Silicone oligomers and curable compositions containing same

<u style="single">Background of the invention</u>Technical field to which the invention belongs The present invention is a silicone useful as a coupling agent, bridging agent and adhesion promoter for curable compositions, such as radical curable filler-containing organic elastomer polymer compositions having specific uses such as insulating paints. With respect to oligomers, compositions using those oligomers, and cured products obtained from them. Description of prior art Silanes are known as coupling agents, bridging agents and adhesion promoters, and are extremely useful as adhesives and paints. In addition, a considerable amount of research has been done on silane compounds that have a large number of alkoxy groups and are useful as coupling agents, bridging agents and adhesion promoters. For example, US Pat. No. 4,179,537 [Inventor: Rykowski] states, for example, vinyl trialkoxysilanes, methacryloxyalkyltrialkoxysilanes, vinyltrihalosilanes, and their analogs. Blends of silanes with such organic functional groups and silanes without organic functional groups, such as alkyltrialkoxysilanes, are disclosed, and such blends are made organic, such as EPDM rubbers. It is disclosed that it is mixed with a resin to improve the adhesion between an inorganic base material such as a clay filler and the resin. This patent does not disclose, teach or suggest mixing siloxane oligomers into the coupling composition, and the presence of siloxane oligomers in this resin-filler system has a detrimental effect on coupling efficiency. It suggests that there may be cases (column 4, lines 54-63). U.S. Pat. No. 4,179,537 also describes the use of silicon-bonded silanes with 2-methoxyethoxy groups, such as vinyl-tris- (2-methoxyethoxy) silanes, as coupling agents. (Column 2, lines 44-47). Vinyl-tris- (2-methoxyethoxy) silanes have long been industrially used as coupling additives in mineral-filled EPM and EPDM wire and cable insulation. EPM is the ASTM name for a copolymer of ethylene and propylene, and EPDM is a ternary copolymer of ethylene, propylene and a diene-based monomer such as ethylidene norbornene or 1,4-hexadiene. Vinyl-tris- (2-methoxyethoxy) silanes have been widely used because of their unique balance between elastomeric fortifying performance and the required degree of electrical stability when wet. However, it releases 2-methoxyethanol as a hydrolysis by-product when used, and unfortunately, this 2-methoxyethanol is currently being investigated as a suspicious malformation-causing factor. Therefore, coupling agent products based on vinyl-tris- (2-methoxyethoxy) silane are currently facing constant replacement pressure on the market. US Pat. No. 4,950,779 [Inventor: Wengrovius, et al., General Electric] states that organic trialkoxysilanes such as methyltrimethoxysilane and vinyltrimethoxysilane are used as formic acids. , A mixture comprising cyclic, linear and branched alkoxyfunctional silicone oligomers, optionally produced by condensation using a strong acid catalyst, is described. US Pat. Nos. 4,499,150 and 4,499,151 teach a copolymer of an ethylene-based unsaturated alkoxysilane and another ethylene-based unsaturated group, which is synthesized by radical polymerization. These interpolymers have limited structure and functionality due to chemical constraints in their formulation. U.S. Pat. No. 5,210,168 [Inventor: Bergstrom, et al.; Dow Corning] uses an organic acid such as formic acid and a catalytic amount of a strong acid to make organic trialkoxy. A mixture of alkoxy functional silicone oligomers made from silanes is described. U.S. Pat. No. 5,298,998<img file="JP4841019B2_D0001.tif" />Describes a mixture of linear and cyclic alkoxy-functional silicone oligomers made from vinyltrialkoxysilanes using a hydrogen chloride catalyst and water. U.S. Pat. No. 5,432,246 [Inventor: Fenn, et al.] States that a second amino-alkoxysilane, a polyisocyanate and, optionally, a silane produced from the mono-isocyanate group. Oligomers are disclosed. Such oligomers are based on the reaction of producing substituted urea from this amine and this isocyanate. In these oligomers, all of the isocyanate groups react with the amine groups, so that the isocyanate groups are absent. In addition, these urea structures can increase in viscosity to an undesired degree. Abstract of the present invention The present inventors are oligomers having a large number of alkoxysilyl groups, and bridge the silicon atoms of the oligomer skeleton by at least one unsaturated group or Si-C bond on the oligomer. We have found novel silicone oligomers that have at least one of the organic silyl functional groups, or both. The unsaturated group may be a vinyl group or any other aliphatic unsaturated hydrocarbon functional group. These silicone oligomers are further radical curable as coupling agents, bridging agents and adhesion promoters, as well as for crosslinkable organic polymer / filler compositions such as wire cable insulating formulations. It is useful for compositions. Since these oligomers are less volatile than the alkoxysilane compounds, they are easier for compounders to handle and may be safer to handle. The silicone oligomers of the present invention are compounds of the following formula.<img file="JP4841019B2_D0002.tif" />During the ceremony Each R is individually B, R¹, -OR², R³And R⁴Selected from the group consisting of; B is an organic silyl functional group bridging the silicon atom of its siloxane oligomer backbone by a Si-C bond; each R¹Are independently saturated aliphatic hydrocarbon groups with 1 to 16 carbon atoms; each R²R independently¹A eel group or an acyl group or an aromatic hydrocarbon group defined for; each R³Is a monovalent organic group that independently contains an aliphatic unsaturated hydrocarbon group; and each R⁴Is a monovalent organic group linked to the Si atom of the siloxane oligomer skeleton by a Si-C bond, does not contain an aliphatic unsaturated hydrocarbon group, and is one or more on top of it. It has a group selected from the above aromatic hydrocarbons, ethers, esters, carbamates, thioethers, polysulfides, protected mercaptans, amides, epoxys, cyanos and oxamate groups; We assume the following: At least 1/4 of all R groups is -OR²Is; R on at least one silicon atom of the oligomer³Grouped, or at least one R is either B, or both; R³If it has a group, it is a vinyl group, and if it has at least one other group, it is a B group or a non-vinyl R.³Is the basis or R⁴Is a group; m is 2 to 20; n is 0 to 50; o is 0 to 20; and p is 0 to 10. In a further aspect, the invention is a curable composition comprising an oligomer of formula (I), wherein the formula is R.³The oligomer having a group has at least one silicon atom, and at least one R is B. Such compositions (1) Organic polymer that can be cured by radical mechanism; (2) Inorganic filler; (3) Siloxane oligomers as described above, Are prepared by mixing at the same time or in any order. The desired composition also comprises a radical catalyst system capable of bridging the organic polymer. Paints and adhesive compositions comprising the oligomers of formula (I) are also prepared. These siloxane oligomers produce little or no volatiles. They are suitable alternatives to commercially available coupling agents used in wire cable insulation formulations, are cost effective and have few health hazards. A further aspect of the present invention is an article in which at least a portion thereof is composed of the cured composition described above. The recommended article is a wire cable that comprises a wire and an insulating coating on the wire, the coating of which comprises a cured composition as described above. Detailed description of the present invention All patents or other publications mentioned elsewhere in this specification are cited in their entirety herein, just in case. Oligomer structure In the structure I above, B is an organic silyl functional group: -AW and contains a silyl group W and a divalent linking group A linked to the silicon atom of the group W and the siloxane oligomer by a Si-C bond. Become. B is preferably an internal group (ie, a non-terminal group) for the oligomer. In a preferred embodiment of the invention, there is at least one B per oligomer. In this particular embodiment, it is more desirable that there are at least two B groups per oligomer molecule. When the B group is attached to the silicon atom of the siloxane skeleton, the other R group (s) on the silicon atom are usually alkoxy groups. In the absence of B, the oligomer would have an ethylene-based unsaturated group as described below. In structure B, the divalent linking group A forms a non-siloxane bridge between the siloxane oligomer and the silyl group. This linking group A contains a heteroatom in its structure as long as the Si-C bond is used at the end of the linking group to form the respective bond to its oligomer and silyl group W. You may. The linking group may be linear, branched, or cyclic, and may be an olefin-based unsaturated group or an aromatic-based unsaturated group. The linking group is, for example, an alkylene, an alkalil alkylene or an alkali-lene, or an ether containing a polyether; an ester containing a polyester; a carbamate containing a polyurethane; an isocyanate; a thioether; a polysulfide containing a disulfide and a tetrasulfide; or similar. It may be an alkylene group interrupted by a hetero atom containing an organic structure such as the structure of. Desirably, this linking group is an alkylene group having 2 to 12 carbon atoms. The linking group A may be substituted with a silyl or siloxy group and also an unsaturated group. In fact, group A may form part of a backbone with a relatively straight siloxane chain attached to any end of the group. An example of linking group A is 1,4-diethylenecyclohexylene:<img file="JP4841019B2_D0003.tif" />Alternatively, 1,3-diethylene-5-triethoxysilylethylcyclohexylene:<img file="JP4841019B2_D0004.tif" />Aliphatic groups such as: ethylene, 1,2-propylene, 1,3-propylene, 1,4-butylene, 1,3-butylene, 1,2-butylene or 2,2-dimethyl-1,3 -Branched or linear aliphatic groups such as propylene; arylene groups such as 1,4-phenylene; 1,4-diethylenephenylene:<img file="JP4841019B2_D0005.tif" />Alkaline alkylene group such as; divalent polyether group of the following formula: -C_rH_2r-(OC_sH_2s)_q--- (In the formula, q is 1-50, preferably 1-5; r and s are integers of 2-6); and a divalent thioether group or the following formula: -C_tH_2t-S_u-C_tH_2t--- Polysulfide-containing groups, (in the formula, t is 2-16, preferably 2-4, and u is 1-8, preferably 2-4). Desirably, the linking group is an alkylene group having 2 to 12 carbon atoms, more preferably 2 to 3 carbon atoms. Structure: The silyl functional group W in -AW is a silyl group having a hydrolyzable functional group such as an alkoxy or acetoxy functional group. Alternatively, the group W is a silicon-linked organosiloxane or polyorganosiloxane group. Desirably, the silyl group W is an alkoxysilyl group or a further siloxane oligomer of an alkoxysilane monomer, more preferably a dialkoxysilyl group, and most preferably a trialkoxysilyl group. The desired B group is -C_fH_2f-SiR¹_g(X)_3-gIndicated by, in the formula, structure: -C_fH_2f-Corresponds to A, and structure: -SiR¹_g(X)_3-gCorresponds to W. Desirably, f is 2 to 12, g is 0 to 2, X is a hydrolyzable group such as halogen, oxime, alkoxy, aryloxy, alkenooxy or acetoxy, and R.¹Is as defined earlier. More preferably, f is 2 to 6, g is 0 to 1, X is a methoxy, ethoxy or acetoxy group, and R.¹Is a methyl group. A typical B group is -C₂H₄Si (OCH₃)₃, -C₂H₄Si (OC₂H₅)₃, -C₂H₄Si (OCH₃)₂(CH₃), -C₂H₄Si (OCH₃)₂Cl, -C₂H₄(C₆H₉) (C₂H₄Si (OCH₃)₃)₂, -C₂H₄(C₅H₈) C₂H₄Si (OC₂H₅)₃-And -C₂H₄Si (OCH₃)₂(OSi (OCH)₃)₃). R¹Is a saturated aliphatic hydrocarbon having 1 to 16 carbon atoms, for example, an alkyl (linear or branched) or cyclic alkyl. Typical R¹The groups are methyl, ethyl, i-propyl, i-butyl, t-butyl, pentyl, cyclohexyl, octyl, decyl and dodecyl groups. Methyl and ethyl groups are the preferred alkyl groups. R²Is R¹Groups as defined in, are aromatic hydrocarbon groups and acyl groups. Typical R²The groups are methyl, ethyl, i-propyl, i-butyl, t-butyl, pentyl, cyclohexyl, octyl, decyl, dodecyl, phenyl, benzyl, naphthyl, acetyl, benzoyl and propionyl groups. Desirable R²The group is a methyl or ethyl group, but multiple Rs are desired if a non-volatile oligomer is desired.²It is suitable that some of the groups are dodecyl groups. R³Is a monovalent organic group containing an aliphatic unsaturated hydrocarbon group. R³May contain ethylene-based and acetylene-based unsaturated bonds. R³Examples of groups are vinyl, allyl, propargyl, acrylic oxyalkyl, methacryloxyalkyl, crotyloxyalkyl, styryl, n-octenyl, linoleyl, line oil groups and the like. Vinyl, acrylic oxypropyl and methacryloxypropyl groups are recommended. Usually R to silicon atom³If so, the other R groups (s) on that silicon atom are -OR.²A group, preferably an alkoxy group. In a preferred embodiment of the invention, at least one R³There is a group. If B does not exist, then R³Must always exist. B and R³Both may be present in one oligomer structure. In addition, R³If there is a group and it is a vinyl group, then there is at least one other group, which is a B group, another R other than a vinyl group.³Group or R⁴Is the basis. The R group on the oligomer is one or more R⁴It may contain a group. R⁴Is a monovalent organic group linked to the Si atom of its siloxane oligomer skeleton by a Si-C bond, does not contain an aliphatic unsaturated hydrocarbon group, and is one or more on top of it. It also contains more aromatic hydrocarbons, ethers, esters, carbamates, isocyanurates, thioethers, polysulfides, protected mercaptans, amides, cyanos, epoxys or oxamate groups. Typical aromatic hydrocarbon groups are phenyl, benzyl or naphthyl groups. Typical ether-containing groups are alkoxyethyl or alkoxypropyl and polyether groups, particularly poly (allyl-started) poly (ethylene oxide) starting with an allyl group and poly (propylene oxide) starting with an allyl group. Alternatively, it is a group obtained as a result of hydrosilylation of an EO / PO copolymer whose starting end is an allylic group. Ether groups are also provided by etherification of silylalkyl hydroxides. Typical ester-containing groups are hydroxyalkyl groups such as acetic acid, propionic acid, octanoic acid, benzoic acid, fatty acids or acid-stopping polyesters, esters such as acetyloxypropyl, propionyloxypropyl, benzoyloxyethyl groups and similar groups. Is. A typical carbamate-containing group is a group obtained by reacting a silylalkylisocyanate with an alcohol, and may contain a polyurethane as well as a mono-carbamate structure. Included in certain such groups are propyl-N-carbamate ethyl; propyl-N-carbamate methyl; ethyl-N-carbamate ethyl and propyl-N-carbamate isopropyl groups. Typical amide-containing groups are successfully derived from aminoalkyl groups amidated with methyl acetate, methyl propionate or fatty acid esters and similar esters. Specific groups of this type are 3-acetamidopropyl, 2-propionamideethyl, 3-cocoamidepropyl groups. Polysulfide in it, -S_n-Contains groups with functional groups, where n is 2-8, preferably 2-4, especially disulfides and tetrasulfides. Included in certain such groups is C₄H₉-SS-C₃H₆-And C₂H₅-SS-C₂H₄-. Protected mercaptan is a functional group produced by the reaction of a mercapto group with a protective agent that can be removed later. Typical protected mercaptan groups are thioesters and other groups as disclosed in the PCT application PCT / US98 / 17391 (Filing Date: August 21, 1998, USA). Typical examples of silanes to be mixed with oligomers to provide a protected mercaptan group are 3-methyldiethoxysilylpropylthioacetate, 3-trimethoxysilylpropylthioacetate, 3-triethoxysilylpropyl. Thioacetate, 3-trimethoxysilylpropylthiopropionate, 3-triethoxysilylpropylthiobenzoate, 3-triethoxysilylethylthioacetate, 3-triethoxysilylmethylthioacetate, 3-triethoxysilylpropylthio Octanoate, and other compounds listed in the PCT / US98 / 17391 (Filing Date: August 21, 1998) specification. An example of a cyano-containing group is a 3-cyanopropipyl group. Examples of epoxy-containing groups are glycidoxypropyl and β- (3,4-epoxycyclohexyl) ethyl groups. Desirably, m + n + o + p <50, more preferably 45, even more preferably <30, and most preferably <15. In its widest range of embodiments, m = 2 to 20, n = 0 to 50, o = 0 to 20, and p = 0 to 10. Desirably, m = 2 to 10, n = 0 to 20, o = 0 to 20 and p = 0 to 10. More preferably, m = 2 to 10, n = 0 to 20, o = 0 to 10, and p = 0 to 5. Even more desirable, m is 2 to 4, n is 1 to 15, o is 0 to 2, and p is 0 to 1, but the number of syroxy units in a given oligomeric batch has a distribution. You should understand that there is. This desirable range also depends on the oligomeric structure itself. Since it is desirable that there are a large number of alkoxy groups available on the oligomer, curing of these oligomers will result in cross-linking between each other and / or, if an inorganic filler is present, with it. there is a possibility. Thus, R is at least 1/4 of its R group, more preferably at least 1/2 of its R group, -OR.², More preferably an ethoxy or methoxy group, while the rest of the R groups are B or R³It is a group, more preferably a trialkoxysilylethyl group, and most preferably a triethoxysilylethyl group. Desirably, in such an embodiment, p = 0, o = 0, m = 2 and n = 2 to 20. Long-chain alkoxy groups, such as octyloxy or dodecyloxy groups, are used to further reduce the volatility of low molecular weight oligomers and / or to reduce VOCs (volatile organic compounds) during curing. , OR²It may also be provided as a basis. This involves using an readily available methoxy or ethoxy group, for example octanol or dodecanol, to C.₈Alternatively, it can be achieved by transesterifying with more alkoxy groups. This transesterified oligomer provides hydrophobicity to the filler-containing composition, and when the compound is usually crosslinked with a peroxide, it is permanently attached to the polymer. As recommended in some embodiments, commercially available co-hydrolyzed products of dimethyl and vinylmethylchlorosilanes are suitable if the low volatile siloxane oligomer contains an ethylene-based unsaturated bond. It was found that there was. In the paint, the degassing phenomenon of methanol or ethanol is reduced or eliminated by using the low volatility oligomer produced by the transesterification described above. When bonding to a filler or substrate is required to improve mechanical properties and / or its oligomers are used as crosslinkers or adhesion promoters in room temperature curing (RTV) silicone formulations. If so, shorter alkoxy moieties are recommended. Oligomers containing both shorter and longer alkoxy groups, for example by partial transesterification of short alkoxy groups, allow for fine adjustment of hydrophobicity and filler binding. Thus, using this synthetic method, an unlimited number of new structures are added within the overall scope of the invention. The oligomer preferably has a viscosity of 0.5 to 500 csks (Stokes) or higher, preferably 0.5 to 200 csks (25 ° C). As will be apparent to experts in the art, the viscosity of this oligomer can be adjusted by adjusting the number of syroxy groups in the oligomer. For most applications, this viscosity will be adjusted for a particular application to ensure that the composition containing the oligomer can be spread or sprayed onto a particular substrate. The preferred formula for this oligomer is [R (R²O)₂SiO_1/2]_m[O_1/2SiR (OR²) O_1/2]_n[SiO_3/2R]_{o o}And here, R, R², M, n and o are as described above. Desirably, R²Is ethyl, o is 0, m is 2, and n is 0 to 15, more preferably 0-15. Examples of oligomers of the invention that do not contain aliphatic unsaturated bonds are the following structures:<img file="JP4841019B2_D0006.tif" /><img file="JP4841019B2_D0007.tif" />A typical oligomer containing an aliphatic unsaturated bond contains the following structures, in which a, b and c are each positive integer, the sum of which is about 2 to about 20, preferably About 15 or less. An example of an oligomer containing both an aliphatic unsaturated bond and a bridging group B contains the following structure, where a, b and c are positive integers, respectively, and their sum is about 2. From about 20, preferably about 15 or less, and u from 1 to 8, preferably 2 to 4.<img file="JP4841019B2_D0008.tif" /><img file="JP4841019B2_D0009.tif" /><img file="JP4841019B2_D0010.tif" /><img file="JP4841019B2_D0011.tif" />Experts in this art will appreciate that the above equations represent only some of the possible structures obtained from the identified condensates. Standardly, these structures are mixtures, have various end groups, and some species are linear, some are cyclic or polycyclic, and some are branched. In the case of low molecular weight oligomers, the volatility can be significantly reduced by introducing an alkoxy group having a long chain length, such as an octyloxy or dodecyloxy group. This allows the readily available methoxy or ethoxy group to be C, for example, an octyloxy or dodecyloxy group.₈Alternatively, it is achieved by transesterification with more alkoxy groups. This transesterified oligomer makes the filler-containing elastomer composition hydrophobic, and when the compound is crosslinked (usually due to a peroxide), it is permanently attached to the polymer. C₁₂Alternatively, longer alkoxy groups, such as dodecyloxy groups, have been observed to have a very low tendency to hydrolyze, so such groups are often non-reactive R.¹A suitable and inexpensive replacement group for the group. The aliphatic unsaturated siloxane oligomers described herein are suitable as substitutions for commercially available co-hydrolyzed products of dimethyl and vinylmethylchlorosilanes. Utilization of a method of producing an oligomer using vinyl alkoxysilane, optionally in combination with alkylalkoxy and / or tetraalkoxysilane, as a starting material reduces the cost of the oligomer. Unexpectedly, for wire and cable applications, elastomeric cable insulation made from this new oligomer improves mechanical properties and electrical stability when wet. In the paint, the degassing phenomenon of methanol or ethanol is reduced or eliminated by using the low volatility oligomer produced by the transesterification described above. Short alkoxy moieties are recommended if it is necessary to bond to the filler for improved mechanical properties. These sites may be attached to the backbone of the oligomer, or may be subsequently hung if a hydrosilylation reaction is used to attach those sites to the vinyl group. For example, oligomers containing both short alkoxy groups and longer alkoxy groups prepared by partial transesterification of short alkoxy groups allow fine adjustment of hydrophobicity and filler binding. Thus, the synthetic method used will add an unlimited number of new structures within the overall scope of the invention. Manufacture of oligomers These oligomers are produced by a condensation reaction of hydrolyzable silane compounds. If the oligomer should contain a B group, this group is either prepared in the starting silane or produced by a subsequent hydrosilylation reaction. In this hydrosilylation reaction, an alkoxyhydride silane or hydridesiloxane and an oligomer having an ethylene-based unsaturated hydrocarbon group such as a vinyl group are used. Condensation reactions are described in U.S. Pat. Nos. 4,950,779 (inventor: Wengrovius et al.), U.S. Pat. No. 5,298,998 (inventor: Horn et al.) And U.S. Pat. No. 5,210,168 (inventor: Berg). Strom et al.), Follow any of the methods disclosed in. R³To provide the groups, silane reaction components containing unsaturated aliphatic hydrocarbon groups will be used. Typical examples of alkoxysilanes containing unsaturated aliphatic hydrocarbon groups are vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinyltriisopropeneoxysilane, and methacryloxypropyltriethoxy. Silane, methacryloxypropyltrimethoxysilane, acrylicoxypropyltrimethoxysilane, acrylicoxypropyltriethoxysilane, acrylicoxyethyltrimethoxysilane, trimethoxysilylpropyl-methylmaleate, styryloxypropyltriethoxysilane, allyltrimethoxysilane , Allyloxypropyltriethoxysilane, allyl-N- (3-trimethoxysilylpropyl) carbamate, methacrylamidepropyltriethoxysilane, methacryloxypropyleneoxypropylmethyldimethoxysilane, crotyloxypropyltrimethoxysilane, and similar thereof. It is a thing. Corresponding compounds in which the silylalkoxy group is replaced with a silyloxyacetyl group are also used. In order to produce an oligomer containing a B group by a one-step method, the condensation reaction may include bis, tris, or a higher order alkoxysilane as a reaction component. Desirably, bis-dialkoxysilane or bis-trialkoxysilane is used as the B-based source in such a method. Typical silanes are 1,4-bis- (triethoxysilylethyl) cyclohexane, 1,3,5-tris- (triethoxysilylethyl) cyclohexane, bis- (triethoxysilylethyl) benzene, tris-triethoxy. Cyril ethyl isocyanurate, and 1,4-bis- (triethoxysilyl) butane. At the time of condensation, other alkoxy or acyloxysilanes may be mixed with the oligomer, and these silanes contain arylsilanes, alkylsilanes, alkylcarbamidesilanes, alkylcyanosilanes, and poly. It is, but is not limited to, alkylene oxide silanes, alkyl ester silanes, alkylamide silanes, or isocyanurate silanes. These silanes must contain at least one alkoxy or acyloxy group, but are preferably di- or tri-alkoxysilanes. Specific examples of these silanes include phenyltrimethoxysilane, phenylmethyldimethoxysilane, naphthylrimethoxysilane, cyanopropyltriethoxysilane, glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl). Trimethoxysilane, (polyethyleneoxy) propyltrimethoxysilane, (poly (ethyleneoxy) (propyleneoxy)) propyltriethoxysilane, 3-trimethoxysilylpropyl acetate, 3-methoxydiethoxysilylpropyl acetate, phenylN -(3-Trimethoxysilylpropyl) carbamate, 3-triethoxysilylpropyl) N-phenylcarbamate, methyl N- (3-trimethoxysilylpropyl) carbamate, 3-methyldiethoxysilylpropyl thioacetate, 3-trimethoxy Cyrilpropyl thioacetate, 3-triethoxysilylpropyl thioacetate, 3-trimethoxysilylpropyl thiopropionate, 3-triethoxysilylpropyl thiobenzoate, 3-triethoxysilylethyl thioacetate, 3-triethoxysilyl Methyl thioacetate, and 3-triethoxysilylpropyl thiooctanoate. Corresponding compounds in which the silylalkoxy group is replaced with a silyloxyacetyl group are also used. Further, in this condensation reaction, dialkoxysiloxy units may be inserted into the oligomer so as to affect the bridging, surface activity and viscoelasticity of the oligomer. This is done with a tetraalkoxysilane such as tetramethoxysilane or tetraethoxysilane. Condensation of these alkoxysilane monomers is successful in the presence of carboxylic acids (eg, acetic acid or formic acid) or water. Alternatively, a strong condensation catalyst, such as a strong acid or an acidic ion exchange resin such as AMBERLYST [Rohm & Haas Co.], is used. Other reaction conditions for this condensation are single doses. It will depend on the type of body silane. However, the reaction temperature is usually in the range of 20-60 ° C. Typical reaction conditions are also US Pat. No. 4,950,779 (Inventor: Wengrovius et al.) , US Pat. No. 5,298,998 (Inventors: Horns) and US Pat. No. 5,210,168 (Inventors: Bergstroms). When synthesizing an oligomer containing a B group by the two-step condensation / hydrosilylation method, the product of the condensation reaction is a large number of unsaturateds linked to the silicon atom of the siloxane oligomer skeleton with a Si-C bond. It is a siloxane oligomer containing a group. The unsaturated functional group-bearing siloxane oligomer thus produced is then treated with hydride silane in the presence of known hydrosilylation catalysts such as platinum, palladium or rhodium-based catalysts. Such hydrosilylation is carried out, for example, according to the methods of US Pat. Nos. 5,530,452 and 5,527,936 cited herein. The hydride silane is preferably a silane having a plurality of hydrolyzable groups, such as trialkoxysilane, which results in many crosslinkable sites on the resulting oligomer. During the reaction, hydride silane reacts with the unsaturated group (s) on its oligomer and between the silicon atom and the unsaturated group (in the case of ethylene, it is saturated during this reaction). A bond is formed in. In order to produce an oligomer having both a cross-linking group B and an aliphatic unsaturated hydrocarbon group, hydride silane, which is insufficient compared to the number of unsaturated groups available on the oligomer, is used, and at least per oligomer molecule. Allows about one unsaturated group to remain after hydrosilylation. This unsaturated group, which remains on the oligomer after hydrosilylation, crosslinks the oligomer with the organic polymer matrix during the subsequent curing reaction of the organic polymer / filler / coupling agent composition of the present invention. Make it possible. Experts in the art have in some cases that B group-bearing oligomers are first used with hydridesilanes such as triethoxysilane and, in some cases, in combination with other silanes as described above. You will recognize that it is synthesized by preparing an oligomer with a hydrosilyl functional group and then hydrosilylating an aliphatic unsaturated silane, such as triethoxyvinylsilane or triethoxymethylvinylsilane. The oligomers of the present invention are useful as bridging agents, coupling agents, adhesion promoters, intermediates for the synthesis of other oligomers, and as filler treatment agents. Typical compositions in which these oligomers are mixed are curable polymer / filler compositions used for wire and cable insulators and similar; hard silicate coatings; adhesion-promoting primers for paints or adhesives. Architectural sealants: UV or electron beam curable acrylic paints; anaerobic adhesives, (meth) acrylate ester adhesives and sealants such as syrup-like adhesives in which polymers are dissolved in monomers; glass fibers, carbon Polyester resin-based; and room temperature curable silicones used to prepare composites reinforced with fiber or Kevlar reinforcements. These oligomers are also converted to hydrolysates, in which OR²The groups are substituted with OH and in their form in aqueous dispersions, as adhesion-promoting or sealing primers, as additives to polymer emulsions, as filler treatment agents, and in curable silicone formulations. ,used. Curable Polymer / Filler Composition The curable polymer / filler composition of the present invention comprises (1) a radical curable organic polymer, (2) an inorganic filler and (3) at least one R as described above.³Contains oligomers with. The composition also contains a radical catalyst or generator. The standard organic polymer used in the present invention is any synthetic or natural rubber, usually with a filler. Examples include natural rubber, styrene-butadiene rubber, ethylene-propylene copolymer, polyethylene, ethylene-vinyl acetate copolymer, and the third monomer component is ethylidene norbornene or 1,4-hexadien. Synthetic rubbers such as ethylene-propylene ternary copolymer rubbers, urethane rubbers, polyisobutylene rubbers and other curable or crosslinkable elastomers. The inorganic filler used in this curable composition is known to experts in the art and is any appropriately finely ground or particulate inorganic material. At the time of mixing with the curable composition, most of the filler is in the form of being finely ground. They are approximately equal volume and have a maximum diameter, i.e. 10 μm, preferably a maximum linear dimension of 5 μm, or they are plate-like or needle-like (fibrous), 20 μm or less, preferably 5 μm. It has a thickness or diameter smaller than that. In practice, compositions containing larger particles have been formulated, but tend to give inferior properties. The minimum particle size of the filler particles is not particularly important, and in this respect any commonly used filler is suitable. Specific fillers used in the present invention include asbestos, powdered glass, kaolin and other clay minerals, silica, calcium silicate, calcium carbonate (heavy calcium carbonate), magnesium oxide, barium carbonate, barium sulfate. With (barite powder), metal fibers and powders, glass fibers, fireproof fibers, titanium oxide, mica, talc, chopped glass, alumina, trihydrate alumina, quartz, wollastonite (calcium silicate), and inorganic color pigments. is there. Kaolin clay is a particularly good filler in the wire and cable industry and is therefore the recommended filler. A thermally activated radical catalyst or generator will normally be mixed with the curable composition of the present invention. However, in some cases, such as when the oligomer contains a disulfide or polysulfide group in the crosslinked structure A of group B, or when other radical sources such as ultraviolet light are used. Radicals may not be needed. If a radical catalyst is used, it may be any existing catalyst or curing agent compound, examples of which are organic peroxides, azonitrile compounds (eg (AIBN) and sulfur. Zinc, calcium, cobalt, copper, Metal drying compounds such as molybdenum, manganese, chromium or nickel fatty acid salts, octanates or naphthoates are also used as curing catalysts. Desirable catalysts are organic peroxides. US Pat. No. 3,148,169 [Invention] Person: Any of the peroxides described or listed in [Martens] is used. This catalyst is a thermally activated compound and is a mixture of organic elastomer and catalyst at a given temperature or temperature. When heated to the area, a bridging reaction occurs. Any other additives commonly used in this radical curable organic polymer / filler system are used in this curable composition. For example, stabilizers and antioxidants, curing boosters, curing activators, curing accelerators, bridging agents, waxes, oils, electrical stabilizers when wet and plasticizers are added. Additional coloring is also prepared, and any other additives for imparting or modifying other properties are also used. Other silane bridging agents such as vinyltrimethoxysilane or (meth) acrylicoxytrimethoxysilane may also be included in the composition, or such silanes may be copolymerized into this organic polymer skeleton. May be introduced in. The proportion of each component in this curable composition is not important in the strict sense and is usually based on parts by weight per 100 parts by weight of the organic elastomer. On this base, the inorganic filler can be varied in the range of 25 to 200, preferably 50 to 150 parts by weight, per 100 parts by weight of the elastomer. Coupling compositions are included in the range of 0.1 to 10, preferably 0.5 to 3 parts by weight per 100 parts by weight of filler, and peroxides or other radical catalysts are from 0.5 to 100 parts by weight of elastomer. It is used in an amount of 10 parts by weight, preferably 2 to 5 parts by weight. This curable composition is usually prepared in a BANBURY mixer [Farrel Co.] or any other powerful mixer, except for the catalytic components. The generally accepted rubber industry kneading technique is used. If a catalyst is used, the catalyst is added to a Banbury mixer or the resulting compound is transferred to a roll mill, rollered, then peroxide is added and mixed to prepare the compound. By either method, a curable composition is obtained, which is then used to coat the electrical conductor for the purpose of insulating it after curing. These compositions are diverse in other applications where small moisture adsorption is desired, such as encapsulation of electrical components and other electrical insulation applications, gaskets, seals, pump diaphragms, automotive ignition wires, sulfur hardened rubber, and the like. It is also used for other purposes. Recommended uses for filler-containing compositions of the present invention are wire and cable insulators. In order to cure this curable composition, it is only necessary to apply heat above the temperature at which the catalyst is activated. It is desirable to choose a peroxide with a decomposition temperature above 200 ° F (93 ° C), preferably 250 ° F (121 ° C). When manufacturing insulated wire cables under conditions that are easily deformed by heating (but below the decomposition temperature of the catalyst), the wire is coated through an extruder and an insulating coating is formed around the wire. After extruding onto the conductor, the composite of the conductor and the coating of the curable composition is placed in an oven or autoclave, and the temperature is raised to a temperature equal to or higher than the decomposition temperature of the peroxide, and the curable composition is crosslinked. Then, a hardened thermosetting insulator coating with high toughness is formed around the lead wire. Other curable compositions These oligomers of formula (1) above are paints or adhesive formulations that are also useful as bridging agents, adhesion promoters, impart radical / humidity-dual curing mechanisms and / or cured coatings. Gives moisture resistance to. These oligomers are almost non-volatile, contribute little or no as volatile organic compounds (VOCs), and are suitable for application or dilute other components so that the entire composition can be spread. Or, it has a viscosity that can be adjusted so that it can be sprayed. In such applications, R³However, oligomers containing acrylates or methacrylate groups are recommended. Such oligomers are building waterproofing agents, paints, anticorrosion systems, and substrates such as cement, metals, polymers (PVC, PVS, EPDM, PE, PP, ABS, EPR, BR, silicone, polycarbonate, etc.). Used above. Further, these oligomers are used for silicate-based hard coats (hard coatings). These oligomers are used alone or in combination with other monomers. These oligomers are copolymerized with unsaturated monomers. These oligomers are particularly useful in automotive transparent paints made by US Pat. No. 5,244,696 [Inventor: Hazan] cited herein. The clear paint made of the oligomers of the invention has good scratch resistance, good gloss (and gloss retention), chemical resistance, image discrimination (DOI) and antifouling properties. In such applications, these oligomers are R³Desirably free of groups, and R³If groups are present, they are preferably acrylic or methacrylic-containing groups. The coating composition containing the oligomer of the present invention may contain many components in order to enhance the formulation of the composition and also to improve the final properties of the coating composition and the final coating film. For example, it is often desirable to contain from about 20 to 90% by weight, preferably 20 to 60% by weight of the film-forming reactive silane polymer of this composition. Such polymers typically have a number average molecular weight of about 500 to 10,000. The silane polymer is about 30-95% by weight, preferably 40-60% by weight of silane-free ethylene unsaturated monomer and about 5-70% by weight, based on the weight of the organic silane polymer. %, Desirably a polymerization product of 10-60% by weight ethylene-based unsaturated silane-containing monomer. Suitable ethylene-based silane-free saturated monomers are alkyl acrylates, alkyl methacrylates and mixtures thereof, the alkyl group of which contains 1-12 carbon atoms, preferably 3-8 carbon atoms. Have. The film-forming composition of this coating composition is called a binder and is dissolved, emulsified or dispersed in other organic solvents or liquid carriers. This binder generally contains all the components that contribute as solid organic components of the curing composition. In general, chemical additives such as pigments and stabilizers are not considered part of the binder. Non-binder solids other than pigments do not exceed about 50% by weight of the composition. The term binder includes oligomers, organic silane polymers, disperse polymers, and all other film-forming components optionally added. This coating composition contains about 50-100% by weight of binder and about 0-50% by weight of organic solvent carrier. Suitable alkyl methacrylates to be used to prepare silane polymers are methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, lauryl methacrylate and the like. It is methacrylate. Suitable alkyl acrylate monomers are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, lauryl acrylate and similar acrylates. Alicyclic methacrylates and acrylates such as trimethylcyclohexyl methacrylate, trimethylcyclohexyl acrylate, iso-butyl cyclohexyl methacrylate, t-butyl cyclohexyl acrylate and t-butyl cyclohexyl methacrylate are also used. Aryl acrylates and aryl methacrylates such as benzyl acrylate and benzyl methacrylate can also be used. Mixtures of two or more of the above monomers are also suitable. In addition to alkyl acrylates and alkyl methacrylates, this silane-modified acrylic polymer contains up to 50% by weight of the polymer silane-free other polymerizable monomers in hardness, appearance, scratches, dents and scratches. It may also be used to impart desired properties such as scratch resistance and similar properties. Examples of such other monomers are styrene, methylstyrene, acrylamide, acrylonitrile, methacrylnitrile, hydroxyethyl acrylate, methacrylic acid and the like. These oligomers are also used in curable compositions comprising ethylene-based unsaturated monomers or prepolymers and radical catalysts. Such compositions are composed of UV or electron beam curable adhesives and paints, resins and gel-coats formulated from unsaturated polyesters, anaerobic curable adhesives, polymers dissolved in monomers (polymers). In-polymer) syrup-based acrylic engineering adhesives, and similar to these. In such applications, the oligomer is a radically curable group, eg, one or more R.³It comprises a group or a curable group such as a protected mercaptan or polysulfide. More preferably, the oligomer comprises at least one vinyl, acrylic or methacrylic group. Such an oligomer has such a composition at an addition level of about 0.5 to about 99%, preferably about 1 to about 50%, depending on the properties obtained or expected to be modified in the cured formulation. Things are used. Adhesives and coating compositions of the present invention typically contain radical catalysts, but, for example, in formulations designed for electron beam curing, or oligomers thereof, in their crosslinking groups B or R.⁴This catalyst is not always necessary if the group contains a polysulfide group. The radical catalyst may be any of the heat activated catalysts or radical photoinitiators described above. The radical photoinitiator contains benzophenone, acetophenone, chlorinated acetophenone, dialkoxyacetophenone, dialkylhydroxyacetophenone, dialkylhydroxyacetophenone ester, benzoin, benzoin acetate, benzoin alkyl ether, dimethoxybenzoin, dibenzylketone, benzoylcyclo. Hexanol and other aromatic ketones, acyloxime esters, acylphosphine oxides, acylphosphonates, ketosulfides, dibenzoyl disulfides, diphenyldithiocarbonates and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxides. The photoinitiator is typically used in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight of the composition. The adhesive or paint composition of the present invention also contains any other components commonly used in typical formulations to which the oligomers are mixed. The present invention is exemplified by the following non-limiting examples. In the examples, parts and percentages are weight-based unless otherwise noted. Example Examples for Oligomer Synthesis with B Group Example 2 To 444.6 g (3.0 mol) of vinyltrimethoxysilane in a 1 L three-necked flask, 115.1 g (2.5 mol) of 99% formic acid was rapidly added at room temperature. While passing nitrogen through this flask, a mixture of methyl formate and methanol (241.7 g in total) was distilled off from the reaction mixture over 3 hours, and 310.9 g was partially hydrolyzed and condensed to have a viscosity of 0.5 cstks (centistokes). Vinyl methoxysilicate was obtained. The above reaction mixture was heated to 100 ° C and a platinum-divinyltetramethyldisiloxane complex containing 1.9% Pt [Karstedt ́s catalyst), see US Pat. No. 3,775,452] 0.29 g was added. From the dropping funnel, 366.0 g (3.0 mol) of trimethoxysilane was added while adjusting the addition rate so as to maintain the reaction temperature at 110-120 ° C. After the addition is complete (4 hours), the flask is heated to 150 ° C. at which point a small amount of black precipitate (platinum metal) is formed. The product was cooled and filtered to give a clear, clear liquid with a viscosity of 32 cstks. Example 3 444.6 g of vinyltrimethoxysilane was reacted with 115.1 g of 99% formic acid in a manner similar to Example 2. During the distillation of the volatile components, the flask was heated to 150 ° C. and unreacted vinylmethoxysilane was distilled. The flask is cooled to 85 ° C, 0.29 g of calsette catalyst is added, then 366.0 g of distilled trimethoxysilane is slowly added, and the temperature of this exothermic reaction is adjusted to the rate of addition of trimethoxysilane. Maintained between 85-100 ° C. When the flask was heated to 150 ° C. after the reaction was completed, a small amount of Pt was deposited on the vessel wall of the flask. Excess trimethoxysilane was distilled off from this reaction mixture. Cooled and filtered to isolate 390 g of a clear, colorless product with a viscosity of 41 cstks.¹³Analysis by CNMR suggested that 78% of the original vinyl groups present were hydrosilylated. Example 4 In the method of Example 2, 48.9 g (0.33 mol) of vinyltrimethoxysilane and 29.8 g (0.17 mol) of 2-cyanoethyltrimethoxysilane were treated with 19.4 g (0.42 mol) of 99% formic acid. The contents of the flask were heated to 85 ° C for 2 hours and the low boiling components were distilled under reduced pressure. This co-oligomer reaction product is hydrosilylated at 110-120 ° C with 40.3 g (0.33 mol) of trimethoxysilane and 0.04 g of calsette catalyst and heated to 150 ° C for excess trimethoxy. Silane was distilled off. The residual catalyst was filtered to give a monoyellow composition with a viscosity of 14 cstks.¹³Analysis by CNMR suggested that 75% of the original vinyl groups present were hydrosilylated. Example 5 In the method of Example 2, 37.1 g (0.25 mol) of vinyltrimethoxysilane and 52.1 g (0.25 mol) of 2-acetoxyethyltrimethoxysilane were treated with a total of 22.1 g (0.48 mol) of 99% formic acid. In this example, 2-acetoxyethyltrimethoxysilane was reacted with 9.7 g (0.21 mol) of formic acid prior to the addition of vinylsilane. After distilling the low boiling point components, this co-oligomer reaction product is hydrosilylated at 110-120 ° C with 30.5 g (0.25 mol) of trimethoxysilane and 0.03 g of calcet catalyst to 150 ° C. Heating was performed to distill off excess trimethoxysilane. The residual catalyst was filtered to give a colorless composition with a viscosity of 50 cstks.¹³Analysis by CNMR suggested that> 90% of the original vinyl groups present were hydrosilylated. Example 6 In the method of Example 2, 24.5 g (0.165 mol) of vinyltrimethoxysilane and 16.9 g (0.085 mol) of phenyltrimethoxysilane were treated with a total of 11.1 g (0.24 mol) of 99% formic acid. This co-oligomer reaction product is hydrosilylated at 110-120 ° C with 20.1 g (0.165 mol) of trimethoxysilane and 0.01 g of calsette catalyst and heated to 150 ° C for excess trimethoxy. Silane was distilled off. The residual catalyst was filtered to give a colorless composition with a viscosity of 100 cstks.¹³Analysis by CNMR suggested that> 80% of the original vinyl groups present were hydrosilylated. Example 7 In the method of Example 2, 18.5 g (0.125 mol) of vinyltrimethoxysilane and 29.1 g (0.125 mol) of 7-octenyltrimethoxysilane were treated with a total of 11.0 g (0.24 mol) of 99% formic acid. In this example, 7-octenyltrimethoxysilane was reacted with 4.8 g (0.21 mol) of formic acid at 84-89 ° C for 1 hour prior to the addition of vinylsilane. The remaining 6.2 g of formic acid was added and the flask was heated at 90-110 ° C for 8 hours. After distilling the low boiling point components, using 30.5 g (0.25 mol) of trimethoxysilane and 0.074 g of calcet catalyst, both olefin moieties of this co-oligoform reaction product are completely flushed at 110-120 ° C. An attempt was made to hydrosilylate and the mixture was heated to 150 ° C to distill off excess trimethoxysilane. The residual catalyst was filtered to give a yellow substance with a viscosity of 85 cstks. Example 8 In the method of Example 2, 48.9 g (0.33 mol) of vinyltrimethoxysilane and 38.5 g (0.17 mol) of 2-phenethyltrimethoxysilane were treated with a total of 22.1 g (0.48 mol) of 99% formic acid. .. After distilling the low boiling point components, this co-oligomer reaction product is hydrosilylated at 120-130 ° C using 40.3 g (0.33 mol) of trimethoxysilane and 0.05 g of calcet catalyst to 150 ° C. Heating was performed to distill off excess trimethoxysilane. The residual catalyst was filtered to give a straw-colored composition with a viscosity of 50 cstks. Example 9 In the method of Example 2, 24.5 g (0.165 mol) of vinyl trimethoxysilane, 32.7 g (0.165 mol) of 2-phenyltrimethoxysilane and 25.1 g (0.165 mol) of tetraethoxysilane were added in a total of 19.3 g (19.3 mol). It was treated with 99% formic acid (0.42 mol) at 87-100 ° C for 4 hours. After distilling the low boiling components, the co-oligomer reaction product is hydrosilylated at 102-145 ° C with 20.3 g (0.165 mol) of trimethoxysilane and 0.05 g of calsette catalyst to 150 ° C. The mixture was heated to distill off excess trimethoxysilane. The residual catalyst was filtered to give a colorless, transparent product with a viscosity of 14 cstks. Example 10 66 g (1.15 mol) in a solution containing 59.3 g (0.4 mol) of vinyltrimethoxysilane, 54.8 g (0.4 mol) of methyltrimethoxysilane and 60.9 g (0.4 mol) of tetraethoxysilane in a round bottom flask. ) Glacial acetic acid and 0.9 g (0.5 wt%) PUROLITE C-175: Acidic dry ion exchange resin [Bro Tech Corp.) Manufactured in the department] was added. The contents of the flask were heated to 90 ° C. for several hours, then 122 g of methanol and methyl acetate were distilled off. The vinyl group-containing oligomer in the flask was then hydrosilylated at 115-145 ° C using 49 g (0.4 mol) of trimethoxysilane and 0.04 g of calsette catalyst. The final product after filtering to remove low boiling components and removing any solids was 145 g and the viscosity was 65 cstks. Example 11 In a reaction similar to Example 10, 59.3 g (0.4 mol) of vinyltrimethoxysilane, 54.8 g (0.4 mol) of methyltrimethoxysilane and 60.9 g (0.4 mol) of tetraethoxysilane in a round bottom flask. To the containing solution was added 52.9 g (1.15 mol) of 99% formic acid and 0.9 g (0.5 wt%) of Purolite C-175: acid dry ion exchange resin. The flask was heated to 85-100 ° C to distill off the produced methanol and methyl formate, and a total of 99.1 g was collected. The reaction mixture was then filtered to remove the ion exchange resin. 110.8 g of vinyl group-containing oligomer was then hydrosilylated at 118-144 ° C. using 49 g (0.4 mol) of trimethoxysilane and 0.04 g of calsette catalyst. The final product after filtering to remove low boiling components and removing any solids was 153.6 g and the viscosity was 27 cstks. Example 12 In a reaction similar to Example 10, 59.3 g (0.4 mol) of vinyltrimethoxysilane, 54.8 g (0.4 mol) of methyltrimethoxysilane and 60.9 g (0.4 mol) of tetraethoxysilane in a round bottom flask. To the containing solution was added 20.7 g (1.15 mol) of distilled water and 0.9 g (0.5 wt%) of Purolite C-175: acid dry ion exchange resin. The reaction mixture was stirred at room temperature for 1 hour and then distilled under reduced pressure to remove 71 g of low boiling point components (mostly methanol). Filtration of the reaction mixture left 116 g of vinyl group-containing oligomers. This component was then hydrosilylated at 110-146 ° C using 49 g (0.4 mol) of trimethoxysilane and 0.04 g of calsette catalyst. The final product after filtering to remove low boiling components and removing any solids was 161 g and a viscosity of 14 cstks. Examples for the property of reducing viscosity Example 13 Synthesis of silane-containing acrylic polymer Silane-containing acrylic polymers similar to those listed in US Pat. No. 4,499,150 are synthesized. In a flask equipped with a condenser, stirrer and thermometer, 218.4 g of butyl acetate, 93.6 g of VM & P naphtha and 62.4 g of toluene were placed and then heated to reflux. The following three loadings were added simultaneously in a nitrogen atmosphere over a period of 2 hours. Loading I: 582.4 g of methyl methacrylate, 291.2 g of butyl acrylate, 364.0 g of styrene and 218.4 g of γ-methacryloxypropyltrimethoxysilane. Load II: 125 g butyl acetate and 72.8 g di-t-butyl peroxide. Loading III: 124.8 g of butyl acetate and 72.8 g of γ-mercaptopropyltrimethoxysilane. After these loadings were complete, additional peroxide (5.85 g) was added and the mixture was refluxed for 1.5 hours to ensure complete progress of the polymerization. The final resin has a solid content of 69 percent and a Gardner-Holt viscosity of Z +. The silane oligomers (20 g) of the above plurality of examples were blended with 100 g of the silane-containing acrylic polymer obtained above. The Gardner viscosity and solid content of the resulting mixture were measured and the results are shown below:<img file="JP4841019B2_D0012.tif" />The viscosity reducing property of these compounds was evaluated by another method. The viscosities of these mixtures were measured using Ford Cup # 4. The resin (silane-containing acrylic polymer) was very sticky and was diluted with a mixed solvent containing 75% toluene and 25% xylene. 85 g of this resin was added to 15 g of the mixed solvent. The solid content of the resulting resin mixture was 59% and the Ford Cup # 4 viscosity was 147 seconds. To this resin mixture, 18.4 g of a silane oligomer or copolymer was added, and its viscosity and solid content percent were measured.<img file="JP4841019B2_D0013.tif" />Examples for improving physical properties The silane oligomer was blended with the silane-containing acrylic polymer according to Table A, and the obtained mixture was applied onto an E-coated panel and cured at 130 ° C. for 30 minutes. The properties of these coating films are listed in Table B.<img file="JP4841019B2_D0014.tif" />1.100 g of acrylic silane polymer, 8.6% butyl acetate, 11.9%, acetone, 16.8% toluene, 56.4% xylene, 4% cellosolve acetate (ethylene glycol monoethyl ether acetate), 2.3% butyl carbitol acetate. A mixed solvent consisting of (diethylene glycol monoethyl ether acetone) was added. 2.10 wt% xylene solution 3.NACURE5925: Amine-protected dodecylbenzene sulfonic acid [from King Industries] 4.TINUVIN328: UV absorber, product of Ciba-Geigy Inc. 5. Prepare a 0.54 wt% solution by dissolving in xylene, DC200 from Dow Corning Corp.<img file="JP4841019B2_D0015.tif" />Examples of oligomers with B groups and aliphatic unsaturated hydrocarbon groups Example 14 To 142.7 g (0.75 mol) of vinyltrimethoxysilane and 52.1 g (0.25 mol) of tetraethoxysilane in a 500 mL three-necked flask, 41.4 g (0.9 mol) of 96% formic acid was rapidly added at room temperature. .. A mixture of ethyl formate, ethanol and unreacted vinyltrimethoxysilane (102.9 g in total) was distilled off from the reaction mixture over 3 hours while passing nitrogen through this flask and heating to 128.1 g, viscosity 0.5. A vinyl group-containing-ethoxysiliconate oligomer of cstks was obtained. The above reaction mixture was heated to 120 ° C and a platinum-divinyltetramethyldisiloxane complex containing 1.9% Pt [Karstedt ́s catalyst), see US Pat. No. 3,775,452] 0.11 g was added. From the dropping funnel, 12.3 g (0.074 mol) of triethoxysilane was added over 30 minutes while adjusting the addition rate so as to maintain the reaction temperature at 120-125 ° C. After the addition was complete, the flask was maintained at 125-130 ° C, at which point a small amount of black precipitate (platinum metal) was formed. The product was cooled and filtered to give 139.5 g of a liquid that was almost colorless and transparent and had a viscosity of 1-2 cstks. Example 15 142.7 g (0.75 mol) of vinyltriethoxysilane and 44.6 g (0.25 mol) of methyltriethoxysilane are reacted with 41.4 g (0.9 mol) of 96% formic acid and heated in a manner similar to Example 14. Then, 120.9 g of ethanol, ethyl formate and unreacted methyltriethoxysilane and vinyltriethoxysilane were distilled off from the reaction mixture. The resulting 120.9 g of vinyl silicate oligomer was hydrosilylated with 12.3 g (0.074 mol) of triethoxysilane in the presence of 0.11 g of calsette catalyst (as described above). The final product, 131.3 g, was clear and colorless and had a viscosity of 1-2 cstks after filtration. Example 16 171.3 g (0.9 mol) of vinyltriethoxysilane and 17.8 g (0.1 mol) of methyltriethoxysilane are reacted with 41.4 g (0.9 mol) of 96% formic acid and heated in a manner similar to Example 14. Then, 101.2 g of ethanol, ethyl formate and unreacted methyltriethoxysilane and vinyltriethoxysilane were distilled off from the reaction mixture. The resulting 126.4 g of vinyl silicate oligomer was hydrosilylated with 14.1 g (0.087 mol) of triethoxysilane in the presence of 0.11 g of calsette catalyst (as in Example 14). The final product, 140.1 g, was clear and colorless and had a viscosity of 1-2 cstks after filtration. Example 17 According to the method of Example 14, 171.3 g (0.9 mol) of vinyltriethoxysilane and 27.7 g (0.1 mol) of octyltriethoxysilane are reacted with 41.4 g (0.9 mol) of 96% formic acid and heated. 103.7 g of ethanol and unreacted vinyltriethoxysilane were distilled off from the reaction mixture. The resulting 137.9 g of vinyl silicate oligomer was hydrosilylated with 14.8 g (0.09 mol) of triethoxysilane in the presence of 0.11 g of calsette catalyst (as in Example 14). The final product, 150.9 g, was clear and colorless and had a viscosity of 3-4 cstks after filtration. Composition Example The compositions described below were synthesized by the following methods. "B" Banbury^RIn the mixer, the cooling water was fully opened and the EPDM polymer was added. Rum down mix (RDM), 116 RPM for 30 seconds. Add clay and silane, RDM 30 seconds. Add the rest of the additive ingredients, except for RDM 30 seconds. Dust down, RDM 20 seconds. Dust down, RDM at 155 RPM until reaching 149 ° C. Discharge the contents of the mixer and use a 5 x 30 cm roll mill with a roll temperature of 80-85 ° C to form a sheet. The resulting product was catalytically activated by adding peroxide on a roll mill at 80-85 ° C and cooled to room temperature. A test plate was made from each rubber compound and cured at 171 ° C for 25 minutes. The mechanical and electrical properties of the test plates from each compound were tested and are shown in Table 1. The formulations used in Table 1 were prepared by mixing the following base formulations with the silanes or oligomers shown in Table 1; the amounts in the table are given by weight. 100 copies of Nordel 2722 EPDM (DuPont) 1.5 parts of AGERITE Resin D Antioxidant [Vanderbilt] 5 parts zinc oxide Corp.) 5 parts of paraffin wax [Internal Wax] 5 parts of ERD90 Komeitan (lead tetraoxide) dispersion [Rhein-Chemie] 2.6 parts DICUP R peroxide [Hercules] In Table 1, A-1751 is the latest industrial oligomer marketed by Witco Corp. for filler-containing elastomeric formulations for wire and cable insulation applications, as a control example, Shown with "additive-free" examples. [table 1] The above examples and disclosures are exemplary and are not intended to be exhaustive. These examples and explanations will suggest many changes and alternatives to the average proficient in this art. All of these alternative methods and changes are considered to be included in the attached claims. Those who are proficient in this technique will be aware of other aspects that are equivalent to the particular embodiments described herein, and it is believed that those equivalents are also included in the appended claims. Be done.<img file="JP4841019B2_D0016.tif" />