CN101652246A - Composite article with excellent fire resistance - Google Patents

Composite article with excellent fire resistance Download PDF

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Publication number
CN101652246A
CN101652246A CN200880010510A CN200880010510A CN101652246A CN 101652246 A CN101652246 A CN 101652246A CN 200880010510 A CN200880010510 A CN 200880010510A CN 200880010510 A CN200880010510 A CN 200880010510A CN 101652246 A CN101652246 A CN 101652246A
Authority
CN
China
Prior art keywords
composite article
pane
organic
silicone composition
aforementioned
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN200880010510A
Other languages
Chinese (zh)
Inventor
朱弼忠
W·R·奥布瑞恩
张原志成
N·P·葛瑞尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Silicones Corp
Original Assignee
Dow Corning Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Publication of CN101652246A publication Critical patent/CN101652246A/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B32B17/10045—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets with at least one intermediate layer consisting of a glass sheet
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B32B17/10045—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets with at least one intermediate layer consisting of a glass sheet
    • B32B17/10055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets with at least one intermediate layer consisting of a glass sheet with at least one intermediate air space
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10293—Edge features, e.g. inserts or holes
    • B32B17/10302—Edge sealing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10366—Reinforcements of the laminated safety glass or glazing against impact or intrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10798—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing silicone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10816—Making laminated safety glass or glazing; Apparatus therefor by pressing
    • B32B17/10825—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts
    • B32B17/10834—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts using a fluid
    • B32B17/10844—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts using a fluid using a membrane between the layered product and the fluid
    • B32B17/10853—Isostatic pressing, i.e. using non rigid pressure-exerting members against rigid parts using a fluid using a membrane between the layered product and the fluid the membrane being bag-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10935—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin as a preformed layer, e.g. formed by extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/20—Layered products comprising a layer of natural or synthetic rubber comprising silicone rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/05—Forming flame retardant coatings or fire resistant coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers

Abstract

Composite article comprises first pane, and described first pane comprises first window layers and the reinforced silicone layer adjacent with first window layers and that arrange contiguously that is formed by vitreous material.Reinforced silicone layer comprises cured silicone composition and fiber enhancer.This composite article comprises with first pane and separating determining second pane in gap betwixt, and adjacent with second pane with first pane and arrange window frame with airtight this gap contiguously.This composite article can be suitable for requirement load-bearing adiabatic and sound insulation and use.

Description

Composite article with excellent fire resistance
Related application
[0001] present patent application requires the U.S. Provisional Application Nos.60/891165 of on February 22nd, 2007 and submission on August 10th, 2007 and rights and interests and all advantages of 60/955245 respectively.
Background of invention
1. invention field
[0002] relate generally to of the present invention has the composite article of good thermal insulation and sound insulation and fire resistance.More specifically, the present invention relates to have a plurality of panes and the composite article in the gap determined between pane, wherein at least one pane has novel enhancing siloxane layer.
2. the explanation of prior art
[0003] known insulation window is used for dwelling house and commercial building is industrial in order to thermal insulation and sound insulation to be provided.The insulation window usually comprises a plurality of panes and usually is designed to gap between the airtight pane.Gas is usually contained in this gap, and for example air, argon gas, helium or nitrogen are to provide thermal insulation and sound insulation.Perhaps can find time to produce vacuum, to improve thermal insulation and sound insulation in this gap.Yet this insulation window is not typically prevented fires, and under heating, after insulation window fault, promptly forms after the breach in pane in ignition process, usually can not keep enough structural intergrities.Can't keep enough structural intergrities and can cause that pane caves in after forming breach, this is not required.
[0004] known fire prevention window uses in dwelling house, commercial and industrial building industry and consumption apparatus and automotive industry, spreads by building or for example carry heat or flame secretly in the space in baking oven in order to prevent flame, smog or a large amount of heat.The fire prevention window typically is rated as 30,60,90 or 120 minutes fire prevention windows, this depend on when the fire prevention window be exposed to cause 30 minutes from the outset after 843 ℃ Exposure Temperature, after 60 minutes 926 ℃, predetermined ignition condition following time of 1093 ℃ in, need spend how long at the indoor formation breach of fire window afterwards 1010 ℃ and 240 minutes after 120 minutes.For example, be exposed to that above predetermined ignition condition surpassed 30 minutes down but less than time period in following time of 60 minutes, at the indoor formation breach of the fire window of 30 minutes grades when window.Fire prevention window desired specific fire-protection rating depends on to be used and the cost consideration factor because the fire prevention window with longer fire-protection rating typically cost be higher than fire prevention window with shorter fire-protection rating.
[0005] carried out many work and developed fire prevention window with sufficient fire-protection rating.Typically form the fire prevention window, comprising the glassy layer and the layer that fire prevention window fire resistance is provided of routine by series of layers.Used many different materials, and formed the layer that fire resistance is provided, yet forming provides the employed many materials of the layer of fire resistance to have shortcoming.For example, when using carbon-based material, especially based on the gross weight of all molecules in the material, mainly have carbon-based material greater than 50 weight portion carbon when forming the layer that fire resistance is provided, this material discharges excessive smog and toxic gas the most at last.
[0006] with when using main carbon-based material compares, do not discharge the layer that other non-carbon-based materials of thickness mist and toxic gas so also are used to provide fire resistance.For example, the inorganic silicon-based material of use in fire prevention provides the layer of fire resistance in the window.In the fire prevention window, form disclosed alkali metal polysilicate silicate cement compound in the U.S. Patent No. 6159606 that the instantiation that the employed inorganic silicon-based material of the layer of fire resistance is provided is included in people such as Gelderie, in people's such as Mennig U.S. Patent No. 5716424 the disclosed composition that obtains by hydrolysis and condensation silicate and in German patent application No.2826261 disclosed silicone elastomer.Although inorganic silicon-based material will burn, compare smog that inorganic silicon-based material production is less and toxic gas with main carbon-based material.Yet, comprise that the existing fire prevention window manufacturing of the layer that is formed by silica-base material extremely takes the labour, heaviness and under heating, during fault, can not keep structural intergrity fully sometimes.More specifically, in case since heating when the indoor formation breach of fire window, this fire prevention window is easy to take place mechanical breakdown.There is similar defective in other application for wherein using flame shield or fire-resistant transparent article.Example comprises fireproof door and curtain wall.
[0007] because there is defective in existing window (comprising the insulation window), therefore following composite article advantageously is provided, described composite article have good thermal insulation and sound insulation and fire-resistant, weight is lighter, with in addition after composite article breaks down under heating, promptly in composite article, form after the breach, can also keep good structural intergrity, and also can not discharge and the composite article that contains main carbon-based material as many smog and toxic gas.
Summary of the invention and advantage
[0008] the invention provides a kind of composite article, it comprises first pane that contains first window layers that formed by vitreous material and strengthen siloxane layer.Siloxane layer is adjacent with first window layers and arrange contiguously.Strengthen siloxane layer and comprise cured silicone composition and fiber enhancer.Second pane and first pane separate, to determine gap betwixt.The window frame and first pane are adjacent with second pane and arrange contiguously.Gap between airtight first pane of window frame and second pane.
[0009] owing to have the gap between first pane and second pane, so this composite article demonstrates good thermal insulation and sound insulation.In addition, owing to have cured silicone composition in strengthening siloxane layer, so this composite article demonstrates good fire resistance and can not discharge and the as many smog of composite article and the toxic gas that contain main carbon-based material.This gap spreading of heat of also can slowing down by the pane in the composite article helps the composite article good fire resistance.Moreover owing to have fiber enhancer in strengthening siloxane layer, therefore even because heat causes forming breach by after the pane, this composite article still keeps good structural intergrity and pane is anti-caves in.Just because of this, composite article of the present invention can be suitable for requiring except good fire resistance, also require in the load-bearing application of adiabatic and sound insulation, and be impossible during the composite article of this employing prior art.
The accompanying drawing summary
[0010] other advantages of the present invention will be understood easily, because when considered in conjunction with the accompanying drawings, by the following detailed description of reference, these will obtain understanding better.
[0011] Fig. 1 is the side cross-sectional view of composite article of the present invention.
[0012] Fig. 1-A is the side cross-sectional view of the centre bore of composite article of the present invention.
[0013] Fig. 2 is the side cross-sectional view of first pane in the composite article of the present invention.
[0014] Fig. 3 is the side cross-sectional view of another embodiment of the present invention.
[0015] Fig. 4 is the side cross-sectional view of another embodiment of the present invention.
[0016] Fig. 5 is the side cross-sectional view of another embodiment of the present invention.
[0017] Fig. 6 is the side cross-sectional view of another embodiment of the present invention.
[0018] Fig. 7 is the side cross-sectional view of another embodiment of the present invention.
[0019] Fig. 8 is the side cross-sectional view of another embodiment of the present invention.
[0020] Fig. 9 is the side cross-sectional view of another embodiment of the present invention.
[0021] Figure 10 is the side cross-sectional view of another embodiment of the present invention.
Detailed Description Of The Invention
[0022] with reference to the accompanying drawings, wherein identical numeral represents corresponding parts in several width of cloth accompanying drawings, Composite article represents with 10 in Fig. 1 usually. Composite article 10 have good adiabatic and every Sound and good fire resistance and can be used for dwelling house, commercial and industrial building industry, and consumption On apparatus and the automotive industry in order to prevent that flame, smog or amount of heat from spreading by building Perhaps in the space, for example in baking oven, carry heat or flame secretly. Composite article 10 of the present invention Also can be suitable for requirement load-bearing adiabatic and sound insulation and use, this is by the following composite article of reference 10 further specify understood.
[0023] composite article 10 comprises first pane 12, and described first pane 12 comprises by First window layers 14 that one vitreous material forms. First window layers 14 typically has at least 80% transparency, yet, be appreciated that the window layers that has less than 80% transparency also can fit Close in purpose of the present invention. First window layers 14 provides the typical wearability of conventional window and antiskid The property.
[0024] first vitreous material of formation first window layers 14 is further defined as and forms window any material commonly used.The instantiation that forms spendable suitable first vitreous material of first window layers 14 comprises common silica based glasses or carbon-based polymer.An instantiation of common silica based glasses is Sodium-silica glass.The instantiation that is suitable for forming the carbon-based polymer of first window layers 14 includes but not limited to polymethyl methacrylate (PMMA), Merlon and polysulfones.
[0025] can form first window layers 14 by the known any method in the field that is used to form window layers.Typically, first window layers 14 is the flotation glass that forms by method for floating.This glass can be annealed by methods known in the art, and heat strengthens, perhaps chemistry or heating tempering.The glass that is appreciated that any kind that forms by any known method is suitable for purpose of the present invention.
[0026] first window layers 14 typically thickness typically is about 0.125 inch for about 1 inch of about 0.002-.The concrete thickness of first window layers 14 depends on the application-specific that composite article 10 is planned.For example, for the application that load-bearing is used or wherein composite article 10 can preferably tolerate significantly big blunt power, first window layers 14 can have the thickness bigger than decorative applications.Yet, be appreciated that composite article 10 of the present invention is not limited to use in load-bearing is used.
[0027] first pane 12 further comprises enhancing siloxane layer 16.Strengthen siloxane layer 16 and contiguously layout adjacent with first window layers 14.Strengthening siloxane layer 16 provides composite article 10 good fire resistance, describes in further detail as following.Strengthen siloxane layer 16 and comprise cured silicone composition and fiber enhancer.Typically, with cured silicone composition impregnation of fibers reinforcing agent, promptly reinforced silicone layer 16 is simple layers of fibre-bearing reinforcing agent and cured silicone composition.Based on the gross weight that strengthens siloxane layer 16, strengthen siloxane layer 16 and typically have, more typically less than 35 weight portion carbon, to guarantee to strengthen siloxane layer 16 discharges enough low contents in combustion process smog and toxic gas less than 50 weight portion carbon.Strengthen siloxane layer 16 and contiguously layout adjacent with first window layers 14.The fixing method that strengthens the siloxane layer 16 and first window layers 14 below will be described in further detail.
[0028] in one embodiment, cured silicone composition is further defined as the silicone composition of hydrosilylation cure.The hydrosilylation catalysts that the silicone composition of hydrosilylation cure is included in (C) catalytic amount exists down, (A) organic siliconresin and (B) consumption each molecule of being enough to solidify this organic siliconresin on average have at least two product with the organic group silicon compound of silicon bonded hydrogen atom.The silicone composition of any hydrosilylation cure known in the art can be suitable for purpose of the present invention; Yet the silicone composition of some hydrosilylation cure is more suitable than other.More specifically, some organic siliconresins (A) are more suitable than other.
[0029] organic siliconresin (A) typically have with the silicon bonded alkenyl or with the silicon bonded hydrogen atom.Organic siliconresin (A) typically is and contains R 2SiO 3/2Unit (being the T unit) and/or SiO 4/2Unit (being the Q unit) is in conjunction with R 1R 2 2SiO 1/2Unit (being the M unit) and/or R 2 2SiO 2/2The copolymer of unit (being the D unit), wherein R 1Be C 1-C 10Alkyl or C 1-C 10The alkyl that halogen replaces, the two does not all contain aliphatic unsaturated bond, and R The 2nd,R 1, alkenyl or hydrogen.For example, organic siliconresin (A) can be DT resin, MT resin, MDT resin, DTQ resin and MTQ resin and MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin or MDQ resin.Term as used herein " does not contain aliphatic unsaturated bond " and is meant that the alkyl that alkyl or halogen replace does not contain aliphatic carbon-to-carbon double bond or carbon-to-carbon triple bond.
[0030] uses R 1The C of expression 1-C 10Alkyl and C 1-C 10The alkyl that halogen replaces more typically has 1-6 carbon atom.Contain the acyclic hydrocarbon group of at least 3 carbon atoms and the alkyl of halogen replacement and can have branching or nonbranched structure.Use R 1The example of the alkyl of expression includes but not limited to: alkyl, for example methyl, ethyl, propyl group, 1-Methylethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl ethyl, amyl group, 1-methyl butyl, 1-ethyl propyl, 2-methyl butyl, 3-methyl butyl, 1,2-dimethyl propyl, 2,2-dimethyl propyl, hexyl, heptyl, octyl group, nonyl and decyl; Cycloalkyl, for example cyclopenta, cyclohexyl and methylcyclohexyl; Aryl, for example phenyl and naphthyl; Alkaryl, for example tolyl and xylyl; And aralkyl, for example benzyl and phenethyl.Use R 1The example of the alkyl that the halogen of expression replaces includes but not limited to 3,3,3-trifluoro propyl, 3-chloropropyl, chlorphenyl, dichlorophenyl, 2,2,2-trifluoroethyl, 2,2,3,3-tetrafluoro propyl group and 2,2,3,3,4,4,5,5-octafluoro amyl group.
[0031] uses R 2The alkenyl of expression can be identical or different in organic siliconresin (A), typically has about 10 carbon atoms of 2-, perhaps 2-6 carbon atom, and exemplify but be not limited to vinyl, pi-allyl, cyclobutenyl, hexenyl and octenyl.In one embodiment, R 2It mainly is alkenyl.In this embodiment, typically at least 50mol% or at least 65mol% or at least 80mol% in organic siliconresin, use R 2The group of expression is an alkenyl.Mol% as used herein is at R 2In alkenyl be defined as in organic siliconresin with the molal quantity of silicon bonded alkenyl and this resin in R 2The ratio of the total mole number of base multiply by 100.In another embodiment, R 2Mainly be hydrogen.In this embodiment, typically at least 50mol% or at least 65mol% or at least 80mol% in organic siliconresin, use R 2The group of expression is a hydrogen.Mol% as used herein is at R 2In hydrogen be defined as in organic siliconresin with the molal quantity of the hydrogen of silicon bonding and this resin in R 2The ratio of the total mole number of base multiply by 100.
[0032] according to first embodiment, the general formula of organic siliconresin (A) is:
(R 1R 2 2SiO 1/2) w(R 2 2SiO 2/2) x(R 2SiO 3/2) y(SiO 4/2) z (I)
R wherein 1And R 2As mentioned above and exemplify, w, x, y and z are molar fractions.Each molecule of organic siliconresin (A) with formula (I) expression on average has at least two and silicon bonded alkenyl.More specifically, the numerical value of subscript w typically is 0-0.9, perhaps 0.02-0.75, perhaps 0.05-0.3.The numerical value of subscript x typically is 0-0.9, perhaps 0-0.45, perhaps 0-0.25.The numerical value of subscript y typically is 0-0.99, perhaps 0.25-0.8, perhaps 0.5-0.8.The numerical value of subscript z typically is 0-0.85, perhaps 0-0.25, perhaps 0-0.15.In addition, the ratio of y+z/ (w+x+y+z) typically is 0.1-0.99, perhaps 0.5-0.95, perhaps 0.65-0.9.In addition, the ratio of w+x/ (w+x+y+z) typically is 0.01-0.90, perhaps 0.05-0.5, perhaps 0.1-0.35.
[0033] works as R 2When mainly being alkenyl, include but not limited to have the resin of following formula with the instantiation of the organic siliconresin (A) of following formula (I) expression:
(Vi 2MeSiO 1/2) 0.25(PhSiO 3/2) 0.75、(ViMe 2SiO 1/2) 0.25(PhSiO 3/2) 0.75、
(ViMe 2SiO 1/2) 0.25(MeSiO 3/2) 0.25(PhSiO 3/2) 0.50、
(ViMe 2SiO 1/2) 0.15(PhSiO 3/2) 0.75(SiO 4/2) 0.1With
(Vi 2MeSiO 1/2) 0.15(ViMe 2SiO 1/2) 0.1(PhSiO 3/2) 0.75, wherein Me is a methyl, Vi is a vinyl, Ph is a phenyl, the outer numerical value subscript of bracket is represented molar fraction, its corresponding to above at the described w of formula (I), x, y or z.Unit sequence in preceding formula never is considered as limiting the scope of the invention.
[0034] works as R 2When mainly being hydrogen, include but not limited to have the resin of following formula with the instantiation of the organic siliconresin (A) of following formula (I) expression:
(HMe 2SiO 1/2) 0.25(PhSiO 3/2) 0.75, (HMeSiO 2/2) 0.3(PhSiO 3/2) 0.6(MeSiO 3/2) 0.1(Me 3SiO 1/2) 0.1(H 2SiO 2/2) 0.1(MeSiO 3/2) 0.4(PhSiO 3/2) 0.4, wherein Me is a methyl, and Ph is a phenyl, and the outer numerical value subscript of bracket is represented molar fraction, and the unit sequence in preceding formula never is considered as limiting the scope of the invention.
[0035] number-average molecular weight (M of the organic siliconresin (A) of usefulness formula (I) expression n) typically be 500-50,000, perhaps 500-10,000, perhaps 1000-3000 wherein by gel permeation chromatography, uses little angle laser light scattering detector or refractive index detector and organic siliconresin (MQ) reference material, determining molecular weight.
[0036] viscosity of organic siliconresin (A) under 25 ℃ with formula (I) expression typically is 0.01-100,000Pa.s, perhaps 0.1-10,000Pa.s, perhaps 1-100Pa.s.
[0037] typically comprises less than 10% (w/w) or less than 5% (w/w) or less than the hydroxyl of 2% (w/w) with the silicon bonding, this passes through with the organic siliconresin (A) of formula (I) expression 29SiNMR measures.
[0038] preparation method with the organic siliconresin (A) of formula (I) expression is well-known in the art; Many these resins are commercially available.Typically by at the organic solvent suitable mixture of cohydrolysis chlorosilane precursor in the toluene for example, the organic siliconresin (A) of system standby mode (I) expression.For example, can be R by cohydrolysis general formula in toluene 1R 2 2First compound of SiCl and general formula are R 2SiCl 3Second compound, preparation contains R 1R 2 2SiO 1/2Unit and R 2SiO 3/2The organic siliconresin of unit (A), wherein R 1And R 2As above define and exemplify, to form aqueous hydrochloric acid and organic siliconresin (A) (it is the hydrolysate of first and second compounds).Separate aqueous hydrochloric acid and organic siliconresin (A), wash organic siliconresin (A) with water, removing residual acid, and in the presence of the condensation catalyst of gentleness, heat organic siliconresin (A), to required viscosity, this is known in the art with " condensing " organic siliconresin (A).
[0039] optionally, can in organic solvent, further handle organic siliconresin (A), with the content of reduction with the hydroxyl of silicon bonding with condensation catalyst.Perhaps, but cohydrolysis contain except chlorine hydrolyzable groups for example-Br ,-I ,-OCH 3,-OC (O) CH 3,-N (CH 3) 2,-NHCOCH 3With-SCH 3First or second compound, form organic siliconresin (A).The performance of organic siliconresin (A) depends on the type of first and second compounds, the mol ratio of first and second compound, condensation level, and processing conditions.
[0040] each molecule of organic group silicon compound (B) on average has at least two and silicon bonded hydrogen atom, and perhaps each molecule has at least three and silicon bonded hydrogen atom.Usually be appreciated that when each molecule in the average of the alkenyl that each molecule in organic silicones (A) has and the organic group silicon compound (B) that have with the average sum silicon bonded hydrogen atom greater than 4 the time, take place crosslinked.Before solidifying, the amount of organic group silicon compound (B) is enough to cured silicone resin (A).
[0041] organic group silicon compound (B) can be further defined as organic group hydrogen silane, organic group hydrogen siloxane or its combination.The structure of organic group silicon compound (B) can be straight chain, side chain, ring-type or resin structure.In acyclic polysilane and polysiloxanes, can be positioned at end, side chain with the silicon bonded hydrogen atom or be positioned at end simultaneously and the side chain position on.Cyclosilane and cyclosiloxane typically have 3-12 silicon atom, perhaps 3-10 silicon atom, perhaps 3-4 silicon atom.
[0042] the organic group hydrogen silane can be single silane, disilane, three silane or polysilane.Work as R 2When mainly being alkenyl, the instantiation that is suitable for the organic group hydrogen silane of the object of the invention includes but not limited to diphenyl silane, 2-chloroethyl silane, two [(to dimetylsilyl) phenyl] ether, 1,4-dimethylformamide dimethyl silylation ethane, 1,3,5-three (dimetylsilyl) benzene, 1,3,5-trimethyl-1,3,5-three silane, poly-(methyl silicylene) phenylene and poly-(methyl silicylene) methylene.Work as R 2When mainly being hydrogen, the instantiation that is suitable for the organic group hydrogen silane of the object of the invention includes but not limited to have the silane of following formula:
Vi 4Si, PhSiVi 3, MeSiVi 3, PhMeSiVi 2, Ph 2SiVi 2And PhSi (CH 2CH=CH 2) 3, wherein Me is a methyl, Ph is that phenyl and Vi are vinyl.
[0043] the organic group hydrogen silane also can have following formula:
HR 1 2Si-R 3-SiR 1 2H (II)
R wherein 1As above define and exemplify, and R 3Be the alkylene that does not contain aliphatic unsaturated bond, it has the general formula that is selected from following structure:
Figure A20088001051000131
Wherein g is 1-6.
[0044] R wherein 1And R 3Instantiation with the organic group hydrogen silane with formula (II) that exemplifies includes but not limited to that general formula is selected from the organic group hydrogen silane of following structure as mentioned above:
Figure A20088001051000132
Figure A20088001051000141
[0045] method for preparing the organic group hydrogen silane is known in the art.For example, can be by making the reaction of RMgBr and alkyl or aryl halogen, preparation organic group hydrogen silane.Especially, can be R by making general formula 3X 2The dihalo aryl and magnesium at the ether internal reaction, produce corresponding RMgBr, be HR with general formula then 1 2The chlorosilane of SiCl is handled this RMgBr, thereby the preparation general formula is HR 1 2Si-R 3-SiR 1 2The organic group hydrogen silane of H, wherein R 1And R 3As mentioned above and exemplify.
[0046] the organic group hydrogen siloxane can be disiloxane, trisiloxanes or polysiloxanes.Work as R 2When mainly being hydrogen, be suitable for including but not limited to have the siloxanes of following formula as the example of the organopolysiloxane of organic group silicon compound (B):
PhSi (OSiMe 2H) 3, Si (OSiMe 2H) 4, MeSi (OSiMe 2H) 3And Ph 2Si (OSiMe 2H) 2, wherein Me is that methyl and Ph are phenyl.
[0047] works as R 2When mainly being alkenyl, the instantiation that is suitable for the organic group hydrogen siloxane of the object of the invention includes but not limited to 1,1,3,3-tetramethyl disiloxane, 1,1,3,3-tetraphenyl disiloxane, phenyl three (dimethyl silane oxygen base) silane, 1,3, gathering gathering (methyl hydrogen siloxane) and comprising HMe of (dimethyl siloxane/methyl hydrogen siloxane), dimethyl hydrogen siloxy end-blocking of poly-(methyl hydrogen siloxane) of 5-trimethyl cyclotrisiloxane, trimethylsiloxy end-blocking, trimethylsiloxy end-blocking 2SiO 1/2Unit, Me 3SiO 1/2Unit and SiO 4/2The resin of unit, wherein Me is a methyl.
[0048] the organic group hydrogen siloxane also can be an organic group hydrogen polysiloxanes resin.Organic group hydrogen polysiloxanes resin typically is and contains R 4SiO 3/2Unit (being the T unit) and/or SiO 4/2Unit (being the Q unit) and in conjunction with R 1R 4 2SiO 1/2Unit (being the M unit) and/or R 4 2SiO 2/2The copolymer of unit (being the D unit), wherein R 1As mentioned above and exemplify.For example, organic group hydrogen polysiloxanes resin can be DT resin, MT resin, MDT resin, DTQ resin and MTQ resin and MDTQ resin, DQ resin, MQ resin, DTQ resin, MTQ resin or MDQ resin.
[0049] uses R 4The group of expression is R 1Or organic group silyl alkyl with at least one and silicon bonded hydrogen atom.Use R 4The organic group silyl alkyl of expression includes but not limited to that general formula is selected from the group of following structure: -CH 2CH 2SiMe 2H ,-CH- 2CH 2SiMe 2C nH 2nSiMe 2H ,-CH 2CH 2SiMe 2C nH 2nSiMePhH ,-CH 2CH 2SiMePhH,
-CH 2CH 2SiPh 2H，-CH 2CH 2SiMePhC nH 2nSiPh 2H，
-CH 2CH 2SiMePhC nH 2nSiMe 2H ,-CH 2CH 2SiMePhOSiMePhH and
-CH 2CH 2SiMePhOSiPh(OSiMePhH) 2，
Wherein Me is a methyl, and Ph is that the numerical value of phenyl and subscript n is 2-10.Typically, in organic group hydrogen polysiloxanes resin, 50mol% or 65mol% or 80mol% R at least at least at least 4The group of expression is the organic group silyl alkyl with at least one and silicon bonded hydrogen atom.As used herein at R 4Interior organic group silyl alkyl mol% be defined as in organic siliconresin with the molal quantity of the organic group silyl alkyl of silicon bonding and this resin in R 4The ratio of the total mole number of base multiply by 100.
[0050] general formula of organic group hydrogen polysiloxanes resin typically is (R 1R 4 2SiO 1/2) w(R 4 2SiO 2/2) x(R 4SiO 3/2) y(SiO 4/2) z(III), R wherein 1, R 4, w, x, y and z separately as mentioned above and exemplify.
[0051] include but not limited to have the resin of following formula with the example of the organic group hydrogen polysiloxanes resin of following formula (III) expression:
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.12(PhSiO 3/2) 0.88，
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.17(PhSiO 3/2) 0.83，
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.17(MeSiO 3/2) 0.17(PhSiO 3/2) 0.66，
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.15(PhSiO 3/2) 0.75(SiO 4/2) 0.10And
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.08((HMe 2SiC 6H 4SiMe 2CH 2CH 2)
Me 2SiO 1/2) 0.06(PhSiO 3/2) 0.86，
Wherein Me is a methyl, and Ph is a phenyl, C 6H 4Expression is represented molar fraction to phenylene and the numerical value subscript outside bracket.Sequence of unit in preceding formula never is regarded as limiting the scope of the invention.
[0052] instantiation of organic group hydrogen polysiloxanes resin includes but not limited to have the resin of following formula:
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.12(PhSiO 3/2) 0.88，
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.17(PhSiO 3/2) 0.83，
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.17(MeSiO 3/2) 0.17(PhSiO 3/2) 0.66，
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.15(PhSiO 3/2) 0.75(SiO 4/2) 0.10And
((HMe 2SiC 6H 4SiMe 2CH 2CH 2) 2MeSiO 1/2) 0.08((HMe 2SiC 6H 4SiMe 2CH 2CH 2)
Me 2SiO 1/2) 0.06(PhSiO 3/2) 0.86, wherein Me is a methyl, Ph is a phenyl, C 6H 4Expression is represented molar fraction to phenylene and the numerical value subscript outside bracket.Sequence of unit in preceding formula never is regarded as limiting the scope of the invention.
[0053] can be at (c) hydrosilylation catalysts and randomly in the presence of (d) organic solvent, containing (a) general formula by making is (R 1R 2 2SiO 1/2) w(R 2 2SiO 2/2) x(R 2SiO 3/2) y(SiO 4/2) zon average have 2-4 with the organic siliconresin of following formula (I) expression and (b) each molecule and react with silicon bonded hydrogen atom and molecular weight reactant mixture less than 1000 organic group silicon compound, the organic group hydrogen polysiloxanes resin that preparation has formula (III), wherein R 1, R 2, w, x, y and z as above define separately and exemplify, condition be each molecule of organic siliconresin (a) on average have at least two with the silicon bonded alkenyl and (b) with the silicon bonded hydrogen atom with (a) in the mol ratio of alkenyl be 1.5-5.Organic siliconresin (a) is with identical or different with the particular silicone resin of the silicone composition of formation hydrosilylation cure as component (A).
[0054] as mentioned above, each molecule of organic group silicon compound (b) on average has 2-4 and silicon bonded hydrogen atom.Perhaps, each molecule of organic group silicon compound (b) on average has 2-3 and silicon bonded hydrogen atom.Similarly, as described above, the molecular weight of organic group silicon compound (b) is typically less than 1000, perhaps less than 750, perhaps less than 500.Organic group silicon compound (b) further comprises the organic group with the silicon bonding, and described organic group can be selected from the alkyl that alkyl and halogen replace, and the two does not all contain aliphatic unsaturated bond, they and above at R 1Describe with exemplify the same.
[0055] organic group silicon compound (b) can be organic group hydrogen silane or organic group hydrogen siloxane, wherein each at length define more than freely with exemplify the same.Organic group silicon compound (b) further can be single organic group silicon compound or the mixture that contains two or more different organic group silicon compounds, wherein separately as mentioned above.For example, organic group silicon compound (B) can be single organic group hydrogen silane, the mixture of two kinds of different organic group hydrogen silanes, single organic group hydrogen siloxane, the mixture of two kinds of different organic group hydrogen siloxanes, the perhaps mixture of organic group hydrogen silane and organic group hydrogen siloxane.Mol ratio with silicon bonded hydrogen atom and the middle alkenyl of organic siliconresin (a) in organic group silicon compound (b) typically is 1.5-5, perhaps 1.75-3, perhaps 2-2.5.
[0056] hydrosilylation catalysts (c) can be any known hydrosilylation catalysts of the compound of platinum group metal (that is, platinum, rhodium, ruthenium, palladium, osmium and iridium) or platinum group metal.Based on its high activity in hydrosilylation reactions, the platinum group metal is platinum preferably.
[0057] the concrete hydrosilylation catalysts that is suitable for (c) comprises that chloroplatinic acid and some contain the complex compound of the organopolysiloxane of vinyl, and is disclosed in U.S. Patent No. 3419593 as Willing, introduces by reference at this.This class catalyst is chloroplatinic acid and 1,3-divinyl-1,1,3, the product of 3-tetramethyl disiloxane.
[0058] hydrosilylation catalysts (c) also can be the bearing type hydrosilylation catalysts that is contained in the solid carrier that has the platinum group metal on its metal surface.Can for example pass through filter reaction mixture, separate bearing type catalyst and the organic group hydrogen polysiloxanes resin of representing with formula (III) easily.The example of bearing type catalyst includes but not limited at the platinum on the carbon, at the palladium on the carbon, at the ruthenium on the carbon, at the rhodium on the carbon, at the platinum on the silica, at the palladium on the silica, at the platinum on the aluminium oxide, at palladium on the aluminium oxide and the ruthenium on aluminium oxide.
[0059] concentration of hydrosilylation catalysts (c) is enough to the addition reaction of catalysis organic siliconresin (a) and organic group silicon compound (b).Typically, based on the combine weight of organic siliconresin (a) with organic group silicon compound (b), the concentration of hydrosilylation catalysts (c) is enough to provide the 0.1-1000ppm platinum group metal, perhaps 1-500ppm platinum group metal, perhaps 5-150ppm platinum group metal.The platinum group metal is when 0.1ppm is following, and reaction speed is very slow.Use does not cause reaction speed significantly to increase greater than the platinum group metal of 1000ppm, and is therefore uneconomical.
[0060] organic solvent (d) is at least a organic solvent.Organic solvent (d) can be under the condition of the inventive method not with organic siliconresin (a), organic group silicon compound (b) or gained organic group hydrogen polysiloxanes resin reaction and with component (a) and (b) and the miscible any non-proton or dipolar aprotic organic solvent of organic group hydrogen polysiloxanes resin.
[0061] example that is suitable for the organic solvent (d) of the object of the invention includes but not limited to saturated aliphatic hydrocarbon, for example pentane, hexane, normal heptane, isooctane and dodecane; Clicyclic hydrocarbon, for example pentamethylene and cyclohexane; Aromatic hydrocarbons, benzene,toluene,xylene and 1,3 for example, 5-trimethylbenzene; Cyclic ethers, for example (THF) is with diox for oxolane; Ketone, for example methyl iso-butyl ketone (MIBK) (MIBK); Halogenated alkane, for example trichloroethanes, and halogenated aryl hydrocarbon, for example bromobenzene and chlorobenzene.Organic solvent (d) can be single organic solvent or the mixture that contains two or more different organic solvents, wherein separately as mentioned above.Based on the gross weight of reactant mixture, the concentration of organic solvent (d) typically is 0-99% (w/w), perhaps 30-80% (w/w), perhaps 45-60% (w/w).
[0062] can in being suitable for any standard reaction device of hydrosilylation reactions, form the reaction of organic group hydrogen polysiloxanes resin with formula (III) expression.Suitable reactor comprises that glass and Teflon are the glass reactor of lining.Typically, this reactor is furnished with and stirs for example mixing plant.In addition, typically, for example under nitrogen or the argon gas, under the situation that does not have moisture, react at inert atmosphere.
[0063] can be according to any order in conjunction with organic siliconresin (a), organic group silicon compound (b), hydrosilylation catalysts (c) and organic solvent (d) randomly.Typically, introduce organic siliconresin (a) and randomly organic solvent (d) before in conjunction with organic radical silicide (b) and hydrosilylation catalysts (c).Typically at 0-150 ℃, perhaps react under the temperature of-115 ℃ of room temperatures (～23 ℃ ± 2 ℃).When temperature during less than 0 ℃, reaction speed is typically very slow.Reaction time is depended on several factors, for example the structure and the temperature of organic siliconresin (a) and organic group silicon compound (b).The following reaction time of temperature-150 ℃ of room temperatures (～23 ℃ ± 2 ℃) typically is 1-24 hour.The best reaction time can be determined by normal experiment.
[0064] can perhaps can separate organic group hydrogen polysiloxanes resin and most of organic solvent (d) at the organic group hydrogen polysiloxanes resin that does not have to use under the situation of isolated or purified with formula (III) expression by conventional method of evaporating.For example, can reduce pressure and add thermal reaction mixture.And, when hydrosilylation catalysts (c) is above-described bearing type catalyst, can pass through filter reaction mixture, easily separate organic group hydrogen polysiloxanes resin and hydrosilylation catalysts (c).Yet hydrosilylation catalysts can keep with organic group hydrogen polysiloxanes mixed with resin and as hydrosilylation catalysts (C).
[0065] organic group silicon compound (B) can be single organic group silicon compound or the mixture that contains two or more different organic group silicon compounds, wherein separately as mentioned above.For example, organic group silicon compound (B) can be single organic group hydrogen silane, the mixture of two kinds of different organic group hydrogen silanes, single organic group hydrogen siloxane, the mixture of two kinds of different organic group hydrogen siloxanes, the perhaps mixture of organic group hydrogen silane and organic group hydrogen siloxane.Especially, organic group silicon compound (B) can be the gross weight that contains based on organic group silicon compound (B), consumption has the organic group hydrogen polysiloxanes resin of formula (III) and the mixture that further contains the organic group silicon compound (B) of organic group hydrogen silane and/or organic group hydrogen siloxane at least 0.5% (w/w) or at least 50% (w/w) or at least 75% (w/w), and wherein said organic group hydrogen siloxane is different from organic group hydrogen polysiloxanes resin.
[0066] concentration of organic group silicon compound (B) is enough to solidify (crosslinked) organic siliconresin (A).The definite consumption of organic group silicon compound (B) depends on required state of cure.In every mole of alkenyl in organic siliconresin (A), the concentration of organic group silicon compound (B) typically is enough to provide 0.4-2mol and silicon bonded hydrogen atom, perhaps 0.8-1.5mol and silicon bonded hydrogen atom, perhaps 0.9-1.1mol and silicon bonded hydrogen atom.
[0067] hydrosilylation catalysts (C) comprises at least a hydrosilylation catalysts that promotes reaction between organic siliconresin (A) and the organic group silicon compound (B).In one embodiment, hydrosilylation catalysts (C) can be with above identical at producing the organic group described hydrosilylation catalysts of hydrogen polysiloxanes resin (c).In addition, hydrosilylation catalysts (C) also can be the catalyst of little platinum group metal of sealing, and it comprises the platinum group metal that is encapsulated in the thermoplastic resin.Little hydrosilylation catalysts of sealing and preparation method thereof is well-known in the art, and for example institute exemplifies in list of references of quoting as proof as U.S. Patent No. 4766176 and Qi Nei and the U.S. Patent No. 5017654.Hydrosilylation catalysts (C) can be single catalyst or contain at least a performance for example structure, form, platinum group metal, complexing ligand two or more different mixture of catalysts different with thermoplastic resin.
[0068] in another embodiment, hydrosilylation catalysts (C) can be the hydrosilylation catalysts of at least a photoactivation.The hydrosilylation catalysts of photoactivation can be to be that radiation following time of 150-800nm can catalysis organic siliconresin (A) and any hydrosilylation catalysts of the hydrosilylation reactions of organic group silicon compound (B) when being exposed to wavelength.The hydrosilylation catalysts of photoactivation can be any well-known hydrosilylation catalysts of the compound of platinum group metal or platinum group metal.The platinum group metal comprises platinum, rhodium, ruthenium, palladium, osmium and iridium.Based on its high activity in hydrosilylation reactions, the platinum group metal typically is platinum.The well-formedness of the hydrosilylation catalysts of the specific light activation that can easily determine in silicone composition of the present invention, to use by normal experiment.
[0069] instantiation of hydrosilylation catalysts that is suitable for the photoactivation of the object of the invention includes but not limited to that the beta-diketon root closes platinum (II) complex compound, for example two (2,4-pentanedione root) closes platinum (II), two (2,4-acetyl butyryl root) closes platinum (II), two (2,4-heptadione root) closes platinum (II), two (1-phenyl-1,3-diacetyl root) closes platinum (II), two (1,3-diphenyl-1,3-propanedione root) closes platinum (II), two (1,1,1,5,5,5-hexafluoro-2,4-pentanedione root) closes platinum (II), (η-cyclopentadienyl group) trialkyl platinum complex, for example (Cp) trimethyl platinum, (Cp) ethyl dimethyl platinum, (Cp) triethyl group platinum, (chloro Cp) trimethyl platinum and (trimethyl silyl-Cp) trimethyl platinum, wherein Cp representative ring pentadienyl; Triazenes oxide-transition metal complex, for example Pt[C 6H 5NNNOCH 3] 4, Pt[p-CN-C 6H 4NNNOC 6H 11] 4, Pt[p-H 3COC 6H 4NNNOC 6H 11] 4, Pt[p-CH 3(CH 2) x-C 6H 4NNNOCH 3] 4, 1,5-cyclo-octadiene Pt[p-CN-C 6H 4NNNOC 6H 11] 2, 1,5-cyclo-octadiene Pt[p-CH 3O-C 6H 4NNNOCH 3] 2, [(C 6H 5) 3P] 3Rh[p-CN-C 6H 4NNNOC 6H 11] and Pd[p-CH 3(CH 2) x-C 6H 4NNNOCH 3] 2, wherein x is 1,3,5,11 or 17; (η-alkadienes) (σ-aryl) platinum complex, for example (η 4-1,5-cyclo-octadiene base) diphenyl platinum, (η 4-1,3,5,7-cyclo-octatetraene base) diphenyl platinum, (η 4-2,5-norbornadiene base) diphenyl platinum, (η 4-1,5-cyclo-octadiene base) two-(4-dimethylaminophenyl) platinum, (η 4-1,5-cyclo-octadiene base) two-(4-acetylphenyl) platinum and (η 4-1,5-cyclo-octadiene base) two-(4-trifluoromethyl) platinum.Typically, the hydrosilylation catalysts of photoactivation is that the beta-diketon root closes Pt (II) complex compound and more typically, and catalyst is that two (2,4-pentanedione root) close platinum (II).Hydrosilylation catalysts (C) can be single photoactivation hydrosilylation catalysts or the mixture that contains two or more different photoactivation hydrosilylation catalysts.
[0070] method of the hydrosilylation catalysts of preparation photoactivation is well-known in the art.For example, and people such as Guo (Chemistry of Materials, 1998,10,531-536) reported and prepared the method that the beta-diketon root closes Pt (II) complex compound.The method of preparation (η-cyclopentadienyl group) trialkyl platinum complex is disclosed in the U.S. Patent No. 4510094.U.S. Patent No. 5496961 discloses the method for preparing triazenes oxide-transition metal complex.The method of preparation (η-alkadienes) (σ-aryl) platinum complex is disclosed in the U.S. Patent No. 4530879.
[0071] concentration of hydrosilylation catalysts (C) is enough to the addition reaction between catalysis organic siliconresin (A) and the organic group silicon compound (B).Based on the combine weight of organic siliconresin (A) with organic group silicon compound (B), the concentration of hydrosilylation catalysts (C) is enough to 0.1-1000ppm typically is provided the platinum group metal, perhaps 0.5-100ppm platinum group metal, perhaps 1-25ppm platinum group metal.
[0072] randomly, the silicone composition of hydrosilylation cure further comprises (D) general formula and is selected from following silicon rubber:
(i) R 1R 2 2SiO (R 2 2SiO) aSiR 2 2R 1(ii) R 5R 1 2SiO (R 1R 5SiO) bSiR 1 2R 5, R wherein 1And R 2As defined above with exemplify the same, R 5Be R 1Or-H, the numerical value of subscript a and the b 1-4 that respectively does for oneself, 2-4 or 2-3, with w, x, y and z also as defined above with exemplify the same, condition be organic siliconresin and silicon rubber (D) (i) each molecule on average have separately at least two with the silicon bonded alkenyl, silicon rubber (D) (ii) each molecule on average have at least two with the silicon bonded hydrogen atom and silicon rubber (D) in the silicon bonded alkenyl or with silicon bonded hydrogen atom and organic siliconresin (A) in and the mol ratio of silicon bonded alkenyl be 0.01-0.5.
[0073] be suitable for the silicon rubber that instantiation as component (D) silicon rubber (i) includes but not limited to have following formula:
ViMe 2SiO (Me 2SiO) aSiMe 2Vi, ViMe 2SiO (Ph 2SiO) aSiMe 2Vi and
ViMe 2SiO (PhMeSiO) aSiMe 2Vi, wherein Me is a methyl, and Ph is a phenyl, and Vi is that the numerical value of vinyl and subscript a is 1-4.Silicon rubber (D) can be single silicon rubber or the mixture that contains two or more different silicon rubber (i), wherein satisfies (D) general formula (i) separately.
[0074] be suitable for the silicon rubber that instantiation as silicon rubber (D) silicon rubber (ii) includes but not limited to have following formula:
HMe 2SiO(Me 2SiO) bSiMe 2H、HMe 2SiO(Ph 2SiO) bSiMe 2H、
HMe 2SiO (PhMeSiO) bSiMe 2H, and HMe 2SiO (Ph 2SiO) 2(Me 2SiO) 2SiMe 2H, wherein Me is a methyl, Ph is that the numerical value of phenyl and subscript b is 1-4.Component (D) (ii) can be single silicon rubber or the mixture that contains two or more different silicon rubber, wherein satisfies (D) general formula (ii) separately.
[0075] in silicon rubber (D) with the silicon bonded alkenyl or with silicon bonded hydrogen atom and organic siliconresin (A) in and the mol ratio of silicon bonded alkenyl typically be 0.01-0.5, perhaps 0.05-0.4, perhaps 0.1-0.3.
[0076] when silicon rubber (D) be that (D) is (i) time, the concentration of organic group silicon compound (B) make in the organic group silicon compound (B) with the molal quantity of silicon bonded hydrogen atom and organic siliconresin (A) and silicon rubber (D) (i) ratio of the molal quantity sum of interior and silicon bonded alkenyl typically be 0.4-2, perhaps 0.8-1.5, perhaps 0.9-1.1.In addition, when silicon rubber (D) is that (D) is (ii) the time, the concentration of organic group silicon compound (B) makes that the ratio of the molal quantity of and silicon bonded alkenyl interior with organic siliconresin (A) with the molal quantity sum of silicon bonded hydrogen atom typically is 0.4-2 in organic group silicon compound (B) and silicon rubber (D) are (ii), perhaps 0.8-1.5, perhaps 0.9-1.1.
[0077] preparation contain with the silicon bonded alkenyl or with the method for the silicon rubber of silicon bonded hydrogen atom be well-known in the art, many these compounds are commercially available.
[0078] in another embodiment of the present invention, the hydrosilylation catalysts that the silicone composition of hydrosilylation cure is included in (C) catalytic amount exists the organic siliconresin of following (A ') modified rubber and the product of organic group silicon compound (B).Can (iii) react by making organic siliconresin (A) and silicon rubber (D) at hydrosilylation catalysts (c) with randomly in the presence of the organic solvent, prepare the organic siliconresin of (A ') modified rubber with following formula:
R 5R 1 2SiO(R 1R 5SiO) cSiR 1 2R 5，R 1R 2 2SiO(R 2 2SiO) dSiR 2 2R 1
R wherein 1And R 5As defined above with exemplify the same, and c and d numerical value separately are 4 to 1000, perhaps 10-500, perhaps 10-50, condition is that each molecule of organic siliconresin (A) on average has at least two and silicon bonded alkenyl, silicon rubber (D) (iii) each molecule on average have at least two with the silicon bonded hydrogen atom, and silicon rubber (D) (iii) in silicon bonded hydrogen atom and organic siliconresin (A) in and the mol ratio of silicon bonded alkenyl be 0.01-0.5.When having organic solvent, the organic siliconresin of modified rubber (A ') is miscible and formation precipitation or suspended substance in organic solvent.
[0079] can by any order in conjunction with organic siliconresin (A), silicon rubber (D) (iii), hydrosilylation catalysts (c) and organic solvent.Typically, introducing hydrosilylation catalysts (c) before, (iii) and organic solvent in conjunction with organic siliconresin (A), silicon rubber (D).
[0080], perhaps reacts under the temperature of room temperature to 100 ℃ typically-150 ℃ of room temperatures (～23 ℃ ± 2 ℃).Reaction time is depended on several factors, comprising organic siliconresin (A) and silicon rubber (D) structure and temperature (iii).Typically allow each component reaction to be enough to finish the time period of hydrosilylation reactions.This means and typically allow each component reaction, up to 95mol% at least or at least 98mol% or at least 99mol% be present in silicon rubber (D) in hydrosilylation reactions, being consumed in (iii) at first with the silicon bonded hydrogen atom, this measures by FTIR spectrum.Under the temperature of-100 ℃ of room temperatures (～23 ℃ ± 2 ℃), the reaction time typically is 0.5-24 hour.Optimum reacting time can be determined by normal experiment.
[0081] silicon rubber (D) is (iii) interior typically is 0.01-5 with silicon bonded hydrogen atom and the interior mol ratio with the silicon bonded alkenyl of organic siliconresin (A), perhaps 0.05-0.4, perhaps 0.1-0.3.
[0082] concentration of hydrosilylation catalysts (c) is enough to catalysis organic siliconresin (A) and silicon rubber (D) addition reaction (iii).Typically, based on the combine weight of resin with rubber, the concentration of hydrosilylation catalysts (c) is enough to provide the 0.1-1000ppm platinum group metal.
[0083] based on the gross weight of reactant mixture, the concentration of organic solvent typically is 0-95% (w/w), perhaps 10-75% (w/w), perhaps 40-60% (w/w).
[0084] can perhaps can pass through the organic siliconresin (A ') and most of solvents of conventional method of evaporating separate rubber modification at the organic siliconresin (A ') that does not have to use under the situation of isolated or purified modified rubber.For example, can reduce pressure and add thermal reaction mixture.And, when hydrosilylation catalysts (c) is above-described bearing type catalyst, can pass through filter reaction mixture, organic siliconresin of separate rubber modification easily (A ') and hydrosilylation catalysts (c).Yet, when the organic siliconresin that does not have the separate rubber modification (A ') with the preparation modified rubber the employed hydrosilylation catalysts of organic siliconresin (A ') (c) time, hydrosilylation catalysts (c) can be used as hydrosilylation catalysts (C).
[0085] silicone composition of hydrosilylation cure of the present invention can comprise extra composition known in the art.The example of extra composition includes but not limited to the inhibitor of hydrosilylation catalysts, 3-methyl-pirylene, 3 for example, 5-dimethyl-3-hexene-1-alkynes, 3,5-dimethyl-1-hexin-3-alcohol, 1-acetenyl-1-cyclohexanol, 2-phenyl-3-butyne-2-alcohol, vinyl cyclosiloxane and triphenylphosphine; Adhesion promotor, for example adhesion promotor of instruction in United States Patent(USP) Nos. 4087585 and 5194649; Dyestuff; Pigment; Antioxidant; Heat stabilizer; The UV stabilizing agent; Fire retardant; The control additive flows; And diluent, for example organic solvent and reactive diluent.
[0086] as the substituting of the silicone composition of hydrosilylation cure, condensation cured silicone composition also is suitable for as silicone composition of the present invention.
[0087] condensation cured silicone composition typically comprises and has and the hydroxyl of silicon bonding or the organic siliconresin of hydrolyzable groups (A ") and randomly having and the crosslinking agent (B ') of the hydrolyzable groups of silicon bonding and the product of condensation catalyst (C ') randomly.(A ") contains T and/or the Q siloxane unit copolymer in conjunction with M and/or D siloxane unit to organic siliconresin typically.
[0088] condensation cured silicone composition can be any condensation cured silicone composition known in the art.Yet some condensation cured silicone compositions can be particularly suitable for purpose of the present invention.According to an embodiment, organic siliconresin (A ") has following formula:
(R 1R 6 2SiO 1/2) w′(R 6 2SiO 2/2) x′(R 6SiO 3/2) y′(SiO 4/2) z′(IV)
R wherein 1As above define with exemplify the same, R 6Be R 1,-H ,-OH or hydrolyzable groups, and w ' is 0-0.8, perhaps 0.02-0.75, with or 0.05-0.3, x ' is 0-0.95, perhaps 0.05-0.8, with or 0.1-0.3, y ' is 0-1, perhaps 0.25-0.8 and or 0.5-0.8, and z ' is 0-0.99, perhaps 0.2-0.8 and or 0.4-0.6, and organic siliconresin (each molecule of A ") on average have at least two with silicon bonded hydrogen atom, hydroxyl or hydrolyzable groups.Term as used herein " hydrolyzable groups " is meant under the situation that does not have catalyst, under any temperature of-100 ℃ of room temperatures (～23 ± 2 ℃), make with the group of silicon bonding and water at several minutes 30 minutes internal reactions for example, form silanol group (Si-OH).Use R 6The example of hydrolyzable groups of expression includes but not limited to-Cl ,-Br ,-OR 7,-OCH 2CH 2OR 7, CH 3C (=O) O-, Et (Me) C=N-O-, CH 3C (=O) N (CH 3)-and-ONH 2, R wherein 7Be C 1-C 8Alkyl or C 1-C 8The alkyl that halogen replaces.
[0089] uses R 7The alkyl that the alkyl of expression and halogen replace typically has 1-8 carbon atom, perhaps 3-6 carbon atom.Contain the acyclic hydrocarbon group of at least 3 carbon atoms and the alkyl of halogen replacement and can have branching or nonbranched structure.Use R 7The example of alkyl of expression includes but not limited to the not alkyl of branching and branching, for example methyl, ethyl, propyl group, 1-Methylethyl, butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl ethyl, amyl group, 1-methyl butyl, 1-ethyl propyl, 2-methyl butyl, 3-methyl butyl, 1,2-dimethyl propyl, 2,2-dimethyl propyl, hexyl, heptyl and octyl group; Cycloalkyl, for example cyclopenta, cyclohexyl and methylcyclohexyl; Phenyl; Alkaryl, for example tolyl and xylyl; Aralkyl, for example benzyl and phenethyl; Alkenyl, for example vinyl, pi-allyl and acrylic; Aryl alkenyl, for example styryl; And alkynyl, for example acetenyl and propinyl.Use R 7The example of the alkyl that the halogen of expression replaces includes but not limited to 3,3,3-trifluoro propyl, 3-chloropropyl, chlorphenyl and dichlorophenyl.
[0090] typically, 5mol% or 15mol% or the R of 30mol% in organic siliconresin at least at least at least 6Base is hydrogen, hydroxyl or hydrolyzable groups.Mol% as used herein is at R 6In group definition be organic siliconresin (A ") in and the molal quantity of the group of silicon bonding and the R in this organic siliconresin (A ") 6The ratio of the total mole number of base multiply by 100.
[0091] (instantiation of the organic siliconresin of the curing that A ") forms includes but not limited to have the organic siliconresin of the curing of following formula: (MeSiO by organic siliconresin 3/2) n, (PhSiO 3/2) n, (Me 3SiO 1/2) 0.8(SiO 4/2) 0.2, (MeSiO 3/2) 0.67(PhSiO 3/2) 0.33, (MeSiO 3/2) 0.45(PhSiO 3/2) 0.40(Ph 2SiO 2/2) 0.1(PhMeSiO 2/2) 0.05, (PhSiO 3/2) 0.4(MeSiO 3/2) 0.45(PhSiO 3/2) 0.1(PhMeSiO 2/2) 0.05(PhSiO 3/2) 0.4(MeSiO 3/2) 0.1(PhMeSiO 2/2) 0.5, wherein Me is a methyl, and Ph is a phenyl, and the outer numerical value subscript of bracket is represented molar fraction, and the numerical value of subscript n makes that the number-average molecular weight of this organic siliconresin is 500-50,000.Unit sequence in preceding formula never is considered as limiting the scope of the invention.
[0092] as mentioned above, (number-average molecular weight (Mn) of A ") typically is 500-50,000 to the organic siliconresin of representing with formula (IV).Perhaps, (Mn of A ") can be at least 300 to organic siliconresin, and perhaps 1000-3000 wherein by gel permeation chromatography, uses little angle laser light scattering detector or refractive index detector and organic siliconresin (MQ) reference material, measures this molecular weight.
[0093] (viscosity of A ") under 25 ℃ typically is 0.01Pa.s to solid to organic siliconresin, perhaps 0.1-100,000Pa.s, perhaps 1-1000Pa.s.
[0094] (preparation method of A ") is well-known in the art to the organic siliconresin of representing with formula (IV); Many these resins are commercially available.Typically by at the organic solvent suitable mixture of cohydrolysis chlorosilane precursor in the toluene for example, the organic siliconresin (A ") of system standby mode (IV) expression.For example, can be R by cohydrolysis general formula in toluene 1R 6 2First compound of SiCl and general formula are R 6SiCl 3Second compound, preparation contains R 1R 6 2SiO 1/2Unit and R 6SiO 3/2The organic siliconresin of unit, wherein R 1And R 6As above define and exemplify.Cohydrolysis technology is as above organic siliconresin at hydrosilylation cure is described.The reactant that can further " condense " cohydrolysis is to required degree, with the content and the viscosity of control crosslinkable base.
[0095] the Q unit can be organic siliconresin (the discrete particle form in the A ") in formula (IV).Granularity typically is 1 nanometer-20 micron.The example of these particles includes but not limited to that diameter is the silica (SiO of 15 nanometers 4/2) particle.
[0096] condensation cured silicone composition can further contain inorganic filler, for example silica, aluminium oxide, calcium carbonate and mica.
[0097] in another embodiment, condensation cured silicone composition comprises the organic siliconresin (A " ') of modified rubber and the product of other optional components.Can be at water, (iv) condensation catalyst is with (v) organic solvent exists down, and being selected from (i) general formula by making is (R 1R 6 2SiO 1/2) w(R 6 2SiO 2/2) x(R 6SiO 3/2) y(SiO 4/2) zOrganic siliconresin and (ii) the organic group silicon compound in the hydrolysable precursors of (i) be R with (iii) general formula 8 3SiO (R 1R 8SiO) mSiR 8 3Silicon rubber reaction, the organic siliconresin of preparation modified rubber (A " '), wherein R 1And R 6As above define and exemplify, R 8Be R 1Or hydrolyzable groups, m is 2-1000, perhaps 4-500, perhaps 8-400, with w, x, y and z as defined above and exemplify, and each molecule of organic siliconresin (i) on average has at least two hydroxyl or hydrolyzable groups with the silicon bonding, silicon rubber (iii) each molecule on average has at least two hydrolyzable groups with the silicon bonding, and silicon rubber (iii) in the hydrolyzable groups of silicon bonding and organic siliconresin (i) in and the hydroxyl of silicon bonding or the mol ratio of hydrolyzable groups be 0.01-1.5, perhaps 0.05-0.8, perhaps 0.2-0.5.
[0098] typically, 5mol% or 15mol% or the R of 30mol% in organic siliconresin (i) at least at least at least 6Base is hydroxyl or hydrolyzable groups.
[0099] number-average molecular weight (Mn) of organic siliconresin (i) typically is at least 300, perhaps 500-10,000, perhaps 1000-3000, wherein pass through gel permeation chromatography, use little angle laser light scattering detector or refractive index detector and organic siliconresin (MQ) reference material, measure this molecular weight.
[00100] instantiation of the organic siliconresin of the curing that is formed by organic siliconresin (i) includes but not limited to have the organic siliconresin of the curing of following formula: (MeSiO 3/2) n, (PhSiO 3/2) n, (PhSiO 3/2) 0.4(MeSiO 3/2) 0.45(PhSiO 3/2) 0.1(PhMeSiO 2/2) 0.05(PhSiO 3/2) 0.3(SiO 4/2) 0.1(Me 2SiO 2/2) 0.2(Ph 2SiO 2/2) 0.4, wherein Me is a methyl, and Ph is a phenyl, and the outer numerical value subscript of bracket is represented molar fraction, and the numerical value of subscript n makes that the number-average molecular weight of this organic siliconresin is 500-50,000.Unit sequence in preceding formula never is considered as limiting the scope of the invention.Organic siliconresin (i) can be single organic siliconresin or the mixture that contains two or more different organic siliconresins, the general formula that wherein has regulation separately.
[00101] term as used herein " hydrolysable precursors " is meant and has the silane with hydrolyzable groups that is suitable for as the parent material (precursor) of preparation organic siliconresin (i).The (ii) available following general formula of hydrolyzable precursor is representative: R 1R 8 2SiX, R 8 2SiX 2, R 8SiX 3And SiX 4, R wherein 1, R 8With X as defined above and exemplify.
[00102] hydrolyzable precursor instantiation (ii) includes but not limited to have the silane of following formula:
Me 2ViSiCl, Me 3SiCl, MeSi (OEt) 3, PhSiCl 3, MeSiCl 3, Me 2SiCl 2, PhMeSiCl 2, SiCl 4, Ph 2SiCl 2, PhSi (OMe) 3, MeSi (OMe) 3, PhMeSi (OMe) 2And Si (OEt) 4, wherein Me is a methyl, Et is that ethyl and Ph are phenyl.
[00103] silicon rubber instantiation (iii) includes but not limited to have the silicon rubber of following formula: (EtO) 3SiO (Me 2SiO) 55Si (OEt) 3, (EtO) 3SiO (Me 2SiO) 16Si (OEt) 3, (EtO) 3SiO (Me 2SiO) 386Si (OEt) 3(EtO) 2MeSiO (PhMeSiO) 10SiMe (OEt) 2, wherein Me is a methyl, Et is an ethyl.
[00104], perhaps under the temperature of room temperature to 100 ℃, carries out this reaction typically from-180 ℃ of room temperatures (～23 ± 2 ℃).
[00105] reaction time is depended on Several Factors, comprising organic siliconresin (i) and silicon rubber structure and temperature (iii).Typically allow each component reaction, its time period is enough to finish condensation reaction.This means typically allow each component reaction up to 95mol% at least or at least 98mol% or at least 99mol% be present in the hydrolyzable groups with silicon bonding of silicon rubber in (iii) at first and in condensation reaction, consume, this passes through 29The SiNMR spectroscopic methodology is measured.Under the temperature of-100 ℃ of room temperatures (～23 ± 2 ℃), the reaction time typically is 1-30 hour.Can measure optimum reacting time by normal experiment.
[00106] further described suitable condensation catalyst below (iv), and appropriate organic solvent is (v) as the organic siliconresin (A ') of above modified rubber is described.Condensation catalyst concentration (iv) is enough to catalysis organic siliconresin (i) and silicon rubber condensation reaction (iii).Typically, based on the weight of organic siliconresin (i), condensation catalyst concentration (iv) is 0.01-2% (w/w), perhaps 0.01-1% (w/w), perhaps 0.05-0.2% (w/w).Based on the gross weight of reactant mixture, (concentration v) typically is 10-95% (w/w) to organic solvent, perhaps 20-85% (w/w), perhaps 50-80% (w/w).
[00107] concentration of water depends on R in the organic group silicon compound in reactant mixture 8The character of base and in silicon rubber with the character of the hydrolyzable groups of silicon bonding.When organic silicones (i) when containing hydrolyzable groups, the concentration of water is enough to carry out the hydrolysis of organic siliconresin (i) and the silicon rubber hydrolyzable groups in (iii).For example, in the organic siliconresin (i) and the (iii) interior hydrolyzable groups of silicon rubber of every mole of combination, the concentration of water typically is the 0.01-3 mole, perhaps the 0.05-1 mole.When organic silicones (i) when not containing hydrolyzable groups, in reactant mixture, require only trace, for example the water of 100ppm.The water of trace is present in reactant and/or the solvent usually.
[00108] as mentioned above, condensation cured silicone composition can further comprise the product of crosslinking agent (B ').The general formula of crosslinking agent (B ') can be R 7 qSiX 4-q, R wherein 7Be C 1-C 8Alkyl or C 1-C 8The alkyl that halogen replaces, X is that hydrolyzable groups and q are 0 or 1.Use R 7Alkyl that the alkyl of expression and halogen replace and the hydrolyzable groups represented with X as mentioned above with exemplify the same.
[00109] instantiation of crosslinking agent (B ') includes but not limited to alkoxy silane, for example MeSi (OCH 3) 3, CH 3Si (OCH 2CH 3) 3, CH 3Si (OCH 2CH 2CH 3) 3, CH 3Si[O (CH 2) 3CH 3] 3, CH 3CH 2Si (OCH 2CH 3) 3, C 6H 5Si (OCH 3) 3, C 6H 5CH 2Si (OCH 3) 3, C 6H 5Si (OCH 2CH 3) 3, CH 2=CHSi (OCH 3) 3, CH 2=CHCH 2Si (OCH 3) 3, CF 3CH 2CH 2Si (OCH 3) 3, CH 3Si (OCH 2CH 2OCH 3) 3, CF 3CH 2CH 2Si (OCH 2CH 2OCH 3) 3, CH 2=CHSi (OCH 2CH 2OCH 3) 3, CH 2=CHCH 2Si (OCH 2CH 2OCH 3) 3, C 6H 5Si (OCH 2CH 2OCH 3) 3, Si (OCH 3) 4, Si (OC 2H 5) 4And Si (OC 3H 7) 4, organic group acetoxylsilane, for example CH 3Si (OCOCH 3) 3, CH 3CH 2Si (OCOCH 3) 3And CH 2=CHSi (OCOCH 3) 3Organic group imino group TMOS, for example CH 3Si[O-N=C (CH 3) CH 2CH 3] 3, Si[O-N=C (CH 3) CH 2CH 3] 4And CH 2=CHSi[O-N=C (CH 3) CH 2CH 3] 3Organic group acetamido silane, for example CH 3Si[NHC (=O) CH 3] 3And C 6H 5Si[NHC (=O) CH 3] 3Amino silane, for example CH 3Si[NH (s-C 4H 9)] 3And CH 3Si (NHC 6H 11) 3With organic group amino oxygen base silane.
[00110] crosslinking agent (B ') can be single silane or the mixture that contains two or more different silane, wherein separately as mentioned above.The method for preparing trifunctional and four functional silanes in addition is well-known in the art; Many these silane are commercially available.
[00111] if use, before forming condensation cured silicone composition, the concentration of crosslinking agent (B ') is enough to solidify (crosslinked) this condensation cured organic siliconresin.The definite consumption of crosslinking agent (B ') depends on required state of cure, and it is usually with (ratio of the interior molal quantity with silicon bonded hydrogen atom, hydroxyl or hydrolyzable groups of A ") increases with the molal quantity of the hydrolyzable groups of silicon bonding and organic siliconresin in the crosslinking agent (B ').Typically, the concentration of crosslinking agent (B ') hydrolyzable groups/mole of being enough to provide 0.2-4 mole and silicon bonding at organic siliconresin (in the A ") with silicon bonded hydrogen atom, hydroxyl or hydrolyzable groups.Can easily measure the optimised quantity of crosslinking agent (B ') by normal experiment.
[00112] condensation catalyst (C ') can be typically to promote to form the employed any condensation catalyst of Si-O-Si key with hydroxyl (silanol group) condensation of silicon bonding.The example of condensation catalyst includes but not limited to amine, and the complex compound of lead, tin, zinc and iron and carboxylic acid.Especially, condensation catalyst (C ') can be selected from tin (II) and tin (IV) compound, for example two laurate tin, two tin octoates and Tetrabutyltin; And titanium compound, for example four butanols titaniums.
[00113] if exist, (gross weight of A "), the concentration of condensation catalyst (C ') typically is 0.1-10% (w/w), perhaps 0.5-5% (w/w), perhaps 1-3% (w/w) based on organic siliconresin.
[00114] when in the presence of condensation catalyst (C '), forming condensation cured silicone composition, typically form condensation cured silicone composition by two parts composition, wherein (A ") and condensation catalyst (C ') are in independent part for organic siliconresin.
[00115] condensation cured silicone composition of the present invention can comprise the described extra composition of known in the art and above organic siliconresin at hydrosilylation cure.
[00116] in an embodiment again, silicone composition can be radical-cured silicone composition.The example of radical-cured silicone composition comprises the silicone composition of peroxide cure, contains the silicone composition of radiation curing of free radical photo-initiation and the silicone composition of high-energy radiation solidification.Typically, radical-cured silicone composition comprises organic siliconresin (A " ") and the product of crosslinking agent (B ") and/or radical initiator (C ") (for example free radical photo-initiation or organic peroxide) randomly.
[00117] organic siliconresin (A " ") can be can be by being selected from (i) in the presence of free radical photo-initiation, exposing organic siliconresin is under the radiation of 150-800nm in wavelength, (ii) in the presence of organic peroxide, heating organic siliconresin (A " ") and (iii) expose organic siliconresin (A " ") solidify any organic siliconresin of (promptly crosslinked) at least a method of electron beam in down.Organic siliconresin (A " ") contains T siloxane unit and/or Q siloxane unit copolymer typically in conjunction with M and/or D siloxane unit.
[00118] for example, organic siliconresin (A " ") can have following formula:
(R 1R 9 2SiO 1/2) w″(R 9 2SiO 2/2) x″(R 9SiO 3/2) y″(SiO 4/2) z″
R wherein 1As above define with exemplify the same, R 9Be R 1, alkenyl or alkynyl, w " being 0-0.99, x " is 0-0.99, y " be 0-0.99, and z " is 0-0.85, and w "+x "+y "+z "=1.
[00119] uses R 9The alkenyl of expression can be identical or different, as above R 2Explanation in the definition with exemplify the same.
[00120] uses R 9The alkynyl of expression can be identical or different, typically has about 10 carbon atoms of 2-, perhaps 2-6 carbon atom, and exemplify but be not limited to acetenyl, propinyl, butynyl, hexin base and octyne base.
[00121] number-average molecular weight (M organic siliconresin (A " ") n) typically be at least 300, perhaps 500-10,000, perhaps 1000-3000 wherein by gel permeation chromatography, uses refractive index detector and organic siliconresin (MQ) reference material, determining molecular weight.
[00122] organic siliconresin (A " ") can contain less than 10% (w/w) or less than 5% (w/w) or less than the hydroxyl of 2% (w/w) and silicon bonding, this passes through 29SiNMR measures.
[00123] be suitable for the organic siliconresin (A " " of the object of the invention) example include but not limited to have the organic siliconresin of following formula:
(Vi 2MeSiO 1/2) 0.25(PhSiO 3/2) 0.75、(ViMe 2SiO 1/2) 0.25(PhSiO 3/2) 0.75、
(ViMe 2SiO 1/2) 0.25(MeSiO 3/2) 0.25(PhSiO 3/2) 0.50、
(ViMe 2SiO 1/2) 0.15(PhSiO 3/2) 0.75(SiO 4/2) 0.1With
(Vi 2MeSiO 1/2) 0.15(ViMe 2SiO 1/2) 0.1(PhSiO 3/2) 0.75, wherein Me is a methyl, and Vi is a vinyl, and Ph is a phenyl, and the outer numerical value subscript of bracket is represented molar fraction.Unit sequence in preceding formula never is considered as limiting the scope of the invention.
[00124] the radical-cured silicone composition in the inventive method can comprise extra composition, comprising but be not limited to silicon rubber; Unsaturated compound; Radical initiator; Organic solvent; The UV stabilizing agent; Sensitizer; Dyestuff; Fire retardant; Antioxidant; Filler, for example reinforcer, increment filler and conductive fillers; And adhesion promotor.
[00125] radical-cured silicone composition can further comprise and is selected from least a organic group silicon compound that (i) each molecule has at least one and silicon bonded alkenyl, (ii) each molecule has at least a organic compound of at least one aliphatic carbon-to-carbon double bond, (iii) contain the product of the unsaturated compound in (i) and the mixture (ii), wherein the molecular weight of this unsaturated compound is less than 500.Perhaps, the molecular weight of this unsaturated compound is less than 400 or less than 300.In addition, unsaturated compound can have straight chain, side chain or circulus.
[00126] organic group silicon compound (i) can be organosilanes or organopolysiloxane.Organosilanes can be single silane, disilane, three silane or polysilane.Similarly, organopolysiloxane can be disiloxane, trisiloxanes or polysiloxanes.Cyclosilane and cyclosiloxane typically have 3-12 silicon atom, perhaps 3-10 silicon atom, perhaps 3-4 silicon atom.In acyclic polysilane and polysiloxanes, can be positioned at end, side group with the silicon bonded alkenyl or be positioned at end simultaneously and the side group position on.
[00127] instantiation of organosilanes includes but not limited to have the silane of following formula:
Vi 4Si, PhSiVi 3, MeSiVi 3, PhMeSiVi 2, Ph 2SiVi 2And PhSi (CH 2CH=CH 2) 3, wherein Me is a methyl, Ph is that phenyl and Vi are vinyl.
[00128] instantiation of organopolysiloxane includes but not limited to have the siloxanes of following formula:
PhSi (OSiMe 2Vi) 3, Si (OSiMe 2Vi) 4, MeSi (OSiMe 2Vi) 3And Ph 2Si (OSiMe 2Vi) 2, wherein Me is a methyl, Vi is that vinyl and Ph are phenyl.
[00129] organic compound can be any organic compound that each molecule contains at least one aliphatic carbon-to-carbon double bond, and condition is that this compound does not hinder organic siliconresin (A " ") solidify to form silicone resin.This organic compound can be alkene, alkadienes, alkatrienes or polyolefin.And, in acyclic organic cpd, carbon-to-carbon double bond can be positioned at end, side group or be positioned at end simultaneously and the side group position on.
[00130] organic compound can contain the one or more functional groups except aliphatic carbon-to-carbon double bond.The example of suitable functional group includes but not limited to-O-,＞C=O ,-CHO ,-CO 2-,-C ≡ N ,-NO 2,＞C=C＜,-C ≡ C-,-F ,-Cl ,-Br and-I.Can pass through normal experiment, easily be determined at the well-formedness of the specific unsaturated organic compound that uses in the radical-cured silicone composition of the present invention.
[00131] organic compound at room temperature can have liquid or solid-state.In addition, organic compound can be soluble in radical-cured silicone composition before solidifying, and part is solvable or soluble.The normal boiling point of organic compound depends on the quantity and the character of molecular weight, structure and the functional group of compound, and can change in wide scope.Typically, the normal boiling point of organic compound is greater than the solidification temperature of composition.In other cases, can remove the organic compound of significant quantity by volatilization in solidification process.
[00132] example that contains the organic compound of aliphatic carbon-to-carbon double bond includes but not limited to 1,4-divinylbenzene, 1,3-hexadienyl benzene and 1,2-divinyl cyclobutane.
[00133] unsaturated compound can be single unsaturated compound or the mixture that contains two or more different unsaturated compounds, wherein separately as mentioned above.For example, unsaturated compound can be single organosilanes, the mixture of two kinds of different organosilanes, single organopolysiloxane, the mixture of two kinds of different organopolysiloxanes, the mixture of organosilanes and organopolysiloxane, single organic compound, the mixture of two kinds of different organic compounds, the mixture of organosilanes and organic compound, the perhaps mixture of organopolysiloxane and organic compound.
[00134] based on the gross weight of radical-cured silicone composition before solidifying, the concentration of unsaturated compound typically is 0-70% (w/w), perhaps 10-50% (w/w), perhaps 20-40% (w/w).
[00135] preparation contain with the organosilanes and the organopolysiloxane of silicon bonded alkenyl and the method that contains the organic compound of aliphatic carbon-to-carbon double bond be well-known in the art; Many these compounds are commercially available.
[00136] radical initiator free radical photo-initiation or organic peroxide typically.And free radical photo-initiation can be to be radiation following time of 200-800nm can cause any free radical photo-initiation that organic siliconresin solidifies (crosslinked) when being exposed to wavelength.
[00137] example of free radical photo-initiation includes but not limited to benzophenone; 4,4 '-two (dimethylamino) benzophenone; Halogenated benzophenone; Acetophenone; The Alpha-hydroxy acetophenone; Chloroacetophenone, for example dichloroacetophenone and trichloroacetophenone; The dialkoxy acetophenone, for example 2, the 2-diethoxy acetophenone; Alpha-hydroxy alkyl phenones, for example 2-hydroxy-2-methyl-1-phenyl-1-acetone and 1-hydroxycyclohexylphenylketone; The alpha-aminoalkyl benzophenone, for example 2-methyl-4 '-(methyl mercapto)-2-morpholinyl propiophenone; Benzoin; Benzoin ether, for example benzoin methylether, benzoin ethyl ether and benzoin isobutyl ether; Benzil ketals, for example 2,2-dimethoxy-2-phenyl acetophenone; Acylphosphine oxide, for example diphenyl (2,4, the 6-trimethylbenzoyl) phosphine oxide; The xanthene ketone derivatives; Thioxanthone derivates; Fluorenone derivatives; The aminomethyl phenyl glyoxalic acid; Acetonaphthone; Anthraquinone derivative; The sulfonic acid chloride of aromatic compounds; With O-acyl alpha-oximinoketone, 1-phenyl-1 for example, 2-propanedione-2-(O-ethoxy carbonyl) oxime.
[00138] free radical photo-initiation also can be a polysilane, the phenyl methyl polysilane that in U.S. Patent No. 4260780, defines of West for example, its disclosure that relates to the phenyl methyl polysilane at this by with reference to introducing; The amination methyl polysilicon alkane that people such as Baney define in U.S. Patent No. 4314956, its disclosure that relates to amination methyl polysilicon alkane is introduced by reference at this; The methyl polysilicon alkane that people such as Peterson define in U.S. Patent No. 4276424, its disclosure that relates to methyl polysilicon alkane is introduced by reference at this; With the poly-sila styrene that people such as West defines in U.S. Patent No. 4324901, its relate to the poly-cinnamic disclosure of sila at this by with reference to introducing.
[00139] free radical photo-initiation can be single free radical photo-initiation or the mixture that contains two or more different free radical photo-initiations.Based on organic siliconresin (A " ") weight, the concentration of free radical photo-initiation typically is 0.1-6% (w/w), perhaps 1-3% (w/w).
[00140] radical initiator also can be an organic peroxide.The example of organic peroxide comprises peroxidating two fragrant acyls, and for example dibenzoyl peroxide, two pairs of chlorobenzoyls of peroxidating and peroxidating are two-2, the 4-dichloro-benzoyl; Dialkyl, di-t-butyl peroxide and 2 for example, 5-dimethyl-2,5-two (t-butylperoxy) hexane; Peroxidating two aralkyl, for example dicumyl peroxide; The peroxidating alkyl aralkyl, tert-butyl peroxide cumyl and 1 for example, two (t-butyl peroxy isopropyl) benzene of 4-; With peroxidating alkyl virtue acyl, for example t-butyl perbenzoate, t-butyl peroxy-acetate and cross the sad tert-butyl ester.
[00141] organic peroxide can be single peroxide or the mixture that contains two or more different organic peroxides.Based on organic siliconresin (A " ") weight, the concentration of organic peroxide typically is 0.1-5% (w/w), perhaps 0.2-2% (w/w).
[00142] can in the presence of at least a organic solvent, further form radical-cured silicone composition.Organic solvent can be not with organic siliconresin (A " ") or the reaction of extra composition and with organic siliconresin (A " ") miscible any non-proton or dipolar aprotic organic solvent.The example of organic solvent includes but not limited to saturated aliphatic hydrocarbon, for example pentane, hexane, normal heptane, isooctane and dodecane; Clicyclic hydrocarbon, for example pentamethylene and cyclohexane; Aromatic hydrocarbons, benzene,toluene,xylene and 1,3 for example, 5-trimethylbenzene; Cyclic ethers, for example (THF) is with diox for oxolane; Ketone, for example methyl iso-butyl ketone (MIBK) (MI BK); Halogenated alkane, for example trichloroethanes, and halogenated aryl hydrocarbon, for example bromobenzene and chlorobenzene.Organic solvent can be single organic solvent or the mixture that contains two or more different organic solvents, wherein separately as mentioned above.
[00143] based on the gross weight of radical-cured silicone composition before solidifying, the concentration of organic solvent typically is 0-99% (w/w), perhaps 30-80% (w/w), perhaps 45-60% (w/w).
[00144] when by one or more extra composition, when for example radical initiator forms above-described radical-cured silicone composition, can be by in single part, comprising organic siliconresin (A " ") and single part composition of optional ingredients, comprise in two or more parts that perhaps many parts composition of component forms radical-cured silicone composition.
[00145] except above-described silicone composition, other cured silicone composition also are suitable for purpose of the present invention.For example, disclose silicone composition suitable for purpose of the present invention in PCT application No.JP2006/315901, its disclosure that relates to silicone composition is introduced by reference at this.In addition, polysilsesquioxane also can be suitable for purpose of the present invention.
[00146] as mentioned above, reinforced silicone layer 16 comprises fiber enhancer.Fiber enhancer can be fibrous any reinforcing agent.The Young's modulus of fiber enhancer under 25 ℃ typically is 3GPa at least.For example, the Young's modulus of this reinforcing agent under 25 ℃ typically is 3-1000GPa, perhaps 3-200GPa, perhaps 10-100GPa.And the hot strength of reinforcing agent under 25 ℃ typically is 50MPa at least.For example, the hot strength of this reinforcing agent under 25 ℃ typically is 50-10,000MPa, perhaps 50-1000MPa, perhaps 50-500MPa.
[00147] fiber enhancer can be a for example cloth of Woven fabric, and supatex fabric is mat or rove for example; Or the fiber of loose (separately).The shape of the fiber in the reinforcing agent typically is cylindrical and diameter is the 1-100 micron, perhaps 1-20 micron, perhaps 1-10 micron.Loose fiber typically is continuous, this means that fiber extends in the mode that does not rupture usually in whole reinforced silicone layer 16.
[00148] heat treatment of fibre reinforcing agent before using typically is to remove organic pollution.For example, typically in air, in the temperature that raises, for example 575 ℃ are heated suitable time period of fiber enhancer, for example 2 hours down.
[00149] instantiation that is suitable for the fiber enhancer of the object of the invention includes but not limited to contain glass fibre, quartz fibre, graphite fibre, nylon fiber, polyester fiber, aramid fibre, for example
Figure A20088001051000361
With
Figure A20088001051000362
Polyethylene fibre, polypropylene fibre, silicon carbide fibre, alumina fibre, silicon oxide carbide fiber, wire for example steel wire and the combination reinforcing agent.
[00150] as mentioned above, typically adopt silicone composition impregnation of fibers reinforcing agent.Can make in all sorts of ways, adopt silicone composition impregnation of fibers reinforcing agent.For example, aforesaid silicone composition can be applied on the barrier liner, form silicone film.Can use conventional coating technique, for example spin coating, dip-coating, spraying, brushing or screen printing are applied to silicone composition on the barrier liner.Apply silicone composition, its consumption is enough to the impregnation of fibers reinforcing agent.Barrier liner can be any hard or soft material, and this material has the surface that after organic siliconresin solidifies reinforced silicone layer 16 can therefrom be removed under situation about damaging because of delamination not.The example of barrier liner includes but not limited to nylon, PET and polyimides.
[00151] then fiber enhancer is embedded in the silicone film, so form the fiber enhancer of embedding.Can be by simply reinforcing agent being placed on the silicone film, and allow silicone composition dipping reinforcing agent, thus fiber enhancer is embedded in the silicone film.Yet, be appreciated that at first deposit fiber reinforcing agent on barrier liner, then apply silicone composition to fiber enhancer.In another embodiment, when fiber enhancer is to weave or during supatex fabric, can pass silicone composition by making reinforcing agent under the situation of not using barrier liner, flood reinforcing agent with silicone composition.Typically, under room temperature (～23 ± 2 ℃), make fabric pass silicone composition with the speed of 1-1000cm/s.
[00152] fiber enhancer of embedding is outgased.Can place under the vacuum by the fiber enhancer with embedding under the temperature of-60 ℃ of room temperatures (～23 ± 2 ℃), make it the degassing, its time period is enough to remove the air of carrying secretly in the reinforcing agent of embedding.For example, typically, at room temperature, can place 1000-20, under the pressure of 000Pa 5-60 minute, make it the degassing by fiber enhancer with embedding.
[00153] after the degassing, extra silicone composition can be applied on the fiber enhancer of embedding, form the fiber enhancer of dipping.Can use above-described conventional method, silicone composition is applied on the fiber enhancer of the embedding that outgased.Also can occur outgasing and apply the additional cycles of silicone composition.
[00154] the also fiber enhancer of compressible dipping removing excessive silicone composition and/or the air of carrying secretly, and reduces the thickness of the fiber enhancer of dipping.Can use conventional equipment, for example stainless steel rider, hydraulic press, rubber rollers or laminating roll device, the fiber enhancer of compression dipping.Typically under the pressure of 1000Pa-10MPa and room temperature (～23 ± 2 ℃) to 50 ℃ temperatures contract the dipping fiber enhancer.
[00155], and forms reinforced silicone layer 16 at the fiber enhancer that is enough to heating dipping under the temperature of curing silicone compositions.The fiber enhancer of dipping can heat under atmospheric pressure, sub-atmospheric pressure or super-atmospheric pressure.Typically, under atmospheric pressure ,-250 ℃ of room temperatures (～23 ± 2 ℃), perhaps room temperature-200 ℃, the perhaps fiber enhancer of heating dipping under the temperature of room temperature-150 ℃.The fiber enhancer of heating dipping, its time period is enough to solidify (promptly crosslinked) silicone composition.For example, fiber enhancer 0.1-3 hour the time that typically heating is flooded under 150-200 ℃ temperature.
[00156] or, can be under vacuum at 100-200 ℃ temperature and 1000-20, the pressure of 000Pa is fiber enhancer 0.5-3 hour of heating dipping down, forms reinforced silicone layer 16.Can use conventional vacuum bag method, the fiber enhancer of heating dipping under vacuum.In typical method, on the fiber enhancer of dipping, apply bleed (for example polyester), (for example on bleed, be applied with micropore paper, nylon, polyester), apply the vacuum bag film (for example, nylon) of being furnished with vacuum nozzle on the micropore paper having, with this assembly of rubber belt sealing, apply vacuum and (for example, 1000Pa) to the sealing assembly, and heat the sack of finding time as mentioned above.
[00157] thickness of reinforced silicone layer 16 depends on the purposes that composite article 10 is planned.Typically, the thickness of reinforced silicone layer 16 is 1mil at least, is 2-100mil more typically, typically is about 5mil most.
[00158] reinforced silicone layer 16 is adjacent with first window layers 14 and arrange contiguously.More specifically, reinforced silicone layer 16 is adhered on first window layers 14.In one embodiment, as shown in Figure 2, can directly on first window layers 14, form reinforced silicone layer 16.In this embodiment, at least one functional group was in order to adhere on cured silicone composition and reinforced silicone layer 16 to first window layers 14 before silicone composition comprised curing.At least one functional group can be selected from but be not limited to silanol group, alkoxyl, epoxy radicals, hydrosilyl group, acetoxyl group and combination thereof.
[00159] as mentioned above, in order directly on first window layers 14, to form reinforced silicone layer 16, can form the fiber enhancer of dipping as mentioned above.Then, before solidifying the fiber enhancer of dipping fully, the fiber enhancer that floods is placed on first window layers 14.In case the fiber enhancer of dipping places on first window layers 14, the fiber enhancer of heating dipping then is with curing silicone compositions and form reinforced silicone layer 16 and adhere to reinforced silicone layer 16 on first window layers 14.When on first window layers 14, directly forming reinforced silicone layer 16, importantly guarantee to form first window layers, 14 employed first vitreous materials and can tolerate the employed temperature of curing silicone compositions and not have deterioration or distortion.When first vitreous material comprised carbon-based polymer, this was especially suitable.
[00160] in another embodiment, as shown in Figure 3, first pane 12 can further comprise the adhesive phase 26 that places between the reinforced silicone layer 16 and first window layers 14.More specifically, adhere on reinforced silicone layer 16 to first window layers 14 with adhesive phase 26.Adhesive phase 26 typically comprises the siloxy group adhesive; Yet, be appreciated that being suitable for adhering to siloxanes is suitable for purpose of the present invention to any adhesive on glass.The siloxy group adhesive can provide composite article 10 further fire resistances, and this is impossible when being to use main carbon back adhesive.The siloxy group adhesive comprises that typically at least one functional group is used for adhesion agent layer 26 to reinforced silicone layer 16, and on adhesion agent layer 26 to first window layers 14.At least one functional group can be selected from but be not limited to silanol group, alkoxyl, epoxy radicals, hydrosilyl group, acetoxyl group and combination thereof.This siloxy group adhesive is known in the art.The siloxy group adhesive can be singly part or many parts system form provide.In one embodiment, can form adhesive by forming reinforced silicone layer 16 employed identical silicone compositions.
[00161] typically, as shown in Figure 4, first pane 12 further comprises by extra vitreous material and forming and adjacent with reinforced silicone layer 16 and contiguously and the extra window layers 28 of relatively arranging with first window layers 14.That is to say that reinforced silicone layer 16 typically is clipped between first window layers 14 and the extra window layers 28, avoid scratching or other damages with protection reinforced silicone layer 16.Extra window layers 28 can be identical or different with first vitreous material with the identical or different and extra vitreous material of first window layers 14.For example, first window layers 14 can have different thickness with extra window layers 28, and can be formed by aforesaid different vitreous material.
[00162] as shown in Figure 5, first pane 12 can comprise the extra adhesive phase 26 that places between reinforced silicone layer 16 and the extra window layers 28.Adhesive phase 26 as mentioned above.
[00163] composite article 10 further comprises second pane 18.Typically, as shown in Figure 6, second pane 18 comprises second window layers 22 that is formed by second vitreous material.Second window layers 22 can be with first window layers 14 and extra window layers 28 identical or different and second vitreous material can be identical or different with first vitreous material and extra vitreous material.For example, first window layers 14 can have different thickness with second window layers 22 with extra window layers 28, and can be formed by aforesaid different vitreous material.
[00164] second pane can further comprise second siloxane layer 32.Second siloxane layer 32 is typically adjacent with second window layers 22 and arrange contiguously.Second siloxane layer 32 can adhere on second window layers 22 in the mode identical with reinforced silicone layer 16.More specifically, as shown in Figure 6, can directly on second window layers 22, form second siloxane layer 32.Perhaps, as shown in Figure 7, composite article 10 can further comprise the adhesive phase 26 that places between second siloxane layer 32 and second window layers 22.Adhesive phase 26 as mentioned above.Second siloxane layer 32 can further comprise fiber enhancer, with second siloxane layer 32 that can the mode identical with above-described reinforced silicone layer 16 prepares the fibre-bearing reinforcing agent.Perhaps, can under the situation that does not have fiber enhancer, form second siloxane layer 32.Second siloxane layer 32 and reinforced silicone layer 16 can be identical or different aspect the type of the type of thickness, fiber enhancer or cured silicone composition.
[00165] as shown in Figure 8, second pane 18 can further comprise by extra vitreous material and forming and adjacent with second siloxane layer 32 and contiguously and the extra window layers 28 of relatively arranging with second window layers 22.That is to say that second siloxane layer 32 can be clipped between second window layers 22 and the extra window layers 28, avoid scratching or other damages to protect second siloxane layer 32.Another adhesive phase 26 can place between second siloxane layer 32 and the extra window layers 28, to adhere to second siloxane layer 32 and extra window layers 28.
[00166] with reference to figure 1 and 1-A, second pane 18 and first pane 12 separate, to determine the gap 20 between first pane 12 and second pane 18.Composite article 10 further comprises and first pane 12 and second pane, 18 adjacent and window frames 24 that arrange contiguously.First pane 12 is also kept and second pane 18 is in spaced relationship in gap 20 between window frame 24 airtight first panes 12 and second pane 18.Window frame 24 typically is adjacent to arrange with the edge of first pane 12 and second pane 18 and window frame 24 can comprise that the adjacent continuous material that extends uninterruptedly with the edge of first pane 12 and second pane 18 is rectangular.Although show window frame 24 with the form that is retained in the gap 20 in the accompanying drawings, other structures that are appreciated that window frame 24 also are possible, as long as window frame 24 is kept first pane 12 and second pane 18 separates and airtight gap 20.It is also understood that gap 20 can be with the interconnection of ambient air fluid with by airtight gap 20, window frame 24 not necessarily needs seal clearance 20 from surrounding environment.Just because of this, " airtight " gap 20 except comprise fully airtight, comprise that also part is airtight.Therefore, window frame 24 can be discontinuous.Yet in one embodiment, window frame 24 can seal clearance 20.
[00167] in one embodiment, form window frame 24 by adhesive.Just because of this, window frame 24 can directly adhere on first pane 12 and second pane 18.Adhesive can comprise above at adhesive phase 26 described siloxy group adhesives; Yet, be appreciated that being suitable for adhering to any adhesive on glass is suitable for purpose of the present invention.Be used for window frame 24 with the use other materials and compare, use the siloxy group adhesive to be used for the fire resistance that window frame 24 can further improve composite article 10.
[00168] can be rectangular and should rectangularly adhere on first pane 12 and/or second pane 18 by at least one adhesive is provided, form window frame 24.That is to say, typically provide adhesive for about 0.5cm-10cm and length corresponding in first pane 12 or second pane, 18 edge length rectangular at width.Be appreciated that rectangular width depends on the overall dimension of first pane 12 and second pane 18.That is to say that first bigger pane 12 and the second bigger pane 18 can require wide rectangular of the first smaller pane 12 and less second pane 18.Be appreciated that the rectangular window frame 24 that forms of can be by of adhesive continuous rectangular or many adhesives.The thickness of window frame 24 depends on the application that composite article 10 is planned.Window frame 24 typically thickness is the about 5mm of about 0.1mm-, the about 3mm of perhaps about 1mm-.
[00169] or, can form window frame 24 by any non-adhesive material that is suitable for separating first pane 12 and second pane 18.The suitable material that separates first pane 12 and second pane 18 includes but not limited to plastics, timber, paper, metal, foams, adhesive and combination thereof.In this embodiment, window frame 24 typically adheres on first pane 12 and second pane 18 by siloxy group adhesive listed above.Yet, be appreciated that and can use any adhesive.In addition, plastic window frame 24 is with mechanical connection first pane 12 and second pane 18.This structure is known in the art.
[00170] owing to have gap 20 between first pane 12 and second pane 18, so composite article 10 demonstrates good thermal insulation and sound insulation.The width in gap 20 depends on the application that composite article 10 is planned.The width in gap 20 typically is the about 30mm of about 1mm-, the about 25mm of perhaps about 5mm-, the about 20mm of perhaps about 10mm-.In one embodiment, 20 pressure inside can be less than about 0.1atm, so that produce vacuum effectively in gap 20 in the gap.In another embodiment, insulator places 20 inside, gap.Any suitable insulation body of adiabatic and sound insulation that provides known in the art can place 20 inside, gap.For example, insulator can be selected from air, argon gas, helium, nitrogen and combination thereof.
[00171] in another embodiment, as shown in Figure 9, composite article 10 can comprise the 3rd pane 30.The 3rd pane 30 typically comprises the 3rd window layers 36 and the trisiloxanes layer 34 that is formed by the 3rd vitreous material.The 3rd window layers 36 can be identical or different with first window layers 14, the extra window layers 28 and second window layers 22.Equally, the 3rd vitreous material can be identical or different with first vitreous material, the extra vitreous material and/or second vitreous material.The 3rd pane 30 can be independently constructed in the mode identical with second pane 18 with above-described first pane 12.Trisiloxanes layer 34 can further comprise fiber enhancer, with the trisiloxanes layer 34 that can the mode identical with above-described reinforced silicone layer 16 prepares the fibre-bearing reinforcing agent.Perhaps can under the situation that does not have fiber enhancer, form trisiloxanes layer 34.Trisiloxanes layer 34 and reinforced silicone layer 16 and/or second siloxane layer 32 can be identical or different aspect the type of the type of thickness, fiber enhancer or cured silicone composition.
[00172] as shown in Figure 9, the 3rd pane 30 can arrange adjacent with first window layers 14 and contiguously, to provide composite article 10 extra structural rigidity and fire resistance.Be appreciated that composite article 10 of the present invention can further comprise a plurality of extra panes 12,18,30, so that provide composite article 10 extra structural rigidity and fire resistance.
[00173] in another embodiment, as shown in figure 10, the 3rd pane 30 can separate with first pane 12 and second pane 18 and can determine betwixt at least one gap 20.That is to say that composite article 10 can comprise a plurality of gaps 20.Can optionally use extra window frame 24 to keep gap 20.The quantity in gap 20 depends on thermal insulation and sound insulation, structural rigidity, flame performance grade and the requirement of anti-mechanical/thermal impact that composite article 10 is required.Usually, the gap 20 of larger amt provides composite article 10 higher thermal insulation and sound insulation in composite article 10.
[00174] can be at least one pane or the low E coating of internal placement.More specifically, can on the outer surface of at least one pane, arrange low E coating.Perhaps, can for example between window layers and reinforced silicone layer, arrange low E coating at least one pane inside.
[00175] composite article 10 of the present invention has good thermal insulation and sound insulation.More specifically, composite article 10 of the present invention typically has the acoustical ratings of STC 31 (according to ASTME90) at least.Composite article 10 of the present invention typically has at least 0.55 adiabatic grade (measuring with " U value " form) (according to ASTM E2188).
[00176] composite article 10 of the present invention has good fire resistance.More specifically, under the situation that does not have the flexible pipe water impact, according to ASTM E 119-05a; Under situation, according to ASTM E 2010-01 with flexible pipe water impact; With according at least a method among the ASTM E 2074-00, composite article 10 of the present invention typically has at least 30 minutes fire-protection rating.Fire-protection rating is the indication of composite article 10 fire resistances, and is when being exposed to the following time of heat that stove provides, needing cost how long to form measuring of breach in composite article 10.In order to set up fire-protection rating according to ASTM E 119-05a, composite article 10 is installed on the opening of stove, and in stove, start flame, with from room temperature rising stove temperature inside to about 200 °F, and increase the fuel supply of flame gradually, produce predetermined temperature curve, and reach about 1950 temperature at last in about 190 minutes time period.Although in the process under being exposed to heat, in composite article 10, form breach, the employed vitreous material of window layers of formation composite article 10 typically melts and reinforced silicone layer 16 is typically burnt.
When [00177] even in a single day forming breach in composite article 10 of the present invention, therefore composite article 10 can keep tangible structural intergrity owing to have fiber enhancer in reinforced silicone layer 16.More specifically, owing to there is fiber enhancer, so composite article 10 typically do not cave in because of himself weight, and irrelevant with the degree of burning.
[00178] following embodiment is used to set forth the present invention and never is considered as limiting the scope of the invention.
Embodiment 1
[00179] by first pane being provided, separating second pane and window frame adjacent with first pane and that arrange contiguously, forms composite article with second pane to determine gap betwixt with first pane.First pane, second pane and window frame are enclosed in the gap between first pane and second pane.
[00180] more specifically, be that about 0.125 inch annealing flotation glass forms first window layers, second window layers and extra window layers by thickness.First window layers, second window layers and extra window layers have about 6 inches width, about 6 inches length and four edges separately.Before using, wash first window layers, second window layers and extra window layers with suds, use rinsed with deionized water, and dry.
[00181] forms adhesive phase by adhesive.By mixing the polydimethylsiloxane fluid and the 40wt% trimethylsiloxy surface-treated pyrogenic silica of 60wt% ethenyl blocking, poly dimethyl methyl hydrogen-siloxanes that the mole of SiH equates with the mole of vinyl in polydimethylsiloxane fluid, with be 10ppm Pt (0) with the complex form of divinyl tetramethyl disiloxane, the preparation adhesive.This adhesive is available commercially from Dow CorningCorporation of Midland, Michigan.Extrusioning adhesive and partly solidified on PS membrane forms adhesive phase.Peel off this adhesive phase from PS membrane, and adhere on first window layers.
[00182] reinforced silicone layer comprises cured silicone composition and fiber enhancer.Crosslinking agent by phenyl silsesquioxane resin that contains ethenyl blocking and liquid SiH official energy (is available commercially from Dow Corning Corporation of Midland, liquid silicone resin Michigan), formation cured silicone composition.Fiber enhancer comprises Style 106 glass fabrics (being available commercially from BGF Industries of Greensboro, North Carolina, and thickness is about 1.5mil).By the saturated fiber enhancer of mixture, and in baking oven, solidify with organic siliconresin and crosslinking agent, thus the preparation reinforced silicone layer.Reinforced silicone layer is adhered on the adhesive phase relative with first window layers.
[00183] in order to form first pane, extra adhesive phase is adhered on the reinforced silicone layer, and extra window layers is adhered on the extra adhesive phase relative with reinforced silicone layer.Airtight first pane and placing in the baking oven in vacuum bag solidifies under vacuum.Oven temperature raises from environment temperature with about 1 ℃/min, is 130 ℃ up to oven temperature.Oven temperature maintain 130 ℃ following 30 hours.After 30 hours, disconnect baking oven and allow cooling.After cooling, from vacuum bag, take out first pane, cleaning is also dry.First pane can be used G 1/ AFA/G AExpression, wherein G 1=the first window layers, A=adhesive phase (or extra adhesive phase) and F=reinforced silicone layer, and G A=extra window layers.
[00184], prepares the method that adhesive phase lists and prepare adhesive according to above in order to form window frame.With adhesive form the about 2mm of thickness the layer and the cutting store up into four rectangular, wherein each rectangular width is 1cm.Rectangular adjacent with edge first pane and arrange contiguously with these four.
[00185], will contain second pane of second window layers and window frame is adjacent and arrange contiguously, to determine the gap in order to form composite article.Under 150 ℃, under the weight applied pressure seal clearance on the composite article, make composite article annealing 30 minutes.The gained composite article can be represented with following:
G 1/AFA/G A/B/G 2
G wherein 1=the first window layers, A=adhesive phase and F=silicone resin layer, G A=extra window layers, B=window frame, and G 2=the second window layers.
[00186] composite article of embodiment 1 provides according to ASTM E90 and is assessed as the sound insulation of STC31 at least.Under the situation that does not have the flexible pipe water impact, according to ASTM E 119-05a, the composite article of embodiment 1 provides at least 30 minutes fire-protection rating.Fire resistance for the composite article of test implementation example 1 this composite article is installed on the opening of stove, and the one side of composite article is exposed under the ambient atmosphere.With ASTM E 119 described speed heating stoves.
Embodiment 2
[00187] by providing two panes preparing in the mode identical and the window frame of embodiment 1 to form composite article with first pane of embodiment 1.In order to form the composite article of embodiment 2, two panes are separated each other, to determine gap betwixt.Arranging window frame between two panes and window frame being adhered on two panes, to be enclosed in two gaps between the pane.Under 150 ℃, under the weight applied pressure seal clearance on the composite article, make composite article annealing 30 minutes.The composite article of embodiment 2 gained can be represented with following:
G 1/AFA/G A/B/G A/AF 2A/G 2
G wherein 1First window layers of=embodiment 1, the reinforced silicone layer of the adhesive phase of A=embodiment 1 and F=embodiment 1, G AThe extra window layers of=embodiment 1, the window frame of B=embodiment 1, F 2The reinforced silicone layer of=embodiment 1, and G 2Second window layers of=embodiment 1.
[00188] according to ASTM E 90, the composite article of embodiment 2 provides and is assessed as the sound insulation of STC31 at least.Under the situation that does not have the flexible pipe water impact, according to ASTM E 119-05a, the composite article of embodiment 2 provides at least 30 minutes fire-protection rating.With the same way as test fire resistance of listing with embodiment 1.
Embodiment 3
[00189] by the composite article of embodiment 1 is provided, extra reinforced silicone layer and extra window layers form composite article.
[00190] in order to form the composite article of embodiment 3, forms extra window layers in the mode identical with the window layers of embodiment 1.By extra siloxane layer is adhered on the extra window layers by adhesive phase, then another adhesive phase is adhered on the extra siloxane layer relative with extra window layers, preparation contains the layered product of extra window layers and extra siloxane layer.That is to say, between two adhesive phases, arrange extra siloxane layer, and extra window layers adheres on one of adhesive phase.This layered product can be expressed as:
G A/AF 2A
G wherein A=extra window layers, A=adhesive phase, and F 2=extra siloxane layer.
[00191] in order to form the composite article of embodiment 3, this layered product is adhered on the composite article of embodiment 1 by the adhesive phase that freely remains in the layered product.The composite article of embodiment 3 can be expressed as:
G A/AF 2A/G 1/AFA/G A/B/G 2
G wherein A=extra window layers, A=adhesive phase, F 2=extra siloxane layer, G 1=the first window layers and F=reinforced silicone layer, B=window frame, and G 2=the second window layers.
[00192] according to ASTM E90, the composite article of embodiment 3 provides and is assessed as the sound insulation of STC31 at least.Under the situation that does not have the flexible pipe water impact, according to ASTM E 119-05a, the composite article of embodiment 3 provides at least 30 minutes fire-protection rating.With the same way as test fire resistance of listing with embodiment 1,
[00193] obvious, in view of above-mentioned instruction, many modifications of the present invention and variation are possible and can describedly particularly within the scope of the appended claims put into practice the present invention in addition.

Claims (28)

1. composite article, it comprises:
First pane, described first pane comprises:
First window layers that forms by vitreous material; With
Adjacent with described first window layers and arrange and comprise the enhancing siloxane layer of cured silicone composition and fiber enhancer contiguously;
Separate to determine second pane in gap betwixt with described first pane;
Adjacent with described first pane and arrange and be enclosed in the window frame in gap between described first pane and described second pane contiguously with described second pane.
2. the composite article of claim 1, wherein said fiber enhancer are further defined as at least a in Woven fabric, supatex fabric and the loose fiber.
3. the composite article of aforementioned any one claim, wherein said fiber enhancer comprise the fiber that is selected from glass fibre, quartz fibre, graphite fibre, nylon fiber, polyester fiber, aramid fibre, polyethylene fibre, polypropylene fibre, silicon carbide fibre, alumina fibre, silicon oxide carbide fiber, wire and the combination thereof.
4. the composite article of aforementioned any one claim wherein floods described fiber enhancer with described cured silicone composition.
5. the composite article of aforementioned any one claim, wherein said cured silicone composition is further defined as the silicone composition of hydrosilylation cure.
6. the hydrosilylation catalysts that the composite article of claim 5, the silicone composition of wherein said hydrosilylation cure are included in (C) catalytic amount exist (A) organic siliconresin down and (B) consumption each molecule of being enough to solidify described organic siliconresin on average have at least two product with the organic group silicon compound of silicon bonded hydrogen atom.
7. any one composite article of claim 1-4, wherein said cured silicone composition is further defined as condensation cured silicone composition.
8. the composite article of claim 7, wherein said condensation cured silicone composition comprise randomly in the presence of the condensation catalyst of (C ') catalytic amount (A ") have at least two with the organic siliconresin of the hydroxyl of silicon bonding or hydrolyzable groups and randomly (B ') have product with the crosslinking agent of the hydrolyzable groups of silicon bonding.
9. claim 7 or 8 composite article, wherein said condensation cured silicone composition further comprises the inorganic filler of granular form.
10. any one composite article of claim 1-4, wherein said cured silicone composition is further defined as radical-cured silicone composition.
11. at least one functional group was in order to adhere to described cured silicone composition on described first window layers before the composite article of aforementioned any one claim, wherein said silicone composition were included in and solidify.
12. the composite article of claim 11, wherein said at least one functional group is selected from silanol group, alkoxyl, epoxy radicals, hydrosilyl group, acetoxyl group and combination thereof.
13. any one composite article of claim 1-10 further comprises the adhesive phase that places between described reinforced silicone layer and described first window layers.
14. the composite article of claim 13, wherein said adhesive phase comprises the siloxy group adhesive.
15. the composite article of aforementioned any one claim, the width of its intermediate gap is the about 30mm of about 1mm-.
16. the composite article of aforementioned any one claim, wherein in the gap pressure inside less than about 0.1atm.
17. the composite article of aforementioned any one claim, wherein insulator places in the gap.
18. the composite article of claim 17, wherein said insulator are selected from air, argon gas, helium, nitrogen and combination thereof.
19. the composite article of aforementioned any one claim wherein forms described window frame by adhesive.
20. the composite article of aforementioned any one claim, wherein said window frame adhere on described first pane and described second pane.
21. it is adjacent with described reinforced silicone layer and contiguously and the extra window layers of relatively arranging with described first window layers that the composite article of aforementioned any one claim, wherein said first pane further comprise.
22. the composite article of aforementioned any one claim, wherein said second pane comprise second window layers and second siloxane layer adjacent with described second window layers and that arrange contiguously that is formed by second vitreous material.
23. the composite article of aforementioned any one claim further comprises the 3rd pane, described the 3rd pane comprises the 3rd window layers that formed by the 3rd vitreous material and trisiloxanes layer and adjacent with described first window layers and arrange contiguously.
24. any one composite article of claim 1-22, further comprise the 3rd pane, described the 3rd pane comprises the 3rd window layers that formed by the 3rd vitreous material and trisiloxanes layer and separates with described first pane and described second pane and determine betwixt at least one gap.
25. the composite article of aforementioned any one claim, wherein said first vitreous material is selected from polymethyl methacrylate, Merlon and polysulfones.
26. the composite article of aforementioned any one claim, it has at least 30 minutes fire-protection rating according at least a method among ASTM E 119-05a, ASTM E 2010-01 and the ASTM E2074-00.
27. the composite article of aforementioned any one claim further comprises the low E coating that places at least one described pane.
28. the composite article of aforementioned any one claim further comprises the low E coating that places at least one described pane inside.
CN200880010510A 2007-02-22 2008-02-21 Composite article with excellent fire resistance Pending CN101652246A (en)

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