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WO2015014799A1 - Préparation de polyorganosiloxane pour semi-conducteurs optiques - Google Patents

Préparation de polyorganosiloxane pour semi-conducteurs optiques Download PDF

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Publication number
WO2015014799A1
WO2015014799A1 PCT/EP2014/066189 EP2014066189W WO2015014799A1 WO 2015014799 A1 WO2015014799 A1 WO 2015014799A1 EP 2014066189 W EP2014066189 W EP 2014066189W WO 2015014799 A1 WO2015014799 A1 WO 2015014799A1
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mol
silicon
radicals
bonded
minutes
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English (en)
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Frank Sandmeyer
Klaus Angermaier
Enno Funk
Georg Lößel
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Wacker Chemie AG
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Wacker Chemie AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on 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; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/852—Encapsulations
    • H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins
    • H10W74/476—

Definitions

  • the invention relates to silicone resin compositions and their use for the production of optical semiconductor elements.
  • addition-crosslinking silicone compositions for the manufacture of LEDs. They consist of at least one organopolysiloxane having at least two aliphatically unsaturated groups in the molecule, and at least one organohydrogenpolysiloxane having two or more Si-H groups in the molecule and at least one hydrosilylation catalyst and often further additives.
  • organopolysiloxane having at least two aliphatically unsaturated groups in the molecule
  • organohydrogenpolysiloxane having two or more Si-H groups in the molecule and at least one hydrosilylation catalyst and often further additives.
  • the following examples refer to proposed solutions for reducing gas permeability.
  • EP2399961B1 discloses such addition-crosslinking silicone resin compositions for LED production where at least one antioxidant must be present as a further additive.
  • US20120256325A1 discloses silicone resin compositions comprising an aryl-silicone resin having at least 2 vinyl groups, an addition catalyst, and an organohydrogenpolysiloxane mixture consisting of two different organohydrogenpolysiloxanes having chain-bonded Si-aryl units, the first an organohydrogenpolysiloxane oil with alpha-omega terminal Si-Ii - Groups and the second a monofunctional organopolyhydro- gensiloxan oil with only one terminal Si-H group.
  • a disadvantage of both solutions is their relatively complex composition, the sometimes problematic preparative accessibility and the associated reduced cost-effectiveness.
  • WO2004 / 107458A2 discloses addition-crosslinking organopolysiloxane preparations which may optionally be self-crosslinking containing either self-crosslinking organopolysiloxanes which must contain resin units which contain both aliphatically unsaturated groups and Si-H groups per molecule or an addition-crosslinkable preparation of organopolysiloxanes , which must also contain resin building blocks, as well as a hydrosilylation catalyst.
  • the disadvantage of the preparations described here is that they consist exclusively of oligomeric or polymeric polyorganosiloxanes and thus the setting of certain processing properties, especially the viscosity, which can vary over a wide range depending on the desired processing process, is very difficult.
  • R 1 to R 6 independently of one another, monovalent, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms, an OH group or a hydrogen atom,
  • -M, D, T, and Q is a number from 0 to ⁇ 1
  • R 7 and R 9 independently of one another, monovalent, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms, where R 7 and R 9 are not an alkenyl group, no OH group and no hydrogen atom,
  • -H is a hydrogen atom
  • a Cl to C36 hydrocarbylene group which may be interrupted by heteroatoms, and such radicals 8 are always bonded to the silicon atoms with a carbon-silicon bond, or an oxygen atom,
  • -g and j can be 0, 1, 2 and 3
  • -h and i can be 1, 2 and 3
  • R 10 independently of one another are monovalent, optionally substituted hydrocarbon radicals which may be interrupted by heteroatoms, where R 10 is not an alkenyl group, no OH group and no hydrogen atom,
  • -H is a hydrogen atom
  • the ratio of Si-alkenyl to Si-H is preferably from 0.5: 1 to 2: 1; preferably 0.6: 1 to 1.8: 1, more preferably 0.6: 1 to 1.6: 1, in particular 0.7: 1 to 1.5: 1.
  • the required and preferred amount of B) can thus be determined.
  • Organopolysiloxanes A) preferably have a molecular weight M w of at least 1000, preferably at least 1300, particularly preferably at least 1800, in particular at least 2000 ha- ben, wherein the polydispersity is at most 15, preferably at most 12, more preferably at most 9, in particular at most 6.
  • Organopolysiloxanes A) have viscosities of at least 1500 mPas, preferably at least 2000 mPas, in particular at least 2500 mPas. In a further preferred embodiment, it is highly viscous A) having a viscosity of at least 8,000 mPas, particularly preferably at least 10,000 mPas, in particular at least 12,000 mPas.
  • A) is at room temperature of 23 ° C no longer flowable stable masses with still tacky surface or tack-free solids with a glass transition temperature of more than 25 ° C. All information on viscosity is valid at 25 ° C and at normal pressure of 1013 mbar.
  • Organic groups R 1 to R s may be linear or branched alkyl radicals having preferably 1 to 10 carbon atoms, or alkenyl radicals preferably having 2 to 8 carbon atoms, or aryl radicals having preferably 6 to 8 carbon atoms.
  • the aforementioned may each contain heteroatoms.
  • the heteroatoms may be, for example, oxygen, nitrogen, silicon, phosphorus or halogen, such as F, Cl, Br.
  • Selected examples of alkyl radicals as radicals R 1 to R 6 are the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert.
  • the methyl and ethyl radicals are the preferred alkyl radicals.
  • Selected examples of alkenyl radicals as radicals R 1 to R 6 are the vinyl radical which may optionally be substituted, the allyl radical, the butenyl radical, the pentenyl radical, the hexenyl radical, the heptenyl radical, the octenyl radical or the cyclohexenyl radical.
  • the vinyl radical is the preferred alkenyl radical.
  • aryl radicals as radicals R 1 to R 6 are phenyl radical, tolyl radicals, xylyl radicals and ethylphenyl radicals, and aralkyl radicals, such as the benzyl radical and the ⁇ -phenylethyl radical.
  • the molar ratio of the silicon-bonded alkenyl groups carrying repeating units to the silicon-bonded hydrogen atoms carrying repeating units in A) is at least 0.75, preferably 0.8, more preferably 0.9.
  • the molar fraction of the silicon atoms carrying at least one aryl radical relative to the total number of silicon atoms in A) is at least 30%, preferably at least 40%, in particular at least 50%.
  • the molar fraction of the alkyl groups in the total number of silicon-bonded radicals in A) is at most 70%, preferably at most 65%, particularly preferably at most 60%, in particular at most 55%.
  • the molar fraction of the OH groups in the total number of silicon-bonded radicals in A) is at most 3%, preferably at most 2.5%, particularly preferably at most 2.0%, in particular at most 1.5%.
  • the molar fraction of hydrogen groups in the total number of silicon-bonded radicals in A) is 0.1-45%, preferably 1 - 42%, more preferably 2 - 39%, in particular 2.5 - 36%.
  • the determination is carried out by means of 9 Si NMR spectroscopy.
  • the molar proportion of vinyl groups 2 - 45% is preferably 4 - 42%, particularly preferably 6 - 39%, in particular 8 - 36%.
  • the determination is carried out by 29 Si NMR spectroscopy.
  • the partial units (R 1 R 2 R 3 Si0 1/2) M according to the general formula (I) in A) is at most 55 mol% present, preferably at most 50 mol%, particularly preferably at most 45 mol%, in particular at most 40 mol%.
  • the radicals R 1 R 2 R 3 are preferably not an aryl group.
  • the partial units (R 4 R 5 Si0 2/2) D according to the general formula (I) in A) is at most 80 mol% present, preferably at most 70 mol%, particularly preferably at most 65 mol%, in particular at most 60 mol%.
  • radicals R 4 R 5 are preferably H, methyl, phenyl, vinyl, methoxy, phenoxy. Particularly preferred are as embodiments of the invention are: (CH 3) 2 Si0 2/2, (CH 3) (C e H 5) Si0 2/2, (CH 3) (H) Si0 2/2.
  • R 6 Si0 3/2) T in accordance with the general formula (I) in A) at least 10 mol% are present, more preferably at least 20 mol%, especially at least 25 mol%.
  • R 6 is an aryl group and not a hydrogen atom and no alkenyl group.
  • aryl group R s the phenyl radical is particularly preferred.
  • at least 1 is preferably present in A), with an aryl radical as R 6 , preferably phenyl radical.
  • the partial units (Si0 4/2) Q of the general formula (I) are present in A) at most to 20 mol%, particularly preferably at most 15 mol%, more preferably no such subunits in A) are present.
  • A) can be prepared from commercially available educts such as alkoxysilanes, chlorosilanes, or combinations thereof, and further using short-chain organosiloxanes. These methods include selection and appropriate combination of hydrolysis, condensation, and equilibration reactions.
  • Possible production processes are discontinuous stirring processes, continuous stirred-tank cascade processes, quasi-continuous processes by interconnecting continuous processes with discontinuous process steps, continuous processes, such as those in loop reactors or column reactors, which can be designed as double-loop or double-column processes by interconnecting several plants.
  • combinations of a loop reactor and a column reactor are conceivable.
  • a preparation process converts alkoxysilanes, optionally in admixture with short-chain organosiloxanes, in a first reaction step via an acidic hydrolysis, and then condenses optionally stepwise or continuously.
  • the reaction mixture is neutralized either by neutralizing the acid or by neutral washing with demineralized water, and then isolating to the desired purity by a suitable combination of the steps of distillation and filtration.
  • Residues R 7 , R 9 , R 10 of the Si-H coupler B) are linear or branched alkyl radicals having preferably 1 to 10 carbon atoms, they may each contain heteroatoms.
  • the heteroatoms may be, for example, oxygen, nitrogen, silicon, phosphorus or halogen, such as F, Cl, Br.
  • alkyl radicals as R 7 , R 9 , R 10 correspond to those mentioned under R 1 to R 6 .
  • the most preferred radical for R 7 , R 9 and R 10 is the methyl radical.
  • the radicals R 8 are substituted or unsubstituted hydrocarbylene radicals, ie divalent and optionally heteroatom-containing hydrocarbon radicals.
  • Examples of preferred alkylene and arylene radicals R 8 are the methylene radical -CH 2 -, the ethylene radical -CH 2 -CH 2 -, the propylene radical - (CH 2 ) 3 -, the butylene radical - (CH 2 ) 4 -, the pentylene radical - (CH 2 ) 5 -, the hexylene radical - (CH 2 ) 6 -, the octylene radical - (CH 2 ) 8 -, and the associated isomeric alkylene radicals, cycloalkylene radicals such as the cyclohexylene radical and substituted cyclohexylene radicals, arylene radicals such as the ortho, meta- or para-phenylene radical -
  • x is an integer from 0 to 8.
  • radical R 8 may represent an oxygen atom. Particularly preferred is the para-phenylene radical for R 8 .
  • Si-H couplers (B) according to formula (III) the following organosiloxanes:
  • the Si-H couplers B) according to formula (III) act like a point crosslinker and bring more hardness into the cured molecular structure than the Si-H couplers B) according to formula (II), especially if they are silicon-bonded Contain hydrogen atoms.
  • Si-H coupler B) according to formula (III) with the very high Si-H functional density of 4 Si-H groups per organosiloxane molecule are very well suited to crosslink high molecular weight A) with low vinyl group number to hard moldings , For this reason, the Si-H couplers B) according to formula (III) are particularly preferred for such applications.
  • Suitable catalysts C) all compounds can be used which promote the attachment of silicon-bonded hydrogen to aliphatic double bonds.
  • platinum metals it is preferably a metal from the group of platinum metals or a compound or a complex from the group of platinum metals.
  • catalysts are metallic and finely divided platinum, which may be supported on supports such as silica, alumina or activated carbon, compounds or complexes of platinum such as platinum halides, eg PtCl 4 , H 2 PtCl 6 .6H 2 O, Na 2 PtCl 4 .4H 2 0, platinum olefin complexes, platinum alcohol complexes, platinum alkoxide complexes, platinum ether complexes, platinum aldehyde complexes, platinum ketone complexes, including reaction products of H 2 PtCl 6 x6H 2 0 and cyclohexanone, platinum vinyl siloxane complexes such as platinum 1, 3 divinyl-1, 1, 3, 3-tetramethyldisiloxane Complexes with or without content of detectable inorganic bound halogen, bis (gamma-picoline)
  • the catalyst is preferably present in the formulations according to the invention in amounts of from 5 to 2000 ppm by weight (parts by weight per million parts by weight), preferably in amounts of from 10 to 1000 ppm by weight, in particular in amounts of from 15 to 500 ppm by weight , calculated in each case as elemental platinum and based on the total weight of the polyorganosiloxanes A), B) and the organosiloxanes and / or organosilanes C).
  • the catalyst used is preferably the Karstedt catalyst (US Pat. No. 3,775,452), which has long been known in the literature and whose active species are described in the Comprehensive Handbook of Hydrosilylation Editor Bogdan Marciniec, Pergamon Press 1992
  • the addition-crosslinking silicone resin composition according to the invention may contain as further optional constituent at least one flexiopolymer D) of the general formula (IV)
  • At least one aryl group as R 12 or R 13 is included.
  • T * is to be kept as small as possible.
  • radicals R 11 'R 12 and R 13 are the same as those already mentioned for R 1 , with the exception that they can not be a hydrogen atom atom.
  • R 11 is preferably an alkenyl, particularly preferably a vinyl radical. Radicals R 11 can be bonded both terminally in D) and chainwise, it being preferred that the R 11 radicals are terminal and more preferably only terminally bonded radicals R 11 are present in D). In a particularly preferred embodiment of the invention, D) has two terminally bonded radicals R 11 , one of the two radicals R 11 being bonded to one terminal silicon atom in each case.
  • radicals R 12 are alkyl and aryl radicals. It is particularly preferred that the radicals R 12 are methyl, ethyl or phenyl radicals, in particular methyl and phenyl radicals. It is particularly preferred that of two radicals R 12 which are bonded to the same silicon moieties, at most only one represents a phenyl radical and the other represents an alkyl radical, preferably a methyl radical. Two radicals R 12 which are bonded to the same silicon atom may represent two identical or different alkyl radicals, it being particularly preferred that in the case of two alkyl radicals, these are methyl radicals.
  • radicals R 13 alkyl or aryl radicals, with aryl radicals being particularly preferred, in particular the phenyl radical.
  • D) consists of at least 3 Si repeating units, preferably at least 5 Si repeating units, particularly preferably at least 8, in particular at least 10 Si repeat units according to the general formula (IV).
  • Suitable flexopolymers D) according to the general formula (IV) are given below, the list being given only by way of example for the invention and not by way of limitation:
  • the indices indicate how often each unit is present in the polyorganosiloxane.
  • the linear flexopolymers D) serve for flexibilization in the silicone resin composition according to the invention. They react as a result of their alkenyl groups R 11 , with Si-H groups of the organopolysiloxanes A) and the Si-H coupler B). In this way, hard resin molecules are bridged with flexibilizing chain segments. D) can be used in the silicone resin composition according to the invention in addition to the flexibilization, and also to the viscosity Adjustment can be used, which can lead to both an increase and a reduction in viscosity.
  • a component contains the catalyst to suppress an undesirably early start of the curing reaction, eg, during storage.
  • the use of D) is unnecessary if both the flexibility and the viscosity meet the desired property. If D) is present, then 5 to 200 parts D) are used, preferably 5 to 150 parts, more preferably 5 to 100 parts, in particular 10 to 80 parts, based on 100 parts A).
  • the addition-crosslinking silicone resin composition according to the invention may comprise further constituents E) which are known to the person skilled in the art.
  • Typical representatives are inhibitors, reinforcing and non-reinforcing fillers, plasticizers, adhesion promoters, soluble dyes, inorganic and organic pigments, fluorescent dyes, solvents, fungicides, perfumes, dispersing aids, rheological additives, corrosion inhibitors, light stabilizers, heat stabilizers, flame retardants, agents for Influence on the electrical properties and means for improving the thermal conductivity.
  • the invention further provides a process for the preparation of the addition-crosslinking silicone resin compositions according to the invention by mixing all components A), B), C) and, if desired, further optional constituents D) and / or E). While the order of mixing ingredients (A), (B) and (C) and other optional ingredients D) and / or E) is not critical, it has been found useful to include catalyst (C) in the mixture of the other ingredients last to be added.
  • Another object of the invention is the use of the silicone resin compositions according to the invention as casting compounds for the production of moldings, or encapsulations in electrical and electronic applications such as LEDs. After filling the desired molds, the subsequent curing takes place at elevated temperature.
  • the crosslinking of the silicone resin compositions according to the invention is preferably carried out at 70 to 170.degree. C., preferably at 100 to 150.degree.
  • energy sources for the crosslinking by heating preferably ovens, eg convection drying cabinets, heating channels, heated rollers, heated plates or heat rays of the infrared range are used.
  • the crosslinking times are preferably 0.5 to 10 hours, preferably 1 to 6 hours.
  • Shaped bodies produced in this way are, provided that no further additives have been mixed in, crystal clear and have a refractive index of at least 1.50, preferably at least 1.60.
  • the shaped bodies produced in this way have, after complete curing, without further additives, such as e.g. Fillers or
  • Plasticizer a Shore D hardness of at least 5, preferably at least 7, preferably in the range of 8 to 65, in particular in the range of 10 to 60 on.
  • the Shore D hardness is determined according to DIN (German Industrial Standard) 53505 (or ASTM D 2240 or ISO 868). This standard also contrasts the Shore D hardness to Shore A.
  • the shaped bodies On account of their temperature and UV resistance, the shaped bodies also show their abilities after 40,000 hours even with HB LEDs (high-brightness LEDs) and LEDs emitting short-wavelength light (380-450 nm) or white light. the operating time no drop in light transmission.
  • the inventive compositions can be used.
  • the silicone resin compositions according to the invention can also be used, for example, for coatings and impregnations or can also be used as additives in other compositions.
  • the refractive indices are determined in the wavelength range of visible light, unless otherwise stated at 589 nm at 25 ° C and normal pressure of 1013 mbar according to the DIN standard
  • the transmission is determined by UV VIS spectroscopy.
  • a suitable device is, for example, the Analytik Jena Specord 200.
  • the measurement parameters used are range: 190-1100 nm
  • Increment 0.2 nm, integration time: 0.04 s, measurement mode:
  • the first step is the reference measurement (background).
  • a quartz plate attached to a sample holder (dimension of the quartz plates: HxB approx. 6 x 7 cm, thickness approx. 2.3 mm) is placed in the sample beam path and measured against air. Thereafter, the sample measurement takes place.
  • compositions are determined by nuclear magnetic resonance spectroscopy (for terms, see ASTM E 386: High Resolution Magnetic Resonance Imaging (NMR): Terms and Symbols), where the 1 H and 29 Si nuclei are measured.
  • Spectrometer Bruker Avance I 500 or Bruker Avance HD 500
  • Probe head 5 mm BBO probe head or SMART probe head (Bruker) Measuring parameters:
  • Pulprog zg30
  • NS 64 or 128 (depending on the sensitivity of the sample head)
  • Sample head 10 mm 1 H / 13 C / 15 N / 29 Si glass-free QNP probe head (Bruker)
  • Pulprog zgig60
  • Molecular weight distributions are determined as weight average M w and as number average M n, using the method of gel permeation chromatography (GPC or Size Exclusion Chromatography (SEC)) with polystyrene standard and refractive index detector (RI detector). Unless otherwise stated, THF is used as the eluent and DIN 55672-1 is used. The polydispersity is the quotient Mw / Mn.
  • the glass transition temperature is determined by differential scanning calorimetry (DSC) according to DIN 53765, perforated crucible, heating rate 10 K / min.
  • Me 2 correspondingly means two methyl radicals.
  • An essential property of the preparations according to the invention is that it has self-crosslinkable, branched polyorganosiloxane components.
  • the syntheses of such products are described below:
  • Examples 1-11 describe various processes for the preparation of branched, self-crosslinking organopolysiloxanes A).
  • CH methyldichlorosilane
  • the exotherm of the reaction leads to a temperature increase of not more than 47 ° C.
  • the mixture is left to stir for 30 minutes and then to settle for 30 minutes without stirring, so that the phases can separate.
  • 24 kg of hydrochloric acid aqueous phase are then separated off.
  • 12 kg of demineralized water are added to the organic phase, the mixture is stirred for 30 minutes and left to stand for 30 minutes without stirring, so that the phases can separate.
  • the water phase is separated and the organic phase washed in the same way three times with 12 kg of deionized water. Following the last wash, the organic phase is heated to 80 ° C, the apparatus is evacuated to 150 mbar internal pressure.
  • R is mainly ethyl, as well as hydrogen.
  • the silanol content can only be estimated roughly and is, according to estimate from the ⁇ "H-NMR spectrum about 6500 ppm because of overlapping signals.
  • the phases are allowed to separate within 40 minutes without stirring.
  • the lower hydrochloric acid aqueous phase is separated off.
  • 500 g of deionized water are added, stirred for 10 minutes, 45 minutes without stirring separate phases and the water phase separated again.
  • the HCl content in the organic phase is less than 5 ppm.
  • the organic phase is concentrated on a rotary evaporator at 150 ° C oil bath temperature and 10 mbar vacuum for 30 minutes, and then increases the pressure of 10 to 20 mbar and the oil bath temperature of 150 ° C to 160 ° C.
  • the mixture is distilled for a further 3 hours and receives a colorless liquid product having a viscosity of 4510 mPas, a density (according to DIN 51757) of 1.161 g / cm 3 , a flash point (DIN 2719) of 178, 5 ° C and an ignition point EN 14522 from 430 ° C.
  • the APHA color number is 12, the total chlorine content is 13 mg / kg.
  • the silanol content which can only be estimated from signal overlays, is about 6400 ppm.
  • the vinyl content is 1.92 mmol / g, the silicon-bonded hydrogen content 2.16 mmol / g.
  • the molar composition is:
  • the reaction mixture is heated to 60 ° C. with a heating hood, then the heating is switched off, the heating hood not yet being removed.
  • the temperature continues to rise as a result of the exothermic reaction and reaches 78 ° C. after a short time, during which the mixture becomes clear and homogeneous. Then it cools down again.
  • the mixture is heated until reflux is reached (82 ° C. in the reaction mixture) and kept at this temperature for 30 minutes.
  • the reaction mixture turns milky white.
  • the mixture is heated for 1 hour at reflux, which sets from 98 ° C bottom temperature. Then 450 g of toluene and 300 g of demineralized water are added, mixed well and then cooled. let the phases separate. The hydrochloric acid aqueous phase is removed.
  • the organic phase is washed by adding 500 g of deionised water. The mixture is stirred, heated to 50 ° C and then turned off the stirrer. After resting for 15 minutes, the phases are separated and the aqueous phase is removed.
  • the organic solvent is then partially removed by distillation.
  • the silanol content is only approximate in 1 H-NMR due to signal overlays and is about 2200 ppm.
  • the vinyl content is 1.89 mmol / g, the silicon-bonded hydrogen content 0.25 mmol / g.
  • the molar composition is:
  • R is mainly ethyl, as well as hydrogen.
  • the mixture is heated to reflux after the end of the dosing (bottom temperature 81 ° C., head temperature 79 ° C. and reflux for 30 minutes).
  • the reaction mixture is whitish cloudy.
  • the silanol content is only approximate in 1 H-NMR due to signal overlays and is about 4200 ppm.
  • the vinyl content is 2.33 mmol / g, the content of silicon-bonded hydrogen 0.57 mmol / g.
  • the molar composition is:
  • R is mainly ethyl, as well as hydrogen.
  • the mixture is heated for 30 minutes at reflux (temperature of the mixture 84 ° C) and receives a whitish cloudy mixture.
  • the organic phase is concentrated by distilling off 886 g of toluene.
  • the silanol content is only approximate in ⁇ -MR due to signal overlays and is about 5500 ppm.
  • the vinyl content is 1.59 mmol / g, the silicon-bonded hydrogen content 0.37 mmol / g.
  • the molar composition is:
  • R is mainly ethyl, as well as hydrogen.
  • Example 4 The further treatment is carried out analogously to Example 4, wherein in each case half the amounts of toluene and water are used.
  • the silanol content is only approximate in 1 H-NMR due to signal overlays and is about 18800 ppm.
  • the vinyl content is 1.79 mmol / g, the silicon-bonded hydrogen content 0.60 mmol / g.
  • the molar composition is:
  • R is mainly ethyl, as well as hydrogen.
  • EXAMPLE 7 16116 g of water, 12240 g of toluene, 5436 g of ethyl acetate and 3108 g of a short-chain, alpha, omega-silanol-functional phenylmethyl oil having the average composition: HO-Si (Me) (Ph) are introduced into a 60 1 glass stirrer.
  • the mixture is then distilled off at atmospheric pressure up to a temperature of 124 ° C., giving 9543 g of distillate and 14,125 g of bottom residue.
  • the silanol content is only approximate in 1 H-NMR due to signal overlays and is about 10052 ppm.
  • the vinyl content is 1.30 mmol / g, the silicon-bonded hydrogen content 1.44 mmol / g.
  • the molar composition is:
  • the silanol content which can only be estimated from signal overlays, is about 10030 ppm.
  • the vinyl content is 0.95 mmol / g, the content of silicon-bonded hydrogen 1.02 mmol / g.
  • the molar composition is:
  • the residue is filtered through a hot water-heated pressure filter chute over a Seitz K 100 filter plate with Seitz filter aid FF.
  • PhSi0 3/2 42.5% where R is mainly ethyl, as well as hydrogen.
  • the silanol content can only be approximately estimated from signal overlays and is estimated to be about 6674 ppm from the 1 H NMR spectrum.
  • the content of vinyl groups is 0.95 mmol / g according to X H-NMR, and the content of silicon-bonded hydrogen is 1.29 mmol / g.
  • Example 10
  • mol% PhSi0 is 3/2 units, wherein the ethoxy and hydroxy groups distributed to the specified structural units, weighed and stirred at 60 ° C until the phenylsilicone has dissolved in phenyltriethoxysilane.
  • 129 g of 1, 3-divinyl-1,1,3,3-tetramethyldisiloxane are successively added first to the preparation thus obtained
  • the silanol content is only approximate in 1 H-NMR due to signal overlays and is about 2200 ppm.
  • the vinyl content is 1.17 mmol / g, the silicon-bonded hydrogen content 0.92 mmol / g.
  • the molar composition is:
  • Example 11 Procedure as in Example 12 with the difference that instead of the linear phenylmethylpolysiloxane having an average of 16 repeating units, a short-chain, alpha, omega-silanol-functional phenylmethyl oil having the average composition is used: HO-Si (Me) (Ph) [O] Si (Me) (Ph) 4 OSi (Me) (Ph) OH, that is a total of 6
  • the solids content is determined to be 89.2% by weight (1 g of the substance was heated to 200 ° C. for half an hour and the residue was determined gravimetrically).
  • the silanol content is in the "" "H-NMR due to overlapping signals only approximate and is about 10100 ppm.
  • the vinyl content is 1.30 mmol / g, the content of silicon-bonded hydrogen 1 14 mmol / g.
  • the molar composition is:
  • R is mainly ethyl, as well as hydrogen.
  • silicone resin compositions examples:
  • the resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for molding first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.
  • the resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.
  • the resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.
  • the 6 mm thick specimen After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 26 Shore D. The transmittance at 550 nm was 97.2%.
  • Example 4 Preparation with Resin According to Example 4 75.2 g (solids content: 60 g) of a 79.8% strength toluene solution of the resin described in Example 4, 40.0 g of a linear siloxane copolymer which, according to 29 Si NMR spectrum has an average of 60 phenylmethylsiloxane units, 12 dimethylsiloxane units and 2 dimethylvinylsiloxane end groups and 10.8 g of 1, 4-bis (dimethylsilyl) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0 , 0026 g of a platinum (0) / sym.
  • Tetramethyldivinyldisiloxan complex (Karstedt catalyst) containing 20 wt .-% of platinum, calculated as elemental metal, homogeneously mixed.
  • the formulation had a refractive index of 1.5273.
  • the resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.
  • the 6 mm thick specimen After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 14 Shore D. The transmission was at 550 nm at 98.4%.
  • the resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for molding first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.
  • the resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.
  • the 6 mm thick specimen After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 37 Shore D. The transmission was 98.1% at 550 nm.
  • Example 7 Preparation with Resin According to Example 7 100.0 g of the liquid resin described in Example 7 and 5.0 g of 1,4-bis (dimethylsilyl) benzene and 0.026 g of an 80% solution of 1-ethynylcyclohexanol in trimethylsilanol and 0.0026 g of a platinum (0) / sym. Tetramethyldivinyldisiloxan complex (Karstedt catalyst) containing 20 wt .-% of platinum, calculated as elemental metal, homogeneously mixed. The formulation had a refractive index of 1.5290.
  • the mixture thus obtained is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth, and the closed stainless steel mold for molding is initially for 15 minutes at 165 ° C and a pressure of 5.45 MPa in vulcanised in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.
  • the 6 mm thick specimen After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 21 Shore D. The transmission was 98.3% at 550 nm.
  • the resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.
  • the 6 mm thick specimen After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 17 Shore D. The transmission was 98.0% at 550 nm.
  • the resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for molding first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.
  • the resulting mixture is poured into a Teflon-coated stainless steel mold of 2 mm depth and a recess of 6 mm depth and vulcanized the closed stainless steel mold for shaping first 15 minutes at 165 ° C and a pressure of 5.45 MPa in a laboratory press. The rest of the curing then takes place without pressure for 6 hours at 150 ° C. in a circulating air drying cabinet.
  • the 6 mm thick specimen After a conditioning time of 16 hours at room temperature, the 6 mm thick specimen had a hardness of 15 Shore D. The transmission was at 97.8% at 550 nm.

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Abstract

L'invention concerne des compositions de résine de silicone et leur utilisation pour la fabrication d'éléments semi-conducteurs optiques.
PCT/EP2014/066189 2013-08-01 2014-07-28 Préparation de polyorganosiloxane pour semi-conducteurs optiques Ceased WO2015014799A1 (fr)

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CN110791101A (zh) * 2019-11-19 2020-02-14 广州信粤新材料科技有限公司 一种有机硅防水耐老化材料及其制备方法

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