JP2003082103A - Process for manufacturing hydroxycarbyl group- containing polyorganosiloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide such a process for manufacturing a hydroxycarbyl group- containing polyorganosiloxane having an excellent external transparency from a hydrogen-modified polyorganosiloxane and an unsaturated alcoholic compound that is unnecessary for the protection of its hydroxyl group and is of shortened steps with an industrial profit and without reducing the yield and purity. SOLUTION: The process for manufacturing the hydroxycarbyl group- containing polyorganosiloxane by reacting the hydrogen-modified polyorganosiloxane with the unsaturated alcoholic compound is characterized by allowing to react them by using a wet type catalyst supporting a noble metal compound and having a water content of 0.5-50 wt.% and without protecting the hydroxyl group of the above unsaturated alcoholic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention
Regarding a method for producing a billigroup-containing polyorganosiloxane,
More specifically, a synthetic tree utilizing the reactivity of polyols
Excellent appearance transparency useful for fat modification or fiber treatment agent
Hydroxylcarbyl group-containing polyorganosiloxane
The present invention relates to a method for producing a compound. [0002] 2. Description of the Related Art Conventionally, polyorganosiloxane compounds
Unique interface such as water repellency, non-adhesion, and stain resistance
Silicone resin is used to impart properties to synthetic resins and fibers.
Polyorganosiloxane compounds such as fats and silicone oils
Is blended or chemically bonded to various synthetic resins
It has been. However, silicone resin and silicone
Ill etc. are poorly compatible with many resins, so
In some cases, bleeding may occur. In this case
Is a polyorganosiloxane compound having a reactive functional group.
Improvements have been made using objects. [0003] The reaction of the reactive hydroxyl groups of the polyol
High, e.g. polyurethane or polyester
As a modified siloxane of a molecular compound, usually, one end,
Has one or more hydroxyl groups at both ends or side chains
Hydroxycarbyl group-containing polyorganosiloxane
Compound is used. These hydroxycarbyl groups
The containing polyorganosiloxane compound generally has one terminal,
Both ends or side chain hydrogen-modified polyorganoshiro
Hydrosilyl compound of xanse compound and unsaturated alcohol compound
The siloxane compound is synthesized by the
Side reaction between H group and -OH group in alcohol compound
Dehydrogenation reaction occurs and the desired hydroxy carb
Extremely high yield of polyorganosiloxane compounds containing
Problems such as lowering and remaining in the product as impurities
Problem occurs. For this reason, conventionally, hydrosilylation reaction
Before performing the above, the hydroxyl group of the unsaturated alcohol compound is
A protecting group, for example, a trimethylsilyl group or an acetyl group;
Protect and after the hydrosilylation reaction, remove the demethylsilyl
A method to remove the protecting group by a group or deacetylation is adopted.
(Japanese Patent Laid-Open No. 4-88024,
9-295524, JP-A-62-195389.
Gazette, Japanese Patent Application No. 62-23888, Japanese Patent Application Laid-Open No. 5-97
868, etc.). However, in the above method,
The disadvantage is that the length of the
Side reaction may occur, and as a result, the yield may not improve.
Was. On the other hand, POLYMER, 30, 553 (1
989) and Polym. J. , 19,1091 (1
987) protects the hydroxyl groups of unsaturated alcohol compounds
Hydrogen-modified polyorganosiloxane compounds without
Large excess of unsaturated alcohol of 50 to 150 times
To the hydroxyl group
Synthesis of polyorganosiloxane compounds containing ruby group
A method is disclosed. However, this synthesis method
Large excess of unsaturated alcohol compounds must be used
Low yield, and industrial production due to long reaction time
Was disadvantageous in terms of cost. Also, Japanese Patent Application Laid-Open No. 9-227
No. 688 uses a platinum-vinylsiloxane complex.
A method has been proposed, in which the compound has one end.
For low molecular weight siloxane compounds such as run and oligomer
Limited to high viscosity polyorganosiloxanes in general
It is not usable and it is a reaction at low temperature
Therefore, a large amount of platinum is required, and temperature control is difficult.
And the resulting hydroxycarbyl group
The polyorganosiloxane compound has an effect on the remaining platinum.
However, its use has been limited due to the occurrence of coloring. [0006] SUMMARY OF THE INVENTION The object of the present invention is to
Solving the problems of the prior art,
Hydrogen-modified polyols without protecting hydroxyl groups
Perform a hydrosilylation reaction with ganosiloxane and recover
In a shortened process without reducing the rate and purity
Superior appearance transparency that can be produced industrially advantageously
Of selected hydroxyl-containing polyorganosiloxane
It is to provide a method. [0007] Means for Solving the Problems The present inventors have achieved the above object.
As a result of intensive studies to achieve this, a homogeneous catalyst
Is to eliminate the coloring because the catalyst remains in the component
Turned out to be difficult. Therefore, pay attention to heterogeneous catalysts.
As a result, a wafer having a water content of 0.5 to 50% by weight was obtained.
Reaction using a supported catalyst of noble metal compounds
That we can achieve our goals by
The present invention has been completed. That is, the present invention provides a hydrogen-modified
Polyorganosiloxane and unsaturated alcohol compound
React with hydroxyl carbyl group-containing polyorganos
In producing loxane, the unsaturated alcohol compound
Without protecting the hydroxyl group of the product, the water content is 0.5 to
Loading of 50% by weight wet type noble metal compound
Excellent transparency characterized by performing reaction using a catalyst
Hydroxylcarbyl group-containing polyorganosiloxane
Is a manufacturing method. [0009] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Hydrogen-modified polyorgano used in the present invention
Loxane has the general formula R¹ _mH_nSiO_{(4- (m + n)) / 2} (However, in the formula, R¹Are the same but different
Hydroxyl, methyl, ethyl, propyl
Alkyl groups such as phenyl and butyl; phenyl, tolyl, xylyl
Aralkyl groups such as chloromethyl, 1,1,1, -to
Illustrated by halogenated carbon groups such as trifluoropropyl
M and n are n / m ≧ 3 and 1.
It is a positive integer satisfying 8 <m + n <2.1. )
These molecular structures are cyclic, chain,
Shape or branched chain shape. This hydrogen
The molecular weight of the ene-modified polyorganosiloxane
But preferably between 144 and 100,000,
Is preferably 144 to 10,000. These c
Hydrogen-modified polyorganosiloxane has a silicon atom
Organosilane or organo containing bound hydrogen atom
It is obtained by hydrolyzing and polymerizing nochlorosilane. Specifically, the following are mentioned.
You. [0011] Embedded image This hydrogen-modified polyorganoshiro
The xane can be a single compound or a mixture of two or more.
There is no. The unsaturated alcohol used in the present invention
The compound represented by the general formula CH_Two= CH_Two(CH_Two)_u− (OR^Four)_v− (OCH_TwoCR^TwoR^ThreeC
H_Two)_w-OH (Where u is an integer of 0 to 7 and v is an integer of 0 to 100)
Number, w is 0 or 1, R ^TwoIs a hydrogen or methyl group or
Is an ethyl group, R^ThreeIs a hydroxyl group or
Tyl group, R^FourRepresents an ethylene group or a propylene group
You. ), Specifically, allyl alcohol
, Methallyl alcohol, ethylene glycol monovinyl
Ether, ethylene glycol monoallyl ether,
Diethylene glycol monoallyl ether, glycerin
Monoallyl ether, trimethylolethane monoallyl
Ether, trimethylolpropane monoallyl ether
, Polyethylene glycol monoallyl ether, poly
Propylene glycol monoallyl ether, Pentaery
Sultol monoallyl ether and the like. This
As for the saturated alcohol compound, two or more kinds
It can be a mixture. The water content used in the present invention is 0.5 to
Loading of 50% by weight wet type noble metal compound
As the catalyst, specifically, as the supported metal, platinum,
Hydrosilylation catalysts such as rhodium and palladium
Noble metal compounds that can be used as Also carrier
Examples include alumina, carbon, silica-alumina,
Olite, silica, titania, silica fiber, etc.
Illustrative, but not limiting. Also these
Noble metal compound supported catalysts can be used alone or in combination of two or more.
It may be used in combination. Regarding the water content, 0.5 to 50 weight
%, Preferably 1.0 to 10% by weight.
If so, there is no particular limitation. However, contains water
If the amount exceeds 50% by weight, it cannot be present in the supported catalyst,
It is inappropriate because it comes out of the catalyst system as water droplets. Usually, when preparing a supported catalyst, moisture is not required.
Therefore, moisture is removed in the final process (this
These are usually called dry types. ). However, this reaction
For supported catalysts used for water, leave moisture in the supported catalysts
(This is usually called a wet type.)
Use. The effect is not clear, but the supported catalyst
Precious metals supported by the reaction system due to the presence of moisture
Metal compounds are difficult to elute, and the supported catalyst becomes unsaturated
Competition for preferential coordination to vinyl group of coal compound
It is not because the dehydrogenation reaction, which is a reaction, is unlikely to occur
It is thought. In carrying out this reaction, the reaction components
Is a supported noble metal, such as a chlorine compound.
It is necessary that there are no impurities that elute the compound.
You. Compounds that have the effect of eluting noble metal compounds are components
When the noble metal compound is supported in the reaction system,
Eluted and a dehydrogenation reaction, which is a side reaction, occurs.
Hydroxycarbyl group-containing polyorganosiloxane
Cannot be obtained with high purity. Hydrogen-modified polyorganosiloxa
For the hydrosilylation reaction of carboxylic acids with unsaturated alcohol compounds
In addition, hydrogen-modified polyorganosiloxane
Of unsaturated alcohols to hydrosilyl groups
It is preferable to use more than one mole of the compound. Unsaturated alcohol
Depending on the type of the compound, it may be preferable to use equimolar or more.
In some cases, it is better to use it in an amount of 1.2 mol or more.
Even if excess unsaturated alcohol is used, the reaction itself
It does not have any adverse effect on
Is disadvantageous industrially due to the reduced
If the amount of coal added is small, the reaction will be slow and the end point of the reaction
Because it takes time to reach
Unless otherwise specified, a range of about 1.2 to 2 moles is preferred.
New The reaction temperature depends on the unsaturated alcohol compound used.
Therefore, it is different, but it is performed in the range of 80 ° C to 130 ° C.
preferable. Also, if it is too low, the reaction is slow and not industrial,
If the temperature is higher than 130 ° C, it is difficult to control the reaction.
I don't. Hydrogen-modified polyorganosiloxane
When the hydrosilyl group concentration is high, the calorific value increases,
The reaction temperature inevitably rises, but in a short time the side reaction
Will not occur. However, hydrosilyl group concentration
Is higher, more preferably hydrogen-modified
It is preferable that the reaction be carried out by dropping a li- organosiloxane. I
However, it is not limited to this method, and the method of addition
Is the hydrogen-modified polyorganosil
Xanth, unsaturated alcohol and supported catalyst are added together
The reaction may be performed after the temperature rise. The reaction is completed by infrared
Absorption of hydroxyl groups due to absorption can no longer be observed.
And can be confirmed. The amount of the supported catalyst of the platinum compound is
In order to obtain economical efficiency and an appropriate reaction,
0.1 to 1000 ppm is preferred based on the total weight
And more preferably 10 to 500 ppm. After this
If the amount is too low, the reaction is slow and impractical.
Also, the filtration and purification process after the completion of the reaction becomes longer, and the platinum catalyst
Is also not preferred because it is expensive. In this reaction, an appropriate inert solvent is used.
A medium such as hexane, heptane, benzene, toluene,
Xylene, mineral spirit, diethyl ether,
Use as a reaction solvent such as propyl ether or tetrahydrofuran
Can be used. The organic unsaturated compound itself polymerizes.
If it is easy, 2,6-di-t-butyl is added to the reaction system.
Add a polymerization inhibitor such as tyl-4-methylphenol
Good to keep. [0021] According to the present invention, there is a need for a conventional manufacturing method.
Protecting the hydroxyl group of the unsaturated alcohol compound, and
It is possible to omit the deprotection process, and the production cost
Can be significantly suppressed, and the above two steps
Side reaction can be avoided, and in addition,
Quality equal to or better than what was manufactured in a short time
Can be industrially advantageously provided by the above reaction.
In addition, simple production that cannot be achieved using a homogeneous catalyst
Hydroxycarbyl group with excellent transparency in appearance
Polyorganosiloxane-containing can be provided. [0022] Next, the present invention will be described with reference to Examples and Comparative Examples.
This will be explained specifically, but it is not limited to this example.
No. In addition, all parts in each example indicate parts by weight, and the viscosity is
The value at 25 ° C. Example 1 Take a stirrer, thermometer, reflux condenser and nitrogen gas inlet.
1600 cP viscosity in 2 liter 4-neck flask
Of both ends hydrogenpolydimethylsiloxane 445
Parts, 5.1 parts of allyl glycol, 40 parts of toluene and water
Wet type 1% platinum alumina with 2% content
0.48 parts of the supported catalyst were blended, and the temperature was raised to 120 ° C.
After heating and stirring for 10 hours, the pressure was reduced to 10 mmHg,
After removing substances and low molecular compounds, cool to 40 ° C and collect
Then, filtration was performed to remove the supported catalyst. Reaction
To check for completeness, the sampled sample is
The solution after the supported catalyst was precipitated was colorless and transparent. The viscosity is 1792 cP and the appearance is colorless and transparent.
The weight loss on heating was 1.73% and the hydroxyl value was 13.
4% (The method for measuring the hydroxyl value was determined according to JIS.
K1557-1970. ). Comparative Example 1 The operation was the same as in Example 1, and the wet type 1% white
0.3% moisture content instead of gold alumina supported catalyst
0.48 parts of dry type 1% platinum alumina supported catalyst
The same procedure was carried out except for the addition. Reaction completion during appearance reaction
To check the degree, the sample
The solution after the medium precipitated was brown. The viscosity is 1842 cP and the appearance is colorless and transparent.
The heat loss was 1.73% and the hydroxyl number was 4.8.
%Met. Comparative Example 2 The operation was the same as in Example 1, and the wet type 1% white
0.3% moisture content instead of gold alumina supported catalyst
0.48 parts of dry type 1% platinum alumina supported catalyst
Addition and addition of 0.01 part of distilled water
I went to. To check the completeness of the reaction during the appearance reaction,
After the supported catalyst precipitates,
The solution was brown. The viscosity is 1760 cP and the appearance is colorless and transparent.
The loss on heating was 1.63% and the hydroxyl number was 4.5.
%Met. Comparative Example 3 The operation was the same as in Example 1, and the wet type 1% white
Bis [divinyl tetrame
Tildisiloxane] platinum (0) (Pt {[(CH_Two= CH) (CH
_Three)_TwoSi]_TwoO}_Two/ Xylene solution (platinum content 3%) 0.16
And the same procedure was performed. The viscosity is 1954 cP and the appearance is
Transparent yellow, heat loss 1.80%, hydroxyl number
Was 6.7%. Example 2 Take a stirrer, thermometer, reflux condenser and nitrogen gas inlet.
Into a 2 liter 4-neck flask [0026] Embedded image Hydrogen polydiene represented by the chemical formula
150 parts of methylsiloxane, 30 parts of allyl alcohol,
130 parts of toluene and 2% water content
0.48 parts of 1% platinum alumina supported catalyst
The temperature was raised to 20 ° C., and the mixture was heated and stirred for 5 hours.
g to remove unreacted substances and low molecular weight compounds.
After cooling to ℃ C, take out and filter to remove the supported catalyst.
Was. To check the completion of the reaction during the reaction,
The solution after the supported catalyst has precipitated is colorless
It was transparent. The hydroxyl number was 61%. Comparative Example 4 The operation was the same as in Example 2, and the wet type 1% white
Chloroplatinic acid (H_TwoPtC_l6)
/ IPA solution (platinum content 1%) 0.48 parts was added
Except for the above, the procedure was the same. Investigate reaction completion during appearance reaction
Therefore, the sampled sample is
Was. The hydroxyl number was 35%.

────────────────────────────────────────────────── ───
[Procedure for Amendment] [Date of Submission] October 5, 2001 (2001.10.
5) [Procedure amendment 1] [Document name to be amended] Description [Item name to be amended] 0027 [Correction method] Change [Content of amendment] 150 parts of hydrogen polydimethylsiloxane represented by the chemical formula of Department,
130 parts of toluene and 0.48 parts of a wet type 1% platinum alumina supported catalyst having a water content of 2% were blended,
The temperature was raised to 20 ° C., and the mixture was heated and stirred for 5 hours.
g to remove unreacted substances and low molecular weight compounds.
After cooling to ℃, it was taken out and filtered to remove the supported catalyst. In order to examine the degree of completion of the reaction during the reaction, the sampled sample was colorless and transparent after the precipitated catalyst was precipitated. The hydroxyl number was 61%. Comparative Example 4 The operation was performed in the same manner as in Example 2, except that the wet type 1% platinum-alumina-supported catalyst was replaced with chloroplatinic acid (H ₂ PtCl ₆ ).
The same procedure was performed except that 0.48 part of a / IPA solution (platinum content 1%) was added. The sample that was sampled was yellow and transparent to check the degree of completion of the reaction during the appearance reaction. The hydroxyl number was 35%.

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Claims (1)

Claims: 1. In producing a hydroxylcarbyl group-containing polyorganosiloxane by reacting a hydrogen-modified polyorganosiloxane with an unsaturated alcohol compound, a hydroxyl group of the unsaturated alcohol compound is protected. A method for producing a hydroxylcarbyl group-containing polyorganosiloxane having excellent transparency, wherein the reaction is carried out without using a wet type noble metal compound supported catalyst having a water content of 0.5 to 50% by weight.