TWI434878B - An organopolysiloxane containing an organofunctional group and a plurality of alkoxy groups having different carbon numbers - Google Patents

Description

Organic polyoxyalkylene containing an organic functional group and a plurality of alkoxy groups having different carbon numbers

The present invention relates to an organopolyoxyalkylene containing a plurality of alkoxy groups having an organic functional group and a carbon number, and particularly relates to an organic functional group having high reactivity in the same molecule and having high hydrolysis reactivity. a novel organic polyoxane which can arbitrarily change the hydrolysis reactivity of an alkoxycarbenyl group, wherein the methoxy group and/or the ethoxy group have a low reactivity with a carbon number of 3 and/or 4 alkoxy groups. .

A polyfluorene oxide alkoxy oligomer of a relatively low molecular weight polyoxyxylene resin, which is blocked by an alkoxymethyl sulfonyl group, is suitable for coating because of good storage stability, no solvation, and no maintenance. Various uses such as coating agents.

Among them, a type having an organofunctional group such as a hydrogenthio group, an epoxy group, a (meth)acryloxy group, an alkene group, a haloalkyl group, and an amine group in the same molecule, and a so-called oligomer type decane couple When the mixture is used in comparison with a monomeric decane coupling agent, the volatility is low, and the amount of the so-called alcohol by-product is small, and the structure can be multi-functionalized. Therefore, it is a useful material for applications such as resin modification.

For example, an organic resin can be modified into a moisture-curing type by reacting an organic resin having reactivity with a reactive organic functional group to introduce an alkoxymethylalkylene group. Further, the decyl alcohol produced by hydrolysis of the alkoxymethyl hydrazine group is hydrophilic, and if the structure is selected, it may be hardened by an organic resin-based paint. The film is provided with scratch resistance, weather resistance, chemical resistance, and antifouling property. For example, JP-A-09-040908, JP-A-09-040911, JP-A-09-040911, JP-A-09-111188 ).

In recent years, polyoxyalkyloxy alkoxy groups having an epoxy group, a thiol group, a (meth) propylene oxy group, and an olefin group can be used for an adhesion promoter or primer composition, and an adhesive composition. A photo-curable optical functional imparting film or a polyolefin-based resin composition for a cable covering material.

As described above, as the application range is expanded, the hydrolysis reactivity of the alkoxycarbenyl group becomes a problem. The polyoxyalkoxy oligomers currently used are in fact having a methoxy group and/or an ethoxy group as an alkoxy group, which are sometimes not deliberate because of their relatively high hydrolysis reactivity. The hydrolysis does not give the desired properties.

In the present invention, an organic polyoxane containing such an organic functional group and a hydrolyzable group is proposed, or a method for producing the same. (Patent Documents 4 and 5: Japanese Laid-Open Patent Publication No. Hei 07-292108, No. Hei 08-134219) In the above-mentioned patent documents, the hydrolyzable group is generally an alkoxy group having 1 to 4 carbon atoms, and further contains a plurality of hydrolyzable groups, but deliberately introduces a plurality of carbon atoms which are different in number. The hydrolysis reaction reactivity of the alkoxy group is not described.

[Patent Document 1] Japanese Patent Publication No. 09-040908

[Patent Document 2] Japanese Patent Publication No. 09-040911

[Patent Document 3] Japanese Patent Publication No. 09-111188

[Patent Document 4] Japanese Patent Publication No. 07-292108

[Patent Document 5] Japanese Patent Publication No. 08-134219

The present invention has been made in view of the above, and it is an object of the invention to provide a plurality of alkoxy groups having an organic functional group and a plurality of carbon atoms, and the hydrolysis reactivity of the alkoxycarbenyl group can be arbitrarily changed depending on the purpose of use. A novel organic polyoxane.

The inventors of the present invention have accumulated the results of intensive studies in order to achieve the above object, and found that the organopolysiloxane containing a highly reactive organic functional group and a hydrolytic decomposable group has high hydrolysis reactivity in the same molecule. a methoxy group or an ethoxy group, an alkoxy group having 3 or more carbon atoms and a tetraoxy group having a low reactivity with a hydrolytically reactive propoxy group or a butoxy group, and the polyfluorene oxide alkoxy oligomer can be arbitrarily changed. The hydrolysis reactivity of the product.

In particular, it has been found to be susceptible to the application of the present invention when it is found to have a polyoxyalkyloxy alkoxy group having a high affinity for water and having a hydrosulfide group or an epoxy group which promotes hydrolysis of an alkoxymethylmethyl group. Since the moisture of the raw material or the moisture generated in the air is hydrolyzed, the storage stability or application characteristics can be improved by containing a plurality of alkoxy groups having different hydrolysis reactivity, and the present invention can be completed.

Accordingly, the present invention provides the following organopolyoxane.

[1] An organopolyoxane which contains a plurality of alkoxy groups represented by the following average composition formula (1) and a plurality of alkoxy groups in _a molecule, Y _a R ¹ _b Si (OCH ₃ ) _c (OC ₂ H ₅ ) _d (OR ² ) _e (OH) _f O _(4-abcdef)/2 (1) (wherein Y is at least one selected from the group consisting of thiol groups, An organic group of an epoxy group, a (meth) propylene decyloxy group, an alkene group, a haloalkyl group and an amine group, and R ¹ is at least one non-substituted one having 1 to 8 carbon atoms which does not have an aliphatic unsaturated bond. a valent hydrocarbon group, R ² is an alkyl group having 3 and/or 4 carbon atoms, and a, b, c, d, e, and f are 0.01 ≦ a ≦ 1, 0 ≦ b < 2, 0 ≦ c ≦ 2, 0 ≦ d≦2,0<e≦2,0≦f≦1,c,d are not 0 at the same time, and satisfy 0.1≦c+d+e≦2.5, and 2≦a+b+c+d+e +f≦3 number).

[2] The organopolyoxane of the above [1], wherein Y in the above average composition formula (1) is an organic group containing a thiol group or an epoxy group.

[3] The organopolyoxane of the above [1] or [2], wherein b in the above average composition formula (1) is a positive number, R ¹ is a methyl group, and R ² is a propyl group or an isopropyl group. .

[4] The organopolyoxane according to the above [1] to [3], wherein c, d is a positive number in the above average composition formula (1).

[5] The organopolyoxane according to the above [1] to [4], wherein the mixture is obtained by partially co-hydrolyzing or polycondensing the mixture, and the mixture is at least one of the following formulas ( 2) an alkoxysilane having an organic functional group and/or a partial hydrolyzate thereof, and at least one alkoxy group-containing decane compound represented by the following formula (3), a partially hydrolyzed product thereof, and One or more of the condensates. YR ¹ _m Si(OCH ₃ ) _n (OC ₂ H ₅ ) _3-mn (2) R ¹ _p Si(OCH ₃ ) _q (OC ₂ H ₅ ) _r (OR ² ) _4-pqr ......... (3) (wherein, Y, R ¹ and R ² each have the same meaning as described above, m is an integer of 0 to 2, n is an integer of 0 to 3, but m+n is in the range of 0 to 3 An integer, p is an integer from 0 to 2, q is an integer from 0 to 4, and r is an integer from 0 to 4. However, p+q+r is an integer ranging from 0 to 4, but contains more than one OR ² base. The component is an alkoxy-containing decane compound of the formula (3).

[6] The organopolyoxane according to the above [5], wherein m in the above formula (2) is 0, and R ¹ in the above formula (3) is a methyl group, and p is 0 and / Or 1.

[7] The organopolyoxane of the above [5] or [6], wherein the alkoxy decane having an organic functional group represented by the above formula (2) is selected from the group consisting of 3-hydrothiopropyl Trimethoxy decane, 3-hydrothiopropyltriethoxy decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2- At least one of (3,4-epoxycyclohexyl)ethyltrimethoxydecane and 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, in the above formula (3) The alkoxy-containing decane compound is selected from the group consisting of methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, methyltriisopropoxydecane, and methyltributyloxy Base decane, methyl triisobutoxy decane, tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, tetraisopropoxy decane, tetrabutoxy decane, tetraisobutoxy decane At least one (but selected from methyl tripropoxydecane, methyl triisopropoxydecane, methyl tributoxydecane, methyl triisobutoxy decane, tetrapropoxy decane, tetraisopropyl Oxydecane, tetrabutoxydecane, tetraisobutoxy At least One as an essential component).

[8] The organopolyoxane according to the above [1] to [7], wherein the average degree of polymerization is from 3 to 100.

The organic polyoxyalkylene of the present invention can be used as a coating, a coating material, an adhesive, which is hardened by reaction with an organic functional group, because it contains an organic functional group and a plurality of alkoxycarbenyl groups in the molecule. a crosslinking agent such as a sealing material or a reactive diluent.

Further, in the case of the oligomer-type decane coupling agent, a reinforcing agent for use as a composite material, which is an organic resin which has been conventionally used as a monomeric decane coupling agent, can be used as a reinforcing agent for a composite material. It is composed of an inorganic material; and it can be applied to various functional materials utilizing the reactivity of an organic functional group or an alkoxymethylcarbonyl group, and can be arbitrarily changed as a polyfluorene in accordance with the purpose of use in any of the fields of application. Since the oxyalkoxy oligomer product has a hydrolysis reactivity, it has high utilization value.

(The best form for implementing the invention)

Hereinafter, the present invention will be described in detail.

The alkoxy group containing a plurality of kinds of the organic functional group and the carbon number of the present invention in one molecule is represented by the following average composition formula (1). Y _a R ¹ _b Si(OCH ₃ ) _c (OC ₂ H ₅ ) _d (OR ² ) _e (OH) _f O _(4-abcdef)/2 (1) Here, the Y system has at least one selected An organic group derived from a thiol group, an epoxy group, a (meth) propylene decyloxy group, an alkene group, a haloalkyl group and an amine group, among these functional groups, a thiol group, an epoxy group, a (meth) group The acryloxy group and the amine group are generally bonded to a ruthenium atom via a linking group, and such a linking group may be, for example, an ether chain (-O-) or an imido group (-NH-). The divalent hydrocarbon group such as an alkylene group or an alkylene-arylene-alkylene group having 1 to 12 carbon atoms of the hetero atom may, for example, contain a methylene group, an ethylene group, a trimethylene group or a hexamethylene group. An alkylene group such as a benzylene group or the like, an aromatic ring containing a methylphenylethyl group having a divalent hydrocarbon group therebetween, and having a methoxymethyl group, a methoxyethyl group, and a A divalent aliphatic group such as an oxygen atom such as an oxypropyl group. The alkenyl group or the haloalkyl group is bonded to the ruthenium atom via a linking group, or may be directly bonded to the ruthenium atom. Specifically, in the case of an organic group having a thiol group, a thiomethylmethyl group, a 3-hydrothiopropyl group, a 6-hydrothiohexyl group, a 10-hydrothioalkyl group, or a 4-hydrogen sulfide can be illustrated. Methyl)phenylethyl or the like, an organic group having an epoxy group, and examples thereof include a glycidoxymethyl group, a 3-glycidoxypropyl group, a 5,6-epoxyhexyl group, and 9,10- Epoxy fluorenyl, 2-(3,4-epoxycyclohexyl)ethyl, 2-(3,4-epoxy-methyl-cyclohexyl)propyl, etc., having (meth) acrylonitrile The organic group of the oxy group may, for example, be an acryloxymethyl group, a 3-propenyloxypropyl group, a 6-propenyloxyhexyl group, a 10-propenyloxycarbonyl group or a methacryloxymethyl group. 3-methylpropenyloxypropyl, 6-methylpropenyloxyhexyl, 10-methylpropenyloxycarbonyl, etc., the organic group having an alkenyl group may be a vinyl group, an allyl group, or a 5- Hexyl, 9-nonenyl, 3-vinyloxypropyl, p-styryl, cyclohexenylethyl, etc., having an organic group of a halogen-based group, exemplified by chloromethyl and 3-chloropropyl , 6-chlorohexyl, 10-chloroindolyl, bromomethyl, 3-bromopropyl, etc., an organic group having an amine group, an amine group can be exemplified , 3-aminopropyl, 6-aminopropyl, N-methyl-3-aminopropyl, N,N-dimethyl-3-aminopropyl, N-phenyl-3-amine Phenyl, N-(2-aminoethyl)-3-aminopropyl, N-(6-aminohexyl)-3-aminopropyl, N-(vinylbenzyl)-2-amine B Alkyl-3-aminopropyl and the like.

In the organopolysiloxane of the present invention, when the organic group having a thiol group, an epoxy group or a (meth) acryloxy group is formed in the above organic functional group, various reactivity is obtained from the high polyreactivity. It is preferred for use, and in particular, those having a hydrogenthio group or an epoxy group have a higher utilization value.

Further, R ¹ is at least one unsubstituted one-valent hydrocarbon group having 1 to 8 carbon atoms which does not have an aliphatic unsaturated bond, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group and a 1-methyl group. Alkyl, aryl, aralkyl groups such as propyl, butyl, isobutyl, tert-butyl, hexyl, octyl, phenyl, tolyl, benzyl, phenylethyl, etc., but steric hindrance The effect or cost of the reactivity of the above organofunctional group is particularly preferably a methyl group.

Further, R ² is an alkyl group having 3 or more carbon atoms, and specific examples thereof include a propyl group, an isopropyl group, a 1-methylpropyl group, a butyl group, an isobutyl group, and a t-butyl group, as the case may be. However, a methoxypropyl group may have an equivalent effect, but the viewpoint of moderately lowering the hydrolysis reactivity, or the effect of the volume of the alkyl group on the content (equivalent) of the above organic functional group is particularly preferably C. Base or isopropyl.

Further, in the above formula, a, b, c, d, e, and f are 0.01≦a≦1, 0≦b<2, 0≦c≦2, 0≦d≦2, 0<e≦2, 0≦f≦ 1, c, d are not 0 at the same time, and satisfy 0.1≦c+d+e≦2.5, and 2≦a+b+c+ The number of d+e+f≦3.

Here, the coefficient a is a numerical value indicating the degree of substitution of the organofunctional group with the ruthenium atom, but if it is too small, the reactivity of the organic functional group which is originally intended cannot be produced when the organopolysiloxane is used. The characteristic is that it must have an organic functional group in at least one molecule. In addition, if the degree of substitution of the organic functional group is more than 1, it is difficult to synthesize or cost, so it must be in the range of 0.01≦a≦1. It is preferably in the range of 0.1≦a≦1, more preferably in the range of 0.1≦a≦0.8.

Further, the coefficient b is a value which does not have a degree of substitution of an aliphatic unsaturated bond to an unsubstituted one-valent hydrocarbon group having 1 to 8 carbon atoms of the halogen atom, and is 0 or a small amount, which is a relative alkoxy group content. It will increase and the help rate for the hydrolysis reaction or the methylation reaction will increase, and, depending on the case, the affinity of the organopolyoxane for water will increase. In addition, when the value is large, the compatibility of the organic polyoxyalkylene with hydrophobicity (alkyl group, etc.), organic compound or organic resin is improved depending on the type of the monovalent hydrocarbon group (phenyl group, etc.), and the organic polyfluorene The cured product of oxyalkylene has an effect of imparting flexibility or release property (methyl), etc., but the content of the alkoxy group is relatively small, so that it is not suitable for the use of a reactive alkoxymethyl sulfonyl group. Therefore, it must be in the range of 0≦b≦2 depending on the purpose of use, and is preferably in the range of 0≦b≦1, more preferably in the range of 0≦b≦0.8.

Further, the coefficients c, d, and e are numerical values indicating the degree of substitution of a plurality of alkoxy groups in which the number of carbon atoms is different from that of the ruthenium atom, c is a degree of substitution of a methoxy group, d is a degree of substitution of an ethoxy group, and e is a The degree of substitution of alkoxy groups having 3 and/or 4 carbon atoms. A methoxy group or an ethoxy group having high hydrolysis reactivity The e-systems having a ratio of c, d, and an alkoxy group having a carbon atom number of 3 and/or 4 which are low in hydrolysis reactivity, such as a propoxy group or a butoxy group, may be hydrolyzed depending on the purpose of use or desired. In the case of the reactivity, it is appropriately set, but the purpose of the present invention in which a plurality of alkoxy groups having different hydrolysis reactivity are present in the same molecule is in the range of 0≦c≦2 and 0≦d≦2, but c And d is not 0 at the same time, and represents a range of 0 < e ≦ 2, and c + d + e of the total substitution degree of the alkoxy group must be in the range of 0.1 ≦ c + d + e ≦ 2.5. Preferably, each is 0≦c≦1.8,0≦d≦1.8, but at least one of c and d is 0.1 or more, 0.1≦e≦1.8, 0.2≦c+d+e≦2.35, and more preferably respectively 0.1≦c≦1.8, 0.1≦d≦1.8, 0.1≦e≦1.8, 0.5≦c+d+e≦2.35.

Further, the coefficient f is a numerical value indicating the degree of substitution of a hydroxyl group with a halogen atom, that is, a content of a decyl alcohol, and the stanol group may retain a methylation reaction or a condensation reaction, and impart hydrophilicity to the organopolyoxane. The effect is preferably as small as possible from the viewpoint of ensuring the preservation stability of the organic polyoxyalkylene. Therefore, it must be in the range of 0≦f≦1, preferably in the range of 0≦f≦0.5, more preferably in the range of 0≦f≦0.2.

Further, the total of the above coefficients a+b+c+d+e+f is determined by [4-(a+b+c+d+e+f)]/ which indicates the degree of condensation of the organopolysiloxane. The value of 2 must be in the range of 2≦a+b+c+d+e+f≦3. Further, the degree of condensation of the organic polyoxane can range from a couple of 矽 atoms to a degree of polymerization of about several hundred 矽 atoms, but when the average degree of polymerization is 2, the organic argon is produced. The content of the monomer in the alkane is increased, and the original purpose of the polyoxyalkyloxy oligomer is deteriorated, and if the average degree of polymerization is too large, It is difficult to handle for high viscosity or paste or solid. Therefore, the average polymerization degree should be in the range of 3 to 100, and more preferably in the range of 3 to 50. From such a point of view, even with respect to the above a+b+c+d+e+f, it is preferably in the range of 2≦a+b+c+d+e+f≦2.67, more preferably 2<a+b +c+d+e+f≦2.67 range.

An organopolyoxyalkylene containing an organic functional group of the present invention and a plurality of alkoxy groups having a different number of carbon atoms in one molecule is represented by the above average composition formula (1), as long as a to f satisfy the above range Alternatively, it may have a linear, branched, ring-shaped, and a combination of these.

Further, an organopolyoxyalkylene group containing a plurality of alkoxy groups of the present invention in an organic functional group and a plurality of carbon atoms in a molecule can be obtained by various known formulations, and the general means can be exemplified. : (A) a method of partially hydrolyzing or polycondensing an alkoxy decane having a plurality of alkoxy groups having an organic functional group and a carbon number different from each other, or (B) an alkoxy decane having an organic functional group and a method comprising partial co-hydrolysis or polycondensation of an alkoxy group having a carbon number different from that of the same, alkoxy decane having no organic functional group, and further, (C) depending on the same partial hydrolysis or polycondensation The transesterification reaction of the obtained organic functional group with an organic polyoxyalkylene group containing a methoxy group and/or an ethoxy group and an alcohol having 3 and/or 4 carbon atoms is carried out.

In the present invention, from the viewpoint of the degree of freedom in the structural design of the organopolyoxane and the ease of obtaining the raw material, it is preferred that at least one of the formulas represented by the following formula (2) is based on the above formula (B). The functional group-based alkoxydecane and/or a partial hydrolyzate thereof, and at least one alkoxydecane compound represented by the following formula (3), a partial hydrolyzate thereof and a condensate thereof The above mixture is partially co-hydrolyzed and polycondensed organic polyoxane. YR ¹ _m Si(OCH ₃ ) _n (OC ₂ H ₅ ) _3-mn (2) R ¹ _p Si(OCH ₃ ) _q (OC ₂ H ₅ ) _r (OR ² ) _4-pqr ......... (3) Here, Y, R ¹ and R ² each have the same meaning as described above, m is an integer of 0 to 2, n is an integer of 0 to 3, but m+n is an integer ranging from 0 to 3. , p is an integer from 0 to 2, q is an integer from 0 to 4, and r is an integer from 0 to 4. However, p+q+r is an integer ranging from 0 to 4, but contains one or more OR ² groups. The component is an alkoxy-containing decane compound of the formula (3).

The alkoxysilane having an organic functional group represented by the above formula (2), specifically, the organofunctional group may be exemplified by having a thiomethyl group, a 3-hydrothiopropyl group, a 6-hydrothiohexyl group, 10-Hydroxythioguanidino, (4-hydrothiomethyl)phenylethyl, glycidoxymethyl, 3-glycidoxypropyl, 5,6-epoxyhexyl, 9 , 10-epoxyindenyl, 2-(3,4-epoxycyclohexyl)ethyl, 2-(3,4-epoxy-4-methylcyclohexyl)propyl, acryloxy Methyl, 3-propenyloxypropyl, 6-propenyloxyhexyl, 10-propenyloxycarbonyl, methacryloxymethyl, 3-methylpropoxypropyl, 6 -Methacryloxymethoxyhexyl, 10-methylpropenyloxycarbonyl, vinyl, allyl, 5-hexenyl, 9-nonenyl, 3-vinyloxypropyl, p-benzene Vinyl, cyclohexenylethyl, chloromethyl, 3-chloropropyl, 6-chlorohexyl, 10-chloroindolyl, bromomethyl, 3-bromopropyl, aminemethyl, 3-aminopropyl 6-amine Propyl, N-methyl-3-aminopropyl, N,N-dimethyl-3-aminopropyl, N-phenyl-3-aminopropyl, N(2-aminoethyl)-3- Trimethoxy decane compound such as amine propyl, N-(6-aminohexyl)-3-aminopropyl, N-(vinylbenzyl)-2-amineethyl-3-aminopropyl, etc. Base hydride compound, methyl dimethoxy decane compound, methyl diethoxy decane compound, ethyl dimethoxy decane compound, ethyl diethoxy decane compound, propyl dimethoxy decane compound, C A bis ethoxy decane compound, a dimethyl methoxy decane compound, a dimethyl diethoxy decane compound, an ethoxy diethoxy decane compound, a methoxy diethoxy decane compound, or the like.

Further, the alkoxy group-containing decane compound represented by the above formula (3), specifically, the alkoxy decane group of p = 0 can be exemplified by tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane. , tetraisopropoxy decane, tetrabutoxy decane, tetraisobutoxy decane, etc., the alkoxy decane of p = 1 can be exemplified by having methyl, ethyl, propyl, isopropyl, 1-methyl Trimethoxy decane, triethoxy decane, tripropoxy oxypropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, phenyl, tolyl, benzyl, phenethyl, etc. a decyl alkane, a triisopropoxy decane, a tributoxy decane, a triisobutoxy decane, etc., and an alkoxy decane of p=2 can be exemplified by dimethyl dimethoxy decane or dimethyl diethoxy group. Decane, dimethyldipropoxydecane, dimethyldibutoxydecane, methylethyldimethoxydecane, diphenyldimethoxydecane, diphenyldiethoxydecane, and the like.

Further, from the viewpoint of easiness of obtaining raw materials or cost, it is preferred to use m in the above formula (2) to be 0, n is 3 or 0, that is, trimethoxydecane or triethoxydecane having an organic functional group or a partial hydrolyzate thereof, and R ¹ in the above formula (3) is a methyl group, p is 1 and/or 0, that is, methyltrialkoxydecane, tetraalkoxynonane, a partial hydrolyzate thereof or Further, it is more preferable that the alkoxy group-containing decane compound, the partial hydrolyzate thereof or the condensate thereof in which q and r in the formula (3) are 0 are essential components.

In particular, in the case of the alkoxysilane having an organic functional group represented by the above formula (2), a 3-hydroxythiopropyltrimethoxydecane, 3-hydrothiopropyltriethoxy group is used. Decane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane And at least one of 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane is preferably selected from the group consisting of alkoxy-containing decane compounds represented by the above formula (3). Methyl trimethoxy decane, methyl triethoxy decane, methyl tripropoxy decane, methyl triisopropoxy decane, methyl tributoxy decane, methyl triisobutoxy decane, four At least one of methoxydecane, tetraethoxydecane, tetrapropoxydecane, tetraisopropoxydecane, tetrabutoxydecane, tetraisobutoxydecane (but selected from methyltripropoxy) Decane, methyl triisopropoxy decane, methyl tributoxy decane, methyl triisobutoxy decane, tetrapropoxy decane, tetraisopropoxy decane, tetrabutoxy decane, tetraisobutyl At least one of oxydecane Species as an essential ingredient).

These organofunctional alkoxy decanes or partial hydrolyzates thereof, alkoxy-containing decane compounds, partial hydrolyzates thereof or condensates thereof may be used in combination of plural kinds, but by the above formula (2) When two or more kinds of alkoxysilanes having an organic functional group and/or a partial hydrolyzate thereof are used, it is preferred to have the same organic functional group. Also, designed for arbitrarily The ratio of the methoxy group, the ethoxy group, the alkoxy group having 3 and/or 4 in the organopolyoxane, the alkoxy group-containing decane compound represented by the above formula (3), In the case of the partial hydrolyzate or the condensate thereof, it is preferred to use two or more kinds of alkoxy groups in combination.

The blending ratio of the above-mentioned organic functional group-containing alkoxysilane and/or a partial hydrolyzate thereof, an alkoxy group-containing decane compound, a partial hydrolyzate thereof or a condensate thereof is not particularly limited, but if the former ratio is too small When the organic polysiloxane is used, it is not possible to exhibit the characteristics of the reactivity of the organic functional group which should originally be present, and it is necessary to convert the Si atom of the two components to have one organic functional group in at least one molecule. Mobibi should range from 1:99 to 99:1, more preferably from 10:90 to 80:20.

Further, the order of mixing or mixing of the various raw materials, and the method of performing partial co-hydrolysis and polycondensation are not particularly limited, and according to a conventionally known method, for example, an alkoxy group having an organic functional group in the above may be used. a mixture of a decyl alkane and/or a partial hydrolyzate thereof, a decyl compound containing an alkoxy group, a partial hydrolyzate thereof or a condensate thereof, in the presence of a hydrolysis or condensation reaction catalyst, partially hydrolyzed and aggregated by adding water The condensation reaction is carried out, and in this case, a suitable organic solvent may be used as needed.

As the catalyst for the hydrolysis and condensation reaction to be used, various conventionally known ones can be used. Specific examples thereof include organic acids such as acetic acid, trifluoroacetic acid, butyric acid, oxalic acid, maleic acid, citric acid, methanesulfonic acid, p-toluenesulfonic acid, and trifluoromethanesulfonic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, and the like. Basic compounds such as inorganic acids, sodium hydroxide, potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, sodium acetate, potassium acetate, ammonia, ammonium hydroxide, triethylamine, potassium fluoride, fluorine A fluorine-containing compound such as ammonium chloride, an organometallic compound such as tetraisopropyl titanate, tetrabutyl titanate, dioctyltin dimylate or an aluminum chelate. The above-mentioned catalysts may be used singly or in combination of plural kinds, but the amount of catalyst used is preferably in the range of 0.0001 to 10 mol%, more preferably 0.001, based on the number of moles of Si atoms present in the entire raw material. ~3% of the range of moles.

As described above, the degree of polymerization of the organopolysiloxane of the present invention is preferably from a couple of two atoms of a ruthenium atom to a polymer of several hundred or so of a ruthenium atom, but is used for water of partial hydrolysis or polycondensation. The amount determines the average degree of polymerization. When water is excessively added, the alkoxy group is hydrolyzed to form a resin having a large number of branched structures, and the desired polyoxyalkyloxy oligomer is not obtained. Therefore, the amount of hydrolyzed water must be strictly determined. For example, when all of the alkoxydecane raw materials used are monomers having one fluorene atom, the organopolyoxyalkylene having an average degree of polymerization Z is used as long as it is used with respect to the alkoxy decane raw material of Z mole ( Z-1) Mohr water can be partially hydrolyzed or polycondensed.

At this time, an organic solvent such as an alcohol, an ether, an ester or a ketone may be used as needed. Specific examples of such an organic solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, and propylene glycol monomethyl ether; ethers such as diethyl ether and dipropyl ether; and methyl acetate. An ester of ethyl acetate or ethyl acetoxyacetate, a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone. Further, a nonpolar solvent such as hexane, toluene or xylene may be used in combination with the above solvent. In particular, alcohols such as methanol, ethanol, and isopropanol are preferably used.

The amount of the organic solvent used is as long as it is relative to the alkoxy group which becomes a raw material. The total amount of the alkane, the partially hydrolyzed product thereof, and the condensate thereof may be in the range of 0 to 1000 parts by mass. However, when the amount used is small, the reaction system at the start of hydrolysis may not be uniform, and even if it is too much, it is not only The above addition effect cannot be seen, and the yield is lowered and economically disadvantageous, so it is preferably in the range of 10 to 500 parts by mass, more preferably in the range of 20 to 200 parts by mass.

The actual operation in the partial (co)hydrolysis and polycondensation reaction is preferably carried out by dropping a specific amount of water or a mixed solution of water/organic solvent in a mixed system of alkoxydecane raw materials, a catalyst and an organic solvent, or A mixed solution of a specific amount of water/catalyst or a mixed solution of water/catalyst/organic solvent is dropped into a mixed system composed of an alkoxydecane raw material and an organic solvent. In this case, an alkoxydecane raw material having a methoxy group or an ethoxy group having a high hydrolysis reactivity, and an alkoxy group having a carbon number of 3 and/or 4 having a hydrolysis-reactive low propoxy group or a butoxy group. The base alkoxydecane raw material is partially hydrolyzed in advance, and the two components are mixed, and further, after partial co-hydrolysis, a polycondensation reaction may be carried out. Each reaction system may be carried out in a temperature range of 0 to 150 ° C. However, in general, the reaction is slowed down at a temperature lower than room temperature, so that it is not practical, and when it is too high, it is also an epoxy group, a hydrogen sulfide group, or the like. The thermal decomposition or the thermal polymerization of acryloxy group has an adverse effect on the organic functional group, and is therefore in the temperature range of 20 to 130 °C. After the reaction, a purification step of neutralization, adsorption, filtration, or the like of the catalyst to be used, or a purification step of distilling off the organic solvent and the by-produced alcohol or the low-boiling substance, etc., can be used to obtain the objective. The inventive organopolyoxane.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the examples are not intended to be merely illustrative of the invention. The present invention is not limited by the following examples as long as it does not exceed the meaning. Further, the analysis of the organopolysiloxane obtained in each of the examples was carried out in the following manner.

(1) The average degree of polymerization of the organopolysiloxane is calculated by gel permeation chromatography (GPC), and the weight average molecular weight determined from the calibration curve prepared from the polystyrene standard sample is used as a reference. .

(2) The alkoxy group content in the organic polyoxane is determined by the alkali fragmentation-gas chromatography (GC) analysis method [refer to the Silicone Handbook, 792-793 (issued by Nikkan Kogyo Co., Ltd.)] The coefficients c, d, and e in the above average composition formula (1).

(3) The structural analysis of the organopolyoxane is carried out by nuclear magnetic resonance spectroscopy ( ²⁹ Si-NMR) analysis and proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR) analysis, and the average composition formula (1) is obtained from the measurement results. The coefficients a, b, f in ).

(4) The organofunctional group equivalent of the organopolyoxane was measured by the following analysis.

(i) thiol equivalent

According to the acetic acid/potassium iodide/potassium iodate addition-sodium thiosulfate solution titration method [Refer to the Analytical Chemistry Handbook, Rev. 2, 432-432 (issued by Maruzen Co., Ltd.)].

(ii) Epoxy equivalents

The epoxy ring-opening (formation of chlorohydrin)-sodium hydroxide solution titration method by hydrochloric acid [refer to Analytical Chemistry Handbook, Revised Second Edition, pp. 334-335 (issued by Maruzen Co., Ltd.)] was measured.

[iii]methacrylic equivalent

The results were obtained from the above-mentioned 矽NMR image ( ²⁹ Si-NMR) analysis and proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR) analysis.

(5) The viscosity of the organopolyoxane was measured by a viscosity at 25 ° C in JIS Z 8803.

[Example 1] Synthesis of organopolyoxane 1

In a flask of 1 liter capacity equipped with a stirring device, a cooling condenser, a temperature device, and a dropping funnel, 62.5 g (0.3 mol) of tetraethoxy decane and 52.9 g (0.2 mol) of tetrapropoxy decane were fed. 62.5 g of ethanol and 52.9 g of isopropyl alcohol were heated in an oil bath while stirring and heating, and the temperature was raised to an internal temperature of 50 °C. While stirring in a flask, a mixed solution of 7.2 g (water: 0.4 mol, hydrochloric acid: 7.2 × 10 ^-4 mol) and 7.2 g of ethanol was added dropwise for 10 minutes for 10 minutes, and the temperature was further raised under reflux. The preliminary hydrolysis reaction liquid A was obtained by aging for 2 hours.

In contrast, in a mixed solution of 39.3 g (0.2 mol) of 3-hydrothiopropyltrimethoxydecane, 40.9 g of methyltrimethoxydecane (0.3 mol), and 80.2 g of methanol, the internal temperature was A mixture of 7.2 g of 0.1 N aqueous hydrochloric acid (water: 0.4 mol, hydrochloric acid: 7.2×10 ^-4 mol) and 7.2 g of ethanol was added dropwise at 20 to 30 ° C for 10 minutes, and further at an internal temperature of 20 to 30 ° C. The preliminary hydrolysis reaction liquid B was obtained by aging for 30 minutes.

After adding the preliminary hydrolysis reaction liquid B to the above-mentioned preliminary hydrolysis reaction liquid A and stirring and mixing, 1.8 g of a 0.1 N hydrochloric acid aqueous solution was added at an internal temperature of 20 to 30 ° C (water: 0.1 mol, hydrochloric acid: 1.8 × 10 ^-4 Mo) After mixing the solution with 1.8 g of ethanol, the mixture was heated in an oil bath and refluxed for 2 hours. Then, 9.3 g (KF: 1.6 × 10 ^-3 mol) of a potassium fluoride in 1% ethanol solution was added, and further, the mixture was aged under reflux for 2 hours to partially co-hydrolyze and polycondensate.

Then, the alcohol component was distilled off while raising the temperature to an internal temperature of 80 ° C, and the temperature was raised to an internal temperature of 100 ° C under a reduced pressure of 30 Torr, and the residual alcohol component and the low boiling component were distilled off, and then filtered to obtain a colorless color. Transparent liquid organopolyoxane 1 (capacity: 127.5 g, yield: 92%).

The organopolyoxane 1 is in the above average composition formula (1), Y is 3-hydrothiopropyl, R ¹ is methyl, and R ² is propyl, from the respective raw materials used (other than the organic solvent) The molar average molecular weight and the average degree of polymerization obtained by the above analysis results, the respective coefficients in the average composition formula (1), the viscosity (mm ² /s), and the hydrogenthio group equivalent are expressed in in FIG. 1.

[Example 2] Synthesis of organopolyoxane 2

In a flask of 1 liter capacity equipped with a stirring device, a cooling condenser, a temperature device, and a dropping funnel, 41.7 g (0.2 mol) of tetraethoxy decane and 79.3 g (0.3 mol) of tetrapropoxy decane were fed. 41.7 g of ethanol and 79.3 g of isopropyl alcohol were heated in an oil bath while stirring and heating, and the temperature was raised to an internal temperature of 50 °C. While stirring in a flask, a mixed solution of 7.2 g (water: 0.4 mol, hydrochloric acid: 3.6 × 10 ^-3 mol) and 7.2 g of ethanol was added dropwise for 10 minutes, and the mixture was further heated to be cooked under reflux. The preliminary hydrolysis reaction liquid A was obtained in 2 hours.

In contrast, 47.7 g (0.2 mol) of 3-hydrothiopropyltriethoxydecane, 40.9 g (0.3 mol) of methyltrimethoxydecane, and 40.9 g of methanol and 47.7 g of ethanol were mixed solutions. In the internal temperature of 20 ~ 30 ° C for 10 minutes, drip 0.5N hydrochloric acid aqueous solution 7.2g (water: 0.4 mol, hydrochloric acid: 3.6 × 10 ^-3 mol) and methanol 7.2g mixed solution, further internal temperature 20 The preliminary hydrolysis reaction liquid B was obtained by aging at 30 ° C for 30 minutes.

After adding the preliminary hydrolysis reaction liquid B to the above-mentioned preliminary hydrolysis reaction liquid A and stirring and mixing, 1.8 g of a 0.5 N hydrochloric acid aqueous solution is added at an internal temperature of 20 to 30 ° C (water: 0.1 mol, hydrochloric acid: 9 × 10 ^-4 Mo) After mixing the solution with 1.8 g of ethanol, the mixture was heated in an oil bath and refluxed for 2 hours. Then, 9.3 g (KF: 8 × 10 ^-3 mol) of a potassium fluoride solution in 5% ethanol was added, and further, the mixture was aged under reflux for 2 hours to partially co-hydrolyze and polycondensate.

Then, the alcohol component was distilled off while raising the temperature to an internal temperature of 80 ° C, and the temperature was raised to an internal temperature of 100 ° C under a reduced pressure of 30 Torr to distill off the residual alcohol component and the low boiling component, followed by filtration. Colorless transparent liquid organopolyoxane 2 (capacity: 136.7 g, yield: 94%).

The organopolyoxane 2 is in the above average composition formula (1), Y is 3-hydrothiopropyl, R ¹ is methyl, and R ² is propyl, from the respective raw materials used (other than the organic solvent) The molar average molecular weight and the average degree of polymerization obtained by the above analysis results, the respective coefficients in the average composition formula (1), the viscosity (mm ² /s), and the hydrogenthio group equivalent are expressed in in FIG. 1.

[Example 3] Synthesis of organopolyoxane 3

In a flask having a capacity of 1 liter equipped with a stirring device, a cooling condenser, a temperature device, and a dropping funnel, 132.2 g (0.5 mol) of tetrapropoxydecane and 132.2 g of isopropyl alcohol were fed, and the mixture was stirred and mixed with oil. The mixture was heated in a bath to raise the temperature to an internal temperature of 50 °C. While stirring in a flask, a mixed solution of 7.2 g (water: 0.4 mol, hydrochloric acid: 7.2 × 10 ^-3 mol) and 7.2 g of isopropyl alcohol was added dropwise for 10 minutes, and the mixture was further heated under reflux. The preliminary hydrolysis reaction liquid A was obtained by aging for 2 hours.

In contrast, 3-hydroxythiopropyltrimethoxydecane 19.6 g (0.1 mol), 3-hydrothiopropyltriethoxydecane 23.8 g (0.1 mol), methyltrimethoxy 1 3.6 g (0.1 mol) of decane, 35.7 g (0.2 mol) of methyltriethoxy decane, and 33.2 g of methanol and 59.5 g of ethanol, and 1 N hydrochloric acid was dropped for 10 minutes at an internal temperature of 20 to 30 ° C. A mixed solution of 7.2 g of an aqueous solution (water: 0.4 mol, hydrochloric acid: 7.2 x 10 ^-3 mol) and 7.2 g of methanol was further aged at 20 to 30 ° C for 30 minutes to obtain a preliminary hydrolysis reaction liquid B.

After adding the preliminary hydrolysis reaction liquid B to the above-mentioned preliminary hydrolysis reaction liquid A and stirring and mixing, 1.8 g of a 1N hydrochloric acid aqueous solution was added at an internal temperature of 20 to 30 ° C (water: 0.1 mol, hydrochloric acid: 1.8 × 10 ^-3 mol) After mixing with a solution of 1.8 g of isopropyl alcohol, the mixture was heated in an oil bath and refluxed for 2 hours. Then, 0.94 g of potassium fluoride (KF: 1.62 × 10 ^-2 mol) was added, and further, the mixture was aged under reflux for 2 hours to partially co-hydrolyze and polycondensate.

Then, the alcohol component was distilled off while raising the temperature to an internal temperature of 80 ° C, and the temperature was raised to an internal temperature of 100 ° C under a reduced pressure of 30 Torr to distill off the residual alcohol component and the low boiling component, followed by filtration. Colorless transparent liquid organopolyoxane 3 (yield: 139.0 g, yield: 91%).

The organopolyoxane 3 is in the above average composition formula (1), Y is 3-hydrothiopropyl, R ¹ is methyl, and R ² is propyl, from the respective raw materials used (other than the organic solvent) The molar average molecular weight and the average degree of polymerization obtained by the above analysis results, the respective coefficients in the average composition formula (1), the viscosity (mm ² /s), and the hydrogenthio group equivalent are expressed in in FIG. 1.

[Example 4] Synthesis of organopolyoxane 4

In a flask of 1 liter capacity equipped with a stirring device, a cooling condenser, a temperature device, and a dropping funnel, 44.1 g (0.2 mol) of methyltriisopropoxydecane and 96.2 g of tetrabutoxydecane were fed. 140.3 g of oxime and isopropanol were heated in an oil bath while stirring and mixing, and the temperature was raised to an internal temperature of 50 °C. While stirring in a flask, a mixed solution of 7.2 g (water: 0.4 mol, hydrochloric acid: 1.08 × 10 ^-2 mol) and 7.2 g of isopropanol was added dropwise for 10 minutes, and the mixture was further heated to reflux. The mixture was aged for 2 hours to obtain a preliminary hydrolysis reaction liquid A.

In contrast, 71.5 g (0.3 mol) of 3-hydrothiopropyltriethoxydecane, 44.1 g (0.2 mol) of methyltriisopropoxydecane, 71.5 g of ethanol, and 44.1 g of isopropanol In the mixed solution of g, a mixed solution of 7.2 g of 1N hydrochloric acid aqueous solution (water: 0.4 mol, hydrochloric acid: 7.2×10 ^-3 mol) and 7.2 g of isopropanol was dropped for 10 minutes at an internal temperature of 20 to 30 ° C. Further, the preliminary hydrolysis reaction liquid B was obtained by aging at an internal temperature of 30 to 30 ° C for 30 minutes.

After adding the preliminary hydrolysis reaction liquid B to the above-mentioned preliminary hydrolysis reaction liquid A, the mixture is stirred and mixed, and then 1.8 g (water: 0.1 mol, hydrochloric acid: 1.8 × 10 ^-3 mol) is added at an internal temperature of 20 to 30 ° C. After a mixed solution of 1.8 g of propanol, the mixture was heated in an oil bath and refluxed for 2 hours. Then, 1.27 g (KF: 2.18 × 10 ^-2 mol) of potassium fluoride was added, and further subjected to partial co-hydrolysis and polycondensation reaction under reflux for 2 hours.

Then, the alcohol component was distilled off while the temperature was raised to an internal temperature of 80 ° C, and the temperature was raised to an internal temperature of 120 ° C under a reduced pressure of 30 Torr to distill off the residual alcohol component and the low boiling component, followed by filtration. Colorless transparent liquid organopolyoxane 4 (capacity: 165.1 g, yield: 96%).

The organopolyoxane 4 is in the above average composition formula (1), Y is 3-hydrothiopropyl, R ¹ is methyl, and R ² is isopropyl and butyl, from the respective raw materials used. The molar ratio (other than the organic solvent), the weight average molecular weight determined by the above analysis results, the average degree of polymerization, the respective coefficients in the average composition formula (1), the viscosity (mm ² /s), and the hydrogen sulfur The base equivalents are shown in Table 1.

[Example 5] Synthesis of organopolyoxane 5

Into a flask of 1 liter capacity equipped with a stirring device, a cooling condenser, a temperature device, and a dropping funnel, 47.3 g (0.2 mol), methyl trisomies, of 3-glycidoxypropyltrimethoxydecane was fed. 66.1 g (0.3 mol) of propoxy decane, 104.2 g (0.5 mol) of tetraethoxy decane, 47.3 g of methanol, 104.2 g of ethanol, 66.1 g of isopropyl alcohol, and 17.4 g of a 1% ethanol solution of potassium fluoride ( KF: 3 × 10 ^-3 mol), while stirring and mixing, heating in an oil bath and raising the temperature to an internal temperature of 50 °C.

While stirring in a flask, a mixed solution of 16.2 g (0.9 mol) of ion-exchanged water and 16.2 g of ethanol was dropped for 30 minutes, and the mixture was further heated to be aged under reflux for 4 hours to partially co-hydrolyze and polycondensate. Then, the alcohol component was distilled off while raising the temperature to an internal temperature of 80 ° C, and the temperature was raised to an internal temperature of 100 ° C under a reduced pressure of 30 Torr to distill off the residual alcohol component and the low boiling component, followed by filtration. Colorless transparent liquid organopolyoxane 5 (capacity: 137.5 g, yield: 91%).

The organopolyoxane 5 is in the above average composition formula (1), Y is 3-glycidoxypropyl, R ¹ is methyl, and R ² is isopropyl, from the respective raw materials used ( The molar average molecular weight, the average degree of polymerization, the respective coefficients in the average composition formula (1), the viscosity (mm ² /s), and the epoxy group obtained by the above analysis results. The equivalents are shown in Table 1.

[Example 6] Synthesis of organopolyoxane 6

In a flask of 1 liter capacity equipped with a stirring device, a cooling condenser, a temperature device, and a dropping funnel, 28.4 g (0.12 mol) of 3-glycidoxypropyltrimethoxydecane, methyltrimethoxy a partially hydrolyzed condensate consisting of 9.1 g of a decyl olefin (in terms of argon atoms: 0.08 mol) and a partial hydrolyzed condensate of tetraethoxy decane, a phthalate ester 35 [Tama Chemical Industry (trade name: product name): 68.5 g (矽 atom conversion: 0.4 mol), methanol 37.5 g, ethanol 68.5 g, and potassium fluoride 1% ethanol solution 19.8 g (KF: 3.4 × 10 ^-3 mol) The mixture was stirred at a temperature of 20 to 30 ° C at an internal temperature, and a mixed solution of 6.1 g (0.34 mol) of ion-exchanged water and 6.1 g of ethanol was dropped for 10 minutes, and further stirred at an internal temperature of 20 to 30 ° C for 30 minutes.

85.3 g of a partial hydrolysis condensate composed of an average of tetrapropoxydecane (in terms of arson atom: 0.4 mol), 85.3 g of isopropyl alcohol, and 1% of a potassium fluoride solution of 11.6 g (KF) were added thereto. : 2 × 10 ^-3 mol), while stirring and mixing, heating in an oil bath and raising the temperature to an internal temperature of 50 °C.

While stirring in a flask, a mixed solution of 3.6 g (0.2 mol) of ion-exchanged water and 3.6 g of ethanol was dropped for 10 minutes, and the mixture was further heated to be aged under reflux for 4 hours to partially co-hydrolyze and polycondensate. Then, the alcohol component was distilled off while raising the temperature to an internal temperature of 80 ° C, and the temperature was raised to an internal temperature of 100 ° C under a reduced pressure of 30 Torr to distill off the residual alcohol component and the low boiling component, followed by filtration. Colorless transparent liquid The organopolyoxane 6 (yield: 139.8 g, yield: 93%).

The organopolyoxane 6 is in the above average composition formula (1), Y is 3-hydrothiopropyl, R ¹ is methyl, and R ² is propyl, from the respective raw materials used (other than the organic solvent) The molar average molecular weight and the average degree of polymerization obtained by the above analysis results, the respective coefficients in the average composition formula (1), the viscosity (mm ² /s), and the epoxy equivalent are expressed in In Table 2.

[Example 7] Synthesis of organopolyoxane 7

In a flask of 1 liter capacity equipped with a stirring device, a cooling condenser, a temperature device, and a dropping funnel, 177.2 g (0.75 mol) of 3-glycidoxypropyltrimethoxydecane was fed, tetraethoxy. 26.0 g (0.125 mol) of decane, 33.1 g (0.125 mol) of tetrapropoxydecane, 177.2 g (0.75 mol) of methanol, 26.0 g of ethanol, 33.1 g of isopropanol and 1% ethanol solution of potassium fluoride 11.6 g (KF: 2 × 10 ^-3 mol) was heated in an oil bath while stirring and heated to an internal temperature of 50 °C.

While stirring in a flask, a mixed solution of 13.5 g (0.75 mol) of ion-exchanged water and 13.5 g of isopropyl alcohol was dropped for 20 minutes, and the mixture was further heated to be aged under reflux for 4 hours to partially co-hydrolyze and polycondensate. Then, the alcohol component was distilled off while the temperature was raised to an internal temperature of 80 ° C, and the temperature was raised to an internal temperature of 90 ° C under a reduced pressure of 30 Torr to distill off the residual alcohol component and the low boiling component, followed by filtration. Colorless transparent liquid organopolyoxane 7 (yield: 172.7 g, yield: 89%).

This organopolyoxane 7 is in the aforementioned average composition formula (1), Y

3-Hydroxythiopropyl, no R ¹ (b=0), R ² is a propyl group, the molar ratio of the molar ratio of each raw material (other than the organic solvent) used, and the above analysis results The molecular weight, the average degree of polymerization, the respective coefficients in the above average composition formula (1), the viscosity (mm ² /s), and the epoxy equivalent are shown in Table 2.

[Example 8] Synthesis of organopolyoxane 8

In a flask of 1 liter capacity equipped with a stirring device, a cooling condenser, a temperature device, and a dropping funnel, 124.2 g (0.5 mol), methyl trioxane, of 3-glycidoxypropyltrimethoxydecane was fed. 44.6 g (0.25 mol) of decane, 55.1 g (0.25 mol) of methyl triisopropoxy decane, 124.2 g of methanol, 44.6 g of ethanol and 55.1 g of isopropyl alcohol were heated in an oil bath while stirring and mixing. The temperature was raised to an internal temperature of 50 °C.

While stirring in a flask, a mixed solution of 17.1 g (water: 0.95 mol, hydrochloric acid: 3.4 × 10 ^-3 mol) and isopropanol 17.1 g of 0.2 N hydrochloric acid aqueous solution was dropped for 30 minutes, and the temperature was further raised to reflux. Cooked for 2 hours. Then, 0.86 g (1.02 × 10 ^-2 mol) of sodium hydrogencarbonate was added, and further, the mixture was aged under reflux for 2 hours to partially co-hydrolyze and polycondensate.

Then, 0.1 g of 4-methylphenol as a polymerization inhibitor was added, and the alcohol component was distilled off while raising the temperature to an internal temperature of 80 ° C at room temperature, and further heated to an internal temperature of 90 ° C under a reduced pressure of 20 Torr. After the alcohol component and the low-boiling component were left, the mixture was filtered to obtain a colorless transparent liquid organopolyoxane 8 (capacity: 154.1 g, yield: 95%).

The organopolyoxane 8 is in the above average composition formula (1), Y is a 3-methylpropenylpropyl group, R ¹ is a methyl group, and R ² is an isopropyl group, from the respective raw materials used (organic The molar ratio of the molar ratio other than the solvent, the average molecular weight obtained by the above analysis results, the respective coefficients in the average composition formula (1), the viscosity (mm ² /s), and the methacryl group The equivalents are shown in Table 2.

[Comparative Example 1] Synthesis of organopolyoxane 9

In a flask of 1 liter capacity equipped with a stirring device, a cooling condenser, a temperature device, and a dropping funnel, 39.3 g (0.2 mol) of 3-hydrothiopropyltrimethoxydecane and methyltrimethoxydecane were fed. 40.9 g (0.3 mol), tetraethoxy decane 104.2 g (0.5 mol), methanol 80.2 g, and ethanol 104.2 g, and 0.1 N hydrochloric acid aqueous solution was dropped for 30 minutes while stirring at an internal temperature of 20 to 30 ° C in a flask. A mixed solution of g (water: 0.9 mol, hydrochloric acid: 1.6 × 10 ^-3 mol) and methanol (6.22 g) was further heated and refluxed for 2 hours under reflux.

Then, 9.3 g (KF: 1.6 × 10 ^-3 mol) of a potassium fluoride in 1% ethanol solution was added, and further subjected to partial cohydrolysis and polycondensation reaction under reflux for 2 hours. Then, the alcohol component was distilled off while raising the temperature to an internal temperature of 80 ° C, and the temperature was raised to an internal temperature of 100 ° C under a reduced pressure of 30 Torr to distill off the residual alcohol component and the low boiling component, followed by filtration. Colorless transparent liquid organopolyoxane 9 (yield: 117.0 g, yield: 90%).

The organopolyoxane 9 is in the above average composition formula (1), Y is 3-methylpropenylpropyl group, R ¹ is a methyl group, and no OR ² (e=0), from each raw material used. The molar ratio (other than the organic solvent), the weight average molecular weight determined by the above analysis results, the average degree of polymerization, the respective coefficients in the average composition formula (1), the viscosity (mm ² /s), and the hydrogen sulfur The base equivalents are shown in Table 2.

[Comparative Example 2] Synthesis of organopolyoxane 10

In a flask of 1 liter capacity equipped with a stirring device, a cooling condenser, a temperature device, and a dropping funnel, 47.7 g (0.2 mol) of 3-hydrothiopropyltrimethoxydecane, methyltriethoxy group was fed. 53.5 g (0.3 mol) of decane, 104.2 g (0.5 mol) of tetraethoxy decane, and 205.4 g of ethanol, and 16.2 g of 0.1 N hydrochloric acid aqueous solution was dripped in the flask at an internal temperature of 20 to 30 ° C for 30 minutes while stirring. A mixed solution of 0.9 mol, hydrochloric acid: 1.6 × 10 ^-3 mol, and 16.2 g of ethanol was further heated to reflux for 2 hours under reflux.

Then, 9.3 g (KF: 1.6 × 10 ^-3 mol) of a potassium fluoride in 1% ethanol solution was added, and further subjected to partial cohydrolysis and polycondensation reaction under reflux for 2 hours. Then, the alcohol component was distilled off while raising the temperature to an internal temperature of 80 ° C, and the temperature was raised to an internal temperature of 100 ° C under a reduced pressure of 30 Torr to distill off the residual alcohol component and the low boiling component, followed by filtration. Colorless transparent liquid organopolyoxane 10 (capacity: 129.5 g, yield: 94%).

The organopolyoxane 10 is in the above average composition formula (1), Y is 3-hydrothiopropyl, R ¹ is methyl, and no OR ² (e=0), from each raw material used ( The molar average molecular weight, the average degree of polymerization, the respective coefficients in the average composition formula (1), the viscosity (mm ² /s), and the hydrogenthio group obtained by the above analysis results. The equivalents are shown in Table 2.

* The expressions of the various alkoxydecane starting materials in Tables 1 and 2 indicate the following compounds.

MP-TMS: 3-Hydroxythiopropyltrimethoxydecane

MP-TES: 3-Hydroxythiopropyltriethoxydecane

GP-TMS: 3-glycidoxypropyltrimethoxydecane

MAP-TMS: 3-methacryloxypropyltrimethoxydecane

M-TMS: methyltrimethoxydecane

M-TMS-some: a partially hydrolyzed condensate composed of the average couple of methyltrimethoxydecane (the molar ratio is expressed as a ruthenium atom)

M-TES: methyl triethoxy decane

M-TPS: methyl triisopropoxy decane

TEOS: tetraethoxy decane

TEOS-some: a partially hydrolyzed condensate composed of an average of tetraethoxy decane (the molar ratio is expressed as a ruthenium atom)

TPOS: tetrapropoxydecane

TPOS-some: a partially hydrolyzed condensate composed of the average couple of tetrapropoxydecane (the molar ratio is expressed as a ruthenium atom)

TBOS: tetrabutoxydecane

(6) Evaluation of hydrolysis of organic polyoxyalkylene

With respect to the organopolyoxane 1, 2, 3, 9, 10 obtained in the above Examples 1 to 3 and Comparative Examples 1 and 2, the hydrolyzability was evaluated by the following method. After 10 parts by mass of the organic polyoxane and 10 parts by mass of acetone were uniformly dissolved in a 50 ml flask, 1 part by mass of ion-exchanged water was added, and the mixture was shaken for 1 hour and dispersed. After the dispersion was allowed to stand at 25 ° C for 20 hours or at 60 ° C for 15 hours, anhydrous sodium sulfate was added thereto to dehydrate the mixture, and the weight average molecular weight was measured by gel permeation chromatography (GPC) analysis. The results are shown in Table 3.

As is apparent from the results shown in Table 3, the organopolysiloxane of the present invention can suppress the hydrolysis reactivity, and is advantageous in the stability of storage stability or the improvement of the stability in the mixed composition of the raw material containing water. .

Claims (10)

An organopolyoxane having a plurality of alkoxy groups having an organic functional group represented by the following average composition formula (1) and having a different number of carbon atoms in one molecule; Y _a R ¹ _b Si (OCH _{3 ) c} (OC ₂ H ₅ ) _d (OR ² ) _e (OH) _f O _(4-abcdef)/2 . . . In the formula (1), the Y group has at least one organic group selected from the group consisting of a hydrogenthio group, an epoxy group, a (meth)acryloxy group, an alkene group, a haloalkyl group, and an amine group, and R ¹ is a methyl group, R ² is propyl or isopropyl, a, b, c, d, e, r is 0.01≦a≦1, 0<b<2, 0<c≦2, 0<d≦2, 0<e≦2 , 0≦f≦1, and satisfies the number of 0.1≦c+d+e≦2.5, and 2≦a+b+c+d+e+f≦3. The organopolyoxane of claim 1, wherein Y in the above average composition formula (1) is an organic group containing a thiol group or an epoxy group. The organopolyoxane of claim 1, wherein the mixture is obtained by partially co-hydrolyzing or polycondensing the mixture, and the mixture is contained in at least one of the following formula (2). And one or two of a functional group-based alkoxysilane and/or a partial hydrolyzate thereof, and at least one alkoxy-containing decane compound represented by the following formula (3), a partial hydrolyzate thereof, and a condensate thereof Above; YR ¹ _m Si(OCH ₃ ) _n (OC ₂ H ₅ ) _3-mn . . . (2) R ¹ _p Si(OCH ₃ ) _q (OC ₂ H ₅ ) _r (OR ² ) _4-pqr . . . (3) where Y, R ¹ and R ² have the same meanings as above, m is an integer of 0 to 2, n is an integer of 0 to 3, but m+n is an integer ranging from 0 to 3. , p is an integer from 0 to 2, q is an integer from 0 to 4, and r is an integer from 0 to 4. However, p+q+r is an integer ranging from 0 to 4, but contains one or more OR ² groups. The component is an alkoxy-containing decane compound of the formula (3). The organopolyoxane of claim 3, wherein m in the above formula (2) is 0, and R ¹ in the above formula (3) is a methyl group, and p is 0 and/or 1 . An organopolyoxyalkylene as claimed in claim 3, wherein the alkoxysilane having an organic functional group represented by the above formula (2) is selected from the group consisting of 3-hydrothiopropyltrimethoxydecane, 3-Hydroxythiopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3,4-ring At least one of oxycyclohexyl)ethyltrimethoxydecane and 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, in the alkoxy group represented by the above formula (3) The decane compound is selected from the group consisting of methyl trimethoxy decane, methyl triethoxy decane, methyl tripropoxy decane, methyl triisopropoxy decane, tetramethoxy decane, tetraethoxy decane. At least one of tetrapropoxydecane and tetraisopropoxydecane (but selected from methyltripropoxydecane, methyltriisopropoxydecane, tetrapropoxydecane, tetraisopropoxydecane) At least one of them is an essential component). For example, the organopolyoxane of the first application of the patent scope, wherein the average degree of polymerization is from 3 to 100. For example, the organopolyoxane of the third application of the patent scope, wherein the average degree of polymerization is from 3 to 100. A method for producing an organopolyoxane having a plurality of alkoxy groups having an organic functional group represented by the following average composition formula (1) and a plurality of carbon atoms in a single molecule, characterized in that the following mixture is obtained Partially co-hydrolyzed, polycondensed, and the mixture is at least one of the alkoxysilane having an organic functional group represented by the following formula (2) and/or a partial hydrolyzate thereof, and at least one of the following formulas ( 3) one or more of an alkoxy group-containing decane compound, a partial hydrolyzate thereof, and a condensate thereof; Y _a R ¹ _b Si(OCH ₃ ) _c (OC ₂ H ₅ ) _d (OR ² ) _e (OH) _f O _(4-abcdef)/2 . . . In the formula (1), the Y group has at least one organic group selected from the group consisting of a hydrogenthio group, an epoxy group, a (meth)acryloxy group, an alkene group, a haloalkyl group, and an amine group, and R ¹ is a methyl group, R ² propyl or isopropyl, a, b, c, d, e, f are 0.01≦a≦1, 0<b<2, 0<c≦2, 0<d≦2, 0<e≦2, 0≦f≦1, and satisfies the number of 0.1≦c+d+e≦2.5, and 2≦a+b+c+d+e+f≦3; YR ¹ _m Si(OCH ₃ ) _n (OC ₂ H ₅ ) _3-mn . . . (2) R ¹ _p Si(OCH ₃ ) _q (OC ₂ H ₅ ) _r (OR ² ) _4-pqr . . . In the formula (3), Y, R ¹ and R ² each have the same meaning as described above, m is an integer of 0 to 2, n is an integer of 0 to 3, but m + n is an integer ranging from 0 to 3. , p is an integer from 0 to 2, q is an integer from 0 to 4, and r is an integer from 0 to 4. However, p+q+r is an integer ranging from 0 to 4, but contains one or more OR ² groups. The component is an alkoxy-containing decane compound of the formula (3). The method for producing an organopolyoxane according to the eighth aspect of the invention, wherein m in the above formula (2) is 0, and in the above formula (3), R ¹ is a methyl group, and p is 0 and / or 1. The method for producing an organopolyoxane according to the eighth aspect of the invention, wherein the alkoxysilane having an organic functional group represented by the above formula (2) is selected from the group consisting of 3-hydrothiopropyltrimethoxy Baseline, 3-hydrothiopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 2-(3, At least one of 4-epoxycyclohexyl)ethyltrimethoxynonane and 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane is represented by the above formula (3) The alkoxy-containing decane compound is selected from the group consisting of methyltrimethoxydecane, methyltriethoxydecane, methyltripropoxydecane, methyltriisopropoxydecane, tetramethoxydecane, and tetraethylidene. At least one of oxoxane, tetrapropoxydecane, and tetraisopropoxydecane (but selected from methyl tripropoxydecane, methyl triisopropoxydecane, tetrapropoxydecane, tetraisopropyl) At least one of oxydecane is an essential component).