WO2014075422A1

WO2014075422A1 - Organosilicon composition and manufacturing method thereof

Info

Publication number: WO2014075422A1
Application number: PCT/CN2013/074012
Authority: WO
Inventors: 杨有忠; 吴飞; 曹添; 池跃芹; 黄伟
Original assignee: 南京四新科技应用研究所有限公司
Priority date: 2012-11-13
Filing date: 2013-04-10
Publication date: 2014-05-22
Also published as: CN103804834B; CN103804834A

Abstract

An organosilicon composition and a manufacturing method thereof. Under the effect of an acid catalyst, random copolymerization reaction is performed jointed between hydrogen-containing polyorganosiloxane, an organosilicon resin and α-olefin, so as to form a alkylation modified polyorganosiloxane with a long branch chain space structure; and mixture processing is performed by adding silicon dioxide. The organosilicon composition has a foam control capability, and particularly, can control the height of foams in a washing process when the organosilicon composition is added in different detergent products.

Description

Silicone composition and preparation method thereof

Technical field

The present invention relates to a silicone composition obtained by co-polymerization of a hydrogen-containing polyorganosiloxane with a silicone resin, an α-olefin, and addition of silica, which can be used for a foam control component of different types of detergent products. Therefore, the present invention belongs to the field of fine chemical preparation technology. Background technique

Bubbles are a common phenomenon in life and work. However, in industrial production, sometimes foaming can bring great harm, such as reducing the working efficiency of the machine, delaying labor time, and affecting the quality of the product. There are mainly physical and chemical methods for eliminating harmful foams. Defoaming defoaming is one of the chemical methods. With the large scale of production and production efficiency of industrial enterprises, defoaming defoaming is more widely used. At present, defoamers have been widely used in papermaking, textile printing and dyeing, oil extraction and refining, coatings, emulsion polymerization, sewage treatment, metal cleaning, solid and liquid detergents, etc. Defoamers have become indispensable in the production process. Functional additives.

The silicone composition is the core of the defoamer, and its defoaming speed and antifoaming properties directly affect the performance of the final product. For silicone-based defoamers, the improvement in the antifoaming properties of the actives is an improved direction of silicone defoamers. The most original silicone antifoam actives are obtained by subjecting polydimethylsiloxane and silica to a specific processing process, such as the antifoam compositions described in U.S. Patent 3,383,327. But because it can't hold Long-term foam suppression, that is, poor foam suppression performance, therefore, researchers at home and abroad have carried out large-scale research on its performance. US 4,338,217 A1 uses an alkoxy polysiloxane instead of a conventional polysiloxane to prepare a silicone composition by mixing with silica particles; US Pat. No. 4,395,352 describes a highly viscous polydimethylorganosilane oil, a finely dispersed hydrophobic particle surface. The anti-caries composition of the active agent may be used as the anti-caries composition itself, or in the form of an emulsion; US3691091 discloses a silicone emulsion for defoaming an aqueous liquid, wherein the siloxane is substantially composed of polydimethylene Silicone fluid, silica, and an alkoxy- and/or silanol-containing organosilicon compound or oligomer; EP0163541 discloses by including one or more hydroxyl groups and/or hydrocarbon oxygen a method for preparing a silicone antifoaming agent by reacting a mixture of a pre-formed polyorganosiloxane polymer, a silicone resin, a filler, a catalyst-promoting catalyst component; US5824739 introducing an amino polyorganosiloxane or a carboxyl group Polysiloxane as a main body of the silicone composition, mixed with silica to obtain a silicone composition; EP163541B1 describes the use of a terminal hydroxyl group-containing polysiloxane in a catalyst Under the action of reacting with polyorganosiloxane containing other reactive functional groups to form a branched polyorganosiloxane, and using this instead of the ordinary polysiloxane and hydrophilic silica mixing treatment, the obtained antifoaming agent formulation has a very High viscosity makes it difficult to disperse this emulsion in water. US 5,153, 258 describes the introduction of lightly crosslinked polyorganosiloxanes into the system to enhance the foam suppression properties of the compositions, such as vinyl-containing polyorganosiloxanes and hydrogen-containing polyorganosiloxanes, hydroxyl-containing polyorganosiloxanes. The alkane and the alkyl silicate undergo a crosslinking reaction under the action of a catalyst, but the degree of crosslinking is difficult to control. US 5,486,306 describes a direct synthesis of a defoamer for use in washing powders by reacting a hydrogen-containing polyorganosiloxane with an alpha-olefin. This process is simple to synthesize, but the defoaming agent obtained has poor defoaming properties and is easily produced in contact with the fabric. Silicon plaque; W02007137948A1 describes hydrogen-containing polyorganosiloxane After the reaction of the alkane and the vinyl polyorganosiloxane, the trimethylsiloxy-terminated polydimethylsiloxane is added, and the hydrogen polyorganosiloxane and the vinyl polyorganosiloxane in the above patent are reacted. The viscosity is large and difficult to control, and the obtained antifoaming composition has poor antifoaming performance.

CN1931417A discloses a high temperature and alkali resistant defoamer composition, which is obtained by crosslinking reaction of polysiloxane and silicone resin, and bubbling test performance in black liquor after preparing active material into emulsion. It has better

Moreover, since the silicone composition has a large viscosity, it is quite difficult to disperse it in water.

The invention adopts a hydrogen-based polyorganosiloxane and a silicone resin, and the α-olefin reacts under the action of an acidic catalyst to generate random copolymerization through the reactive groups - Η and -OH, CH ₂ =CH-. An alkyl-modified polyorganosiloxane having the following structure is obtained:

Then, a silica mixing treatment is added. The obtained silicone composition is formed by co-reacting a silicone resin and an α-olefin to form a silicone structure having a long-chain branched structure, an alkyl-modified polyorganosiloxane; and an α-olefin to a polyorganosiloxane. The alkane modification reduces the surface tension of the silicone composition, making it spread rapidly and uniformly; therefore, the obtained silicone composition has strong bubble control ability. Especially when used in detergent products, the foam height during the washing process can be efficiently controlled. Summary of the invention

The present invention relates to a random copolymerization reaction based on a hydrogen-containing polyorganosiloxane and a silicone resin, an α-olefin, and a silicone composition obtained by adding silica after the reaction, which can be used for different types of detergent products. Bubble control ingredients.

Technical solutions

A silicone composition characterized in that it consists of:

Α. Hydrogen-containing polyorganosiloxane

At least one hydrogen-containing polyorganosiloxane having the following structural formula:

Me ₃ SiO (MeHSiO) _a (Me ₂ SiO) ^SiMes

It is a methyl group, the subscript a is an integer of 2 to 100, the subscript is an integer of 2CT300, and each molecule has at least 2 silicon-bonded hydrogen atoms. The hydrogen-containing polyorganosiloxane has a kinematic viscosity at 25 ° C of 50 to 1, 500 mPa · s, and the hydrogen-containing polyorganosiloxane is used in an amount of from 45 to 75% by weight based on the total mass of the silicone composition.

B. Silicone resin

Silicone resin consists of chain links CH ₃ Si0 _1/2 (called M units in silicone chemistry) and chain links The unit composition of Si0 _4/2 (referred to as Q unit in silicone chemistry), the molar ratio between the two is (0.4 to 1.2): 1.0, preferably (0.5 to 0.8): 1.0. The silicone resin is used in an amount of 10% by weight based on the total mass of the silicone composition.

C. σ-olefin

The structural formula of the α-olefin is as follows:

CH ₂ =CH (CH ₂ ) _n H

Subscripts are integers from 4 to 26, specifically including α-hexene, α-octene, α-pinene, α-dodecene, α-tetradecene, α-hexadecene, α-octadecene, The α-icosene, the linear alpha olefin mixture of C20 to C24, the linear alpha olefin mixture of C24 to C28, and the α-trienol may be used singly or in any ratio. The amount of the α-olefin is from 10 to 50% based on the total mass of the silicone composition.

D. Catalyst

The catalyst is used to catalyze the polymerization of the component hydrogen-containing polyorganosiloxane and the silicone resin and the α-olefin. The catalyst is selected from the group consisting of a platinum-alcohol complex, a platinum-olefin complex, a platinum-alkoxide complex, a platinum-ether complex, a platinum-ketone complex, a chloroplatinic acid isopropanol solution, The platinum-vinyl complex is preferably a solution of chloroplatinic acid isopropanol. The catalyst is used in an amount of 20 ppm (in terms of platinum) of the total mass of the hydrogen-containing polyorganosiloxane oxime, silicone resin oxime and α-olefin C.

E. Silica

According to the manufacturing method, it is divided into two types: precipitated silica and fumed silica, and is classified into hydrophilic silica and hydrophobic silica according to surface properties. The present invention is preferably a hydrophobic silica comprising a vapor phase hydrophobic silica and a precipitation hydrophobic silica, the specific surface of which The product is 50~500m ² /g. The amount of silica used is from 2 to 6% by weight based on the total mass of the silicone composition. A method for preparing a silicone composition is as follows:

5〜1. 5h; 5h; 5h;

5〜3小时; 2, the addition of the α-olefin, and the addition of the catalyst at 5 ° C (T80 ° C reaction 0. 5~3h;

3。 After adding silica, in 10 (T160 ° C insulation for 5h; after the end of the heat, at 0. 01~0. 08MPa vacuum maintained 0. 1. 5h. Finally, cooled to room temperature to get silicone combination.

The silicone composition obtained by the present invention can be used for preparing a solid particle defoaming agent. A method for preparing such a solid antifoaming agent is known, and the silicone composition, the emulsifier and the structurant are thoroughly mixed first, and then adsorbed to the carrier. Finally, water is added, and granulation and drying processes form solid particles with good fluidity.

The structurant is selected from the group consisting of polyacrylic acid, maleic acid-acrylic acid copolymer, sodium carboxymethylcellulose, sodium citrate, potassium citrate and polyvinylpyrrolidone, used alone or in combination.

The carrier is selected from the group consisting of one or more of elemental powder, sodium tripolyphosphate, modified starch, zeolite, calcium carbonate and diatomaceous earth. detailed description

Example 1

Add 500g of hydrogen-containing polyorganosiloxane with a viscosity of 1200mPa * s to the vessel.

Me ₃ SiO (MeHSiO) ₄₅ (Me ₂ SiO) ₂ 6oSiMe ₃ , 18g silicone resin (M: Q = 0.7: 1), After incubation at 70 ° C for 0.5 h, 165 g of a-dodecene was added, and 10 ppm of chloroplatinic acid isopropanol solution (in terms of platinum) was added; the temperature was raised to 150 ° C for 2 h, and 30 g of specific surface area was added to be 90 m ² /g. The precipitated hydrophobic silica was cooled to 120 ° C for 4 h, maintained at a vacuum of 0.05 MPa for 1.5 h, and after dropping to room temperature, a silicone composition S1 having a viscosity of 10, OOO mPa · s was obtained.

Example 2

500 g of a hydrogen-containing polyorganosiloxane Me ₃ SiO (MeHSiO) ₅₅ (Me ₂ SiO) ₁₄ oSiMe ₃ , 45 g of a silicone resin (M: Q = 0.66:1), at 80, was added to the vessel at a viscosity of 500 mPa*s. After incubating for 1.5 h at ° C, 435 g of a-pinene was added, and 12 ppm of chloroplatinic acid isopropanol solution (in terms of platinum) was added; the temperature was raised to 130 ° C for 1.5 h, and then 45 g of a specific surface area of 200 m ² /g was added. The vapor phase hydrophobic silica was heated to 150 ° C for 3 h, maintained at a vacuum of 0.04 MPa for 1 h, and after dropping to room temperature, a silicone composition S2 having a viscosity of 8000 mPa · s was obtained.

Example 3

500 g of a hydrogen-containing polyorganosiloxane Me ₃ Si0 (MeHSiO) ₇₅ (Me ₂ SiO) ₂ 2oSiMe ₃ , 35 g of a silicone resin (M: Q = 0.68:1), at 60, was added to the vessel. After incubating for 1 h at ° C, 205 g of a-hexadecene was added. When the temperature was raised to 80 ° C, 15 ppm of chloroplatinic acid isopropanol solution (in terms of platinum) was added; the temperature was raised to 160 ° C for 2 h, and then 28 g of specific surface area was 380 m ^{2 .} The gas phase hydrophobic silica of /g was cooled to 130 ° C for 5 h, maintained at -0.06 MPa vacuum for 0.5 h, and after dropping to room temperature, a silicone composition S3 having a viscosity of 10, OOO mPa · s was obtained. Example 4

500 g of a hydrogen-containing polyorganosiloxane Me ₃ SiO (MeHSiO) ₄ (Me ₂ SiO) 6 ₆ SiMe ₃ , 60 g of a silicone resin (M: Q = 0.8:1) having a viscosity of 80 mPa* _s was added to the vessel. , reacting at 50 ° C for 1 h; adding 92 g of C2CTC24 linear alpha olefin mixture, heating to 70 ° C, adding 18 ppm chloroplatinic acid isopropanol solution (in platinum); heating to 150 ° C for 2 h, then adding 40 g ratio A fumed silica having a surface area of 150 m ² /g, heated to 160 ° C for 3 h, maintained at a vacuum of 0.08 MPa for 1 h, and lowered to room temperature to obtain a silicone composition S4 having a viscosity of 5000 mPa · s. .

Example 5

500 g of a hydrogen-containing polyorganosiloxane Me ₃ SiO (MeHSiO) ₅ (Me ₂ SiO) ₈₀ SiMe ₃ , 39 g of a silicone resin (M: Q = 0.60:1) having a viscosity of 100 mPa*s was added to the vessel, at 70 °C reaction for 1.5h; add 100g α-hexadecene and 200g α-octadecene, and add 14ppm chloroplatinic acid isopropanol solution (in platinum); heat up to 180 ° C reaction for 2h, then add 40g specific surface area Immersed to 130 m ² /g of hydrophobic silica, cooled to 150 for 5 h, maintained at 0. l~1.5 h under a vacuum of 0.08 MPa, and reduced to room temperature to obtain a silicone composition having a viscosity of 7000 mPa · s. S5.

Comparative example 1

500 g of a hydrogen-containing polyorganosiloxane Me ₃ Si0 (MeHSiO) ₇₅ (Me ₂ SiO) ₂ 2oSiMe ₃ , 205 g of α-hexadecene and 15 ppm of isopropylplatinic acid isopropanol solution were added to the vessel (900 gPa * s) In platinum, after reacting at 120 ° C for 1.5 h; cooling to 80 ° C, adding 35 g of silicone resin (M: Q = 0.68:1) and 28 g of fumed silica having a specific surface area of 380 m ² /g , heat up to 130 ° C for 5 h, maintained at a vacuum of 0.055 MPa 0. l~1. 5h, a silicone composition having a viscosity of 1800 mPa * s after being lowered to room temperature

S6.

Example 6~11

According to the preparation technology of the solid particle defoamer known to those skilled in the art, the solid particle defoamer is prepared by using S Guang S6 respectively, and the preparation method is as follows:

5h. After drying, the granulation is dried at 0. 5h. After granulation, the mixture is dried at 120 ° C 0. 5h That is, solid particle defoamers G1 to 6 are obtained.

Solid particle defoamer performance test

The washing machine used in this test is a gold-plated drum washing machine, model: ZWH6125, with a capacity of 7kg.

Test method: 150 g of commercially available washing powder, 0.75 g of solid particle defoamer and 20 kg of water were added to the washing machine, and the test procedure was a cotton and linen program. The window of the washing machine is marked with 5 metrics, which are 0, 25%, 50%, 75%, and 100% of the window height. "0" is the starting point, indicating no bubble, "100%" means full of bubbles. The bubble height is recorded every 5 minutes and recorded when the machine is stopped. The larger the value, the higher the bubble scale value in the washing machine, and the worse the foam inhibition is. The lower the bubble scale value in the same time, the better the foam suppression performance of the product. The test results are shown in Table 1: Table 1 Washing machine test results

It can be seen from the viscosity of the synthesized silicone composition that the viscosity of the silicone composition obtained by the silicone resin not participating in the co-reaction is small; as shown in Table 1, it can be seen that the silicone compositions S1 to 5 of Examples 1 to 5 are synthesized. Solid particle defoamer Gl~5 is added to the washing machine for machine washing The antifoaming performance, the foaming height should be less than 50%; and the solid silicone defoaming agent G6 synthesized by the silicone resin and the silicone composition S6 which is not involved in the reaction rises rapidly during the washing process. Finally, the foam fills the entire washing machine, causing the clothes to take a long time and using a lot of water to clean.

Claims

Rights request

A silicone composition and a preparation method thereof, characterized in that it consists of: a hydrogen-containing polyorganosiloxane in an amount of 45 to 75% by weight based on the total mass of the silicone composition; a silicone resin, in an amount of a total of 10% of the total mass of the silicone composition;

Α-olefin, the structural formula is as follows:

CH ₂ =CH (CH ₂ ) _n H

The subscript n is an integer of 4 to 26, and the amount of the α-olefin is 10 to 50% of the total mass of the silicone composition;

a catalyst, preferably a solution of chloroplatinic acid isopropanol;

Silica, preferably hydrophobic silica, having a specific surface area of 5 (T500 m ² /g, in an amount of ² to 6% of the total mass of the silicone composition;

The silicone composition is prepared as follows:

5〜1. 5h; 5h; 5h;

5〜3小时; The reaction was carried out at 5 ° C (T200 ° C reaction 0. 5~3h;

3, adding silica, and maintaining at 100~160 ° C for l~5h; then maintaining at 0. 01~_0. 08MPa vacuum degree 0. 1. 5h _; finally, cooling to room temperature to obtain a silicone composition.

2. A silicone composition according to claim 1 and a process for the preparation thereof, wherein the hydrogen-containing polyorganosiloxane contains at least one of the following structural formulas:

Me ₃ SiO (MeHSiO) _a (Me ₂ SiO) _A SiMe ₃

Where: is a methyl group, the subscript a is an integer from 2 to 100, and the subscript is an integer of 2CT300. Each molecule has at least 2 silicon-bonded hydrogen atoms; the hydrogen-containing polyorganosiloxane has a kinematic viscosity at 25 ° C of 80 to 2, OOO mPa · s.

3. The organosilicon composition according to claim 1 and a method for producing the same, wherein the silicone resin is composed of a chain link CH ₃ Si0 _1/2 and a chain node Si0 _4/2 , and the molar ratio of the two is preferably

(0.5~0.8): 1.0.

4. A silicone composition according to claim 1 and a process for the preparation thereof, wherein the α-olefin is selected from the group consisting of a-hexene, α-octene, α-pinene, α-dodecene, α_fourteen Alkene, α-hexadecene, α-octadecene, α-icosene, a linear alpha olefin mixture of C2CTC24, a linear alpha olefin mixture of C24 to C28, α-trienylene, may be used alone or Mix in any ratio.