JPH09227688A - Preparation of hydroxy-containing siloxane compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for preparing a hydroxy-contg. siloxane compd. which can conduct a hydrosilyl reaction of an unsatd. alcohol compd. with a hydrogen-modified siloxane compd. without protecting the hydroxyl group of the unsatd. alcohol compd. and, at the same time, enables a hydroxy-contg. siloxane compd. to be industrially advantageously prepared by reduced steps without sacrificing the yield and the purity. SOLUTION: This process for preparing a hydroxy-contg. siloxane compd. comprises reacting a hydrogen-modified dimethylsiloxane compd. with an unsatd. alcohol compd., wherein the reaction is conducted without protecting the hydroxyl group of the unsatd. alcohol compd. in the presence of a vinylsiloxane complex of platinum as a catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a hydroxyl group-containing siloxane compound, and more particularly to a method for producing a hydroxyl group-containing siloxane compound useful for modifying a synthetic polymer resin by applying the reactivity of a polyol. .

[0002]

2. Description of the Related Art Polysiloxane compounds such as silicone resin and silicone oil have been used for the purpose of imparting to synthetic resins unique interface properties such as water repellency, non-adhesiveness, and antifouling property, which polysiloxane compounds have conventionally possessed. Used by being blended or chemically bonded to synthetic resins. However, since silicone resins have poor compatibility with many synthetic resins, bleeding may occur with mere blending. In this case, improvement is attempted by using a siloxane compound having a reactive functional group.

As a modified siloxane of a high molecular compound such as polyurethane or polyester, which is synthesized by a reaction of a reactive hydroxyl group of a polyol, usually, one end,
A hydroxyl group-containing siloxane compound having one or more hydroxyl groups at both ends or side chains is used. These hydroxyl group-containing siloxane compounds are
Generally, it is synthesized by a hydrosilylation reaction of one end, both ends or a side chain hydrogen-modified siloxane compound with an unsaturated alcohol compound.
A dehydrogenation reaction, which is a side reaction, occurs between the i-H group and -OH in the alcohol compound, resulting in an extremely low yield of the desired hydroxyl group-containing siloxane compound, and as an impurity in the product. Problems such as remaining will occur.

Therefore, conventionally, before carrying out the hydrosilylation reaction, the hydroxyl group of the unsaturated alcohol compound is protected with a suitable protecting group such as trimethylsilyl group or acetyl group, and after the hydrosilylation reaction, detrimethylsilylation or A method of removing the protective group by deacetylation or the like has been adopted (JP-A-4-88024, JP-A-5-58).
9-229524, JP-A-62-195389,
Japanese Patent Application No. 62-23888, JP-A-5-97868.
No.). However, the above method has a disadvantage that the production process is lengthened, and a side reaction occurs when the protective group is eliminated, and as a result, the yield may not be improved (JP-A-4-88024).

On the other hand, POLYMER, 30, 553 (1
989) and Polym. J. , 19, 1091 (1
987) discloses a method of synthesizing a hydroxyl-modified siloxane compound by hydrosilylating a hydrogen-modified siloxane compound without protecting the hydroxyl group of an unsaturated alcohol compound. However, these synthetic methods require the use of a large excess of the unsaturated alcohol compound in a molar amount of 50 to 150 times with respect to the hydrogen-modified siloxane compound, and the reaction time is long, which is costly for industrial production. Was not suitable for.

[0006]

The object of the present invention is to solve the above-mentioned problems of the prior art, to carry out a hydrosilylation reaction with a hydrogen-modified siloxane compound without protecting the hydroxyl groups of the unsaturated alcohol compound, and It is an object of the present invention to provide a method for producing a hydroxyl group-containing siloxane compound which can be industrially advantageously produced in a shortened process without lowering the rate and the purity.

[0007]

The inventions claimed in this application are as follows. (1) When a hydroxyl group-containing siloxane compound is produced by reacting a hydrogen-modified dimethylsiloxane compound with an unsaturated alcohol compound, a platinum vinylsiloxane complex is used as a catalyst without protecting the hydroxyl group of the unsaturated alcohol compound. A method for producing a hydroxyl group-containing siloxane compound, which comprises performing the reaction as described above.

(2) The reaction product obtained in (1) has the general formula (I)

Embedded image [However, 1 and m in the formula are integers from 0 to 1000, A
Is a methyl group, a butyl group or

Embedded image In the above A and B, n is an integer of 2 to 9 and p is 0.
To 100, q is 0 or 1, R ₁ is hydrogen, a methyl group or an ethyl group, R ₂ is a hydroxyl group or a hydroxymethyl group, and R ₃ is an ethylene group or a propylene group. ] The hydroxyl-group containing siloxane compound represented by these, The manufacturing method of the hydroxyl-group containing siloxane compound characterized by the above-mentioned.

The hydrogen-modified dimethyl siloxane compound used in the present invention is represented by the following general formula (II)

Embedded image (However, 1 and m in the formula are 0 to 1,000 in the meaning of the number average degree of polymerization of the polydimethylsiloxane linear portion, and A'is hydrogen, a methyl group or a butyl group.) Specific examples include pentamethyldisiloxane and the like.

When the compound produced by the production method of the present invention is used for introducing a polydimethylsiloxane chain into a polymer such as polyurethane and polyester having a polyol as one of the monomers, the desired weight of the compound is used. Although l and m in the general formula (II) vary depending on the properties of the united product, usually, l and m are 1,000 or less, and those having a number average molecular weight of 50,000 or less can be preferably used.

Further, the general formula (III)

[Chemical 6] (However, s represents an integer of 3 to 8) and / or the general formula (IV)

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(Wherein t is an integer of 0 to 8, u is an integer of 0 to 8 and t + u does not include 0, 1 and 2), lithium trimethylsilanolate or butyllithium is used. Living polymerization by dimethylchlorosilane to a desired average degree of polymerization as a polymerization terminator, in the presence of lithium hydroxide, living polymerization with water as an initiator, or equilibration polymerization in the presence of an acid catalyst. It is also possible to use tetramethyldisiloxane or pentamethyldisiloxane as a terminal terminating agent and use one end, both ends or a side chain hydrogen-modified siloxane compound having a desired average degree of polymerization.

The unsaturated alcohol compound used in the present invention is represented by the general formula (V)

Embedded image (However, in the formula, r is an integer of 0 to 7, p is an integer of 0 to 100, q is 0 or 1, R ₁ is hydrogen, a methyl group or an ethyl group, R ₂ is a hydroxyl group or a hydroxymethyl group, R ₃ means an ethylene group or a propylene group), specifically, allyl alcohol-
Ethylene glycol monovinyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, glycerin monoallyl ether,
Examples include trimethylolethane monoallyl ether, trimethylolpropane monoallyl ether, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, and the like.

The vinyl siloxane complex of platinum used in the present invention is not particularly limited, but Pt {[(CH ₂ =
_{CH) (CH 3) 2 Si} ] 2 O} 2, HPt 2 {[CH 2
_{= CH) (CH 3) 2} Si] 2 O} 2 other such, platinum-vinylsiloxane complexes described in U.S. Patent No. 3,715,334 can be suitably used.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as shown in the following formula, a hydrogen-modified dimethylsiloxane compound represented by the general formula (II) and an unsaturated alcohol compound represented by the general formula (V) are treated with platinum. By carrying out the hydrosilylation reaction using the vinyl siloxane complex as a catalyst, the desired hydroxyl group-containing dimethylsiloxane compound represented by the general formula (I) can be obtained in a short time while suppressing side reactions.

[0016]

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In the hydrosilylation reaction of the hydrogen-modified siloxane compound and the unsaturated alcohol compound, it is preferable to use the unsaturated alcohol compound in an equimolar amount or more with respect to the hydrosilyl group of the hydrogen-modified siloxane compound. Depending on the type of unsaturated alcohol compound used, it may be used in an equimolar amount or preferably in an amount 1.2 times or more the molar amount. Further, even if an excess amount of unsaturated alcohol is used, it does not adversely affect the reaction itself, but unless there is a reason to use it more than necessary, it may be about 1.2 to 2 times by mole.

The reaction temperature varies depending on the unsaturated alcohol compound used, but it is preferably from room temperature to 80 ° C. On the other hand, if it is too high, side reactions may occur, so it is preferably carried out at 20 ° C to 80 ° C. When the concentration of the hydrosilyl group in the hydrogen-modified siloxane compound is high, the calorific value increases and the reaction temperature inevitably rises, but no side reaction occurs in a short time. However, when the concentration of the hydrosilyl group is high, the reaction temperature is more preferably room temperature, or when the reaction temperature is 60 ° C. or higher, the hydrogen-modified siloxane compound may be fed and reacted. The completion of the reaction can be confirmed by the fact that the absorption of hydroxyl group is not observed due to infrared absorption. The amount of platinum vinylsiloxane complex used is
In order to obtain economy and proper reaction, 0.1 to 10,000 p is used for the hydrogenene-modified siloxane compound.
pm is preferable, more preferably 1.0 to 1,000 p
m.

[0019]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. Example 1 (hydrosilylation of pentamethyldisiloxane and allyl alcohol) 100 ml equipped with a stirrer and a cooling device
The three-necked flask was replaced with N ₂ , and pentamethyldisiloxane (7.4 g, 0.05 mol) and allyl alcohol (5.8 g) were added.
(0.10 mol, twice the mol of Si-H) is charged. This bis [divinyltetramethyldisiloxane] showed the following formula at room temperature (VI) platinum (0) Pt {[(CH 2 = CH) (CH 3) 2 Si] 2 O} 2 (VI) (3 wt % Xylene solution) 18.8 μl (2.5 × 1
0 ^-6 mol, 5 × 10 ^-5 mol per Si-H) was added. An exotherm was immediately observed, and the mixture was aged for 1 hour while being left at room temperature. Gas chromatography analysis (GC
By analysis), no peak of pentamethyldisiloxane was observed. From the reaction product thus obtained, the low boiling point component was distilled off at 55 ° C./266 Pa for 2 hours, and the target siloxane compound was added to the residue in the GC purity of 95.5.
Obtained in almost quantitative yield in%. The ¹ H-NMR spectrum and IR spectrum data of the obtained siloxane compound are as follows, and the structure of the following formula was confirmed.

[0020]

Embedded image

¹ H-NMR (CDCl ₃ ): δppm 0.1 (Si—C H ₃ , s, 15H) 0.4 to 0.8 (Si—C H ₂ , m, 2H) 1.3 to 1 _{.8 (Si-CH 2 -C H} 2, m, 2H) 2.3 (OH, s, 1H) 3.6 (C H 2 -O, t, 2H) IR (KBr): cm -1 3330 ( O-H) 2960 (CH) 1260 (Si-CH 3) 1120~1030 (Si-O)

Example 2 (Hydrosilylation of pentamethyldisiloxane and ethylene glycol monoallyl ether) A 100 ml three-necked flask equipped with a stirrer and a cooling device was replaced with N ₂ to obtain 7.4 g (0.05 mol of pentamethyldisiloxane). ) And ethylene glycol monoallyl ether 10.2 g (0.1
0 mol and 2 times mol relative to Si-H) are charged. To this was added 18.8 μl (2.5 × 10 ⁻⁶ mol, 5 × 10 ⁻⁵ mol with respect to Si—H) of the platinum catalyst represented by the formula (VI) (3 wt% xylene solution) at room temperature. An exotherm was immediately observed, and the mixture was aged for 1 hour while being left at room temperature. By GC analysis, no peak of pentamethyldisiloxane was observed. From the reaction product thus obtained, low-boiling components were distilled off at 100 ° C./133 Pa for 2 hours, and the target siloxane compound was obtained in the bottom of the kettle with a GC purity of 98.7% in a substantially quantitative yield. ¹ of the obtained siloxane compound
The data of 1 H-NMR spectrum and IR spectrum are as follows, and the structure of the following formula was confirmed.

[0023]

Embedded image

¹ H-NMR (CDCl ₃ ): δppm 0.1 (Si—C H ₃ , s, 15H) 0.4 to 0.8 (Si—C H ₂ , m, 2H) 1.3 to 1 _{.8 (Si-CH 2 -C H} 2, m, 2H) 2.3 (OH, broad, 1H) 3.2~3.9 (C H 2 -O-C H 2 -C H 2 -O, m,
6H) IR (KBr): cm -1 3420 (O-H) 2960 (CH) 1260 (Si-CH 3) 1100~1010 (Si-O)

Example 3 (Hydrosilylation of pentamethyldisiloxane with glycerin monoallyl ether) A 100 ml three-necked flask equipped with a stirrer and a cooling device was replaced with N ₂ to obtain 7.4 g of pentamethyldisiloxane (0.05 mol). ) And glycerin monoallyl ether 13.2 g (0.1 mol, Si-H
(2 times the mole). At this temperature, the platinum catalyst represented by the formula (VI) (3 wt% xylene solution) was added at 18.8 μm at room temperature.
1 (2.5 × 10 ^-6 mol, 5 × 10 ^-5 relative to Si-H
Mol) was added. An exotherm was immediately observed, and the mixture was aged for 1 hour while being left at room temperature. By GC analysis, no peak of pentamethyldisiloxane was observed. From the reaction product thus obtained, a low boiling point component was added at 140 ° C /
After distilling off at 133 Pa for 2 hours, the target siloxane compound was obtained in the bottom of the kettle with a GC purity of 98.7% in a substantially quantitative yield. The ¹ H-NMR spectrum and IR spectrum data of the obtained siloxane compound are as follows, and the structure of the following formula was confirmed.

[0026]

Embedded image

¹ H-NMR (CDCl ₃ ): δppm 0.1 (Si—C H ₃ , s, 15H) 0.3 to 0.7 (Si—C H ₂ , m, 2H) 1.3 to 1 _{.8 (Si-CH 2 -C H} 2, m, 2H) 3.2~3.9 (C H 2 - O-C H 2 - C H (O H) -C H 2 - O
H, m, 9H) IR ( KBr): cm -1 3420 (O-H) 2960 (CH) 1260 (Si-CH 3) 1100~1010 (Si-O)

Example 4 (Hydrosilylation of pentamethyldisiloxane with trimethylolpropane monoallyl ether) A 100 ml three-necked flask equipped with a stirrer and a cooling device was replaced with N ₂ to obtain 7.4 g of pentamethyldisiloxane. (05 mol) and trimethylolpropane monoallyl ether 1
Charge 7.4 g (0.1 mol, 2 times mol relative to Si-H). To this was added 18.8 μl (2.5 × 10 ⁻⁶ mol, 5 × 10 ⁻⁵ mol with respect to Si—H) of the platinum catalyst represented by the formula (VI) (3 wt% xylene solution) at room temperature. An exotherm was immediately observed, and the mixture was aged for 1 hour while being left at room temperature. By GC analysis, no peak of pentamethyldisiloxane was observed. The low boiling point component was distilled off from the reaction product thus obtained at 150 ° C./133 Pa for 2 hours, and the target siloxane compound was obtained in the bottom of the reactor with a GC purity of 93.0% and a substantially quantitative yield. . The ¹ H-NMR spectrum and IR spectrum data of the obtained siloxane compound are as follows, and the structure of the following formula was confirmed.

[0029]

Embedded image

¹ H-NMR (CDCl ₃ ): δppm 0.1 (Si—C H ₃ , s, 15H) 0.3 to 0.7 (Si—C H ₂ , m, 2H) 0.9 (- _{C H 3, t, 3H)} 1.3 (-C H 2 -, q, 2H) 1.3~1.8 (Si-CH 2 -C H 2, m, 2H) 3.2~3.9 _{(C H 2 - O-C} H 2 - C (C H 2 -O H)
_{2, m, 10H) IR (} KBr): cm -1 3400 (O-H) 2970 (CH) 1260 (Si-CH 3) 1120~1050 (Si-O)

Comparative Example 1 (Hydrosilylation of pentamethyldisiloxane with chloroplatinic acid and allyl alcohol) As the hydrosilylation catalyst, the platinum catalyst (3 wt% xylene solution) represented by the formula (VI) was replaced with hexachloroplatinum ( IV) A reaction was carried out in the same manner as in Example 1 except that a solution of hydrogen in isopropyl alcohol was used and the reaction temperature was changed to 60 ° C. G after the reaction
From the C analysis, no peak of pentamethyldisiloxane was observed. Two types of by-products in the reaction mixture thus obtained were mainly observed by GC measurement. A by-product having a boiling point lower than that of the target product was confirmed to have the following structure A from the GC-mass spectrum. The by-product having a higher boiling point than the target product was presumed to be the following structure B. The GC composition ratio with the target siloxane compound was target product: A: B = 1: 3: 1. Since a large amount of by-products are generated in this manner, both the yield and the purity are lowered.

[0032]

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Comparative Example 2 (Hydrosilylation of pentamethyldisiloxane and allyl alcohol using platinum-acetylacetone complex) Bisacetyl was used as the hydrosilylation catalyst instead of the platinum catalyst (3% by weight xylene solution) represented by the formula (VI). Acetonatoplatinum (II) was used, and the reaction was performed in the same manner as in Example 1 except that the reaction temperature was set to 60 ° C. After the completion of the reaction, a large amount of the raw material was found by GC analysis, and it was confirmed that the reaction was not completed. When further aged at 60 ° C. for 12 hours, IR measurement revealed that Si-
Absorption of H was observed. The raw materials were also found by GC measurement, and low-boiling by-products and high-boiling by-products were found from the target product. A by-product having a boiling point lower than that of the target product was confirmed to have the following structure A from the GC-mass spectrum. The by-product having a higher boiling point than the target product was presumed to be the following structure B. The GC composition ratio with the target siloxane compound is as follows: target product: A: B = 1:
It was 0.02: 0.03. The amount of by-products produced was not so large, but the reaction rate was slow, and it was not suitable for industrial production.

[0034]

Embedded image

Example 5 (Hydrosilylation of siloxane compound having hydrosilyl group at α-position and ethylene glycol monoallyl ether) 30 equipped with a stirrer, a cooling device and a dropping device
In a 0 ml three-necked flask, 66.7 g (0.05 equivalent of 1-terminal Si-H-modified dimethylsiloxane oligomer (hydrogen equivalent of 1300, and thus number average molecular weight of 1300)) was added.
Mol) and ethylene glycol monoallyl ether 30.
Charge 9 g (0.30 moles, 2 moles relative to Si-H). To this was added 57.1 μl (7.6 × 10 ⁻⁶ mol, 5 × 10 ⁻⁵ mol with respect to Si—H) of the platinum catalyst represented by the formula (VI) (3 wt% xylene solution) at room temperature. Immediate heat generation was observed, and 133.3 g (0.10 mol) of the remaining one-terminal Si—H-modified dimethylsiloxane oligomer was added dropwise over 35 minutes, followed by aging for 1 hour while leaving it at room temperature. From the IR spectrum, no peak derived from Si—H of the Si-H modified dimethylsiloxane oligomer having one terminal end was observed at all. From the reaction product thus obtained, low-boiling components were distilled off at 100 ° C./133 Pa for 2 hours and then filtered through a membrane filter to obtain 212 g of a colorless transparent liquid. IR spectrum of this thing,
The results of hydroxyl equivalent and gel permeation chromatography (hereinafter GPC) are as described below, and the structure of the following formula was confirmed.

[0036]

Embedded image

IR (KBr): cm ⁻¹ 3420 (O—H) 2960 (C—H) 1260 (Si—CH ₃ ) 1120 to 1010 (Si—O) Hydroxyl group: 1.48%, therefore hydroxyl group equivalent 1150 GPC : Polystyrene-equivalent number average molecular weight (Mn) 1280 weight average molecular weight (Mw) 1610 dispersity (Mw / Mn) 1.26

Example 6 (Hydrosilylation of a siloxane compound having a hydrosilyl group at the α-position and ethylene glycol monoallyl ether) Instead of pentamethyldisiloxane in Example 2, a Si-H-modified dimethylsiloxane oligomer having one terminal (hydrogen) was used. An equivalent weight of 8100, and thus an oligomer having a number average molecular weight of 8100) of 2000 g (0.
247 mol) and 92.8 μl (1.2 × 1) of the platinum catalyst (3 wt% xylene solution) represented by the formula (VI).
0 ^-5 mol, 5 x 10 ^-5 mol relative to Si-H),
Ethylene glycol monoallyl ether 50.4g
The reaction was performed in the same manner as in Example 2 except that (0.494 mol, twice the mol of Si-H). From the reaction product thus obtained, the low-boiling component was added at 100 ° C./133 Pa to 2
After evaporating over time, the mixture was filtered through a membrane filter to obtain 1950 g of a colorless transparent liquid. The results of IR spectrum, hydroxyl equivalent and GPC of this product are as described below, and were confirmed to have the structure of the following formula.

[0039]

Embedded image

IR (KBr): cm ⁻¹ 3420 (O—H) 2960 (C—H) 1260 (Si—CH ₃ ) 1100 to 1020 (Si—O) Hydroxyl group: 0.19%, therefore hydroxyl group equivalent 8860 GPC : Polystyrene equivalent number average molecular weight (Mn) 10400 weight average molecular weight (Mw) 11700 dispersity (Mw / Mn) 1.13

Example 7 (Hydrosilylation of a siloxane compound having a hydrosilyl group at the α-position and glycerin monoallyl ether) Instead of the pentamethyldisiloxane in Example 3, a Si-H-modified dimethylsiloxane oligomer having one terminal (hydrogen equivalent) was used. 1300, and thus 50 g of an oligomer having a number average molecular weight of 1300 (equivalent to 0.038 mol as a hydrosilyl group), 16.8 μl (1.9 × 3) of a platinum catalyst (3 wt% xylene solution) represented by the formula (VI) was used. 10 ^-6 mol, Si
The reaction was performed in the same manner as in Example 3 except that 10 g of glycerin monoallyl ether (0.076 mol, twice the mol of Si-H) was present in the presence of 5 x 10 ^-5 mol with respect to -H). From the reaction product thus obtained, 15 low-boiling components were removed.
After distilling off at 0 ° C./133 Pa for 2 hours, the mixture was filtered through a membrane filter to obtain 52.6 g of a colorless transparent liquid.
The results of IR spectrum, hydroxyl equivalent and GPC of this product are as described below, and were confirmed to have the structure of the following formula.

[0042]

Embedded image

IR (KBr): cm ⁻¹ 3420 (O—H) 2960 (C—H) 1260 (Si—CH ₃ ) 1120 to 1010 (Si—O) Hydroxyl group: 2.83%, therefore hydroxyl group equivalent 600 GPC : Polystyrene equivalent number average molecular weight (Mn) 1000 weight average molecular weight (Mw) 1380 dispersity (Mw / Mn) 1.38

Example 8 (Hydrosilylation of a siloxane compound having a hydrosilyl group at the α-position and allyl alcohol) In a 100 ml three-necked flask equipped with a stirrer, a cooling device and a dropping device, a Si-H-modified dimethylsiloxane oligomer having one end (hydrogen 12.5 g (0.0095 mol) of an equivalent of 1300, and therefore an oligomer having a number average molecular weight of 1300 and 4.41 g of allyl alcohol (0.076 mol, twice the mol of Si-H) are charged. At this temperature, 16.8 μl of platinum catalyst (3 wt% xylene solution) represented by the formula (VI) at 60 ° C. (0.
19 × 10 ^-6 mol, 5 × 10 ^-5 mol relative to Si-H)
Was added. Immediate fever was observed and the remaining one end Si-
37.5 g of H-modified dimethylsiloxane oligomer (0.
(0285 mol) was added dropwise over 3 minutes, followed by aging for 1 hour while being left at room temperature, and 8.4 μl (0.1 ×) of the platinum catalyst (3% by weight xylene solution) represented by the formula (VI).
(10 ⁻⁶ mol, 2.5 × 10 ⁻⁵ mol relative to Si—H) was added and the mixture was aged for 30 minutes. From the IR spectrum, the Si-end of the Si-H modified dimethylsiloxane oligomer with one end is
No peak derived from H was observed. From the reaction product thus obtained, a low boiling point component was added at 60 ° C / 133P.
After distilling off with a for 2 hours, it was filtered through a membrane filter to obtain 49.5 g of a colorless transparent liquid. IR of this thing
The results of the spectrum, hydroxyl equivalent and GPC are as described below, and the structure of the following formula was confirmed.

[0045]

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IR (KBr): cm ^-1 3420 (O-H) 2960 (C-H) 1260 (Si-CH ₃ ) 1120 to 1010 (Si-O) Hydroxyl group: 1.51%, therefore hydroxyl equivalent 1120 GPC : Polystyrene equivalent number average molecular weight (Mn) 1220 weight average molecular weight (Mw) 1580 dispersity (Mw / Mn) 1.30

Example 9 (Hydrosilylation of a siloxane compound having a hydrosilyl group at the α-position and allyl alcohol) In a 100 ml three-necked flask equipped with a stirrer, a cooling device and a dropping device, a Si-H-modified dimethylsiloxane oligomer having one end (hydrogen) was added. 12.5 g (0.0095 mol) of an equivalent of 1300, and therefore an oligomer having a number average molecular weight of 1300 and 4.41 g of allyl alcohol (0.076 mol, twice the mol of Si-H) are charged. At 60 ° C., 4.2 μl (0.0% of platinum catalyst (3% by weight xylene solution) represented by the formula (VI) was added.
48 × 10 ^-6 mol, 1.25 × 10 ^-5 relative to Si-H
Mol) was added. Immediate heat generation was observed, and 37.5 g of the remaining one-terminal Si-H-modified dimethylsiloxane oligomer
(0.0285 mol) and the platinum catalyst represented by the formula (VI) (3
Wt% xylene solution) 12.6 μl (0.143 × 1)
(0 ⁻⁶ mol, 3.75 × 10 ⁻⁵ mol with respect to Si—H) was simultaneously added dropwise over 3 minutes, and then the mixture was left to stand at room temperature for aging for 1 hour. From the IR spectrum, one end Si
No peak derived from Si—H of the —H-modified dimethylsiloxane oligomer was observed. From the reaction product thus obtained, the low boiling point component was added at 60 ° C./133 Pa to 2
After evaporating over time, the mixture was filtered through a membrane filter to obtain 49.5 g of a colorless transparent liquid. The results of IR spectrum, hydroxyl equivalent and GPC of this product are as described below, and were confirmed to have the structure of the following formula.

[0048]

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IR (KBr): cm ⁻¹ 3420 (O—H) 2960 (C—H) 1260 (Si—CH ₃ ) 1120 to 1010 (Si—O) Hydroxyl group: 1.51%, therefore hydroxyl group equivalent 1120 GPC : Polystyrene equivalent number average molecular weight (Mn) 1220 weight average molecular weight (Mw) 1580 dispersity (Mw / Mn) 1.30

Example 10 (Hydrosilylation of a siloxane compound having a hydrosilyl group at the α and ω positions and ethylene glycol monoallyl ether) Si-H modified dimethyl siloxane oligomer having both ends (hydrogen equivalent of 1240, therefore number average molecular weight of 2480) ) 1100 g (equivalent to 0.885 mol as a hydrosilyl group) and 180.5 g (1.77 mol) of ethylene glycol monoallyl ether and the formula (VI)
The platinum catalyst (3 wt% xylene solution) shown in 332.
7 μl (4.42 × 10 ⁻⁵ mol, 5 × relative to Si-H
The reaction was performed in the same manner as in Example 5 except that the amount was 10 ⁻⁵ mol). Next, the reaction product was filtered through a membrane filter to obtain 1150 g of a colorless transparent liquid. The IR spectrum, hydroxyl group quantification and GPC results of this product are as described below.
The structure was confirmed by the following formula.

[0051]

[Chemical 21]

IR (KBr): cm ⁻¹ 3450 (O—H) 2960 (C—H) 1260 (Si—CH ₃ ) 1100 to 1020 (Si—O) Hydroxyl group: 1.20%, therefore hydroxyl equivalent 1420 GPC : Polystyrene equivalent number average molecular weight (Mn) 3270 weight average molecular weight (Mw) 3890 dispersity (Mw / Mn) 1.19

Example 11 (Hydrosilylation of a siloxane compound having a hydrosilyl group at the α-position and polyethylene glycol monoallyl ether) Si-H modified dimethyl siloxane oligomer with one terminal (hydrogen equivalent 1320, therefore number average molecular weight 1320)
50 g (0.1 as hydrosilyl group).
(Corresponding to 038 mol) in the presence of 2 μl of platinum catalyst (3% by weight xylene solution) represented by the formula (VI) (5 × 10 ⁻⁶ mol with respect to Si—H) Allyl ether (Oil and Fat Products Co., Ltd .; Uniox PKA-5001 [H (OCH ₂ CH ₂ ) m O
CH ₂ CH = CH ₂ ]; vinyl group equivalent = 217) 12.
The reaction was performed in the same manner as in Example 2 except that the amount was 4 g (0.057 mol, 1.5 times mol based on Si-H). From the IR spectrum of the reaction solution, a spectrum derived from Si-H was not recognized. From the reaction product thus obtained, low-boiling components were distilled off at 120 ° C./133 Pa for 2 hours and then filtered through a membrane filter to obtain 58.2 g of a slightly yellow transparent liquid. The results of IR spectrum, hydroxyl equivalent and GPC of this product are as described below, and were confirmed to have the structure of the following formula.

[0054]

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IR (KBr): cm ⁻¹ 3440 (O—H) 2960 (C—H) 1260 (Si—CH ₃ ) 1100 to 1020 (Si—O) Hydroxyl group: 1.12%, therefore hydroxyl group equivalent 1520 GPC : Polystyrene equivalent number average molecular weight (Mn) 1760 weight average molecular weight (Mw) 2200 dispersity (Mw / Mn) 1.25

[0056]

EFFECTS OF THE INVENTION According to the present invention, it is possible to omit the hydroxyl group protecting step and the deprotecting step, which are required in the conventional production method, and it is also possible to carry out the reaction at room temperature, so that the heating can be performed as in the conventional method. The production cost can be remarkably suppressed by eliminating the necessity of the above, and further, the side reaction caused by the above two steps can be avoided, and at the same time, the product of the quality equal to or higher than that produced by the above two steps. Can be industrially advantageously provided by a short reaction time.

Claims (2)

[Claims] 1. When a hydrogen-modified dimethylsiloxane compound is reacted with an unsaturated alcohol compound to produce a hydroxyl group-containing siloxane compound, a platinum vinylsiloxane complex of platinum is obtained without protecting the hydroxyl group of the unsaturated alcohol compound. A method for producing a hydroxyl group-containing siloxane compound, characterized in that the reaction is carried out using as a catalyst. 2. The reaction product obtained in claim 1 has the general formula (I): [However, 1 and m in the formula are integers from 0 to 1000, A
Is a methyl group, a butyl group or In the above A and B, n is an integer of 2 to 9 and p is 0.
To 100, q is 0 or 1, R ₁ is hydrogen, a methyl group or an ethyl group, R ₂ is a hydroxyl group or a hydroxymethyl group, and R ₃ is an ethylene group or a propylene group. ] The hydroxyl-group containing siloxane compound represented by these, The manufacturing method of the hydroxyl-group containing siloxane compound characterized by the above-mentioned.