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    • 专利摘要:
    1534709 Heat stable organopolysiloxane composition TORAY SILICONE CO Ltd 3 Dec 1975 [6 Dec 1974] 49627/75 Heading C3T A mixture for imparting heat stability to organopolysiloxanes comprises (1) a reaction product of (a) an alkali metal siloxanolate having from 1 to 3 organic groups attached to each Si through silicon-carbon bonds and containing an average of at least 3 organosiloxane units per molecule, with (b) a cerium salt of an organic carboxylic acid or cerium chloride, the said cerium salt being soluble in an aromatic hydrocarbon solvent or a chlorinated hydrocarbon solvent, and (2) at least one metal compound selected from organic carboxylic acid salts and alkoxy compounds of zirconium, titanium and iron. The organopolysiloxane which is heat stabilized may be a fluid or a silicone rubber stock and is generally an essentially linear diorganopolysiloxane of unit formula R x SiO (4-x)/2 , where R is an alkyl radical of less than 7 carbon atoms, phenyl, a #-perfluoroalkylethyl radical of 3-9 carbon atoms or a C 2 -C 6 alkenyl radical and x is 1À98 to 2À01. The organopolysiloxane composition may also contain inorganic fillers, metal soaps, pigments, vulcanizing agents and crosslinking agents. The alkali metal siloxanolate is preferably prepared by preparing a siloxanolate having alkali metal atoms on each of the terminal siloxane units and then further reacting with a linear diorganopolysiloxane to form a siloxanolate having alkali metal atoms on only one terminal siloxane unit. Suitable organic carboxylic acid cerium salts include cerium-2- ethyl-hexanoate and cerium naphthenate. Suitable Zr, Ti or Fe salts of organic carboxylic acids include those of 2-ethylhexanoic acid, naphthenic acid, oleic acid, lauric acid and stearic acid. In the Examples heat stability mixtures are prepared (1) by mixing either zirconium 2-ethyl hexanoate or tetrabutylzirconate with a reaction product prepared by reacting either cerium 2-ethyl-hexanoate or cerium chloride with a potassium siloxanolate, which siloxanolate has been prepared from KOH, hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane followed by further reaction with a trimethyl silyl-endblocked dimethylpolysiloxane of viscosity 20 c.s. in the presence of hexamethylphosphoramide; or (2) by mixing either tetrabutyltitanate or iron-2-ethylhexanoate with a reaction product obtained by reacting sodium trimethylsilanolate with a trimethyl silyl - endblocked dimethylpolysiloxane (20 c.s.) and then with either cerium chloride or cerium - 2 - ethyl hexanoate. The above heatstability mixtures were used to stabilize dimethylpolysiloxane fluids or a phenylmethylsiloxane-dimethylsiloxane copolymer fluid.
    公开号:SU795497A3
    申请号:SU752195656
    申请日:1975-12-04
    公开日:1981-01-07
    发明作者:Кисимото Кейичи；Кода Есинобу；Сасаки Сосаку；Сузуки Масахико
    申请人:Торей Силиконз Компани Лимитед(Фирма)；
    IPC主号:
    专利说明:

    In order to achieve a homogeneous distribution of the modifying agents in dimethylpolysiloxane, it is preferable to introduce the metal compound in such amounts that the molar ratio of the metal compound to the amount of cerium present in the composition is from 0.5: 1 to 2.0: 1. The composition may also contain inorganic fillers: smoky silica, silica gel, precipitated silica, infusorial earth, ground quartz, may contain such colorants and vulcanizing agents. Sample preparation 1.
    Potassium siloxanol t is prepared as follows.
    100 g of dimethylpolysiloxane with terminal trimethylsiloxy groups having a viscosity of 0.02 Pa-s at 25 ° C, 3.34 g of a solution containing 45 g of CO in 55 g of water, 50 g of toluene and 12.5 g: methyl cellosolve are placed in a mixture of salts equipped with a stirrer, a thermometer and a condenser with a water separator.
    The components are stirred with a stirrer. The temperature of the mixture is slowly increased to and. maintained at 138t3 ° C for 5 hours. A small amount of water is observed to condense in the water trap of the separator.
    The temperature of the mixture is lowered to 125-130 ° C and held at 125-130 for 19 hours. Condensed water is removed, Toluene is distilled off from the reaction product by keeping at 140 + 5 ° C for 2 hours. After cooling, the remaining liquid (t. e. 116 g of siloxanol (potassium) is placed in a polyethylene container, sunk in a stream of dry nitrogen.
     The viscosity of the resulting siloxanol-t .0.0b PaC at 25s, the equivalent of neutralization is 4840, and the water content is less than 0.1% by weight.
    then 67 g of dimethyl polysiloxane having a trimethylsilyl group having a viscosity of 20 cSt, 3 g of hexamethylphosphoramide are mixed with 33 g of potassium siloxanol and the reaction mixture is heated at 115 under nitrogen gas for 1 hour. After that, 120 g of xylene dehydrated and 16 g of 2 - ethylhexanoate cerium is added to the reaction mixture and the reaction is carried out under heating with a vertical condenser for 2.5 hours. The reaction mixture is cooled at room temperature and neutralized with the addition of 2 g of trimethylchlorosilane. The precipitate is removed by filtration, and xylene is distilled off, the resulting reaction product is a light yellow transparent liquid (component 1). The cerium concentration in the resulting product is 1.2%.
    Further 5 weight parts. of zirconium 2-ethylhexanoate solution in ligroin
    (metal salt concentration 53%) was added to 100 parts by weight. the reaction product (component 1) and the mixture is stirred to obtain a homogeneous solution.
    Sample preparation 2.
    To a mixture consisting of 60 g of potassium siloxanol and potassium, obtained as described in the sample preparation method 1 sample and 0.5 g of hexamethylphosphoramide, 120 g of the above trimethylsilyl group dimethyl polysiloxane are added. The mixture is heated for 2 hours under nitrogen. Next, 100 g of the mixture is dissolved in 150 g of isopropyl alcohol and 2.5 g of a solution of anhydrous cerium chloride in alcohol (50 g of ethyl alcohol and 50 g of isopropyl alcohol) are added dropwise to the solution obtained above while. After stirring, the resulting reaction mixture is filtered and the solvent is removed by distillation in vacuo at 40-50 s. The resulting filtrate is again filtered to remove traces of precipitate, and the reaction product is obtained as a light yellow liquid containing 0.8% cerium.
    Next to 100 ses.ch. The resulting reaction product was added with 2.2 parts by weight of tetrabutyl zirconate, and the mixture was stirred until a homogeneous raatvor was obtained.
    Sample preparation 3.
    Sodium trimethylsiloxanol t is prepared according to the procedure described in the preparation of sample 1.
    70 g of sodium trimethylsiloxanol are added to 25 g of toluene. Then, 100 g of dimethylpolysiloxane with a viscosity of 20 cSt and 6.75 g of dimethylformamide are added to the resulting solution. The mixture is heated at 105-110 ° C for 3 hours and 5.25 g of a 2.5% solution of anhydrous cerium chloride in n-butyl alcohol is added dropwise with stirring. Then the reaction mixture is treated according to the method described in the preparation of sample 1. A light yellow liquid containing 1.7% cerium is obtained. To 100 weight.h. 4.1 parts by weight of product obtained are added. tetrabutyl titanium and the mixture is stirred until a homogeneous solution is obtained.
    Sample preparation 4.
    40 g of dimethylpolysiloxaia are mixed with terminal trimethylsiloxy groups with a viscosity of 20 cSt, 2.7 g of dimethylformamide and a solution consisting of 2.8 g of sodium trimethylsiloxanol prepared according to the method of Sample 3, and 10 g of toluene. The reaction mixture is kept at 105-110 ° C for 3 hours, 65 g of xylene and 11.5 g of cerium 2-ethylhexanoate are added and the mixture is heated with a HbJM refrigerator for 3 hours.
    Next, the reaction mixture is cooled to room temperature and neutralized with trimethylchlorosilane. Xylene and dimethylformamide are distilled off in vacuo, the precipitate is filtered off. A liquid product containing 1.3% cerium is obtained.
    Further, 4.7 weight.h. a solution of iron 2-ethylhexanoate in alcohol containing 11% iron was added to 100 weight% of the reaction product. The mixture is stirred until a homogeneous solution is obtained.
    Example. 1 kg of dimethylpolysiloxane with an initial viscosity of 100 cSt is placed in a 2-liter beaker, a. then 64.3 g of sample 1 are injected. A homogeneous transparent solution is obtained - sample 1 a.
    To control 64 g of the reaction product obtained prior to the addition of zirconium 2-ethylhexanoate in the preparation of Sample 1, is introduced into 1 kg of dimethylprylisiloxane with a viscosity of 100 cSt to obtain a homogeneous transparent solution characterizing Sample 16.
    Example 2. 1 kg of dimethylpolysiloxane with a viscosity of 350 cSt is placed in a 2 liter beaker and 96.2 g of the product obtained is added to sample 3 to obtain a homogeneous clear solution (sample 2a).
    Using the same method as described above, 96.0 g of the reaction product obtained prior to the introduction of tetrabutyl zirconate into the product obtained in sample 2 is added to 1 kg of di-methylpolysiloxane with a viscosity of 350 cSt and a homogeneous transparent solution is obtained (sample 2 b ).
    Samples 2a and 2b are placed in a furnace circulating hot air heated to 100 ° C. A white precipitate is formed in the sample 2b after 10 days of heating in the furnace, while in sample 2 a white precipitate appears Only after 21 days in the oven. Example 3. 1 kg copolymer / consisting of 60 mol.% phenylmethylsiloxane and FO mol.% dimethylsiloxane with a viscosity of 350 cSt is loaded into a 2 liter beaker and the product obtained according to sample 3 until a homogeneous clear solution is obtained (sample 3a
    Under the same conditions as described above, 45 g of the reaction product obtained prior to the introduction of tetrabutyl titanate during sample preparation 3 is added to 1 kg of a copolymer of phenylmethylsiloxane and dimethylsiloxane obtained above, and a homogeneous, clear solution is obtained (sample 36).
    Samples 3 a and 3 b are placed in a furnace circulating hot air heated to 100 ° C. A white precipitate appeared in the sample 3 b after a 12-day stay in the oven, and the sample
    3a remained in the oven for 23. more of a white precipitate.
    Example 4. 1 kg dimethylpolysiloxane having in. 100 cSt viscosity, loaded into a 2-liter beaker. As in the previous examples, 59.3 g of sample 4 was quickly dispersed in polysiloxane to obtain a homogeneous transparent mixture (solution) (sample 4 a).
    To control 1 kg of dimethylpolysiloxane with a viscosity of 100 cSt is placed
    15 in a 2. L glass beaker and to it 59 g of the reaction product obtained prior to addition is added. 2-ethylhexganate of iron in the preparation of sample 4, and a clear homogenous solution is obtained (sample 4 b).
    Samples 4 a and 4 b are placed in a room at a temperature of 20-23 ° C and a relative humidity of from 50 to 70%. White precipitate appeared in the sample.
    4b after 67 days, in sample 4 and 5 only after 115 days.
    Example 5. A mixture of 150 g of dimethylpolysiloxane with a viscosity of 100 cSt and 3.3 g of the reaction product obtained prior to the addition of 2-ethylhexanate AO1) Koni, when preparing sample 1, are loaded into a 300 ml beaker to obtain a sample C.
    3.3 g of sample 1 obtained after
    5 additions of zirconium 2-ethylhexanoate are added to 150 g of dimethylpolysiloxane with a viscosity of 100 cSt to obtain sample D.
    4.8 g of the reaction product obtained
    0, prior to the addition of tetrabutyl zirconate in the preparation of sample 2, is added to 150 g of dimethyl polysiloxane with a viscosity of 100 cSt to obtain sample E.
    4.8 g of sample 2, obtained after the addition of tetrabutyl zirconate, is added to 150 g of dimethylpolysiloxane with a viscosity of 100 cSt to obtain sample F.
    2.3 g of the reaction product obtained before the introduction of tetrabutyl titanate in the preparation of sample 3 was added to 150 g of dimethyl polysiloxane with a viscosity of 100 cSt to obtain sample G.
    five
    2.3 g of sample 3 obtained after the introduction of tetrabutyl titanate is added to 150 g of dimethylpolysiloxane: with a viscosity of 100 cSt to obtain sample N.
    0
    3.0 g of the reaction product obtained before the introduction of iron 2-ethylhexanoate in the preparation of sample 4 was added to 150 g of dimethylpolysiloxane with a viscosity of 100 cSt to obtain sample 11.
    3.0 g of the sample 4, obtained after the introduction of iron 2-ethylhexanoate, is added to 150 g of dimethylpolysiloxane, with a viscosity of 100 cSt, to obtain sample K.
    For comparison, 150 g of dimethylpolysiloxane with a viscosity of 100 cSt, free from all additives, are taken from sample L.
    All of these 9 samples are heated for 48 hours in a circulating oven.
    Viscosity at after 48 h heating, 129
    Gel after 24 h heating
    权利要求:
    Claims (2)
    [1]
    1. US Patent No. 3008901, cl. 252-49.7, publ. 1970.
    [2]
    2. German Patent No. 2362954,
    cl. 12 o 5/04, publ. 1974 (prototype).
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    同族专利:
    公开号 | 公开日
    JPS5312541B2|1978-05-01|
    GB1534709A|1978-12-06|
    DE2554498C2|1984-11-29|
    AU8657675A|1977-05-19|
    DE2554498A1|1976-06-10|
    CA1059306A|1979-07-31|
    BE836339A|1976-06-08|
    FR2293462A1|1976-07-02|
    JPS5166344A|1976-06-08|
    FR2293462B1|1978-05-12|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    DE4204200A1|1992-02-13|1993-08-19|Daimler Benz Ag|Liq. useful as heat transfer and insulating media - comprises mixt. of poly-alpha-olefin and/or isoparaffin with poly:di:methyl:siloxane and/or poly:alkyl -/poly:aryl:siloxane|
    US5099006A|1988-01-14|1992-03-24|Rhone-Poulenc Inc.|Alkoxy-type derivative compounds and process for preparing alkoxy-type derivatives of trivalent group 3b metals|
    JP2838208B2|1988-03-29|1998-12-16|東レ・ダウコーニング・シリコーン株式会社|Transparent flame-retardant silicone rubber composition|
    JPH09183904A|1995-12-28|1997-07-15|Toray Dow Corning Silicone Co Ltd|Organopolysiloxane composition|
    JP4565491B2|2003-04-15|2010-10-20|東レ・ダウコーニング株式会社|Thermally conductive addition-curable liquid silicone rubber composition|
    CN113214651A|2013-08-28|2021-08-06|杜邦东丽特殊材料株式会社|Curable silicone composition, cured product thereof, and optical semiconductor device|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP13962274A|JPS5312541B2|1974-12-06|1974-12-06|
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