CN111961209A - Low-volatility organic silicon surfactant and preparation method thereof - Google Patents
Low-volatility organic silicon surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention provides a low-volatility organosilicon surfactant, the structural formula of which is shown as follows,
wherein: m and n are both greater than 0, and the value of m + n is 2-50; r1、R2And R3Any one group selected from H, methyl or polyoxypropylene ether, and R1、R2And R3Not methyl at the same time. The invention also provides a preparation method of the surfactant, which adopts a chromium carbene catalyst and comprises the following steps ofHydrogen double-end-capping agent MDxM、DxAnd high hydrogen-containing silicone oil M 'D'yM' is prepared by hydrogen-containing silicone oil and then is obtained by the addition reaction of the hydrogen-containing silicone oil and polyoxypropylene ether. The invention realizes double catalysis by adopting one catalytic component, has simple formula and convenient operation, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of chemical industry, and relates to a low-volatility organosilicon surfactant, in particular to a low-volatility organosilicon surfactant and a preparation method thereof.
Background
The polyether organic silicon copolymer is an important organic silicon surfactant and is widely applied to the industries such as coating industry, polyurethane, pesticide, daily chemical industry and the like. In the polyurethane industry, silicone surfactants are essential raw materials for the preparation of polyurethane molded high resilience foams. The present organosilicon surfactant (commonly called 'high resilience silicone oil') used for polyurethane molding high resilience foam has a volatilization value of about 1000ppm, and the main reason is that polysiloxane with smaller molecular weight is remained in the high resilience silicone oil, and the influence of the polysiloxane with small molecular weight on VOC and smell is very large.
At present, foreign documents report a process of a low-volatility organic silicon surfactant, and the main strategy is to extract small molecular residues of the organic silicon surfactant by adopting high vacuum and high temperature (more than 120 ℃). The method can basically realize that the volatilization value of siloxane is about 1000ppm, but the performance of products at high temperature is reduced, such as the surface tension, activity and foam stability of a surfactant, and meanwhile, a rectification and condensation recovery device is required in the process, otherwise, the waste of raw materials, the pollution of micromolecule volatilization to the environment and the cost of energy consumption are increased.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a low-volatility organosilicon surfactant and a preparation method thereof, and aims to solve the problems of performance reduction of products and complex process equipment caused by high-temperature preparation conditions in the prior art.
The invention provides a low-volatility organosilicon surfactant, which has the following structural formula:
wherein: m and n are both greater than 0, and the value of m + n is 2-50; r1、R2And R3Any one group selected from H, methyl or polyoxypropylene ether group, and R1、R2And R3Not methyl at the same time.
The invention provides a preparation method of a low-volatility organosilicon surfactant, which is characterized in that hydrogen-containing silicone oil and polyoxypropylene ether are used as raw materials, chromium carbene is used as a catalyst, and the low-volatility organosilicon surfactant is prepared by a continuous one-pot method and has the following structural formula:
wherein: m and n are both greater than 0, and the value of m + n is 2-50; r1、R2And R3Any one group selected from H, methyl or polyoxypropylene ether, and R1、R2And R3Not being methyl at the same time;
the polyoxypropylene ether is an existing substance, is prepared from hydroxypropyl methacrylate and propylene oxide by using boron trifluoride as a catalyst, and the specific synthesis process refers to Chinese patent CN 107513158A 'a refining process of polyoxypropylene ether'.
The structural formula of the chromium carbene catalyst is shown as follows,
in the structure, two nitrogen heterocyclic carbene units are combined with a chromium metal center through a coordination bond, R4，R5，R6，R7，R8，R9Is any one of hydrogen atom, straight chain or branched chain alkyl, aryl or halogen, G is counter anion, and the counter anion is selected from halogen ion or acetate.
The catalyst can be prepared by mixing corresponding carbene ligand and metal chromium salt according to the mass ratio of 1: 1 and the carbene ligands can be prepared by reacting the corresponding precursor imidazopyridinium salts with a suitable base.
Specifically, the preparation method of the low-volatility organosilicon surfactant comprises the following steps:
(1) weighing hydrogen-containing double-end-capping reagent MDxM、DxAnd high hydrogen-containing silicone oil M 'D'yM', the hydrogen double-end capping agent MDxM、DxAnd high hydrogen-containing silicone oil M 'D'yThe mass ratio of M' is 1: 20-30: 1-5, wherein x is more than or equal to 2; m represents (CH)3)2SiHO1/2(ii) a D represents (CH)3)2SiO; d' represents CH3SiHO; m' represents (CH)3)3SiO1/2Y is a number from 10 to 50; adding hydrogen-containing double-end capping agent MD into a reaction vesselxM、DxAnd high hydrogen-containing silicone oil M 'D'yM', fully stirring, and adding a chromium carbene catalyst, wherein the dosage of the chromium carbene catalyst is hydrogen double-end capping agent MDxM、DxAnd high hydrogen-containing silicone oil M 'D'y1-3% of the total weight of M', reacting for 3-7h at the temperature of 30-80 ℃ to obtain hydrogen-containing silicone oil;
(2) and adding polyoxypropylene ether into the container of the previous step, heating to 60-80 ℃ under normal pressure, and reacting for 1-10h to obtain the low-volatility organosilicon surfactant.
Compared with the prior art, the invention has the advantages of positive and obvious technical effect. The invention uses a novel chromium carbene catalyst which catalyzes the reaction of hydrogen-containing double-end capping agent MDxM、DxAnd high hydrogen-containing silicone oil M 'D'yM' is used for preparing hydrogen-containing silicone oil and catalyzing addition reaction of the hydrogen-containing silicone oil and polyoxypropylene ether. Avoids the use of expensive platinum catalyst, and realizes double catalysis of one catalytic component to two-step reaction at lower temperature. The residue of polysiloxane micromolecules of the prepared organosilicon surfactant is less than 100 ppm; meanwhile, the method avoids the reduction of the performance of the product at high temperature because the reaction temperature is lower than 80 ℃. The method is cheaper, simpler in formula, more convenient to operate, green, safe, efficient and environment-friendly, and is suitable for industrial production.
Detailed Description
Example 1 preparation of chromium carbene catalyst:
the preparation method of the chromium carbene catalyst used in the invention refers to the following documents: ORGANIC LETTERS 2011Vol.13, No. 195256-5259; journal of Organometallic Chemistry 775(2015) 155-163; journal of organic Chemistry 820(2016) 1-7; journal of Catalysis 319(2014) 119-126; tetrahedron: Asymmetry 24(2013) 492-498.
The specific preparation method takes the above structure as an example, and comprises the following steps:
(1)：
23 g of (5-isopropyl-2-pyridyl) phenyl ketone, 200 ml of methanol and 5.4 g of o-phenylenediamine are sequentially added into a 500ml reaction vessel, hydrochloric acid gas is introduced under the condition of fully stirring until the solution is saturated, the solution is filtered after 5 hours of reaction at room temperature, and a filter cake is washed three times by 20 ml of methanol to obtain 28 g of the product of the diimidazole salt, wherein the yield is 90%.
(2)
Dispersing 6.2 g of the diimidazole salt prepared in the previous step in 100 ml of tetrahydrofuran, cooling to 0 ℃, adding 0.5 g of sodium hydride, naturally heating to room temperature for reaction for 2 hours, then adding 1.6 g of anhydrous chromium trichloride, continuing to react at room temperature for 1 hour, then refluxing for reaction for 2 hours, finally cooling to room temperature, filtering, washing a filter cake with 20 ml of deionized water for three times, and then washing with 20 ml of diethyl ether for three times to obtain 6.3 g of a target product with the yield of 86%.
Example 2 a method of preparing a low volatile silicone surfactant:
the chromium carbene catalyst used in this example was from example 1 and has the following structure:
(1) 5g of MD are added into a 500ml four-neck flask with a fixing device, a constant temperature function, mechanical stirring, a thermocouple and nitrogen gas5M, 140g decamethylcyclopentasiloxane (abbreviated as D)5) 14g of high hydrogen silicone oil M 'D'20M'; after stirring is started for half an hour, adding a chromium carbene catalyst, wherein the dosage of the chromium carbene catalyst is MD5M, decamethylcyclopentasiloxane (abbreviated as D)5) And high hydrogen-containing silicone oil M 'D'201% of the total mass of the M, the reaction for 3 hours at the temperature of 40 ℃ to obtain hydrogen-containing silicone oil;
(2) and (3) continuously adding 150g of allyl polyether into the container of the previous reaction, heating to 70 ℃ under the protection of nitrogen at normal pressure, and reacting for 3h to obtain the polyether organic silicon copolymer, wherein the copolymer is called as the organic silicon surfactant and is a clear and transparent light yellow liquid.
To compare the volatile component content of the silicone surfactants, commercially available U.S. air chemical
Organosilicon DC-6070 as a comparative example, a gas chromatography-MASS spectrometry (GC-MASS) was performed for comparative example and example 2 to determine the amount of small molecules remaining in the silicone surfactant, temperature program: keeping the temperature at 40 ℃ for 4min, and heating to 300 ℃ at the speed of 10 ℃/min for 30 min.
The TVOC (total volatiles) of example 2 was 80ppm, volatiles were: d5(decamethylcyclopentasiloxane), peak very small; the comparative example had a TVOC (Total volatiles) of 580ppm, more volatiles and a higher peak. Thus, this example successfully prepared a low volatility silicone surfactant.
Example 3 a method of preparing a low volatile silicone surfactant:
the structure of the nickel carbene catalyst used in this example is as follows, and its preparation method is as in example 1:
(1) 5g of MD are added into a 500ml four-neck flask with a fixing device, a constant temperature function, mechanical stirring, a thermocouple and nitrogen gas5M, 140g decamethylcyclopentasiloxane (abbreviated as D)5) 14g of high hydrogen silicone oil M 'D'20M'; after stirring is started for half an hour, adding a chromium carbene catalyst, wherein the dosage of the chromium carbene catalyst is MD5M, decamethylcyclopentasiloxane (abbreviated as D)5) And high hydrogen-containing silicone oil M 'D'20Reacting for 5 hours at the temperature of 30 ℃ to obtain hydrogen-containing silicone oil, wherein the mass of M is 2 percent of the total mass of the three components;
(2) and (3) continuously adding 150g of allyl polyether into the container of the previous reaction, heating to 70 ℃ under the protection of nitrogen at normal pressure, and reacting for 3h to obtain the polyether organic silicon copolymer, wherein the copolymer is called as the organic silicon surfactant and is a clear and transparent light yellow liquid.
To compare the volatile component content of the silicone surfactants, commercially available U.S. air chemical
Organosilicon DC-6070 as a comparative example, a gas chromatography-MASS spectrometry (GC-MASS) was performed for comparative example and example 3 to determine the amount of small molecules remaining in the silicone surfactant, temperature program: keeping the temperature at 40 ℃ for 4min, and heating to 300 ℃ at the speed of 10 ℃/min for 30 min.
The TVOC (total volatiles) of example 3 was 70ppm, volatiles were: d5(decamethylcyclopentasiloxane), peak very small; the comparative example had a TVOC (Total volatiles) of 580ppm, more volatiles and a higher peak. Thus, this example successfully prepared a low volatility silicone surfactant.
Example 4 a method of preparing a low volatile silicone surfactant:
the nickel carbene catalyst used in this example has the following structure, and its preparation method is as in example 1:
(1) 5g of MD are added into a 500ml four-neck flask with a fixing device, a constant temperature function, mechanical stirring, a thermocouple and nitrogen gas5M, 140g decamethylcyclopentasiloxane (abbreviated as D)5) 14g of high hydrogen silicone oil M 'D'20M'; after stirring is started for half an hour, adding a chromium carbene catalyst, wherein the dosage of the chromium carbene catalyst is MD5M, decamethylcyclopentasiloxane (abbreviated as D)5) And high hydrogen-containing silicone oil M 'D'20Reacting for 6 hours at 50 ℃ to obtain hydrogen-containing silicone oil, wherein the mass of M is 3 percent of the total mass of the three components;
(2) and (3) continuously adding 150g of allyl polyether into the container of the previous reaction, heating to 60 ℃ under the protection of nitrogen at normal pressure, and reacting for 3h to obtain the polyether organic silicon copolymer, wherein the copolymer is called as the organic silicon surfactant and is a clear and transparent light yellow liquid.
To compare the volatile component content of the silicone surfactants, commercially available U.S. air chemical
Organosilicon DC-6070 as a comparative example, comparative example and example 4 gas chromatography-MASS spectrometry (GC-MASS) was performed to determine the amount of small molecules remaining in the silicone surfactant, temperature program: keeping the temperature at 40 ℃ for 4min, and heating to 300 ℃ at the speed of 10 ℃/min for 30 min.
The TVOC (total volatiles) of example 4 was 50ppm, volatiles were: d5(decamethylcyclopentasiloxane), peak very small; the comparative example had a TVOC (Total volatiles) of 580ppm, more volatiles and a higher peak. Thus, this example successfully prepared a low volatility silicone surfactant.
Example 5 a method of preparing a low volatile silicone surfactant:
the nickel carbene catalyst used in this example has the following structure, and its preparation method is as in example 1:
(1) 5g of MD are added into a 500ml four-neck flask with a fixing device, a constant temperature function, mechanical stirring, a thermocouple and nitrogen gas5M, 140g decamethylcyclopentasiloxane (abbreviated as D)5) 14g of high hydrogen silicone oil M 'D'20M'; after stirring is started for half an hour, adding a chromium carbene catalyst, wherein the dosage of the chromium carbene catalyst is MD5M, decamethylcyclopentasiloxane (abbreviated as D)5) And high hydrogen-containing silicone oil M 'D'20Reacting for 7 hours at the temperature of 70 ℃ to obtain hydrogen-containing silicone oil, wherein the mass of M is 2 percent of the total mass of the three components;
(2) and (3) continuously adding 150g of allyl polyether into the container of the previous reaction, heating to 50 ℃ under the protection of nitrogen at normal pressure, and reacting for 3h to obtain the polyether organic silicon copolymer, wherein the copolymer is called as the organic silicon surfactant and is a clear and transparent light yellow liquid.
To compare the volatile component content of the silicone surfactants, commercially available U.S. air chemical
Organosilicon DC-6070 as a comparative example, comparative example and example 5 gas chromatography-MASS spectrometry (GC-MASS) was performed to determine the amount of small molecules remaining in the silicone surfactant, temperature program: keeping the temperature at 40 ℃ for 4min, and heating to 300 ℃ at the speed of 10 ℃/min for 30 min.
The TVOC (total volatiles) of example 5 was 80ppm, volatiles were: d5(decamethylcyclopentasiloxane), peak very small; the comparative example had a TVOC (Total volatiles) of 580ppm, more volatiles and a higher peak. Thus, this example successfully prepared a low volatility silicone surfactant.
Claims (3)
1. A low-volatility silicone surfactant is characterized by having a structural formula as follows:
wherein: m and n are both greater than 0, and the value of m + n is 2-50; r1、R2And R3Any one group selected from H, methyl or polyoxypropylene ether group, and R1、R2And R3Not methyl at the same time.
2. The preparation method of the low-volatility organosilicon surfactant according to claim 1, characterized in that the low-volatility organosilicon surfactant is prepared by a continuous one-pot method by using hydrogen-containing silicone oil and polyoxypropylene ether as raw materials and chromium carbene as a catalyst, and has a structural formula shown as follows:
wherein: m and n are both greater than 0, and the value of m + n is 2-50; r1、R2And R3Any one group selected from H, methyl or polyoxypropylene ether group, and R1、R2And R3Not being methyl at the same time;
the structural formula of the chromium carbene catalyst is shown as follows,
in the structure, two nitrogen heterocyclic carbene units are combined with a chromium metal center through a coordination bond, R4，R5，R6，R7，R8，R9Is any one of hydrogen atom, straight chain or branched chain alkyl, aryl or halogen, G is counter anion, and the counter anion is selected from halogen ion or acetate.
3. The method for preparing the low-volatility organosilicon surfactant according to claim 2, characterized by comprising the following steps:
(1) weighing hydrogen-containing double-end-capping reagent MDxM、DxAnd high hydrogen-containing silicone oil M 'D'yM', the hydrogen double-end capping agent MDxM、DxAnd high hydrogen-containing silicone oil M 'D'yThe mass ratio of M' is 1: 20-30: 1-5, wherein x is more than or equal to 2; m represents (CH)3)2SiHO1/2(ii) a D represents (CH)3)2SiO; d' represents CH3SiHO; m' represents (CH)3)3SiO1/2Y is 10 to 50; adding hydrogen-containing double-end capping agent MD into a reaction vesselxM、DxAnd high hydrogen-containing silicone oil M 'D'yM', fully stirring, and adding a chromium carbene catalyst, wherein the dosage of the chromium carbene catalyst is hydrogen double-end capping agent MDxM、DxAnd high hydrogen-containing silicone oil M 'D'y1-3% of the total weight of M', reacting for 3-7h at the temperature of 30-80 ℃ to obtain hydrogen-containing silicone oil;
(2) and adding polyoxypropylene ether into the container of the previous step, heating to 60-80 ℃ under normal pressure, and reacting for 1-10h to obtain the low-volatility organosilicon surfactant.
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