CN112724452A - Surfactant, preparation method and application thereof - Google Patents
Surfactant, preparation method and application thereof Download PDFInfo
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- CN112724452A CN112724452A CN202011589722.7A CN202011589722A CN112724452A CN 112724452 A CN112724452 A CN 112724452A CN 202011589722 A CN202011589722 A CN 202011589722A CN 112724452 A CN112724452 A CN 112724452A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
The invention discloses a surfactant, and a preparation method and application thereof, and belongs to the field of surfactants. The surfactant contains diluent including at least one of vegetable oil such as corn oil, soybean oil, castor oil, sunflower seed oil, cotton seed oil, rapeseed oil, olive oil and palm oil. By using the substances as the diluent, the VOC and the atomization of the organic silicon surfactant can be effectively controlled, the environment is protected, no pollution is caused, and meanwhile, the cost can be saved by 10-30%. The preparation method is simple and convenient, and can be used for industrial production. When the polyurethane foam modifier is applied to polyurethane foam, the VOC value and the FOG value of the polyurethane foam can be effectively reduced.
Description
Technical Field
The invention relates to the technical field of surfactants, and particularly relates to a surfactant and a preparation method and application thereof.
Background
The high-resilience polyurethane foam plastic is a kind of foam plastic with excellent performance, and is developed rapidly at home and abroad at present, and has wide application. High resilience polyurethane foam is most widely used in automotive interior parts, such as automobile cushions, headrests, ceilings, armrests and the like. According to the sampling and measuring method of organic matters and aldehyde and ketone substances in automobiles, the volatilization value of the organosilicon surfactant for the polyurethane high-resilience foam in the current market is about 1000ppm, and the organosilicon surfactant is mainly a micromolecular organosilicon monomer, and the micromolecular volatile matters can often cause VOC (volatile matter total amount) of the foam and influence atomization of glass.
The organic silicon surfactant is a necessary raw material for preparing polyurethane high-resilience foam, so that the development of the low-volatility low-atomization environment-friendly organic silicon surfactant is better beneficial to promoting the development of the industry.
In view of this, the invention is particularly proposed.
Disclosure of Invention
An object of the present invention includes providing a surfactant to solve the above technical problems.
The second object of the present invention is to provide a method for preparing the above surfactant.
The invention also provides the application of the surfactant in preparing polyurethane foam.
The fourth object of the present invention is to provide a polyurethane foam containing the above surfactant in the raw material.
The application can be realized as follows:
in a first aspect, the present invention provides a surfactant comprising a diluent which is a vegetable oil.
In an alternative embodiment, the vegetable oil comprises at least one of corn oil, soybean oil, castor oil, sunflower seed oil, cottonseed oil, rapeseed oil, olive oil, and palm oil.
In an alternative embodiment, the diluent is present in the surfactant in an amount of 60 to 99 wt%.
In an alternative embodiment, the acid value of the diluent is less than 1 mgKOH/g.
In an alternative embodiment, the surfactant further comprises a surfactant of the formula
The polydimethylsiloxane of (1). Wherein q has a value of 4.0 to 15.0.
In an alternative embodiment, q has a value of 5.0 to 12.0.
In an alternative embodiment, the polydimethylsiloxane is present in the surfactant in an amount of 1 to 20 wt%.
In an alternative embodiment, the surfactant further comprises a surfactant of the formula
The polyoxyethylene propylene grafted silicone oil and/or the structural formula thereof is
The polyoxyethylene propylene grafted silicone oil.
Wherein m is 1.0-10.0, n is 1.0-5.0, and m + n is 2.0-12.0. The value of a is 1.0-10.0. R is-CH2CH2CH2O(CH2CH2O)x(CH2CH(CH3)O)yR1X is 0-5.0, y is 1.0-10.0, x + y is 1.0-10.0, R1Is C1-C4 alkyl.
In an alternative embodiment, the polyoxyethylene propylene graft silicone oil is present in the surfactant in an amount of no more than 20 wt%.
In an alternative embodiment, the surfactant is a surfactant having the formula
The polyoxyethylene propylene grafted silicone oil has the structural formula
The polyoxyethylene propylene grafted silicone oil.
In an alternative embodiment, the formula is
The polyoxyethylene propylene grafted silicone oil has the structural formula
The mass ratio of the polyoxyethylene propylene grafted silicone oil is 1-10: 1, preferably 1 to 5: 1.
in a second aspect, the present application provides a method for preparing a surfactant according to the previous embodiment, comprising the steps of: and preparing the diluent into the surfactant.
In an alternative embodiment, when the surfactant further contains polyoxyethylene propylene graft silicone oil and polydimethylsiloxane, the polyoxyethylene propylene graft silicone oil, the polydimethylsiloxane and the diluent may be mixed.
In an alternative embodiment, the mixing and stirring is carried out at 30-40 ℃ for 1-2 h.
In an alternative embodiment, the polyoxyethylene propylene grafted silicone oil is prepared by: reacting hydrogen-containing silicone oil with allyl polyether in the presence of a catalyst.
In an alternative embodiment, the hydrogen-containing silicone oil is reacted with the allyl polyether at the temperature of 120-150 ℃ for 3-6 h.
In an alternative embodiment, the allyl polyether is a methyl terminated polyether.
In an alternative embodiment, the catalyst is used in an amount of 6 to 10 ppm.
In an alternative embodiment, the polydimethylsiloxane is obtained by reacting octamethylcyclotetrasiloxane and hexamethyldisiloxane.
In an alternative embodiment, the polydimethylsiloxane is reacted with octamethylcyclotetrasiloxane and hexamethyldisiloxane at 30-70 ℃ for 3-7 h.
In an alternative embodiment, the polydimethylsiloxane is reacted via octamethylcyclotetrasiloxane and hexamethyldisiloxane under the action of an acidic cation exchange resin.
In an alternative embodiment, further comprising purifying the polydimethylsiloxane via the reaction product of octamethylcyclotetrasiloxane and hexamethyldisiloxane.
In a third aspect, the present application also provides the use of a surfactant according to any one of the preceding embodiments in the preparation of a polyurethane foam.
In a fourth aspect, the present application also provides a polyurethane foam comprising a surfactant according to any one of the preceding embodiments as a starting material.
In an alternative embodiment, the polyurethane foam has a VOC of 120-160 μ g/g and a FOG of 300-450 μ g/g.
The beneficial effect of this application includes:
by using at least one of vegetable oils such as corn oil, soybean oil, castor oil, sunflower seed oil, cottonseed oil, rapeseed oil, olive oil, palm oil and the like as the diluent in the surfactant, VOC and atomization of the silicone surfactant can be effectively controlled, the environment is protected, no pollution is caused, and meanwhile, the cost can be saved. The preparation method of the surfactant is simple and convenient, and can be used for industrial production. When the polyurethane foam modifier is applied to polyurethane foam, the VOC value and the FOG value of the polyurethane foam can be effectively reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The surfactant provided by the present application, and the preparation method and application thereof are specifically described below.
At present, the diluent used in the surfactant for polyurethane foam is usually organic reagent, such as propoxylated butanol polyether and organic esters containing benzene ring, such as dioctyl phthalate, dioctyl sebacate, etc., which not only have large odor, but also easily generate volatile organic substances in the production process, which is not only not environment-friendly, but also not beneficial to human health.
In view of this, the inventors have creatively proposed the use of an environmentally friendly diluent as a component in the surfactant. The environment-friendly diluent may include at least one of corn oil, soybean oil, castor oil, sunflower seed oil, cottonseed oil, rapeseed oil, olive oil, and palm oil, for example.
In alternative embodiments, the diluent may be present in the surfactant in an amount of 60 to 99 wt%, such as 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or 99 wt%, and the like, and may be any other value within the range of 60 to 99 wt%.
In an alternative embodiment, the acid value of the diluent is less than 1 mgKOH/g.
By using the vegetable oil as the diluent in the surfactant, the volatile organic substance content (represented by a VOC value) and the atomization performance (represented by a FOG value) of the organic silicon surfactant can be effectively controlled, the environment is protected, no pollution is caused, and meanwhile, the cost can be saved (10-30% of the cost is saved compared with the diluent used in the prior art).
Further, the surfactant also contains a structural formula
The polydimethylsiloxane of (1). Wherein q has a value of 4.0 to 15.0, such as 4, 5, 8, 10, 12, or 15, and the like. Preferably, q has a value of 5.0 to 12.0.
In alternative embodiments, the polydimethylsiloxane may be present in the surfactant in an amount of 1 to 20 wt%, such as 1 wt%, 5 wt%, 10 wt%, 15 wt%, or 20 wt%, etc.
Further, the surfactant also contains a structural formula
The polyoxyethylene propylene grafted silicone oil and/or the structural formula thereof is
The polyoxyethylene propylene grafted silicone oil.
Wherein m is 1.0-10.0, n is 1.0-5.0, and m + n is 2.0-12.0. The value of a is 1.0-10.0. R is-CH2CH2CH2O(CH2CH2O)x(CH2CH(CH3)O)yR1X is 0-5.0, y is 1.0-10.0, x + y is 1.0-10.0, R1Is C1-C4 alkyl.
The structural formula is
The skeleton structure of the hydrogen-containing silicone oil in the polyoxyethylene propylene grafted silicone oil is a side chain type, and for the convenience of distinguishing, the hydrogen-containing silicone oil is defined as the first polyoxyethylene propylene grafted silicone oil in the application. The structural formula is
The skeleton structure of the hydrogen-containing silicone oil in the polyoxyethylene propylene grafted silicone oil is straight-chain type, and the hydrogen-containing silicone oil is defined as second polyoxyethylene propylene grafted silicone oil in the application.
In an alternative embodiment, the surfactant contains both the first polyoxyethylene propylene graft silicone oil and the second polyoxyethylene propylene graft silicone oil. The mass ratio of the first polyoxyethylene propylene grafted silicone oil to the second polyoxyethylene propylene grafted silicone oil may be 1-10: 1, as 1: 1. 2: 1. 5: 1. 8: 1 or 10: 1, etc. Preferably 1 to 5: 1, as 1: 1. 2: 1. 3: 1. 4: 1 or 5: 1.
in an alternative embodiment, the polyoxyethylene propylene graft silicone oil is present in the surfactant in an amount of no more than 20 wt%. That is, the surfactant may not contain polyoxyethylene propylene grafted silicone oil, and only consists of diluent and polydimethylsiloxane.
In the application, the polydimethylsiloxane and the polyoxyethylene propylene grafted silicone oil are used in the surfactant, so that the balance between the porosity and the stability of the polyurethane high-resilience foam can be realized, and the special requirements of the high-resilience foam on volume, ventilation, surface, shearing and dimensional stability are met. Meanwhile, the use of the raw materials can also avoid the problem that other raw materials adopted by the prior similar surfactants need to adopt high vacuum to extract the micromolecule residues of the organic silicon surfactants at high temperature in the later period.
In addition, the application also provides a preparation method of the surfactant, which comprises the following steps: and preparing the diluent into the surfactant. Specifically, when the surfactant further contains polyoxyethylene propylene graft silicone oil and polydimethylsiloxane, the polyoxyethylene propylene graft silicone oil, polydimethylsiloxane and diluent may be mixed.
In alternative embodiments, the mixing process can be carried out at 30-40 deg.C (e.g., 30 deg.C, 35 deg.C, or 40 deg.C, etc.) for 1-2h (e.g., 1h, 1.5h, or 2h, etc.).
In an alternative embodiment, the above polyoxyethylene propylene graft silicone oil may be prepared by: reacting hydrogen-containing silicone oil with allyl polyether in the presence of a catalyst.
For reference, the hydrogen-containing silicone oil and the allyl polyether can be reacted for 3-6h (e.g., 3h, 4h, 5h, or 6h, etc.) under the conditions of 120-150 ℃ (e.g., 120 ℃, 130 ℃, 140 ℃, or 150 ℃, etc.).
Wherein, the hydrogen-containing silicone oil can be obtained by reacting octamethylcyclotetrasiloxane and tetramethyl dihydrodisiloxane, or by reacting octamethylcyclotetrasiloxane, high hydrogen-containing silicone oil and hexamethyldisiloxane. The process can be carried out at 30-70 deg.C (such as 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C or 70 deg.C) for 3-7h (such as 3h, 4h, 5h, 6h or 7 h).
The allyl polyether is preferably a methyl-terminated polyether.
The catalyst may be a chloroplatinic acid catalyst and may be used in an amount of 6 to 10ppm, such as 6ppm, 7ppm, 8ppm, 9ppm, or 10 ppm.
In an alternative embodiment, the polydimethylsiloxane herein may be obtained by reacting octamethylcyclotetrasiloxane and hexamethyldisiloxane.
As a reference, polydimethylsiloxane can be reacted for 3 to 7 hours at 30 to 70 ℃ via octamethylcyclotetrasiloxane and hexamethyldisiloxane.
In an alternative embodiment, the polydimethylsiloxane is reacted via octamethylcyclotetrasiloxane and hexamethyldisiloxane under the action of an acidic cation exchange resin to increase the reaction conversion.
Further, the polydimethylsiloxane may be purified by the reaction product of octamethylcyclotetrasiloxane and hexamethyldisiloxane to increase the purity of the polydimethylsiloxane.
In addition, the application also provides the application of the surfactant in preparing polyurethane foam (polyurethane high-resilience foam).
Correspondingly, the application also provides a polyurethane foam (polyurethane high-resilience foam), and the raw materials of the polyurethane foam contain the surfactant.
In an alternative embodiment, the polyurethane foam has a VOC of 120-160 μ g/g and a FOG of 300-450 μ g/g.
In summary, the surfactant provided by the present application not only can effectively regulate and control the openness and stability of polyurethane high resilience foams, but also has low volatility and low fogging value. The surfactant is used for preparing high resilience foam, can effectively regulate and control the dimensional stability of the foam, and has low volatility and low fogging value.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
This example provides a surfactant, which can be obtained by:
(1) synthesis of polyoxyethylene propylene grafted silicone oil
90.93g of octamethylcyclotetrasiloxane, 48.75g of high hydrogen-containing silicone oil and 30.38g of hexamethyldisiloxane are reacted for 7 hours at 30 ℃ under the action of concentrated sulfuric acid to obtain the hydrogen-containing silicone oil.
60.00g of the hydrogen-containing silicone oil and 61.37g of allyl polyether are put into a four-neck flask, and the temperature is raised to 130 ℃ under normal pressure under the catalysis of 8ppm of chloroplatinic acid catalyst, and the reaction is carried out for 6 hours, so as to obtain the polyoxyethylene propylene grafted silicone oil. The structural formula of the polyoxyethylene propylene grafted silicone oil is as follows:
(2) Preparation of polydimethylsiloxane
355.44g octamethylcyclotetraSiloxane and 194.33g hexamethyldisiloxane react for 6h at 40 ℃ under the action of acidic cation exchange resin, and polydimethylsiloxane is obtained after separation and purification. The average structural formula of the polydimethylsiloxane is as follows:
(3) 3.58g of the above polyoxyethylene propylene graft silicone oil, 5.73g of the above polydimethylsiloxane and 226.80g of soybean oil having an acid value of 0.28mgKOH/g were stirred at 30 to 40 ℃ for 1 hour to obtain surfactant A for a low-fogging polyurethane high resilience foam.
Example 2
This example provides a surfactant, which can be obtained by:
(1) synthesis of polyoxyethylene propylene grafted silicone oil
87.69g of octamethylcyclotetrasiloxane, 41.46g of high hydrogen silicone oil and 29.52g of hexamethyldisiloxane are reacted at 60 ℃ for 5 hours under the action of acid clay to obtain the hydrogen silicone oil.
50.39g of the hydrogen-containing silicone oil and 49.47g of allyl polyether are put into a four-neck flask, and the temperature is raised to 140 ℃ under normal pressure under the catalysis of 10ppm of chloroplatinic acid catalyst, and the reaction is carried out for 3 hours, so as to obtain the polyoxyethylene propylene grafted silicone oil. The structural formula of the polyoxyethylene propylene grafted silicone oil is as follows:
(2) Preparation of polydimethylsiloxane
388.74g of octamethylcyclotetrasiloxane and 170.16g of hexamethyldisiloxane react for 5 hours at 60 ℃ under the action of acidic cation exchange resin, and the polydimethylsiloxane is obtained after separation and purification. The average structural formula of the polydimethylsiloxane is as follows:
(3) 4.62g of the above polyoxyethylene propylene graft silicone oil, 7.36g of the above polydimethylsiloxane and 197.49g of sunflower oil having an acid value of 0.34mgKOH/g were stirred at 30 to 40 ℃ for 1 hour to obtain surfactant B for low-fogging polyurethane high resilience foam.
Example 3
This example provides a surfactant, which can be obtained by:
(1) synthesis of polyoxyethylene propylene grafted silicone oil
118.48g of octamethylcyclotetrasiloxane and 53.65g of tetramethyldihydrodisiloxane react for 7 hours at 30 ℃ under the action of concentrated sulfuric acid to obtain the hydrogen-containing silicone oil.
71.35g of the hydrogen-containing silicone oil and 75.27g of allyl polyether are put into a four-neck flask, and the temperature is raised to 150 ℃ under normal pressure under the catalysis of 8ppm of chloroplatinic acid catalyst, and the reaction is carried out for 3 hours, so as to obtain the polyoxyethylene propylene grafted silicone oil. The structural formula of the polyoxyethylene propylene grafted silicone oil is as follows:
(2) Preparation of polydimethylsiloxane
479.36g of octamethylcyclotetrasiloxane and 211.40g of hexamethyldisiloxane react for 4 hours at 70 ℃ under the action of acidic cation exchange resin, and the polydimethylsiloxane is obtained after separation and purification. The average structural formula of the polydimethylsiloxane is as follows:
(3) 2.56g of the above polyoxyethylene propylene graft silicone oil, 8.24g of the above polydimethylsiloxane and 228.42g of rapeseed oil having an acid value of 0.28mgKOH/g were stirred at 30 to 40 ℃ for 2 hours to obtain surfactant C for a low-fogging polyurethane high resilience foam.
Example 4
This example provides a surfactant, which can be obtained by:
(1) synthesis of polyoxyethylene propylene grafted silicone oil
136.98g of octamethylcyclotetrasiloxane, 74.13g of high hydrogen silicone oil and 88.88g of hexamethyldisiloxane are reacted at 70 ℃ for 4 hours under the action of acid clay to obtain hydrogen silicone oil 1. 100.00g of octamethylcyclotetrasiloxane and 60.5g of tetramethyl dihydrodisiloxane are reacted for 4 hours at 70 ℃ under the action of acid clay to obtain hydrogen-containing silicone oil 2.
30.00g of the hydrogen-containing silicone oil 1, 28.47g of the hydrogen-containing silicone oil 2 and 64.58g of allyl polyether are put into a four-neck flask, and the temperature is raised to 120 ℃ under normal pressure under the catalysis of 10ppm of chloroplatinic acid catalyst, and the reaction is carried out for 6 hours, so as to obtain the polyoxyethylene propylene grafted silicone oil. The structural formula of the polyoxyethylene propylene grafted silicone oil is as follows:
wherein R is represented by the structural formula: -CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)5CH3。
(2) Preparation of polydimethylsiloxane
337.65g of octamethylcyclotetrasiloxane and 146.85g of hexamethyldisiloxane react for 6 hours at 50 ℃ under the action of acidic cation exchange resin, and the polydimethylsiloxane is obtained after separation and purification. The average structural formula of the polydimethylsiloxane is as follows:
(3) 3.68g of the above polyoxyethylene propylene graft silicone oil, 4.82g of the above polydimethylsiloxane and 176.64g of modified soybean oil having an acid value of 0.16mgKOH/g were stirred at 30 to 40 ℃ for 2 hours to obtain surfactant D for low-fogging polyurethane high resilience foam.
Example 5
This example provides a surfactant, which can be obtained by:
(1) synthesis of polyoxyethylene propylene grafted silicone oil
65.18g of octamethylcyclotetrasiloxane, 45.15g of high hydrogen silicone oil and 40.26g of hexamethyldisiloxane are reacted for 5 hours at 50 ℃ under the action of concentrated sulfuric acid to obtain the hydrogen silicone oil.
58.36g of the hydrogen-containing silicone oil and 60.15g of allyl polyether are put into a four-neck flask, and the temperature is raised to 140 ℃ under normal pressure under the catalysis of 6ppm of chloroplatinic acid catalyst, and the reaction is carried out for 4 hours, so as to obtain the polyoxyethylene propylene grafted silicone oil. The structural formula of the polyoxyethylene propylene grafted silicone oil is as follows:
(2) Preparation of polydimethylsiloxane
533.92g of octamethylcyclotetrasiloxane and 262.68g of hexamethyldisiloxane react for 7 hours at 30 ℃ under the action of acidic cation exchange resin, and the polydimethylsiloxane is obtained after separation and purification. The average structural formula of the polydimethylsiloxane is as follows:
(3) 2.96g of the above polyoxyethylene propylene graft silicone oil, 8.18g of the above polydimethylsiloxane and 185.83g of cottonseed oil having an acid value of 0.26mgKOH/g were stirred at 30 to 40 ℃ for 1.5 hours to obtain surfactant E for a low-fogging polyurethane high resilience foam.
Example 6
This example provides a surfactant, which can be obtained by:
(1) synthesis of polyoxyethylene propylene grafted silicone oil
370.76g of octamethylcyclotetrasiloxane and 270.04 g of tetramethyldihydrodisiloxane react for 6 hours at 40 ℃ under the action of concentrated sulfuric acid to obtain the hydrogen-containing silicone oil.
72.95g of the hydrogen-containing silicone oil and 69.49g of allyl polyether are put into a four-neck flask, and the temperature is raised to 130 ℃ under normal pressure under the catalysis of 8ppm of chloroplatinic acid catalyst, and the reaction is carried out for 6 hours, so as to obtain the polyoxyethylene propylene grafted silicone oil. The structural formula of the polyoxyethylene propylene grafted silicone oil is as follows:
(2) Preparation of polydimethylsiloxane
495.57g of octamethylcyclotetrasiloxane and 225.25g of hexamethyldisiloxane react for 6 hours at 40 ℃ under the action of acidic cation exchange resin, and the polydimethylsiloxane is obtained after separation and purification. The average structural formula of the polydimethylsiloxane is as follows:
(3) 1.97g of the above polyoxyethylene propylene graft silicone oil, 4.86g of the above polydimethylsiloxane and 190.84g of modified sunflower oil having an acid value of 0.23mgKOH/g were stirred at 30 to 40 ℃ for 1.5 hours to obtain a surfactant F for low-fogging polyurethane high-resilience foam.
Example 7
This example provides a surfactant, which can be obtained by:
(1) preparation of polydimethylsiloxane
495.57g of octamethylcyclotetrasiloxane and 225.25g of hexamethyldisiloxane react for 6 hours at 40 ℃ under the action of acidic cation exchange resin, and the polydimethylsiloxane is obtained after separation and purification. The structural formula of the polydimethylsiloxane is as follows:
(2)5.15G of the polydimethylsiloxane and 141.99G of modified sunflower oil with an acid value of 0.22mgKOH/G are stirred for 2 hours at 30-40 ℃ to obtain the surfactant G for the low-atomization polyurethane high-resilience foam.
Comparative example
This comparative example provides a surfactant, which can be obtained by:
(1) synthesis of polyoxyethylene propylene grafted silicone oil
65.18g of octamethylcyclotetrasiloxane, 45.15g of high hydrogen silicone oil and 40.26g of hexamethyldisiloxane are reacted for 5 hours at 50 ℃ under the action of concentrated sulfuric acid to obtain the hydrogen silicone oil.
58.36g of the hydrogen-containing silicone oil and 60.15g of allyl polyether are put into a four-neck flask, and the temperature is raised to 140 ℃ under normal pressure under the catalysis of 6ppm of chloroplatinic acid catalyst, and the reaction is carried out for 4 hours, so as to obtain the polyoxyethylene propylene grafted silicone oil. The structural formula of the polyoxyethylene propylene grafted silicone oil is as follows:
(2) Preparation of polydimethylsiloxane
533.92g of octamethylcyclotetrasiloxane and 262.68g of hexamethyldisiloxane react for 7 hours at 30 ℃ under the action of acidic cation exchange resin, and the polydimethylsiloxane is obtained after separation and purification. The average structural formula of the polydimethylsiloxane is as follows:
(3) 2.96g of the above polyoxyethylene propylene graft silicone oil, 8.18g of the above polydimethylsiloxane and 185.83g of propoxylated butanol polyether were stirred at 30 to 40 ℃ for 1.5 hours to give surfactant H for polyurethane high resilience foam.
Polyurethane high resilience foams prepared from the surfactants obtained in examples 1 to 7 and comparative example were subjected to the following performance tests, wherein the hardness was measured in GB10807-2006, the resilience was measured in GB6670-2008, the tensile strength and elongation at break were measured in GB6344-2008, the VOC value and the FOG value were measured in VDA 278-laid material 2011, which is characterized by thermal desorption analysis of organic emissions from non-metallic materials for automobiles, and the results are shown in tables 1 and 2.
TABLE 1 test results
TABLE 2 test results
| Surface active agent | VOC/ug/g | FOG/ug/g |
| A | 142.08 | 357.20 |
| B | 147.22 | 404.06 |
| C | 131.98 | 350.86 |
| D | 150.12 | 416.42 |
| E | 151.66 | 431.56 |
| F | 138.82 | 333.65 |
| G | 129.13 | 302.46 |
| H | 198.72 | 562.10 |
As can be seen from tables 1 and 2, the surfactants provided herein are able to achieve properties in hardness, resilience, tensile strength and elongation at break even exceeding those of the comparative examples, while also having significantly lower VOC and FOG than those of the comparative examples. The surfactant provided by the application can effectively regulate and control the porosity and stability of the polyurethane high-resilience foam, and has low volatility and low fogging value. The surfactant is used for preparing high resilience foam, can effectively regulate and control the dimensional stability of the foam, and has low volatility and low fogging value.
In summary, the vegetable oil provided by the present application is used as the diluent in the surfactant, so that the volatile organic substance content (characterized by the VOC value) and the atomization performance (characterized by the FOG value) of the silicone surfactant can be effectively controlled, the silicone surfactant is environment-friendly and pollution-free, and the cost can be saved (10-30% of the cost is saved compared with the diluent used in the prior art). Furthermore, the polydimethylsiloxane and the polyoxyethylene propylene grafted silicone oil are used in the surfactant, so that the balance of the porosity and the stability of the polyurethane high-resilience foam can be realized, and the special requirements of the high-resilience foam on volume, ventilation, surface, shear and dimensional stability are met. Meanwhile, the use of the raw materials can also avoid the problem that other raw materials adopted by the prior similar surfactants need to adopt high vacuum to extract the micromolecule residues of the organic silicon surfactants at high temperature in the later period.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The surfactant is characterized by comprising a diluent, wherein the diluent is vegetable oil;
preferably, the vegetable oil comprises at least one of corn oil, soybean oil, castor oil, sunflower oil, cottonseed oil, rapeseed oil, olive oil, and palm oil.
2. The surfactant according to claim 1, wherein the diluent is present in the surfactant in an amount of 60 to 99 wt%;
preferably, the acid value of the diluent is less than 1 mgKOH/g.
3. The surfactant according to claim 1 or 2, wherein the surfactant further comprises a surfactant of formula
Poly (di)Methyl siloxane; wherein the value of q is 4.0-15.0;
preferably, said q has a value of 5.0 to 12.0;
preferably, the polydimethylsiloxane is present in the surfactant in an amount of 1 to 20 wt%.
4. The surfactant of claim 3, further comprising a surfactant of formula
And/or structural formula
Polyoxyethylene propylene grafted silicone oil of (1);
wherein m is 1.0-10.0, n is 1.0-5.0, and m + n is 2.0-12.0; the value of a is 1.0-10.0; r is-CH2CH2CH2O(CH2CH2O)x(CH2CH(CH3)O)yR1X is 0-5.0, y is 1.0-10.0, x + y is 1.0-10.0, R1Is C1-C4 alkyl;
preferably, the polyoxyethylene propylene graft silicone oil is contained in the surfactant in an amount of not more than 20 wt%.
5. The surfactant of claim 4, wherein the surfactant is a surfactant having the formula
The polyoxyethylene propylene grafted silicone oil has the structural formula
Polyoxyethylene propylene grafted silicone oil of (1);
preferably, the structural formula is
The polyoxyethylene propylene grafted silicone oil has the structural formula
The mass ratio of the polyoxyethylene propylene grafted silicone oil is 1-10: 1, more preferably 1 to 5: 1.
6. a process for preparing a surfactant as claimed in any one of claims 1 to 5, comprising the steps of: preparing the diluent into the surfactant;
preferably, when the surfactant further contains the polyoxyethylene propylene graft silicone oil and the polydimethylsiloxane, the polyoxyethylene propylene graft silicone oil, the polydimethylsiloxane and the diluent are mixed;
preferably, the mixing is carried out at 30-40 ℃ for 1-2 h.
7. The production method according to claim 6, characterized in that the polyoxyethylene propylene graft silicone oil is produced by: reacting hydrogen-containing silicone oil with allyl polyether in the presence of a catalyst;
preferably, the hydrogen-containing silicone oil and the allyl polyether are reacted for 3-6h at the temperature of 120-150 ℃;
preferably, the allyl polyether is a methyl terminated polyether;
preferably, the catalyst is used in an amount of 6 to 10 ppm.
8. The method according to claim 6, wherein the polydimethylsiloxane is obtained by reacting octamethylcyclotetrasiloxane and hexamethyldisiloxane;
preferably, the polydimethylsiloxane is reacted for 3 to 7 hours by octamethylcyclotetrasiloxane and hexamethyldisiloxane at the temperature of 30 to 70 ℃;
preferably, the polydimethylsiloxane is reacted with octamethylcyclotetrasiloxane and hexamethyldisiloxane under the action of acidic cation exchange resin;
preferably, the method further comprises purifying the polydimethylsiloxane by a reaction product of octamethylcyclotetrasiloxane and hexamethyldisiloxane.
9. Use of a surfactant as claimed in any one of claims 1 to 5 in the preparation of a polyurethane foam.
10. A polyurethane foam characterized in that a raw material of the polyurethane foam contains the surfactant according to any one of claims 1 to 5;
preferably, the VOC value of the polyurethane foam is 120-160 mu g/g, and the FOG value is 300-450 mu g/g.
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| CN1184133A (en) * | 1996-10-31 | 1998-06-10 | 奥西特殊品有限公司 | Hydrosilation in high boiling natural vegetable oils |
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| CN111040229A (en) * | 2019-12-27 | 2020-04-21 | 江苏美思德化学股份有限公司 | Open-cell type organic silicon surfactant, preparation method and application thereof, and high-resilience foam |
| CN111748099A (en) * | 2020-07-08 | 2020-10-09 | 上海麦豪新材料科技有限公司 | Preparation method of polyether organic silicon copolymer |
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| CN1184133A (en) * | 1996-10-31 | 1998-06-10 | 奥西特殊品有限公司 | Hydrosilation in high boiling natural vegetable oils |
| WO2005118668A1 (en) * | 2004-05-25 | 2005-12-15 | General Electric Company | Process for preparing polyurethane foams having reduced voc emissions |
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