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    Silicone isocyanates
    29.
    发明授权
    Silicone isocyanates 失效
    有机硅异氰酸酯

    公开(公告)号：US3170891A

    公开(公告)日：1965-02-23

    申请号：US22380162

    申请日：1962-09-14

    Applicant: DOW CORNING

    Inventor： SPEIER JOHN L

    IPC: C07F7/08 ,  C07F7/18 ,  C08G18/71 ,  C08G18/77 ,  C08G77/00 ,  C08G77/26 ,  C08G77/48

    CPC classification number: C08G77/00 ,  C07F7/0818 ,  C07F7/0829 ,  C07F7/0834 ,  C07F7/0852 ,  C07F7/182 ,  C08G18/718 ,  C08G18/778 ,  C08G77/26 ,  C08G77/48

    Abstract: The invention comprises compounds of the general formula and silanes of the formula wherein each R is a divalent radical free from aliphatic unsaturation and is a hydrocarbon radical or a hydrocarbon ether radical having not more than one oxygen atom attached to any one C atom therein, each R1 is a monovalent hydrocarbon or halohydrocarbon radical free from aliphatic unsaturation, each R11 is divalent oxygen or R or haloarylene radical, X is a hydrocarbon radical, preferably lower alkyl, m has a value from greater than 0 to 1, n is 0, 1, 2 or 3, such that the sum of m + n averages at least 1 in the molecule, and s is 0, 1 or 2. When m is 1 and n is 3, the compound is a silane; when m is 1 and n is 2, the compound is a disilylcarbane, a disiloxane or a disilylcarbane ether; and when m is 1 and n is less than 2, a polymer is obtained. The compounds may be made either (1) by reacting with an alkenyl isocyanate or an alkenyl isocyanate ether, usually in the presence of a Pt catalyst, or (2) by reacting with to yield the product which decomposes on heating to yield phenol and the desired compound. The silanes can be made by these methods, though the second method is restricted to phenoxy silanes because of the probability of phenol interchange if other hydrocarbonoxy radicals are present. The isocyanates are stable in the absence of moisture, but polymerize on exposure to moisture. Fillers, e.g. C-black, silicas (fume, aerogel, xerogel and treated), powdered metals, metal oxides and carbonates, talc, wood flour and asbestos, pigments and other additives may also be added. Examples are given of the above preparation of (1) which reacted spontaneously with to yield an organosilicon-urea polymer; (2) which reacted with ethylene diamine at room temperature to yield a gel urea structure; (3), (7) various silane and siloxane isocyanates. In further Examples (5) a siloxane diisocyanate was reacted with a polyether to yield a foamed polyurethane; (6) the isocyanate of Example (2) was reacted with a hydroxy-terminated dimethylpolysiloxane; and (8) a silane of the formula was reacted with and the product heated to expel phenol to yield Uses.-As caulking, sealing and coating compositions. The isocyanates are useful as catalysts in siloxane polymerization reactions, as described in Specification 836,954. They may also be reacted with hydroxylated polyethers to provide silyl methane end-groups which may be polymerized or with polyesters to prepare polyurethanes, or in the preparation of organosilicon-urethane copolymers as disclosed in Specification 1,006784. The compounds can also be reacted with organic or organosilicon compounds containing active hydrogen.

    Nitrogen-containing cyclic silanes, their preparation and hydrolysis
    30.
    发明授权
    Nitrogen-containing cyclic silanes, their preparation and hydrolysis 失效
    含氮环状硅烷，其制备和水解

    公开(公告)号：US3146250A

    公开(公告)日：1964-08-25

    申请号：US14429761

    申请日：1961-10-11

    Applicant: DOW CORNING

    Inventor： SPEIER JOHN L

    IPC: C07F7/08 ,  C07F7/10 ,  C08G18/10 ,  C08G77/00 ,  C08G77/26 ,  C23F11/14

    CPC classification number: C23F11/149 ,  C07F7/0854 ,  C07F7/0874 ,  C07F7/10 ,  C08G18/10 ,  C08G77/00 ,  C08G77/26 ,  C08G18/38

    Abstract: The invention comprises cyclic silanes of general formula and also siloxanes and copolymeric siloxanes thereof, wherein R is a monovalent substituent which is hydrogen, a hydrocarbon radical, a hydrocarbon radical containing oxygen in the form of an ether linkage, an amino-alkyl, aminophenyl, halogenophenyl or an organosilyl radical of general formula (XR1)Y2Si-, wherein each Y is a monovalent hydrocarbon radical and X is a chlorine, bromine, iodine or hydrogen atom, each R1 is a divalent saturated aliphatic hydrocarbon radical wherein the silicon atom is attached to a carbon atom which is at least the third and not more than the sixth carbon atom away from the other substituent attached to R1 and each R11 is a monovalent substituent which is a hydrocarbon radical, a hydrocarbon radical containing oxygen in the form of ether linkages, an alkoxy radical, an aliphatic saturated radical bonded to silicon through a C-O-Si linkage containing oxygen in the form of ether linkages or a phenoxy radical. R may be hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl, ethoxymethyl, ethoxyethyl, methoxyphenyl, aminomethyl, aminoethyl, aminohexyl, aminooctyl, aminophenyl, p-chlorophenyl and m-bromophenyl. R1 may be radicals containing 3 to 6 methylene groups which may be substituted by methyl or ethyl groups. R11 may be methoxy, ethoxy, butoxy, -OCH2CH2OCH3, -OCH2 CH2CH2OCH2CH3, OCH2OCH2CH3 or phenoxy. Preferably, the nitrogen atom is attached to a carbon atom which is the third carbon atom away from the silicon atom. They are prepared by (1) reacting a compound with a compound of formula RNH2 and when R=H intermediate compounds of formula HN[Si(R11)2(R1X)]2 are formed. The reaction proceeds in presence of either a large excess of amine, e.g. 7 to 10 mols. per mol. of the silane or in presence of tributylamine, pyridine and quinoline as hydrogen halide acceptors; the symbols XR1 and R11 have the values given above; (2) heating above 100 DEG C. a compound of general formula (RNHR1 -Si(R11)a(OZ)3-a, wherein R1 and R are defined as above but R cannot be (XR1)-SiY2-; Z is phenyl, alkyl or an alkyl group containing ether linkages; and a is 0, 1 or 2. The invention further comprises (a) siloxanes of general unit formula They are prepared by hydrolysing compounds of formula the symbols R, R1, R11 and a having the values given above. When the cyclic silane contains no alkoxy or phenoxy radicals disiloxanes are produced; (b) end blocked diorganosiloxanes of general formula where x is at least 1. They are prepared by reacting hydroxy and blocked diorganosiloxanes with the above cyclic silanes. R111 is a monovalent hydrocarbon radical which may be halogenated, e.g. chloromethyl or 3,3,3-trifluoropropyl, and (c) copolymer siloxanes containing the units (RNHR1) R11SiO and R111 2SiO wherein the symbols R, R1, R11, R111 are as defined above. These polymers may be end blocked by hydrogen, monovalent hydrocarbon radicals which may be substituted. They are prepared by cyclic silanes of the invention wherein R11 is alkoxy or phenoxy with one or more hydroxyl containing silanes or siloxanes. Many examples are given which include

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