JPH10182827A - Production of amino-containing organopolysiloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an organopolysiloxane containing at least one amino group of the average per molecule and not becoming turbid with the lapse of time by reacting an amino-containing silicone or a mixture containing an amino- containing organosiloxane and an amino-free organosiloxane by heating in the presence of a specified amount of a basic equilibration catalyst and water. SOLUTION: It is desirable that the siloxane or the siloxane mixture as the starting material has a degree of polymerization of 100 or below. It may be any of cyclic, branched and linear siloxanes. The basic equilibrate catalyst is exemplified by an alkali metal hydroxide or an onium hydroxide compound, especially desirably a quat. phosphonium compound or a silanolate compound thereof which emits less aminic odor and is used in an amount of 0.001-1 pt.wt. per 100 pts.wt. starting material. The reaction is carried out in the presence of 0.01-20 pts.wt. water. The obtained product is represented by the formula (wherein R<1> is an amino-containing group; R<2> is another hydrocarbon group or the like; n/m>=3; and 1.8<m+n<2.1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an amino group-containing organopolysiloxane, and more particularly to a method for producing an amino group-containing organopolysiloxane which does not cause white turbidity over time.

[0002]

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION Amino group-containing silanes or siloxanes are compounds useful as glass fiber treating agents or polishing additives, but these compounds have their amino groups oxidized during storage. However, there is a disadvantage that the target product to be obtained undergoes discoloration such as coloring or cloudiness. Therefore, in order to prevent coloring or discoloration, production of amino group-containing silane or siloxane may be performed in an atmosphere of an inert gas such as nitrogen gas or argon gas, but special equipment is required. This is generally difficult. JP-A-53-5124 proposes an improvement by adding a mercapto group-containing compound during the production of the compound as described above. However, since the mercapto group-containing compound is relatively expensive, It is not an industrial solution, and cannot be used for cosmetics.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above disadvantages and to provide a method for producing an amino group-containing organopolysiloxane which does not cause white turbidity over time.

[0004]

The present inventors have conducted intensive studies to achieve the above object, and as a result, focused on the production conditions of an amino group-containing organopolysiloxane, and used water in combination with a basic equilibration catalyst to reduce cloudiness. Finding that the occurrence is suppressed,
The present invention has been completed. That is, the present invention provides: a) 100 parts by weight of a mixture of an amino group-containing organosiloxane or an amino group-containing silane and an amino group-free organosiloxane; b) 0.001 to 1 part by weight of a basic equilibration catalyst. A mixture consisting of 0.01 to 20 parts by weight of water is reacted by heating,

[0005]

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(Wherein, R ¹ is a monovalent organic group containing an amino group, and R ² is a monovalent hydrocarbon group having 1 to 8 carbon atoms not containing an amino group or an alkoxy group having 1 to 6 carbon atoms.) , M,
n is a number that satisfies 1.8 <m + n <2.1, where n / m ≧ 3), and obtains an organopolysiloxane containing an average of at least one amino group in a molecule represented by the formula: This is a method for producing polysiloxane.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The starting material in the present invention is an organosiloxane containing an amino group or a mixture of a silane containing an amino group and an organosiloxane containing no amino group. Since all of these siloxanes are advantageous in operation, the degree of polymerization is preferably 100 or less, but they may be any of cyclic siloxane, branched siloxane, and linear siloxane. . The amino group-containing organosiloxane or silane is represented by the general formula (I)

[0008]

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An amino group-containing silane or amino group-containing siloxane having a siloxy unit represented by the following formula: Wherein Z is a hydrogen atom, a phenyl group or a formula

[0010]

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Wherein e is an integer of 1 to 10, R ⁵ is a divalent hydrocarbon group having 1 to ⁶ carbon atoms, and R ⁶ is a monovalent hydrocarbon group having 1 to 8 carbon atoms. And Y is a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, c is 0, 1 or 2, d
Is 0, 1, 2 or 3, provided that 0 ≦ c + d ≦ 3.
Examples of other siloxy units include those represented by the following formula (II). R ⁷ _k SiO _{(4-k) / 2} (II) Here, R ⁷ is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and k is 0, 1, 2, or 3. Specific examples of such an amino group-containing silane include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, and 3-aminopropylmethyldimethoxysilane. Silane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, aminomethyltrimethoxysilane, aminoethyltrimethoxysilane, aminomethylmethyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl- Examples of 3-aminopropylmethyldimethoxysilane and the like, and examples of the amino group-containing siloxane include those represented by the following formulas, and their molecular structures are cyclic, linear, or branched. You may. Particularly preferred is a siloxane obtained by hydrolyzing and polymerizing only an amino group-containing silane.

[0012]

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Examples of the organosiloxane containing no amino group include those composed of siloxy units represented by the above formula (II), and examples thereof include the following.

[0014]

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The component (a) in the present invention is an aminosiloxane containing an amino group or a mixture of an amino group-containing silane and an amino group-free organosiloxane as described above. The ratio may be determined arbitrarily according to the amount of amino groups to be contained in the target organopolysiloxane, but is preferably based on 100 parts by weight of the amino group-containing organosiloxane or the amino group-containing silane. The aminosiloxane-free organosiloxane is used in an amount of from 100 to 10,000 parts by weight, particularly preferably from 500 to 5,000 parts by weight. Furthermore, in the obtained siloxane, the amino group content is
It is preferable to mix them so as to be 0.01 to 20% by weight, particularly 0.05 to 5% by weight.

The basic equilibration catalyst of the component (b) used in the present invention includes alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, ethyl lithium and ethyl sodium. ,
Alkali metal alkyl such as butyl lithium, biphenyl sodium, phenyl lithium, potassium naphthalene, alkali metal aryl such as lithium naphthalene,
Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-
Onium hydroxide compounds such as butylphosphonium hydroxide and phenyltrimethylphosphonium hydroxide, and 1,8-diazabicyclo [5.4.0]
Examples include nitrogen-containing heterocyclic compounds such as -7-undecene (abbreviation: DBU), and silanolates of these compounds. Silanolates are preferred because the equilibration reaction proceeds favorably, and amine odors over time are also preferred. A quaternary phosphonium compound and a silanolate thereof are preferred because a compound which is less likely to be generated is easily obtained. As the siloxane used for silanolation, the above-mentioned organosiloxane containing no amino group can be used. If the basic equilibration catalyst is added in an amount of less than 0.001 part by weight with respect to 100 parts by weight of the organosiloxane mixture as the component (a), the equilibration reaction of the organosiloxane is slowed down, and the addition amount is more than 1 part by weight. However, no further effect can be obtained, so the amount may be in the range of 0.001 to 1 part by weight, but the preferable range is 0.01 to 0.1 part by weight. In the case of a silanolate compound, the range of the addition amount is determined by the amount converted to the amount of the basic compound to be reacted with siloxane as a raw material.

The water of the component (c) used in the present invention is not particularly limited, and may be any water such as city water, industrial water, ion-exchanged water and natural water.
Above all, ion-exchanged water containing less impurities is preferably used. Conventionally, in the synthesis of siloxane, it has been known to add water as a terminal stopper in order to introduce a silanol group, or to use an aqueous solution to make the equilibration catalyst easier to handle. It has not been known to mix water to carry out an equilibrium reaction in order to prevent turbidity over time. If the amount of water of component (c) is less than 0.01 part by weight based on 100 parts by weight of the organosiloxane mixture as component (a), the effect of preventing white turbidity is not sufficient. Not only the above effects cannot be obtained, but also because the production of silanol increases, it is difficult to control the progress of the equilibration of the organosiloxane to a desired degree.
It may be in the range of parts by weight, but the preferred range is 0.3 to 10
Parts by weight, particularly preferably 0.5 to 8 parts by weight.

The preparation of the organopolysiloxane according to the present invention comprises the above-mentioned (a) a mixture of an organosiloxane containing an amino group or a silane containing an amino group and an organosiloxane containing no amino group,
After mixing a predetermined amount of the basic equilibration catalyst as the component (b) and the water as the component (c) to make the mixture uniform, the mixture may be heated and mixed to carry out an equilibration reaction.
The reaction may be carried out at 240 ° C., preferably 80 to 130 ° C., for 30 minutes to 48 hours, preferably 1 to 5 hours. Before mixing water, component (a) may be heated and dehydrated in advance. After equilibration,
To remove water and other low distillates and to reduce silanol groups, heat mixing is performed while gas is being supplied or distillation is performed under reduced pressure. Heating in this case, 80-200
C., preferably at 120 to 180.degree. C., for 30 minutes to 10 hours, preferably 1 to 5 hours. After equilibration, if necessary,
The basic equilibration catalyst is neutralized by an acidic compound. However, in the case of a catalyst that decomposes by heating, such as an onium hydroxide compound, the neutralization may be omitted.

[0019]

Industrial Applicability The present invention is a general-purpose siloxane which is relatively free to control the viscosity and the like of the product by equilibrating an amino-containing siloxane or a siloxane and an amino-free siloxane. Is characterized in that the turbidity over time, which has conventionally been a problem, is reduced, and the obtained amino group-containing siloxane can be used for a wider range of uses.

[0020]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Synthesis Example 1 N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane 1800 was placed in a 2-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet.
g, and the mixture was heated to 35 ° C. and stirred. Ion exchange water 1
56 g were added dropwise over 30 minutes. After dropping, the temperature was raised to 80 ° C,
The pressure was gradually reduced, and the stirring was continued for 3 hours after the degree of reduced pressure reached 20 mmHg or less, cooled to normal temperature to break the reduced pressure, colorless and transparent, having a viscosity of 300 cP, and having an amino group content of 17.2% by weight.
Amino group-containing organopolysiloxane (synthesis-1)
I got Synthesis Example 2 [(CH ₃ ) ₂ was added to a reactor equipped with a stirrer, a decompression device, a heater, a solvent inlet, a cooler, a receiver, and an inlet for introducing nitrogen through a dehydration tube and a decarbonation tube. SiO] ₃ 4.8 wt%, [(CH _{3) 2} SiO] ₄ 77.4 wt%, [(CH _{3) 2} SiO] ₅ 17.4 wt% and [(CH _{3) 2} SiO] cyclic polydimethyl of ₆ 0.4 wt% 136 g of a siloxane mixture and tetra-n-hydroxide
10 g of an aqueous solution containing 40% by weight of butylphosphonium was charged, and stirring was performed while maintaining the temperature at 30 ° C. while supplying a small amount of nitrogen from which water and carbon dioxide had been removed. Under these conditions, the pressure was gradually reduced. After the degree of reduced pressure reached 50 mmHg or less, stirring was continued for 8 hours. After confirming that no water distilled out of the reactor at all, the mixture was cooled at room temperature to break the reduced pressure to obtain a viscous and transparent liquid phosphonium group-containing polysiloxane (synthesis-2). The phosphonium group content of the obtained phosphonium group-containing polysiloxane is 2.2% by weight.
Met.

Example 1 1650 g of octamethylcyclotetrasiloxane was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 in which the molecular chain ends are blocked with trimethylsilyl groups was charged, heated at 110 ° C. for 30 minutes, refluxed and dehydrated, and then dried (n
A mixture of 0.5 g of -C ₄ H ₉ ) ₄ POH and 18.0 g of water was added dropwise, and an equilibration reaction was performed at 110 ° C for 2 hours with stirring. After the completion of the reaction, slowly raise the temperature to 150 ° C for 1 hour,
The unreacted product was stripped by heating at 140 to 150 ° C. under a reduced pressure of mmHg for 2 hours to obtain Compound A. This is a pale yellow transparent liquid, volatile matter (105 ℃ x 3 hours)
The content was 2.4% by weight, the viscosity was 820 cP, the refractive index was 1.4079, and the amino group content was 0.930% by weight.

Example 2 1650 g of octamethylcyclotetrasiloxane was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 in which the molecular chain ends are blocked with trimethylsilyl groups were charged, heated at 150 ° C. for 30 minutes, refluxed, and dehydrated.
After adding 23 g of the compound-2 prepared in Synthesis Example 2 and 35.5 g of water, and performing an equilibration reaction at 110 ° C. for 2 hours with stirring, the temperature was slowly raised to 150 ° C. for 1 hour, and then 10 mm
The unreacted material was stripped by heating at 140 to 150 ° C. for 2 hours under reduced pressure of Hg to obtain Compound B. This is a pale yellow transparent liquid, volatile (105 ° C x 3 hours) 2.1
% By weight, viscosity 740 cP, refractive index 1.4078, and amino group content 0.930% by weight.

Example 3 1650 g of octamethylcyclotetrasiloxane was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 in which the molecular chain terminals are blocked with trimethylsilyl groups were charged, heated at 110 ° C. for 30 minutes, refluxed and dehydrated, and then dried (C
A mixture of 0.1 g of H ₃ ) ₄ NOH and 90 g of water was added dropwise, and an equilibration reaction was performed at 90 ° C. for 5 hours while stirring while bubbling nitrogen gas. After the completion of the reaction, the temperature was slowly raised to 150 ° C. over 1 hour, and then 140 to 1 hour under reduced pressure of 10 mmHg.
When unreacted material was stripped by heating at 50 ° C,
Compound C was obtained. This is a pale yellow transparent liquid,
2.0% by weight of volatiles (105 ° C x 3 hours), viscosity 780cP, refractive index
At 1.4078, the amino group content was 0.930% by weight.

Example 4 1650 g of octamethylcyclotetrasiloxane was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 in which the molecular chain ends are blocked with trimethylsilyl groups were charged, heated at 150 ° C. for 30 minutes, refluxed and dehydrated, and then 0.01 g of potassium hydroxide, 30 g of water and A mixture of 10 g of DMF (dimethylfuran) was added, an equilibration reaction was performed at 150 ° C. for 8 hours with stirring, and 0.03 g of phosphoric acid was added for neutralization. After completion of the reaction, the temperature was slowly raised to 150 ° C. over 1 hour, and then the mixture was heated at 140 to 150 ° C. under a reduced pressure of 10 mmHg for 2 hours to strip the unreacted product. As a result, Compound D was obtained. This is a pale yellow transparent liquid, volatile
(105 ° C x 3 hours) 2.2% by weight, viscosity 730cP, refractive index 1.4078
And the amino group content was 0.930% by weight.

Example 5 1650 g of octamethylcyclotetrasiloxane and N-β (aminoethyl) γ- were placed in a 2-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet.
180 g of aminopropylpurmethyldimethoxysilane, and 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 and having a molecular chain terminal blocked with a trimethylsilyl group, were charged to 120 g.
After heating, refluxing and dehydrating at 30 ° C for 30 minutes, (nC ₄ H ₉ ) ₇ POH
A mixture of 0.07 g and 20 g of water was added dropwise while stirring.
The equilibration reaction was performed at 20 ° C. for 3 hours. After the reaction is over, 150
After slowly raising the temperature to 1 ° C. over 1 hour, the mixture was heated at 140 to 150 ° C. under a reduced pressure of 10 mmHg for 2 hours to strip the unreacted product. As a result, Compound E was obtained. This was a yellow transparent liquid, having a volatile content (105 ° C. × 3 hours) of 2.1% by weight, a viscosity of 550 cP, a refractive index of 1.4078 and an amino group content of 0.880% by weight.

Comparative Example 1 1650 g of octamethylcyclotetrasiloxane was placed in a two-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 in which the molecular chain ends are blocked with trimethylsilyl groups was charged, heated at 110 ° C. for 30 minutes, refluxed and dehydrated, and then dried (n
A mixture of 0.5 g of -C ₄ H ₉ ) ₄ POH and 0.15 g of water was added dropwise, and an equilibration reaction was performed at 110 ° C for 2 hours with stirring. After the completion of the reaction, slowly raise the temperature to 150 ° C for 1 hour,
Unreacted materials were stripped by heating at 140 to 150 ° C. for 2 hours under reduced pressure of mmHg to obtain Compound F. This is a pale yellow transparent liquid, volatile matter (105 ℃ x 3 hours)
The content was 3.2% by weight, the viscosity was 710 cP, the refractive index was 1.4079, and the amino group content was 0.930% by weight.

Comparative Example 2 1650 g of octamethylcyclotetrasiloxane was placed in a 2-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 in which the molecular chain ends are blocked with trimethylsilyl groups were charged, heated at 150 ° C. for 30 minutes, refluxed, and dehydrated.
After adding 23 g of the compound-2 prepared in Synthesis Example 2 and 35.5 g of water, and performing an equilibration reaction at 110 ° C. for 2 hours with stirring, the temperature was slowly raised to 150 ° C. for 1 hour, and then 10 mm
The unreacted material was stripped by heating at 140 to 150 ° C. for 2 hours under reduced pressure of Hg to obtain Compound G. This is a pale yellow transparent liquid, volatile (105 ° C x 3 hours)
% By weight, viscosity 630 cP, refractive index 1.4078, and amino group content 0.910% by weight.

Comparative Example 3 1650 g of octamethylcyclotetrasiloxane was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 in which the molecular chain terminals are blocked with trimethylsilyl groups were charged, heated at 110 ° C. for 30 minutes, refluxed and dehydrated, and then dried (C
A mixture of 0.07 g of H ₃ ) ₄ NOH and 0.15 g of water was added dropwise, and an equilibration reaction was performed at 90 ° C. for 5 hours with stirring. After completion of the reaction, slowly raise the temperature to 150 ° C for 1 hour, then
The unreacted material was stripped by heating at 140 to 150 ° C. under a reduced pressure of Hg for 2 hours to obtain Compound H. This is a pale yellow transparent liquid, volatile (105 ° C x 3 hours) 2.5
% By weight, viscosity 680 cP, refractive index 1.4078, and amino group content 0.910% by weight.

Comparative Example 4 1650 g of octamethylcyclotetrasiloxane was placed in a 2 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet.
93.5 g, 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 whose molecular chain ends are blocked with trimethylsilyl groups, and heated, refluxed and dehydrated at 150 ° C. for 30 minutes, and then potassium hydroxide 0.01 g and 1,3 A mixture of 10 g of dioxolane was added, an equilibration reaction was carried out at 130 ° C. for 8 hours with stirring, and 0.03 g of phosphoric acid was added for neutralization. After completion of the reaction, slowly raise the temperature to 150 ° C for 1 hour,
The unreacted material was stripped by heating at 140 to 150 ° C. under a reduced pressure of 10 mmHg for 2 hours to obtain Compound I.
This is a yellow transparent liquid, volatile matter (105 ℃ x 3 hours)
The content was 3.1% by weight, the viscosity was 670 cP, the refractive index was 1.4078, and the amino group content was 0.910% by weight.

Comparative Example 5 1650 g of octamethylcyclotetrasiloxane and N-β (aminoethyl) γ- were placed in a 2-liter four-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet.
180 g of aminopropylpurmethyldimethoxysilane, and 31.9 g of dimethylpolysiloxane having an average degree of polymerization of 10 and having a molecular chain terminal blocked with a trimethylsilyl group, were charged to 120 g.
After heating, refluxing and dehydrating at 30 ° C. for 30 minutes, 23
g was dropped, and an equilibration reaction was performed at 120 ° C. for 3 hours while stirring. After completion of the reaction, the temperature was slowly raised to 150 ° C. over 1 hour, and then the mixture was heated at 140 to 150 ° C. for 2 hours under a reduced pressure of 10 mmHg to strip the unreacted product. As a result, Compound J was obtained. It is a clear, yellow liquid that contains volatiles (1
(05 ° C x 3 hours) 3.1% by weight, viscosity 620cP, refractive index 1.4078
And the amino group content was 0.850% by weight.

[Evaluation] 80 g of each of the compounds A to J obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were placed in a 100 cc glass bottle, and allowed to stand at room temperature for 2 weeks in an open state. The first appearance and the last appearance at that time were evaluated. Table 1 shows the results.

[0032]

[Table 1]

Claims (1)

[Claims] 1. A) 100 parts by weight of a mixture of an amino group-containing organosiloxane or an amino group-containing silane and an amino group-free organosiloxane; b) 0.001 to 1 part by weight of a basic equilibration catalyst c) A mixture consisting of 0.01 to 20 parts by weight of water is reacted by heating to obtain a compound represented by the general formula: (Where R ¹ is a monovalent organic group containing an amino group, R ²
Is a monovalent hydrocarbon group having 1 to 8 carbon atoms containing no amino group or an alkoxy group having 1 to 6 carbon atoms, and m and n are n / m
≧ 3, a number satisfying 1.8 <m + n <2.1). A method for producing an amino group-containing organopolysiloxane, characterized in that an organopolysiloxane containing an average of at least one amino group in a molecule represented by the formula: