CN112724452B - Surfactant, preparation method and application thereof - Google Patents
Surfactant, preparation method and application thereof Download PDFInfo
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- CN112724452B CN112724452B CN202011589722.7A CN202011589722A CN112724452B CN 112724452 B CN112724452 B CN 112724452B CN 202011589722 A CN202011589722 A CN 202011589722A CN 112724452 B CN112724452 B CN 112724452B
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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 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 foams are most widely used in automotive upholstery, such as automotive seat cushions, head rests, roofs, arm rests, 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, the organosilicon surfactant is mainly a micromolecular organosilicon monomer, and the micromolecular volatile matters can often cause VOC (total volatile matter) of the foam and affect 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 favorable for 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 99wt%.
In an alternative embodiment, the acid value of the diluent is less than 1mgKOH/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 alternative embodiments, 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 20wt%.
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, m + n is 2.0-12.0. The value of a is 1.0-10.0.R = -CH 2 CH 2 CH 2 O(CH 2 CH 2 O) x (CH 2 CH(CH 3 )O) y R 1 X has a value of 0-5.0, y has a value of 1.0-10.0, x + y has a value of 1.0-10.0，R 1 Is 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 20wt%.
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 a polyoxyethylene propylene graft silicone oil and a 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 1-2h.
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 120-150 ℃ for 3-6h.
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 10ppm.
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 3-7h.
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 alternative embodiments, the polyurethane foam has a VOC of 120 to 160 μ g/g and a FOG of 300 to 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 provided by the application 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 carried out according to 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 environmentally friendly diluent may include at least one of corn oil, soybean oil, castor oil, sunflower 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 ranging from 60wt% to 99wt%, such as 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, or 99wt%, and the like, and may be any other value within the range of 60wt% to 99wt%.
In an alternative embodiment, the acid value of the diluent is less than 1mgKOH/g.
By using the vegetable oil as the diluent in the surfactant, the content of volatile organic substances (characterized by VOC value) and the atomization performance (characterized by FOG value) of the organosilicon surfactant can be effectively controlled, the environment is protected, no pollution is caused, and 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
Of (2) a polydimethyl etherA siloxane. 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 20wt%, such as 1wt%, 5wt%, 10wt%, 15wt%, or 20wt%, 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 graft silicone oil of (1).
Wherein m is 1.0-10.0, n is 1.0-5.0, m + n is 2.0-12.0. The value of a is 1.0-10.0.R = -CH 2 CH 2 CH 2 O(CH 2 CH 2 O) x (CH 2 CH(CH 3 )O) y R 1 X is 0-5.0, y is 1.0-10.0, x + y is 1.0-10.0, R 1 Is 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 shown in 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 grafted silicone oil is present in the surfactant in an amount of no more than 20wt%. 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: 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 allyl polyether can be reacted for 3-6h (e.g., 3h, 4h, 5h, or 6h, etc.) at 120-150 deg.C (e.g., 120 deg.C, 130 deg.C, 140 deg.C, or 150 deg.C, etc.).
The hydrogen-containing silicone oil can be obtained by reacting octamethylcyclotetrasiloxane and tetramethyldihydrodisiloxane, or can be obtained 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 the amount of the catalyst may be 6 to 10ppm, such as 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, or the like.
In an alternative embodiment, the polydimethylsiloxane herein may be obtained by reacting octamethylcyclotetrasiloxane and hexamethyldisiloxane.
For reference, polydimethylsiloxane can be reacted for 3 to 7 hours at 30 to 70 ℃ by 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 alternative embodiments, the polyurethane foam has a VOC of 120 to 160 μ g/g and a FOG of 300 to 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 react 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 6 hours 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-containing silicone oil and 29.52g of hexamethyldisiloxane are reacted at 60 ℃ for 5 hours under the action of acid clay to obtain the hydrogen-containing 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 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
Reacting 388.74g of octamethylcyclotetrasiloxane and 170.16g of hexamethyldisiloxane at 60 ℃ for 5 hours under the action of acidic cation exchange resin, and separating and purifying to obtain the polydimethylsiloxane. 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 seed oil having an acid value of 0.34mgKOH/g were stirred at 30 to 40 ℃ for 1 hour to obtain surfactant B for a 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 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 octamethylcyclotetrasiloxane and 211.40g hexamethyldisiloxane are reacted at 70 deg.C for 4h under the action of acidic cation exchange resin, and then separated and purified to obtain polydimethylsiloxane. 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-containing silicone oil and 88.88g of hexamethyldisiloxane are reacted for 4 hours at 70 ℃ under the action of acid clay to obtain the hydrogen-containing silicone oil 1. 100.00g of octamethylcyclotetrasiloxane and 60.5g of tetramethyldihydrodisiloxane are reacted for 4 hours at 70 ℃ under the action of acid clay to obtain the 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: -CH 2 CH 2 CH 2 O(CH 2 CH 2 O) 2 (CH 2 CH(CH 3 )O) 5 CH 3 。
(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 a modified soybean oil having an acid value of 0.16mgKOH/g were stirred at 30 to 40 ℃ for 2 hours to obtain a surfactant D for a 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-containing 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-containing 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 dimethyl polysiloxane 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 the 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 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 tetramethyl dihydrodisiloxane react for 6 hours at 40 ℃ under the action of concentrated sulfuric acid to obtain 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 octamethylcyclotetrasiloxaneAnd 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 the modified sunflower seed 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 dimethyl polysiloxane 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
The present 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-containing 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-containing 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
And reacting 533.92g of octamethylcyclotetrasiloxane and 262.68g of hexamethyldisiloxane at 30 ℃ for 7 hours under the action of acidic cation exchange resin, and separating and purifying to obtain the polydimethylsiloxane. 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 were prepared from the surfactants obtained in examples 1 to 7 and comparative examples, and the foams 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 278-2011, which are thermal desorption analytical characterization of organic emissions of 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 can achieve or even exceed the properties of the surfactants of the comparative examples in terms of hardness, rebound, tensile strength and elongation at break, while also having significantly lower VOC and FOG than the surfactants 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, 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 micromolecular 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 (8)
1. The surfactant is characterized in that the surfactant contains a diluent, and the diluent is vegetable oil;
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;
the content of the diluent in the surfactant is 85-99wt%; the acid value of the diluent is less than 1mgKOH/g;
the surfactant also contains a surfactant with a structural formula
The polydimethylsiloxane of (1); wherein the value of q is 4.0-15.0; the content of the polydimethylsiloxane in the surfactant is 1-15wt%;
the surfactant also contains a surfactant with a structural formula
And structural formula
Polyoxyethylene propylene grafted silicone oil of (1); wherein m is 1.0-10.0, n is 1.0-5.0, m + n is 2.0-12.0; the value of a is 1.0-10.0; r = -CH 2 CH 2 CH 2 O(CH 2 CH 2 O) x (CH 2 CH(CH 3 )O) y R 1 X is 0-5.0, y is 1.0-10.0, x + y is 1.0-10.0, R 1 Is C1-C4 alkyl;
the content of the polyoxyethylene propylene grafted silicone oil in the surfactant is not more than 2.2wt%; structural formula is
Of polyethylene oxideThe allyl grafted silicone oil has the structural formula
The mass ratio of the polyoxyethylene propylene grafted silicone oil is 1-10:1.
2. the surfactant of claim 1, wherein q has a value of 5.0 to 12.0.
3. The surfactant of claim 1 wherein the formula is
The polyoxyethylene propylene grafted silicone oil has the structural formula
The mass ratio of the polyoxyethylene propylene grafted silicone oil is 1-5:1.
4. a process for preparing a surfactant as claimed in any one of claims 1 to 3, comprising the steps of: mixing the polyoxyethylene propylene grafted silicone oil, the polydimethylsiloxane and the diluent;
mixing at 30-40 deg.C for 1-2h.
5. The method of preparing according to claim 4, wherein the polyoxyethylene propylene graft silicone oil is prepared by: reacting hydrogen-containing silicone oil with allyl polyether in the presence of a catalyst;
the hydrogen-containing silicone oil and the allyl polyether react for 3 to 6 hours at the temperature of between 120 and 150 ℃;
the allyl polyether is methyl terminated polyether;
the dosage of the catalyst is 6-10ppm.
6. The method according to claim 4, wherein the polydimethylsiloxane is obtained by reacting octamethylcyclotetrasiloxane and hexamethyldisiloxane;
the polydimethylsiloxane is reacted for 3 to 7 hours by octamethylcyclotetrasiloxane and hexamethyldisiloxane at the temperature of 30 to 70 ℃;
the polydimethylsiloxane is reacted with octamethylcyclotetrasiloxane and hexamethyldisiloxane under the action of acidic cation exchange resin;
further comprising purifying the polydimethylsiloxane by the reaction product of octamethylcyclotetrasiloxane and hexamethyldisiloxane.
7. Use of a surfactant as claimed in any one of claims 1 to 3 in the preparation of a polyurethane foam.
8. A polyurethane foam characterized in that a raw material of the polyurethane foam contains the surfactant according to any one of claims 1 to 3;
the polyurethane foam has a VOC value of 120-160 [ mu ] g/g and a FOG value of 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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