherein said reactive functional groups come from multiaspect silicious sesquioxane part and functionalized reagent's reaction, wherein said functionalized reagent is selected from dimethyl vinyl methoxy silane and dimethyl vinyl Ethoxysilane.
75. the polymer materials of claim 69, wherein at least a linking agent are selected from two functionalized or the polysiloxane of two or polysiloxane, Si-H of alkenyl functionalization, aliphatics two and polyenoid.
76. the polymer materials of claim 69, wherein at least a linking agent are selected from two or the polysiloxane that on average comprises the vinyl-functional of three vinyl at least, on average comprise two functionalized or the polysiloxane of Si-H of the H atom of three bonding Si at least.
77. one kind reveals radioparent polymkeric substance in the 380nm following table, comprises following polymerisate
A) comprise the monomer mixture of one or more multiaspect silicious sesquioxanes (A), the approximate general formula Si that is equivalent to of its cage nO 1.5nWherein n is 6 to 12, wherein use the Siliciumatom of the functionalized described multiaspect silicious sesquioxane of complementary interaction functional group (A), the feasible first complementary interaction group that has about 20～80mol%, and there is the second complementary interaction group of about 80～about 20mol%, and there is the non-reacted group of no more than 80mol%, described first or at least a described Siliciumatom that partly is connected to described multiaspect silicious sesquioxane (A) by spacer of the described second complementary interaction group; Or
B) monomer mixture comprises
B) one or more multiaspect silicious sesquioxanes (B) i), the approximate general formula Si that is equivalent to of its cage nO 1.5n, wherein n is 6 to 12, and 20 to 100mol% Siliciumatom of wherein said multiaspect silicious sesquioxane (B) partly is connected to first reactive group by spacer, and the excess silicon atom of described cage silicious sesquioxane (b) is connected to non-functional group;
B) ii) one or more other approximate general formula Si randomly nO 1.5nMultiaspect silicious sesquioxane (C), the cage Siliciumatom of wherein said multiaspect silicious sesquioxane (C) is connected to the identical reactive group of reaction type with described first reactive group of described multiaspect silicious sesquioxane (B), or be connected to complementary interaction group with respect to described first reactive group of described multiaspect silicious sesquioxane (B)
Wherein when described first reactive group that does not have the described multiaspect silicious sesquioxane of complementary interaction group (B) is just not polymerisable, then there is multiaspect silicious sesquioxane (C), the optional Siliciumatom that partly is connected to multiaspect silicious sesquioxane (C) by spacer of the reactive group of described multiaspect silicious sesquioxane (C) with complementary interaction group; Or
C) a) and b) mixture.
78. the polymkeric substance of claim 77 comprises the polymerisate of multiaspect silicious sesquioxane (A).
79. the polymkeric substance of claim 78, wherein said mixture further comprises at least a of functionalized multiaspect silicious sesquioxane (D) of hydrogen or multiaspect silicious sesquioxane (E), wherein said multiaspect silicious sesquioxane (D) has the hydrogen of the Siliciumatom that is bonded to described multiaspect silicious sesquioxane (D), and described multiaspect silicious sesquioxane (E) has the hydrogenation siloxy-or the dihydro siloxy-of the Siliciumatom that is connected to described multiaspect silicious sesquioxane (D).
80. the polymkeric substance of claim 77, wherein for described multiaspect silicious sesquioxane (A),
A) i) described first reactive group comprises the hydrogen of Direct Bonding to the Siliciumatom of described multiaspect silicious sesquioxane (A), and described complementary interaction group comprises the alkenyl or alkynyl that partly is connected to the described Siliciumatom of described multiaspect silicious sesquioxane (A) by spacer;
A) ii) described first reactive group comprises the hydrogen of bonded silica that partly is connected to the Siliciumatom of described multiaspect silicious sesquioxane (A) by spacer, and described complementary interaction group comprises Direct Bonding to the Siliciumatom of described multiaspect silicious sesquioxane (A) or partly be connected to the alkenyl or alkynyl of the Siliciumatom of described multiaspect silicious sesquioxane by spacer; Or
A) iii) described first reactive group and described complementary interaction group all partly are connected to the Siliciumatom of described multiaspect silicious sesquioxane (A) by spacer.
81. a method for preparing the multiaspect silicious sesquioxane (A) of claim 77 comprises following a kind of:
A) in the presence of hydrosilylation catalysts, make multiaspect silicious sesquioxane and a certain amount of unsaturated compound reaction of the hydrogen that contains bonded silica with two olefinics or the unsaturated site of acetylene series, the mol ratio of unsaturated compound and reaction times obtain multiaspect silicious sesquioxane (A), and described multiaspect silicious sesquioxane (A) comprises the unsaturated part of spacer connection and retains the hydrogen of unreacted bonded silica; Or
B) in the presence of hydrosilylation catalysts, make the multiaspect silicious sesquioxane and the SiH of the thiazolinyl that comprises the Siliciumatom that is connected to described multiaspect silicious sesquioxane (A) 2-functionalized compound reaction, wherein SiH 2-functionalized the compound and the mol ratio of thiazolinyl and time obtain multiaspect silicious sesquioxane (A), described multiaspect silicious sesquioxane (A) comprises the SiH functional group that partly is connected to described multiaspect silicious sesquioxane (A) by alkylen spacer, and comprises the unreacted thiazolinyl of the Siliciumatom that is connected to described multiaspect silicious sesquioxane (A); Or
C) with any order or make approximate general formula Si simultaneously nO 15n N+Negatively charged ion and the chlorosilane reaction that has the chlorosilane of first reactive functional groups and have complementary interaction functional group.
82. the method for claim 81, the wherein functionalized multiaspect silicious sesquioxane compound reaction functionalized of Si-H with the alkenyl or alkynyl that comprises at least two thiazolinyls, alkynyl or thiazolinyl and alkynyl, wherein hydrosilylation catalysts is the heterogeneous hydrosilylation catalysts of solid, further comprises from the hydrosilylation reactions product separating the heterogeneous catalyzer of described solid.
83. the method for claim 82, wherein said hydrosilylation catalysts comprises PtO 2
84. a method for preparing transparent inorganic/organic hybrid polymkeric substance comprises
The monomer mixture of selecting claim 77 a), b) or c) a kind of as monomer mixture, and the described monomer mixture of polymerization is to form inflexible non-elastic clear polymkeric substance, wherein its synthetic back purifying multiaspect silicious sesquioxane (A), (B) or (C) at least a, to remove at oligopolymer that produces between its synthesis phase and polymkeric substance.
85. a method for preparing transparent inorganic/organic hybrid polymkeric substance comprises polymerization one or more kind multiaspect silsesquioxane monomers by the method preparation of claim 82.
CNA2005800464217A 2004-12-07 2005-12-05 Ultraviolet transmissive polyhedral silsequioxane polymers Pending CN101098911A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105814155A (en) * 2013-12-09 2016-07-27 3M创新有限公司 Curable silsesquioxane polymers, compositions, articles, and methods
CN109689735A (en) * 2016-09-30 2019-04-26 美国陶氏有机硅公司 Bridging organic siliconresin, film, electronic device and associated method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105814155A (en) * 2013-12-09 2016-07-27 3M创新有限公司 Curable silsesquioxane polymers, compositions, articles, and methods
US10066123B2 (en) 2013-12-09 2018-09-04 3M Innovative Properties Company Curable silsesquioxane polymers, compositions, articles, and methods
CN109689735A (en) * 2016-09-30 2019-04-26 美国陶氏有机硅公司 Bridging organic siliconresin, film, electronic device and associated method
CN109689735B (en) * 2016-09-30 2021-11-26 美国陶氏有机硅公司 Bridged silicone resins, films, electronic devices, and related methods

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