JPH07126392A - Polyether/siloxane block copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the subject copolymer excellent in thickenability and emulsifiability by polycondensing a specified ester-group-terminated siloxane compound with specified glycols. CONSTITUTION:An ester-group-terminated siloxane compound of formula II (wherein R<1> is a 1-18C alkyl or an aryl; R<3> is a 1-18C alkylene which may contain 1-4 O, S or N atoms in the carbon chain; R<4> is a 1-4C alkyl or H; and (n) is a positive number of 0-1000, provided that n>=1) and a glycol represented by formula III (wherein (x) and (y) are each a positive number of 0-1000, provided that x+y>=3) and formula IV (wherein R<2> is the same as R<3> in formula II). The formed polyether/siloxane block copolymer is represented by formula I (wherein R<1> to R<3>, (n), (x) and (y) are as defined in formulas II to IV; (a) is a positive number of 0-100; and (b) and (c) are each a positive number of 5-1000).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is excellent in thickening and emulsifying properties. Therefore, when it is used as a surfactant for cosmetics, for example, it is possible to obtain a product having a good emulsifying property and an excellent feel. TECHNICAL FIELD The present invention relates to an ether-siloxane block copolymer and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, polyether-containing siloxane compounds have been used as silicone-based surfactants for cosmetics, defoaming agents, etc. A high molecular weight product of this siloxane compound has been attracting attention as a raw rubber having.

As a method for increasing the molecular weight of this siloxane compound, as disclosed in US Pat. No. 3,836,560, (1) deamine reaction between SiNMe ₂ and HO--, and (2) SiH a hydrosilylation reaction with _{CH 2 = CH-CH 2 O~} , (3) isocyanate method of Si~NCO and HO~, (4) but Si~COCl with an acid chloride method and HO～ the like, (1) has a problem of hydrolysis, and (2) has a problem of side reaction as pointed out in US Pat. No. 4,150,048,
(3) has a problem that the isocyanate group of the raw material is highly irritating and is not suitable for cosmetic use, and (4) has a problem that the dehydrochlorinating agent remains and causes coloring. Therefore, it is desired to develop a manufacturing method that overcomes these problems.

The present invention has been made in order to meet the above-mentioned demands, and is a polyether-siloxane block copolymer having excellent thickening and emulsifying properties, and such a polyether-siloxane block copolymer without coloring or odor. It is an object to provide a manufacturing method capable of manufacturing a coalescence.

[0005]

Means and Actions for Solving the Problems As a result of intensive studies for achieving the above object, the present inventor has found that both end-ester group-containing siloxane compounds represented by the following general formula (2) and the following general formula ( It was found that the above problems can be solved by polycondensing the divalent glycols represented by 3) and (4). That is, generally, when polycondensation of the siloxane compound of the formula (2) and only the polyether glycol of the formula (3), it is a necessary condition to achieve a high molecular weight to react at a strict ratio of 1: 1. However, such precise control is difficult in mass production. In the present invention, these two compounds are allowed to react by adding an excessively low-molecular weight glycol represented by the formula (4) to the reaction, and the glycol of the formula (4) is removed little by little under reduced pressure to facilitate the above requirement. Made it possible to achieve. Therefore, it is possible to obtain a polyether-siloxane block copolymer represented by the following formula (1) having a high molecular weight (number average molecular weight of 30,000 or more). Excellent in viscosity,
Therefore, it was found that a product having a good emulsification property and an excellent feel can be obtained when it is used as a silicone-based surfactant, particularly as a surfactant in the field of cosmetics, and the present invention has been accomplished.

[0006]

[Chemical 4] (In the formula, R ¹ is an alkyl group or aryl group having 1 to 18 carbon atoms, R ² and R ³ are alkylene groups having 1 to 18 carbon atoms, and 1 to 1 oxygen, sulfur or nitrogen atom is contained in the carbon chain. 4 may be included, a is a positive number satisfying the condition 0 <a ≦ 100, n, x, y is a positive number 0 to 1,000 satisfying the condition n ≧ 1, x + y ≧ 3, b, c is a positive number of 5 to 1,000.)

[0007]

[Chemical 5] (In the formula, R ¹ , R ³ and n have the same meanings as described above, and R ⁴
Is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. )

[0008]

[Chemical 6] (In the formula, R ² , x and y have the same meanings as described above.)

Therefore, the present invention provides a polyether-siloxane block copolymer represented by the above formula (1), a siloxane compound containing both terminal ester groups represented by the above formula (2) and the above general formula (3). And a method for producing a polyether-siloxane block copolymer represented by the above formula (1), which comprises polycondensation with a divalent glycol represented by (4).

The present invention will be described in more detail below. The polyether-siloxane block copolymer of the present invention is represented by the following formula (1).

[0011]

[Chemical 7]

Here, R ¹ is an alkyl group or an aryl group having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group and hexyl group. And the like. Specific examples of the aryl group include a phenyl group and a tolyl group.

R ² and R ³ are alkylene groups having 1 to 18 carbon atoms, preferably 2 to 10 carbon atoms. Specific examples of the alkylene group include ethylene group, propylene group, butylene group and decylene group. R ² and R ³ may contain 1 to 4 oxygen, sulfur or nitrogen atoms in the carbon chain. A is 0 <a ≦ 100, preferably 0 <a ≦ 5
A positive number satisfying the condition of 0, n ≧ 1, n = x, y = x + y ≧
3, preferably 1 ≦ n ≦ 100, a positive number of 0 to 1,000, preferably 1 to 100, and b and c of 5 to 1,000, preferably 5 to 500. It is a positive number. The number average molecular weight is 30,000 to 3,
, 000,000, especially 30,000 to 1,000,000
It is preferably 0.

Specific examples of the polyether-siloxane block copolymer represented by the above formula (1) include those shown below.

[0015]

[Chemical 8]

The siloxane compound represented by the above formula (1) is a siloxane compound containing both end ester groups represented by the following formula (2) and a divalent glycol represented by the following formulas (3) and (4). It can be produced by polycondensing and.

[0017]

[Chemical 9]

In the formula, R ^{1 to} R ³ , n, x and y have the same meanings as described above, and R ⁴ is an alkyl group having 1 to ⁴ carbon atoms or a hydrogen atom.

In this case, from the viewpoint of easy availability of raw materials, R
Methyl group, a phenyl group preferably as ^1, as R ³ is _{-C 10 H 20 -, - CH} 2 CH 2 -, - C 3 H 6 OCH 2 C
_{H 2 OCH 2 -, - C} 3 H 6 NHCOC 2 H 4 - is preferable.
From the viewpoint of reactivity, R ⁴ is preferably a methyl group or an ethyl group.

Specific examples of the both-end ester group-containing siloxane compound represented by the above formula (2) include those shown below.

[0021]

[Chemical 10]

Specific examples of the polyoxyalkylene glycol represented by the above formula (3) include those shown below.

[0023]

[Chemical 11]

Specific examples of the divalent glycol represented by the above formula (4) include those shown below. HOCH ₂ CH ₂ OH, CH ₃ N (CH ₂ CH ₂ OH) ₂ , C
H ₃ CH (OH) CH ₂ OH, HOCH ₂ CH ₂ OCH ₂ C
H ₂ OH, CH ₃ CH (CH ₂ CH ₂ OH) ₂

The proportion of the siloxane compound of the above formula (2) and the divalent glycol of the above formula (3) used is such that the formula (3) is used in less than equimolar amount to the formula (2). The divalent glycol of 4) can be used in an equimolar amount or more with respect to the formula (2).

The siloxane compound of the above formula (2) and the above formula
When polycondensing the divalent glycol of (3) and (4)
Includes (C_FourH₉)₂Sn (OH) OSn (NCS) (C_Four
H₉)₂, (C H₃)₂Sn (NCS) OSn (NCS)
(C H₃)₂, Ti (OCH₃)_Four, Ti (OC₂H_Five)_Four，
Ti (OC_FourH₉)_Four, Ti (OCH (CH₃)₂)_Four, Zn
(CH₃COO)₂・ 2H₂Lewis acid touch selected from O
Medium or Sb₂O₃, Sb₂(OCH₃)₃, Pb (CH₃CO
O)₃・ 3H₂O, Mn (CH₃COO)₂・ 4H₂O, G
eO₂It is preferred to add a metal catalyst selected from
The amount of catalyst used must be removed after the reaction.
Therefore, the compounds represented by the formulas (2), (3) and (4)
It is preferable that the amount is 5% by weight or less with respect to the total amount.

The copolymer of the above formula (1) is obtained by mixing the siloxane compound of the formula (2) and the divalent glycol of the formulas (3) and (4) at 130 to 260 ° C., preferably 150 to 260 ° C. Heat to 240 ° C and add catalyst, and add 2 at normal pressure.
After reacting for 4 hours at a temperature similar to the above under reduced pressure of 2 mmHg or less for 3 to 6 hours, ethanol and water were added to hydrolyze the catalyst to remove the product generated by hydrolysis. After that, the low boiling point substance in the solution can be obtained by distilling off under reduced pressure.

The polyether-siloxane block copolymer thus obtained has a high molecular weight of 30,000 or more and a viscosity at 25 ° C. of 100,000 centipoise (cp) or more. Therefore, as will be apparent from the examples described below, it is more excellent in emulsion thickening than conventional polyether-containing siloxane compounds, and therefore, for example, the polyether-siloxane block copolymer of the present invention can be used as a surfactant for cosmetics. When used as an agent, it is possible to obtain a product having good emulsification characteristics and excellent feel.

[0029]

INDUSTRIAL APPLICABILITY According to the present invention, a polyether-siloxane block copolymer having excellent thickening and emulsifying properties can be produced without coloring or odor. The polymer is suitable for applications such as cosmetic surfactants.

[0030]

EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. Prior to the description of the examples, a synthesis example of a siloxane compound containing ester groups at both ends will be described. In each example, the viscosity and the refractive index are values at 25 ° C.

[Synthesis Example] Methyl undecylenate 64.8
g (0.33 mol), toluene 74 g, platinum catalyst 0.4
A solution of 3 g (2.2 mg in terms of platinum) is heated to reflux,
Siloxane compound 16 represented by the following average composition formula (5)
0 g (0.11 mol) was added dropwise and reacted for 5 hours.

[0032]

[Chemical 12]

After completion of the reaction, volatile components were distilled off under reduced pressure (200 ° C.).
/ 2 mmHg) to obtain 190 g of the desired product (yield 93%).

The ¹ H-NMR spectrum and infrared absorption spectrum of this product are as shown below, and it was found from the analysis results that the product was a siloxane compound represented by the following average composition formula (6). The siloxane compound (6) had a viscosity of 36 centistokes (cs) and a refractive index of 1.4163.

[0035]

[Chemical 13] ( ¹ H-NMR spectrum) CCl ₄ standard δ = 0.0 ppm (s, SiCH ₃ ) δ = 0.4 to 0.7 ppm (m, SiCH ₂ ) δ = 1.1 to 1.7 ppm (br, CH ₂ ) δ = 3.5ppm (s, CH 3 O) ( infrared absorption ^{spectrum) 1746cm -1 (C = O)} 1260cm -1 (SiCH 3) 1024cm -1 (SiOSi)

Example 1 170 g (0.09 mol) of a siloxane compound containing ester groups at both ends of the above formula (6) and a polyethylene glycol of the formula HO- (CH ₂ CH ₂ O) ₉ -H 33. A mixed solution of 1 g (0.08 mol) and 19.0 g (0.18 mol) of diethylene glycol was heated to about 150 ° C. under nitrogen, and then 3 g (8.8 mmol) of tetrabutyl titanate was added. The reaction was carried out under normal pressure for 1 hour and then under conditions of 200 ° C./2 mmHg for 5 hours. After the reaction, ethanol 200g, water 10g
To hydrolyze the tetrabutyl titanate ester,
The TiO ₂ formed was removed by filtration. The low boiling point component of the obtained filtrate was distilled off under reduced pressure (150 ° C./2 mmHg) to give a product having a viscosity of 660,000 cp and a refractive index of 1.4264.
5 g was obtained.

This product was analyzed by ¹ H-NMR spectrum analysis, IR analysis and GPC analysis to give the following average composition formula (7).
It was found to be a polyether siloxane copolymer represented by.

[0038]

[Chemical 14] ( ¹ H-NMR spectrum) CCl ₄ reference δ = 0.0 ppm (s, SiCH ₃ ) δ = 1.1 to 1.4 ppm (br, CH ₂ ) δ = 3.5 ppm (s, CH ₂ CH ₂ O) (infrared absorption ^{spectrum) 1739cm -1 (C = O)} 1261cm -1 (SiCH 3) 1093cm -1 (SiOSi) GPC ( number average molecular weight): 69,000

Example 2 80 g (0.04 mol) of the siloxane compound containing ester groups at both ends of the above formula (6) and polyethylene glycol of the formula HO- (CH ₂ CH ₂ O) ₁₃ -H. A solution of 4 g (0.03 mol) and 5.0 g (0.08 mol) of ethylene glycol was added under nitrogen to 1
After heating to 50 ° C., 1.0 g (2.9 mmol) of tetrabutyl titanate was added, and the reaction was carried out under normal pressure for 1 hour and subsequently at 200 ° C./2 mmHg for 6 hours.
After the reaction was completed, 200 g of ethanol and 10 g of water were added to hydrolyze the tetrabutyl titanate ester to generate T.
The iO ₂ was removed by filtration. The low boiling point substance of the obtained filtrate was distilled off under reduced pressure (150 ° C./2 mmHg) to give a viscosity of 600.
87 g of a product having 10,000 cp and a refractive index of 1.4288 was obtained.

This product was analyzed by ¹ H-NMR spectrum analysis, IR analysis and GPC analysis to give the following average composition formula (8).
It was found to be a polyether siloxane copolymer represented by.

[0041]

[Chemical 15] ( ¹ H-NMR spectrum) CCl ₄ reference δ = 0.1 ppm (s, SiCH ₃ ) δ = 1.1 to 1.5 ppm (br, CH ₂ ) δ = 3.9 ppm (s, CH ₂ CH ₂ O) (infrared absorption ^{spectrum) 1738cm -1 (C = O)} 1256cm -1 (SiCH 3) 1065cm -1 (SiOSi) GPC ( number average molecular weight): 480,000

Comparative Example 1 Average composition formula CH ₂ = CHCH ₂
Represented by _{O- (CH 2 CH 2 O)} 9.6 -CH 2 CH = CH 2, carbon - polyethers 34.8 having a carbon-carbon double bond
g (0.07 mol) and 0.48 g of platinum catalyst (2.4 mmg in terms of platinum) dissolved in 60 g of toluene was heated and refluxed, and 115 g of siloxane compound represented by the following average composition formula (9) ( 0.07 mol) was added dropwise and the reaction was carried out for 5 hours. After the reaction was completed, volatile components were distilled off under reduced pressure (120 ° C).
/ 1mmHg), viscosity 1260cp, refractive index 1.42
123 g of the polyether-containing compound of 05 were obtained.

[0043]

[Chemical 16]

Next, the following tests were conducted on the compounds obtained in Examples 1 and 2 and Comparative Example. The results are shown in Table 1. Emulsion thickening test After dissolving 10 g of each polyether-siloxane block copolymer and polyether-containing siloxane compound in 40 g of decamethylcyclopentasiloxane, 65 g of water was added to emulsify and the viscosity of water-free one was added. (Blank) was compared. Washing and removing test A 0.1% emulsion of polyether-siloxane copolymer and highly polymerized polydimethylsiloxane was prepared, and the hair was dipped in the emulsion to obtain 2% SDS (sodium dodecyl sulfate).
After washing with an aqueous solution and washing with water, dry the hair and apply FIIR.
The residual ratio of siloxane chains was determined according to the following formula by (ATR method).

[0045]

[Equation 1]

[0046]

[Table 1]

Claims (3)

[Claims] 1. A polyether-siloxane block copolymer represented by the following general formula (1). [Chemical 1] (In the formula, R ¹ is an alkyl group or aryl group having 1 to 18 carbon atoms, R ² and R ³ are alkylene groups having 1 to 18 carbon atoms, and 1 to 1 oxygen, sulfur or nitrogen atom is contained in the carbon chain. 4 may be included, a is a positive number satisfying the condition 0 <a ≦ 100, n, x, y is a positive number 0 to 1,000 satisfying the condition n ≧ 1, x + y ≧ 3, b, c is a positive number of 5 to 1,000.) 2. A polycondensation of a siloxane compound containing ester groups at both ends represented by the following general formula (2) and a divalent glycol represented by the following general formulas (3) and (4). A method for producing a polyether-siloxane block copolymer represented by the formula (1) according to claim 1. [Chemical 2] (In the formula, R ¹ , R ³ and n have the same meanings as described above, and R ⁴
Is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. ) [Chemical 3] (In the formula, R ² , x and y have the same meanings as described above.) 3. The manufacturing method according to claim 2, wherein Ti
(OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC
₄ H ₉ ) ₄ , Ti (OCH (CH ₃ ) ₂ ) ₄ , Zn (CH ₃ C
OO) ₂ .2H ₂ O Lewis acid catalyst or Sb
_{2 O 3, Sb 2 (OCH} 3) 3, Pb (CH 3 COO) 3 · 3
A metal catalyst selected from H ₂ O, Mn (CH ₃ COO) ₂ .4H ₂ O and GeO ₂ is used in an amount of 5% by weight or less based on the total amount of the compounds represented by the formulas (2), (3) and (4). A method for producing a siloxane compound, characterized in that the method is used in the amount of.