WO2013097167A1

WO2013097167A1 - Silicone surfactant, and preparation method and use thereof

Info

Publication number: WO2013097167A1
Application number: PCT/CN2011/084992
Authority: WO
Inventors: 黄振宏; 谢秀鸿
Original assignee: 广东标美硅氟新材料有限公司
Priority date: 2011-12-27
Filing date: 2011-12-30
Publication date: 2013-07-04
Also published as: CN103182271B; CN103182271A

Abstract

Disclosed are a silicone surfactant, and a preparation method and the use thereof. The silicone surfactant has a structure as shown in formula (I), wherein c is not 0; a, b, c are all integers and 10< a + b + c < 200; m = 0-40; n = 0-30; x = 3-30; x，m，and n are all integers, and m and n are not both 0; R is a C₆ _- ₂₀ linear or branched long-chain alkyl, or an alkyl phenyl; and R' is H, CH₃, C₂H₅, C₃H₇, or C₄H₉. The silicone surfactant has a novel structure, and an excellent emulsifying ability. The silicone surfactant has a good emulsifying ability for polydimethyl siloxanes and a variety of modified polydimethyl siloxanes in a very wide viscosity range. A good emulsifying effect can be achieved using the surfactant alone without formulating with other emulsifiers, and the emulsifying process thereof is simple and convenient to use without needing any homogenizer or any other special emulsifying process, in order to obtain a stable O/W type silicone oil emulsion.

Description

Silicone surfactant and preparation method and application thereof

Technical field

The invention relates to the field of silicone surfactant chemistry, and in particular to a silicone surfactant and a preparation method and application thereof.

Background technique

Silicone surfactants are a new type of surfactant developed with new silicone materials. It has won a wide range of survival and development space with its unique properties. It has become an increasingly important surfactant.

The silicone surfactant mainly refers to a class of surfactants in which polydimethylsiloxane is a hydrophobic main chain and one or more organic polar groups are introduced therein. In addition to the general surfactant, it also has better surface activity than ordinary surfactants. It is a kind of high-efficiency surfactant with emulsifying property, dispersibility, easy spreading property, wettability and resistance. Electrostatic, defoaming, foam stabilization, foaming and other properties. These properties are due to the low surface tension and weak intermolecular forces of polydimethylsiloxane.

Emulsifiers are an important part of the emulsion and are a bridge between the oil and water phases. In order to make the system stable over the life of the system, a wide variety of emulsifiers have been developed, either as a single component or as a compound, or as a general purpose or a dedicated type.

With the development of silicone materials, the variety of silicone emulsifiers has been increasing and the performance has been continuously improved. However, the single-use 0/W silicone emulsifier used in silicone oil emulsion formulations has rarely been reported. If you want to obtain a stable Si/W emulsion, the existing method is to match the HLB value of the emulsifier system with the HLB value of the emulsified silicone oil by compounding different emulsifiers of HLB value, or by mechanical homogenization. Special emulsification process such as machine. However, silicone oils with different viscosities have different requirements for the HLB value of emulsifiers. Different modified silicone oils have a certain difference in HLB. This requires the formula engineer to Different silicone oil emulsion systems are compounded with different emulsifier systems.

Summary of the invention

It is an object of the present invention to provide a silicone surfactant. The structural feature of the silicone surfactant is that the polyorganosiloxane oxime side chain is hydrolyzed by a hydrosilylation reaction, and a polyether terminated with a long chain sulfhydryl group or a nonylphenyl group is grafted to a large viscosity range. Polydimethylsiloxane and various modified polydimethylsiloxanes have excellent emulsifying ability, can achieve good emulsifying effect by single use, do not need to be compounded with other emulsifiers, and the emulsification process is simple. No need for a homogenizer or other special emulsification process, you can make a stable silicone oil emulsion, easy to use.

It is also an object of the present invention to provide the use of the silicone surfactant in a 0/W type silicone oil emulsion formulation.

The above object of the present invention is achieved by the following scheme:

A silicone surfactant having the structure of formula (I):

(I)

Where c is not zero; a, b, c are integers and 10<a+b+c<200;m=0~40;n=0~30;x=3~30; x, m, n Is an integer, and m, n are not 0 at the same time; R is C ₆ 〜 ₂ . Linear or isomeric long chain fluorenyl, or nonylphenyl; R' is H, CH ₃ , C ₂ _3⁄4 , C ₃ H ₇ , C ₄ H ₉ o

As a preferred embodiment, the structure of the silicone surfactant is preferably a=0~150; b=0~60: c=l~60. As a preferred embodiment, the structure of the silicone surfactant is preferably a=l~60; b=l~20; c=l~20; a, b, c are integers and 20<a+b+ c<100;

m=5~15; n=6~20; x=6~12; x, m, n are integers;

R is a linear or isomeric long chain fluorenyl group of C ₈ ～ ₁₆ .

The preparation method of the silicone surfactant is as follows:

The method comprises the following steps: adding an allyl polyether having a structure of the formula (III) or the formula (11) and the formula (III) and a hydrogen-containing silicone oil to the reaction vessel, stirring under a nitrogen atmosphere, heating and heating to 80. At ~100 ° C, a chloroplatinic acid-isopropanol catalyst was added, and heating was continued until 110 to 180 ° C until the system became transparent, and the silicone surfactant was obtained.

H ₂ C=CHCH ₂ -0~ CH ₂ CH ₂ 0)~{CH ₂ CH0)~R'

'm, ' n

CH ₃

(II);

(III).

The silicone surfactant is a colorless to pale yellow liquid or paste.

The use of the silicone surfactant in an emulsifier.

The silicone surfactant has excellent emulsifying properties and can be used alone as an emulsifier for the 0/W type silicone oil emulsion formulation.

When the silicone surfactant is used as an emulsifier for the 0/W type silicone oil emulsion formulation, the amount is based on the mass ratio of the silicone surfactant: silicone oil = 1: 2 ~ 6.

When the silicone surfactant is used as an emulsifier for the cream formulation, the amount is based on the mass ratio of the silicone surfactant: to be emulsified system =1: 5~9.

The silicone surfactant of the present invention has a large viscosity range (for example, about 2 cSt to 12500 cSt). Polydimethylsiloxane and various modified polydimethylsiloxanes have excellent emulsifying ability. Compared with the prior art, the present invention has the following advantages:

The novel silicone surfactant of the present invention comprises polysiloxane and two hydrophobic segments of anthracene hydrocarbon directly connected to the polyether chain, and a plurality of polar polyether hydrophilic groups in the middle. Therefore, it has excellent emulsifying ability; the novel silicone surfactant has excellent emulsifying ability for polydimethylsiloxane and various modified polydimethylsiloxanes in a large viscosity range, and can be used alone. A good emulsification effect can be achieved, no need to be compounded with other emulsifiers, and the emulsification process is simple, and a stable 0/W type silicone oil emulsion can be obtained without using a homogenizer or other special emulsification process, and is convenient to use.

Detailed ways

The invention is further explained by the following examples, but the examples are not intended to limit the invention in any way.

In the examples, the catalyst used is a chloroplatinic acid-isopropanol catalyst commonly used in the art.

Example 1

In a three-necked flask equipped with a stirring device, a drum N ₂ device and a thermometer, 0.3 mol of allyl polyether (II) (m=10, n=6, R' is C ₃ H ₇ ), 0.3 mol Allyl polyether (III) (x=9, R is C ₁₂ H ₂₅ ), 0.5 mol of hydrogen-containing silicone oil having a hydrogen content of about 0.3% (% by mass) (a+b+c^80, Thus, b+c^ 18, a: b: c^62: 9: 9), under the protection of nitrogen atmosphere, when heating to 80 ° C, adding 0.03 g of catalyst, continue heating to 120 ° C ~ 130 The reaction was carried out at ° C until the system became transparent, that is, a pale yellow transparent silicone surfactant was obtained.

Example 2

In a three-necked flask equipped with a stirring device, a drum N ₂ device and a thermometer, 0.2 mol of allyl polyether (II) (m = 38, n = 0, R' is H), 0.3 mol of allyl grouping was added. Ether (III) (x=3, R is C ₁₆ H ₃₃ ), 0.4 mol of hydrogen-containing silicone oil having a hydrogen content of about 0.2% by mass (a+b+c^l30, from which b+c^ can be seen) 20, a: b: c^ HO: 8: 12), under the protection of nitrogen atmosphere, when heating to 100 ° C, add 0.03g of catalyst, continue heating to 150 ° C ~ 160 ° C reaction, until the system becomes transparent, that is, light yellow Transparent silicone surfactant.

Example 3

In a three-necked flask equipped with a stirring device, a drum N ₂ device and a thermometer, 0.18 mol of allyl polyether (Π) (m=2, n=30, R' is H), 0.2 mol of allyl group was added. Ether (III) (x=28, R is C ₁₈ H ₃₇ ), 0.32 mol of hydrogen-containing silicone oil having a hydrogen content of about 0.35% by mass (a+b+c 30, thus b+c ^20 , a: b: c^22: 5: 3), under the protection of nitrogen atmosphere, when heating to 90 ° C, add 0.03g catalyst, continue heating to 130 ° C ~ 140 ° C reaction, until the system becomes transparent That is, a pale yellow transparent silicone surfactant is obtained.

Example 4

In a three-necked flask equipped with a stirring device, a drum N ₂ device and a thermometer, 0.25 mol of allyl polyether ( II ) (m = 16, n = 10, R' is CH ₃ ), 0.22 mol of allyl group was added. Polyether (III) (x=7, R is C ₆ H ₁₃ ), 0.4 mol of hydrogen containing a value of about 0.17% (% by mass) of hydrogen-containing silicone oil (a+b+c^l40, thus visible b +c ^20, a: b: c^ l20: 11 : 9 ), under the protection of nitrogen atmosphere, when heating to 94 ° C, add 0.03g of catalyst, continue heating to 160 ° C ~ 170 ° C reaction, Until the system becomes transparent, a pale yellow transparent silicone surfactant is obtained.

Example 5

In a three-necked flask equipped with a stirring device, a drum N ₂ device and a thermometer, 0.33 mol of allyl polyether (III) (x = 25, R is C ₂ .H ₄₁ ) was added, and the hydrogen content of 0.3 mol was about 0.28% (mass%) of hydrogen-containing silicone oil (a+c^95, which shows b=0, c^20, a: c^75: 20), under the protection of nitrogen atmosphere, the heat of the mouth is heated up to At 90 ° C, 0.03 g of catalyst was added and heating was continued to 160 ° C to 170 ° C until the system became transparent, resulting in a pale yellow transparent silicone surfactant. Example 6 20 parts of dimethyl siloxane (different viscosity) and 6 parts of the silicone surfactant obtained in Example 1 were added to the emulsifier, and after stirring uniformly, about 6 parts of distilled water (or purified water) was added at once. ), continue to mix well and mix well, at this time the system is in the form of a transparent paste. Subsequently, the remaining 68 parts of water were slowly added under stirring to obtain a bluish milky white liquid. 2500r/minx l5min centrifugation, no stratification. See Table 1 for details. Table 1 Dimethyl silicone oils with different emulsifications Formulation 1 Formulation 2 Formulation 3 Formulation 4 Silicone oil phase

Dimethyl siloxane composite ring 20

lOOcSt Dimethicone 20

lOOOcSt dimethicone 20

12500cSt Dimethicone 20 Example 1 Silicone Surfactant 6 6 6 6 Aqueous Phase

Distilled or deionized water 74 74 74 74 Centrifugal stability (2500r/minx l5 min) Stable Stable Stable Stable

Example 7 20 parts of modified silicone oil and 6 parts of the silicone surfactant obtained in Example 1 were added to the emulsified kettle, and after stirring uniformly, about 6 parts of distilled water (or purified water) was added at once, and the mixture was thoroughly stirred and uniformly mixed. At this time, the system is in the form of a transparent paste. Subsequently, the remaining 68 parts of water were slowly added under stirring to obtain a bluish milky white liquid. 2500r/minx l5min centrifugation, no stratification. See Table 2 for details. Table 2 Emulsified Different Modified Silicone Ingredients Formulation 1 Formulation 2 Formulation 3 Formulation 4

20

Amino silicone oil 20

Hydroxy silicone oil 20

Sulfhydryl silicone oil

The silicone surfactant obtained in Example 1 6 6 6

water box

Distilled or deionized water 74 74 74 74 Centrifugal stability (2500r/minx 15 min) Stable, stable and stable Example 8 20 parts of silicone oil and 7 parts of the silicone surfactant obtained in Example 4 were added to the emulsifier and stirred well. Thereafter, about 5 parts of distilled water (or purified water) was added in one portion, and the mixture was further stirred and uniformly mixed, and the system was in the form of a transparent paste. Subsequently, the remaining 68 parts of water were slowly added under stirring to obtain a bluish milky white liquid. 2500r/minx l5min centrifugation, no stratification. See Table 3 for details. Table 3 Emulsified different silicone oils Ingredients Formula 1 Formulation 2 Formulation 3 Formulation 4 lOOOcSt Dimethicone 20

12500cSt Dimethicone 20

Amino silicone oil 20

Phenyl silicone oil

The silicone surfactant obtained in Example 1 7 7 7

^相

Distilled or deionized water 73 73 73 73 Centrifugal stability (2500r/minx 15 min) Stable Stable Stable

Claims

A silicone surfactant characterized by having a structure represented by the formula (I):

(I)

Where c is not zero; a, b, c are integers and 10<a+b+c<200;m=0~40;n=0~30;x=3~30; x, m, n Is an integer, and m, n are not 0 at the same time; R is C ₆ 〜 ₂ . a linear or isomeric long chain thiol group, or a nonylphenyl group; R' is H, CH ₃ , C ₂ _3⁄4 , C ₃ H ₇ , C ₄ H ₉ .

Ccsll

H H

2. The silicone surfactant according to claim 1, 3, a = 0 to 150; b = 0 to 60; c = 1 to 60.

The silicone surfactant according to claim 1, wherein said a = 1 to 60; b = 1 to 20; c = 1 to 20; a, b, and c are integers and 20 < a +b+c<100;m=5~15;n=6~20;x=6~12; x, m _: n are integers; R is a linear or isomeric long chain fluorenyl group of C ₈ ～ ₁₆ .

The method for producing a silicone surfactant according to claim 1, 2 or 3, which comprises the steps of: allylic having a structure of formula (III) or a structure of formula (11), formula (III) The polyether and the hydrogen-containing silicone oil are added to the reaction vessel, and the temperature is raised to 80-100 ° C under the protection of a nitrogen atmosphere, and the chloroplatinic acid-isopropanol catalyst is added, and the reaction is further heated to 110-180 ° C until the system changes. Transparent to obtain the silicone surfactant;

H ₂ C=CHCH ₂ — 0~ CH ₂ CH ₂ o W)~{CH ₂ CI HO ')~ n R'

CH ₃

(II):

(111).

5. Use of a silicone surfactant according to claim 1, 2 or 3 in an emulsifier.

6. Use according to claim 5, characterized in that the silicone surfactant alone acts as an emulsifier for the 0/W type silicone oil emulsion formulation.

7. The use according to claim 5, wherein the silicone surfactant is used as an emulsifier for the 0/W type silicone oil emulsion formulation, and the amount is based on the mass ratio of the silicone surfactant: silicone oil=1. : 2~6.

8. The use according to claim 5, wherein the silicone surfactant is used as an emulsifier for a cream formulation, and the amount thereof is a silicone surfactant: a system to be emulsified