WO2012031500A1

WO2012031500A1 - Organic silicon compound, preparation method and use thereof

Info

Publication number: WO2012031500A1
Application number: PCT/CN2011/076753
Authority: WO
Inventors: 黄振宏; 谢秀鸿; 黄晓梅
Original assignee: 广东标美硅氟新材料有限公司
Priority date: 2010-09-10
Filing date: 2011-07-01
Publication date: 2012-03-15
Also published as: CN101942083B; CN101942083A

Abstract

An organic silicon compound and the preparation method thereof are disclosed. The organic silicon compound has a structure as shown by formula (I), in which a=0~40; b=0~30; c=0~40; a, b, and c are integers and a+b+c>6. The preparation method comprises the following steps: α-hydrogen-ω-hydroxyl polyether and halogenated propylene are reacted in the presence of alkali metal hydroxide to form diallyl polyether; the obtained diallyl polyether and 1,1,1,3,5,5,5-heptamethyl trisiloxane are reacted in the presence of Pt catalyst to produce an organic silicon compound. The organic silicon compound has oil-collecting effect and can be used in treating oil spilt in an aqueous environment.

Description

Organic silicon compound and preparation method and application thereof

The invention belongs to the technical field of organosilicon compound synthesis, and particularly relates to an organosilicon compound and a preparation method and application thereof.

Background technique

Silicone surfactant is a new type of surfactant developed with new silicone materials. Like fluorosurfactants, it has won a wide range of survival and development space with its unique properties. It has become an increasingly important specialty surfactant.

Offshore oil exploitation and transportation often cause oil spills and oil spills caused by accidents or other technical reasons, which not only cause huge economic losses to enterprises, but also cause serious environmental pollution. After the oil leaks into the waters, it will spread out quickly, forming a very thin oil layer, making recovery difficult. Surfactant-based oil collectors can reduce the surface tension of seawater, reduce the oil spill area and form a certain thickness of the oil layer, and can effectively control the spread of oil spills. Great significance.

Chinese patent CN 1149612A (published date: May 14, 1997) discloses an oil spill collector composition for oil spills of diesel oil, from 1% to 10% by mass of natural carboxylic acid and 90% by mass. ~ 99% alcohol or kerosene organic solvent composition; oil collector for crude oil spill, from 1% to 10% by mass of natural carboxylic acid and polyoxyethylene oleate and 90% to 99% of the above organic solvent composition.

Chinese Patent CN 1473767A (published on Feb. 11, 2004) discloses a surface oil film oil collecting agent having an active component and a carrier, the active component being a solid fatty alcohol, a solid fatty carboxylic acid, and a water-poor pear One, two or three of the alcohol fatty acid esters, and their total weight percentage is from 1 to 25%.

It can be seen that the current oil collectors are generally hydrocarbon surfactants. Surfactant oil collection The effect is limited, and the oil collector composition composed of the same is complicated, and the use is not very convenient, and the organic solvent used may cause secondary pollution to the environment.

Summary of the invention

The object of the present invention is to solve the problems of limited effect and inconvenient use of the oil collecting agent in the prior art, and to provide a novel organosilicon compound having a unique structure and flooding oils of various hydrocarbon oils. It has a good effect, is easy to use, and is environmentally friendly. It can be used as an oil collector for oil spill treatment in waters.

It is also an object of the present invention to provide a process for the preparation of the organosiliconated book composition.

It is also an object of the present invention to provide an application of the organosilicon compound in a surface oil spill treatment. It is also an object of the present invention to provide the use of the organosilicon compound in the preparation of an oil repellency collector. The above object of the present invention is achieved by the following technical solutions:

An organosilicon compound having the formula (I)

(I)

Where a = 0 to 40; b = 0 to 30; c = 0 to 40; a, b, c are integers and a + b + c > 6.

The preparation method of the organosilicon compound is a molecule of "hydrogen-omega-hydroxy polyether and two molecules of halogenated propylene. Under the action of an alkali metal hydroxide, two molecules of halogenation are removed by a Williamson reaction. Hydrogen, giving a bisallyl polyether; then one molecule of bisallyl polyether with two molecules Description

Under the action of a 1,1,1,3,5,5,5-heptamethyltrisiloxane catalyst, an addition reaction occurs to obtain the organosilicon compound.

A method for preparing the organosilicon compound, comprising the steps of:

(1) reacting with -hydrogen-omega-hydroxy polyether and halogenated propylene as raw materials to form a bisallyl polyether under the action of an alkali metal hydroxide;

(2) The obtained bisallyl polyether and 1,1,1,3,5,5,5-heptamethyltrisiloxane are reacted under the action of a Pt catalyst to prepare an organosilicon compound.

As a preferred solution, the preparation method of the organosilicon compound includes the following steps:

(1) adding α-hydrogen-omega-hydroxy polyether and alkali metal hydroxide to the reaction vessel, stirring, adding dropwise halogenated propylene; after the addition is completed, heating is heated, and the reaction is carried out at 70 to 110 ° C. 7h; after completion of the reaction, the mixture was distilled under reduced pressure at 70 to 120 ° C, and the low boiler was removed and filtered to obtain a transparent liquid of bisallyl polyether.

(2) The bisallyl polyether obtained above and 1,1,1,3,5,5,5-heptamethyltrisiloxane are added to the reaction vessel, stirred, heated, and added at 50 to 100 ° C. The Pt catalyst is further heated to a temperature of 110 to 170 ° C to obtain the organosilicon compound.

In the step (1), the molar ratio of the three raw materials of the α-hydrogen-omega-hydroxy polyether, the halogenated propylene, and the alkali metal hydroxide is from 1:2 to 2.5:2 to 2.2.

In the step (2), the molar ratio of the bisallyl polyether, 1,1,1,3,5,5,5-heptamethyltrisiloxane is 1.4:2.

In the step (2), referring to the conventional art in the art, the Pt catalyst is preferably H ₂ PtCl ₆ , and the H ₂ PtCl ₆ is preferably used in the amount of bisallyl polyether and 1,1, 1,3,5. 0.005% of the total weight of 5,5-heptamethyltrisiloxane. .

The "-hydro-ω-hydroxy polyether has the structure represented by the formula (Π): Instruction manual

(II)

Wherein: a = 0 to 40; b = 0 to 30; c = 0 to 40; a, b, c are integers and a + b + c > 6.

The alkali metal hydroxide is preferably sodium hydroxide.

The halopropene is preferably allyl chloride.

The use of the organosilicon compound in oil spill treatment.

The use of the organosilicon compound in the preparation of an oil spill inducing agent.

Compared with the prior art, the present invention has the following beneficial effects:

The organosilicon compound of the invention has a hydrophobic structure at both ends, a hydrophilic structure in the middle section, and a special structure. Compared with other hydrocarbon surfactants, the surface tension is lower, the preparation is simple, and the oil collecting effect is better. It is convenient to use, and is non-toxic and environmentally friendly; the preparation method of the organosilicon compound adopts two molecules of halogenated propylene to simultaneously treat both ends of the -hydro-ω-hydroxy polyether to obtain diene. The polyether is further reacted with the organosilicon oxime to obtain an organosilicon compound having a novel structure; the organosilicon compound acts as a surfactant to drive a variety of hydrocarbon oils leaking on the surface of the water to a small extent, and then Recycling it has great application value for the removal and recovery of oil spills in the waters.

DRAWINGS

Figure 1 is a comparison of the oil collection effects of different surfactants.

Figure 2 is a reaction formula for preparing a bisallyl polyether.

Figure 3 is a reaction formula for preparing the organosilicon compound.

detailed description

The invention will be further explained below in conjunction with the examples, but the examples do not take any form of the invention. Description

Limited.

Example 1

In a four-necked flask equipped with a stirring device, a reflux condenser, a thermometer and a dropping funnel, adding - hydrogen-omega-hydroxy polyoxypropylene ether (a = 3, b = 8, c = 3) 0.2 mol, NaOH 0.43 mol, stirring, 0.5 mol of allyl chloride was added dropwise in 1.0 hour, and then the reaction was kept at about 100 ° C for about 5 hours. After the reaction was completed, the mixture was distilled under reduced pressure at 70 to 110 ° C for about 2 hours, and the extraction was low. The boil, until the unreacted allyl chloride was substantially removed, and the light yellow transparent double-end allyl polyether was isolated by filtration, and the yield was 88%.

Take 65 parts of the above product, 35 parts of 1,1,1,3,5,5,5-heptamethyltrisiloxane (ie, the molar ratio of the two is 1.0: 2), stir and heat, at 70 ° C H ₂ PtCl ₆ catalyst (H ₂ PtCl ₆ is used in an amount of 0.005% by weight of the reactant), heating is continued to 150 ° C, and the reaction is refluxed to be transparent and cooled to obtain the desired product.

The data obtained by infrared analysis and ¹ H-NMR analysis are as follows:

IRCKBr cm" ¹ ): The characteristic absorption peaks are classified as: ~ 2958, ~1352 (CH), ~1255 (C-0). ^-NMR (CDC1 ₃ , ppm): The characteristic absorption peaks are classified as: 3·380~3·802 (—CH ₂ —), δ 1·501~1·639 (≡C-CH ₃ ), 33·301~ ₃ ·362 (—CH— ), δ 0·129~0· 248 (≡Si — CH ₃ ) o

According to the IR spectrum and the ¹ H-NMR spectrum, the obtained product has a structure represented by the general formula (I) according to the division of the characteristic peaks.

Example 2

In a four-necked flask equipped with a stirring device, a reflux condenser, a thermometer and a dropping funnel, add - hydrogen-omega-hydroxy polyoxyethylene ether (b = 0, a + c = 9) 0.3 mol, NaOH 0.6 mol , stirring, 0.7mol of allyl chloride was added dropwise within 1.5 hours, and then the reaction was kept at about 90 ° C for about 3 hours. After the reaction was completed, the mixture was distilled under reduced pressure at 70 to 100 ° C for about 2 hours to remove low boilers. Until the unreacted allyl chloride is basically removed Description

It was cleaned and separated by filtration to obtain a yellow transparent double-end allyl polyether in a yield of 85%.

Take 52 parts of the above product, 48 parts of 1,1,1,3,5,5,5-heptamethyltrisiloxane (ie, the molar ratio of the two is 1.1:2), stir and heat, at 80 ° C H ₂ PtCl ₆ catalyst (H ₂ PtCl ₆ is used in an amount of 0.005% by weight of the reactant), heating is continued to 150 ° C, and the reaction is refluxed to be transparent and cooled to obtain the desired product.

The data obtained by infrared analysis and ¹ H-NMR analysis are as follows:

IRCKBr cm" ¹ ): The characteristic absorption peaks are divided into: ~ 2870, ~1350 (CH), ~1255 (C-0). ^-NMR (CDC1 ₃ , ppm): The classification of characteristic absorption peaks is divided into: 3 3·404~3·724 (—CH ₂ —), δ 0.102— 0.265 (≡Si—CH ₃ ) o

Example 3

In a four-necked flask equipped with a stirring device, a reflux condenser, a thermometer and a dropping funnel, adding - hydrogen-omega-hydroxy polyoxyethylene ether (b = 0, a + c = 15) 0.2 mol, NaOH 0.4 mol , stirring, adding 0.4 mol of allyl chloride in 1 hour, and then holding the reaction at 80 to 90 ° C for about 4 hours. After the reaction is completed, the mixture is distilled under reduced pressure at 70 to 120 ° C for about 2 hours, and the extraction is low. The boil, until the unreacted allyl chloride was substantially removed, and the pale yellow transparent target compound double-end allyl polyether was isolated by filtration, and the yield was 82%.

Take 65 parts of the above product, 35 parts of 1,1,1,3,5,5,5-heptamethyltrisiloxane (ie, the molar ratio of the two is 1.2:2), stir and heat, about 76 ° C H ₂ PtCl ₆ catalyst (H ₂ PtCl _{6 is added in} an amount of about 0.005% by weight of the reactants), heating is continued to 140 ° C, refluxing is carried out until it is transparent, and cooling is carried out to obtain the target product by infrared analysis and ¹ H. - NMR analysis, the data obtained is as follows:

IRCKBr cm" ¹ ): The characteristic absorption peaks are divided into: ~ 2868, ~1352 (CH), ~1246 (C-0). Instruction manual

^-NMR (CDC1 ₃ , ppm): The characteristic absorption peaks are classified as: 3 3·364~3·667 (—CH ₂ —), 5 0.129—0.256 (≡Si—CH ₃ ).

Example 4

In a four-necked flask equipped with a stirring device, a reflux condenser, a thermometer and a dropping funnel, adding - hydrogen-omega-hydroxy polyoxypropylene ether (b = 0, a + c = 20) 0.2 mol, NaOH 0.44 mol , stirring, adding 0.48 mol of allyl chloride in 1 hour, and then holding the reaction at 70 to 90 ° C for about 6 hours. After the reaction is completed, the mixture is distilled under reduced pressure at 70 to 120 ° C for about 2 hours, and the extraction is low. The boil, until the unreacted allyl chloride was substantially removed, and the light yellow transparent target compound double-end allyl polyether was isolated by filtration, and the yield was 90%.

Take 72 parts of the above product, 28 parts of 1,1,1,3,5,5,5-heptamethyltrisiloxane (ie, the molar ratio of the two is 1.3:2), stir and heat, about 98 ° C H ₂ PtCl ₆ catalyst (H ₂ PtCl ₆ is used in an amount of 0.005% by weight of the reactant), heating is continued to 160 ° C, and the reaction is refluxed to be transparent and cooled to obtain the desired product.

The data obtained by infrared analysis and ¹ H-NMR analysis are as follows:

IRCKBr cm" ¹ ): The characteristic absorption peaks are classified as: ~ 2872, ~1346(CH), ~1250(CO). ^-NMR (CDC1 ₃ , ppm): The classification of characteristic absorption peaks is divided into: 3 3· 370~3·800 (—CH ₂ —), δ 1·500~1·632 (≡C-CH ₃ ), δ 0·125~0·243 (≡Si—CH ₃ ).

Example 5

In a four-necked flask equipped with a stirring device, a reflux condenser, a thermometer and a dropping funnel, adding - hydrogen-omega-hydroxy polyoxypropylene ether (a = 3, b = 8, c = 0) 0.3 mol, NaOH 0.62mol, stirred, at 1.5 small Description

In the meantime, 0.74 mol of allyl chloride was added dropwise, and then the reaction was kept at 80 to 106 ° C for about 6 hours. After the completion of the reaction, the mixture was distilled under reduced pressure at 80 to 110 ° C for about 2 hours, and the low boiler was removed until not The allyl chloride of the reaction was substantially removed, and the light-yellow transparent target compound double-end allyl polyether was isolated by filtration, and the yield was 86%.

Take 68 parts of the above product, 32 parts of 1,1,1,3,5,5,5-heptamethyltrisiloxane (ie, the molar ratio of the two is 1.4:2), stir and heat, at 90 ° C H ₂ PtCl ₆ catalyst (H ₂ PtCl ₆ is used in an amount of 0.005% by weight of the reactant), heating is continued to 130 ° C, and the reaction is refluxed to be transparent and cooled to obtain the desired product.

The data obtained by infrared analysis and ¹ H-NMR analysis are as follows:

IR (KBr cm" ¹ ): The classification of characteristic absorption peaks is divided into: ~2866, ~1346(CH), -1250 (CO) o

^-NMR (CDC1 ₃ , ppm): The classification of characteristic absorption peaks is divided into: 3 3·380~3·722 (—CH ₂ —), δ 1·491~1·635 (≡C-CH ₃ ), 33 ·293~3·360 (—CH— ), δ 0·122~0·245 (≡Si — CH ₃ ) o

Example 6

Take a water tank 80cm long, 8cm wide and 10cm deep. Add 4L of seawater to it and add 80g of 50# oil. After it is completely spread on the water surface, inject 20 squirting agent from the oil-water interface at one end. The oil layer was quickly driven to the other end.

The results of Table 1 were obtained by oil collection tests of different surfactants.

Table 1 Comparison table of oil collection effects of different surfactants The maximum oil displacement area of the oil displacement, the time required for various surfactants to drive oil for a certain distance/s

(20 L) Distance /cm

30cm 45cm 60cm /% sodium decyl sulfonate 40.12 \ \ 30 30 octylphenol ethoxylate 25.66 43.82 \ 53 55 Example 2 4.58 10.85 39.82 63 65 Example 3 6.30 8.34 10.91 72 74 Example 1 5.35 7.70 10.9 70 72 It can be seen from Fig. 1 and Table 1 that the oil collecting effect of the organosilicon compound prepared by the invention as an oil repellency agent is significantly higher than that of the existing surfactant, and the organic preparation prepared by the invention Silicon compounds can quickly reach longer distances in a short period of time and have longer oil displacement distances and larger oil displacement areas.

Claims

Claim

An organosilicon compound characterized by having the structure represented by the formula (I):

(I);

2. A method of preparing an organosilicon compound according to claim 1, comprising the steps of

(1) using α-hydrogen-omega-hydroxy polyether or halogenated propylene as a raw material, and reacting under the action of an alkali metal hydroxide to form a bisallyl polyether;

(2) The bisallyl polyether obtained above and 1,1,1

Under the action of a chemical agent, the reaction produces a product.

Propylene generation; after the addition is completed, the temperature is raised by heating, and the reaction is carried out at 70 to 110 ° C for 3 to 7 hours;

Distilled under reduced pressure at 120 ° C, and filtered to obtain a transparent liquid of bisallyl polyether;

(2) The bisallyl polyether obtained above and 1,1,1,-heptamethyltrisiloxane are added to the reaction vessel, stirred, heated, and Pt catalyst is added at 50 to 100 ° C, and heating is continued until The reaction was carried out at 110 to 170 ° C to obtain a product.

4. A method of preparation according to any one of claims 2 or 3, characterized by the step Claim

The molar ratio of the α-hydrogen-omega-hydroxy polyether, the halogenated propylene, and the alkali metal hydroxide in (1) is 1:2 to 2·5:2 to 2·2.

5. A method of preparation according to any one of claims 2 or 3, characterized by the step

The molar ratio of the bisallyl polyether, 1,1,1,3,5,5,5-heptamethyltrisiloxane in (2) is from 1 to 1.4:2.

The preparation method according to any one of claims 2 or 3, wherein the Pt catalyst in the step (2) is 13⁄4? ₁₆ , and the amount of the H ₂ PtCl ₆ is bisallyl. Polyether and

1,1, 1,3,5,5,5- the total weight of the silicone embankment heptamethyl ₀ 0.005%.

The process according to any one of claims 2 or 3, wherein the α-hydrogen-omega-hydroxy polyether has a structure represented by the formula (Π):

(II)

The process according to any one of claims 2 or 3, wherein the alkali metal hydroxide is sodium hydroxide; and the halogenated propylene is allyl chloride.

9. The use of an organosilicon compound according to claim 1 in an oil spill treatment in a water zone.

10. Use of an organosilicon compound according to claim 1 in the preparation of an oil repellency collector.