CN112694617A - Modified silicone oil, surfactant, preparation method and application thereof - Google Patents
Modified silicone oil, surfactant, preparation method and application thereof Download PDFInfo
- Publication number
- CN112694617A CN112694617A CN202011576227.2A CN202011576227A CN112694617A CN 112694617 A CN112694617 A CN 112694617A CN 202011576227 A CN202011576227 A CN 202011576227A CN 112694617 A CN112694617 A CN 112694617A
- Authority
- CN
- China
- Prior art keywords
- silicone oil
- surfactant
- modified silicone
- catalyst
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Cosmetics (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses modified silicone oil, a surfactant, and a preparation method and application thereof, and belongs to the technical field of surfactants. The structure of the modified silicone oil is
m is 1-20, n is 1-15, p is 1-15, m + n + p is 3-20, R1Is R2Or R3。R2is-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR4A is 1-10, b is 0-10, and a + b is 1-15, R4Is C1-C4 alkyl. R3Has the structural formula
Or
R5Selected from hydrogen atoms, alkyl groups having C2-C10, cycloalkyl groups having C3-C10, and aryl or substituted aryl groups having C6-C10, R6And R7Are respectively selected from ester group, nitrile group, ketone group, aldehyde group, sulfone group or hydrogen atom. The surfactant prepared from the modified silicone oil has obvious effects on adjustment of the foam cell structure of the foam, control of the foam stability and the like.
Description
Technical Field
The invention relates to the technical field of surfactants, and particularly relates to modified silicone oil, a surfactant, and preparation methods and applications thereof.
Background
High resilience polyurethane foam (HR) is a kind of foam with excellent performance, and is developed fast at home and abroad and widely used. Compared with common soft foam plastics, the product has the characteristics of light weight, good resilience, sound absorption and shock absorption, is an ideal mat and cushion material, and is widely applied to the aspects of manufacturing seats, back cushions and headrests of vehicles (automobiles, trains, airplanes and the like).
Surfactants play a very important role in the foaming of high resilience polyurethanes. The silicone surfactants currently used to prepare high resilience polyurethane foams are typically polydimethylsiloxanes, organofunctional polydimethylsiloxanes or silicone polyether copolymers. Wherein, the single polydimethylsiloxane component or the mixture of the polydimethylsiloxane and the siloxane polyether copolymer is taken as the main component. However, the mixing regulation of the pure polyether modified silicone has certain limitations in the application performance, especially in the regulation of the pore-opening performance.
Along with the widening of the high-resilience polyurethane foam in different application fields, various special performance requirements are generated, and higher requirements are provided for the high-resilience polyurethane foam surfactant.
In view of this, the invention is particularly proposed.
Disclosure of Invention
One of the objects of the present invention consists in providing a modified silicone oil which can be used for the preparation of surfactants to solve the above technical problems.
The second purpose of the invention is to provide a preparation method of the modified silicone oil.
The third object of the present invention is to provide the use of the above-mentioned modified silicone oil, for example, for preparing a surfactant.
The fourth object of the present invention is to provide a surfactant containing the modified silicone oil.
The fifth purpose of the invention is to provide a preparation method of the surfactant.
The sixth purpose of the invention is to provide a polyurethane foam added with the surfactant in the preparation process.
The application can be realized as follows:
in a first aspect, the present application provides a modified silicone oil having a structural formula
Wherein m has a value of 1-20, n has a value of 1-15, p has a value of 1-15, and m + n + p has a value of 3-20, R1Is R2Or R3. Wherein R is2Has the structure simple formula of-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR4A has a value of 1-10, b has a value of 0-10, and a + b has a value of 1-15, R4Is an alkyl group having 1 to 4 carbon atoms;
R3has the structural formula
Wherein R is5Is selected from hydrogen atom, alkyl of C2-C10, cycloalkyl of C3-C10 and aryl or substituted aryl of C6-C10, and R6 and R7 are respectively and independently selected from ester group, nitrile group, ketone group, aldehyde group, sulfone group or hydrogen atom.
In alternative embodiments, R5Selected from phenyl, n-heptyl, furyl, 4-tolyl, alpha-naphthyl, 4-chlorophenyl, 2-chlorobenzene or a hydrogen atom.
In alternative embodiments, R6And R7Each independently selected from-CO2Me、-CO2Et、-CO2n-Bu、-CN、-COCH3、-CH3or-H.
In a second aspect, the present application also provides a method for preparing the modified silicone oil according to any one of the preceding embodiments, including the steps of: reacting hydrogen-containing silicone oil with allyl polyether, allyl chloride derivative, a first catalyst and a cocatalyst, wherein the hydrogen-containing silicone oil is obtained by reacting octamethylcyclotetrasiloxane, high hydrogen-containing silicone oil and hexamethyldisiloxane or reacting octamethylcyclotetrasiloxane, high hydrogen-containing silicone oil and 1,1,3, 3-tetramethyldisiloxane under the action of a second catalyst.
In an alternative embodiment, the reaction temperature for preparing the hydrogen-containing silicone oil is 30-90 ℃ and the reaction time is 5-8 h.
In an alternative embodiment, the reaction temperature for preparing the modified silicone oil is 70-150 ℃ and the reaction time is 2-10 h.
In an alternative embodiment, the second catalyst is an acidic catalyst.
In an alternative embodiment, the acidic catalyst comprises at least one of acid clay, sulfuric acid, trifluoromethanesulfonic acid, and an acidic resin.
In an alternative embodiment, the acidic catalyst is an acid clay.
In an alternative embodiment, the acidic catalyst comprises 3 to 6 wt% of the total mass of the feedstock for the preparation of hydrogen-containing silicone oil.
In an alternative embodiment, the first catalyst is a platinum-containing catalyst.
In an alternative embodiment, the first catalyst is a chloroplatinic acid catalyst.
In an alternative embodiment, the first catalyst accounts for 3 to 20ppm of the total amount of raw materials for preparing the modified silicone oil.
In alternative embodiments, the co-catalyst comprises at least one of acetamide, diethanolamine, N-butylethanolamine, triethanolamine, and triethylamine.
In an alternative embodiment, the co-catalyst is present in an amount of 50 to 2000ppm based on the total amount of raw materials for preparing the modified silicone oil.
In a third aspect, the present application also provides the use of a modified silicone oil as in any one of the preceding embodiments, for example for the preparation of a surfactant.
In a fourth aspect, the present application also provides a surfactant containing the modified silicone oil according to any one of the preceding embodiments.
In an alternative embodiment, the modified silicone oil is present in the surfactant in an amount of 5 to 30% by weight.
In an alternative embodiment, the surfactant further comprises a surfactant of the formula
Wherein q is 5 to 10.
In an alternative embodiment, the weight percentage of dimethicone in the surfactant is 1-10%.
In an alternative embodiment, the surfactant further comprises a copolymer having terminal hydroxyl groups derived from a polyol, wherein the polyol comprises a low molecular weight polyol.
In alternative embodiments, the low molecular weight polyol comprises ethylene glycol, 1, 2-propylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerol, or n-butanol.
In an alternative embodiment, the molecular weight of the copolymer is 300-3000.
In an alternative embodiment, the weight percentage of the copolymer in the surfactant is 60-90%.
In a fifth aspect, the present application also provides a method of preparing a surfactant according to any one of the preceding embodiments, comprising the steps of: and preparing the modified silicone oil into a surfactant.
In an alternative embodiment, when the raw material of the surfactant further contains dimethylsilicone oil and a copolymer having terminal hydroxyl groups derived from a polyol, the surfactant is obtained by mixing the modified silicone oil with dimethylsilicone oil and a copolymer having terminal hydroxyl groups derived from a polyol.
In a sixth aspect, the present application also provides a polyurethane foam prepared by adding a surfactant according to any one of the preceding embodiments.
The beneficial effect of this application includes:
the modified silicone oil with the specific structure is beneficial to preparing the surfactant capable of improving the strength of polyurethane foam and adjusting the porosity and the foam stability of the polyurethane high-resilience foam. The preparation method is simple and easy to operate. The surfactant containing the modified silicone oil can effectively improve the product performance of polyurethane foam. The polyurethane foam containing the surfactant has good open-cell performance and stability.
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 modified silicone oil, the surfactant, the preparation method and the application thereof provided by the application are specifically described below.
The application provides modified silicone oil with a structural formula
Wherein m has a value of 1-20, n has a value of 1-15, p has a value of 1-15, and m + n + p has a value of 3-20, R1Is R2Or R3. Wherein R is2Has the structure simple formula of-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR4A has a value of 1-10, b has a value of 0-10, and a + b has a value of 1-15, R4Is an alkyl group having 1 to 4 carbon atoms.
R3Has the structural formula
Wherein R is5Is selected from hydrogen atom, alkyl of C2-C10, cycloalkyl of C3-C10 and aryl or substituted aryl of C6-C10, and R6 and R7 are respectively and independently selected from ester group, nitrile group, ketone group, aldehyde group, sulfone group or hydrogen atom.
In reference, m may have a value of 1, 5, 10, 15, 20, etc., or any other value within the range of 1 to 20. n and p may each independently have a value of 1, 5, 10, 12, 15, etc., or may have values ofAny other value within the range of 1-15. The value of a may be 1,2, 5, 8, 10, etc., or may be any other value within the range of 1 to 10. The value of b may be 0, 2, 5, 8, 10, etc., or may be any other value within the range of 0 to 10. R4May be an alkyl group having 1,2, 3 or 4 carbon atoms. R5May be an alkyl group having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, or a cycloalkyl group having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, or an aryl group or substituent having 6, 7, 8, 9 or 10 carbon atoms.
In alternative embodiments, R5Selected from phenyl, n-heptyl, furyl, 4-tolyl, alpha-naphthyl, 4-chlorophenyl, 2-chlorobenzene or a hydrogen atom.
In alternative embodiments, R6And R7Each independently selected from-CO2Me、-CO2Et、-CO2n-Bu、-CN、-COCH3、-CH3or-H.
The co-modified silicone oil is obtained by introducing allyl chloride derivatives with different structures on the basis of single polyether modified silicone oil, so that the strength of the elastomer can be improved, and new properties are endowed to the elastomer.
The preparation method of the modified silicone oil can refer to the following steps: reacting hydrogen-containing silicone oil with allyl polyether, allyl chloride derivative, a first catalyst and a cocatalyst.
The reaction temperature for preparing the modified silicone oil can be 70-150 ℃, such as 70 ℃, 80 ℃, 100 ℃, 120 ℃ or 150 ℃ and the like, and the reaction time can be 2-10h, such as 2h, 4h, 5h, 8h or 10h and the like.
Wherein the hydrogen-containing silicone oil is obtained by reacting octamethylcyclotetrasiloxane, high hydrogen-containing silicone oil and hexamethyldisiloxane or octamethylcyclotetrasiloxane, high hydrogen-containing silicone oil and 1,1,3, 3-tetramethyldisiloxane under the action of a second catalyst.
In alternative embodiments, the reaction temperature for preparing the hydrogen-containing silicone oil may be 30-90 ℃, such as 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃ and the like, and the reaction time may be 5-8h, such as 5h, 6h, 7h or 8h and the like.
In an alternative embodiment, the second catalyst is an acidic catalyst, and may include at least one of acid clay, sulfuric acid, trifluoromethanesulfonic acid, and an acidic resin, for example. In a preferred embodiment, the acidic catalyst is an acid clay.
The acidic catalyst may be referred to as 3 to 6 wt%, such as 3 wt%, 4 wt%, 5 wt%, or 6 wt%, etc., of the total mass of the raw material for preparing the hydrogen-containing silicone oil.
In an alternative embodiment, the first catalyst is a platinum-containing catalyst, such as a chloroplatinic acid catalyst.
The first catalyst may be referred to as 3 to 20ppm, such as 3ppm, 5ppm, 10ppm, 15ppm or 20ppm, etc., based on the total amount of the raw materials for preparing the modified silicone oil.
In alternative embodiments, the co-catalyst may include, for example, at least one of acetamide, diethanolamine, N-butylethanolamine, triethanolamine, and triethylamine.
The co-catalyst may, by reference, be present in an amount of 50 to 2000ppm, such as 50ppm, 100ppm, 500ppm, 1000ppm, 1500ppm or 2000ppm, etc., based on the total amount of the raw materials for preparing the modified silicone oil.
Further, the application also provides the application of the modified silicone oil, such as the modified silicone oil which can be used for preparing a surfactant, especially a surfactant for polyurethane foam.
Correspondingly, the application provides a surfactant which contains the modified silicone oil with the specific structural formula and is beneficial to improving the strength of the polyurethane foam and adjusting the porosity and stability of the polyurethane high-resilience foam.
In the present application, the weight percentage of the modified silicone oil in the surfactant may be 5 to 30%, such as 5%, 10%, 15%, 20%, 25%, or 30%.
Further, the surfactant provided by the application also contains a surfactant with a structural formula shown in the specification
Wherein q has a value of 5 to 10, such as 5, 6, 7, 8, 9 or 10, etc.
In alternative embodiments, the weight percentage of dimethicone in the surfactant may be 1-10%, such as 1%, 2%, 5%, 8%, or 10%, etc.
In addition, the surfactants provided herein also contain copolymers having terminal hydroxyl groups derived from polyols, wherein the polyols include low molecular weight polyols.
In alternative embodiments, the low molecular weight polyol comprises ethylene glycol, 1, 2-propylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerol, or n-butanol.
In an alternative embodiment, the molecular weight of the copolymer is 300-3000.
In alternative embodiments, the weight percentage of the copolymer in the surfactant may be 60-90%, such as 60%, 65%, 70%, 75%, 80%, 85%, or 90%, etc.
On the basis, the obtained co-modified silicone oil and the dimethyl silicone oil are blended, so that the open pore property and the stability of the polyurethane foam (polyurethane high-resilience foam) can be further effectively regulated, and the foam pores and the surface property of the polyurethane foam can be further effectively regulated.
In addition, the application also provides a preparation method of the surfactant, which comprises the following steps: and preparing the surfactant from the modified silicone oil.
When the raw material of the surfactant contains dimethylsilicone oil and a copolymer having a terminal hydroxyl group derived from a polyhydroxy compound, the surfactant is obtained by mixing modified silicone oil with dimethylsilicone oil and a copolymer having a terminal hydroxyl group derived from a polyhydroxy compound.
It is to be noted that the mixing of the modified silicone oil, the dimethylsilicone oil and the copolymer having terminal hydroxyl groups derived from the polyol compound may be carried out at 55 to 65 ℃ for 1.5 to 2.5 hours, preferably at 60 ℃ for 2 hours.
Further, the present application also provides the use of the above surfactant, for example, for the preparation of polyurethane foam (polyurethane high resilience foam). Correspondingly, the application also provides a polyurethane foam, and the surfactant is added in the preparation process of the polyurethane foam. The system compatibility of the polyurethane foam, the surface property and the dimensional stability of the polyurethane foam can be effectively regulated and controlled.
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 prepared by the following procedure:
(1) synthesis of modified Silicone oil A1
116.55g of octamethylcyclotetrasiloxane, 28.72g of high hydrogen-containing silicone oil and 34.73g of hexamethyldisiloxane are reacted at 60 ℃ for 7 hours under the action of acid clay to obtain the hydrogen-containing silicone oil.
Adding 60g of the hydrogen-containing silicone oil, 48.36g of allyl polyether and 5.7g of allyl chloride into a reactor, heating to 90 ℃ under normal pressure under the conditions of 10ppm of chloroplatinic acid catalyst and 200ppm of diethanolamine cocatalyst, and reacting for 7 hours to obtain modified silicone oil A1, wherein the molecular formula is as follows: si (CH)3)3-O-[Si(CH3)2-O]7-[Si(CH3)R2-O]1-[Si(CH3)R3-O]1-Si(CH3)3Wherein R is2＝-CH2CH2CH2O(CH2CH2O)7(CH2CH(CH3)O)2CH3；R3＝-CH2CH2CH2Cl。
(2) The modified silicone oil A1, dimethyl silicone oil B1 and copolymer C1 with terminal hydroxyl groups derived from polyhydroxy compounds are stirred and mixed for 2 hours at the temperature of 60 ℃ according to different proportions (shown in Table 1) to obtain the surfactant.
The dimethyl silicone oil B1 has a structural formula
The simethicone b1 and the simethicone b2, wherein the q of the simethicone b1 is 5, and the q of the simethicone b2 is 6. Substances of dimethicone b1 and dimethicone b2The quantity ratio is 1: 1.
the copolymer C1 with terminal hydroxyl groups derived from a polyol is a polyether polyol with propylene glycol as initiator and has a molecular weight of 500.
Example 2
This example provides a surfactant prepared by the following procedure:
(1) synthesis of modified Silicone oil A2
108.42g of octamethylcyclotetrasiloxane, 40.08g of high hydrogen silicone oil and 31.51g of hexamethyldisiloxane are reacted for 6 hours at 80 ℃ under the action of acid clay to obtain the hydrogen silicone oil.
Adding 60g of the hydrogen-containing silicone oil, 69.21g of allyl polyether and 5.3 g of allyl chloride into a reactor, heating to 90 ℃ under normal pressure under the conditions of 10ppm of chloroplatinic acid catalyst and 200ppm of diethanolamine cocatalyst, and reacting for 10 hours to obtain modified silicone oil A2, wherein the molecular formula is as follows: si (CH)3)3-O-[Si(CH3)2-O]7-[Si(CH3)R2-O]2-[Si(CH3)R3-O]1-Si(CH3)3Wherein R is2＝-CH2CH2CH2O(CH2CH2O)7(CH2CH(CH3)O)2CH3；R3＝-CH2CH2CH2Cl。
(2) The modified silicone oil A2, dimethyl silicone oil B2 and copolymer C2 with terminal hydroxyl groups derived from polyhydroxy compounds are stirred and mixed for 2 hours at the temperature of 60 ℃ according to different proportions (shown in Table 2) to obtain the surfactant.
The dimethyl silicone oil B2 has a structural formula
The simethicone b3 and the simethicone b4, wherein the q of the simethicone b3 is 5, and the q of the simethicone b4 is 7. The mass ratio of the dimethyl silicone oil b3 to the dimethyl silicone oil b4 is 1: 1.
the copolymer C2 with terminal hydroxyl groups derived from a polyol is a polyether polyol with propylene glycol as initiator and has a molecular weight of 500.
Example 3
This example provides a surfactant prepared by the following procedure:
(1) synthesis of modified Silicone oil A3
122.58g of octamethylcyclotetrasiloxane, 29.37g of high hydrogen silicone oil and 28.06g of hexamethyldisiloxane are reacted at 85 ℃ for 5 hours under the action of acid clay to obtain the hydrogen silicone oil.
Adding 60g of the obtained hydrogen-containing silicone oil, 56.34g of allyl polyether and 6.11 g of allyl chloride into a reactor, heating to 90 ℃ under normal pressure under the conditions of 10ppm of chloroplatinic acid catalyst and 300ppm of triethanolamine cocatalyst, and reacting for 9 hours to obtain modified silicone oil A3, wherein the molecular formula is as follows: si (CH)3)3-O-[Si(CH3)2-O]9-[Si(CH3)R2-O]1.4-[Si(CH3)R3-O]1.1-Si(CH3)3Wherein R is2＝-CH2CH2CH2O(CH2CH2O)8(CH2CH(CH3)O)4CH3；R3＝-CH2C(CH3)CH2Cl。
(2) The modified silicone oil A3 was mixed with dimethicone B3 and copolymer C3 having terminal hydroxyl groups derived from a polyhydroxy compound at different ratios (as shown in Table 3) at 60 deg.C with stirring for 2h to obtain a surfactant.
The dimethyl silicone oil B3 has a structural formula
The simethicone b5 and the simethicone b6, wherein the q of the simethicone b5 is 5, and the q of the simethicone b6 is 6. The mass ratio of the dimethyl silicone oil b5 to the dimethyl silicone oil b6 is 1: 1.
the copolymer C1 with terminal hydroxyl groups derived from polyols was a polyether polyol with 1, 4-butanediol as initiator and a molecular weight of 500.
Example 4
This example provides a surfactant prepared by the following procedure:
(1) synthesis of modified Silicone oil A4
110.39g of octamethylcyclotetrasiloxane, 45.49g of high hydrogen silicone oil and 24.13g of hexamethyldisiloxane are reacted at 85 ℃ for 5 hours under the action of acid clay to obtain the hydrogen silicone oil.
Adding 60g of the hydrogen-containing silicone oil, 83.36g of allyl polyether and 10.01 g of allyl chloride into a reactor, heating to 90 ℃ under normal pressure under the conditions of 10ppm of chloroplatinic acid catalyst and 300ppm of triethanolamine cocatalyst, and reacting for 9 hours to obtain modified silicone oil A4, wherein the molecular formula is as follows: si (CH)3)3-O-[Si(CH3)2-O]9-[Si(CH3)R2-O]2.3-[Si(CH3)R3-O]2-Si(CH3)3Wherein R is2＝-CH2CH2CH2O(CH2CH2O)8(CH2CH(CH3)O)4CH3；R3＝-CH2C(CH3)CH2Cl。
(2) The modified silicone oil A4 was mixed with dimethicone B4 and copolymer C4 having terminal hydroxyl groups derived from a polyhydroxy compound at different ratios (as shown in Table 4) at 60 deg.C with stirring for 2h to obtain a surfactant.
The dimethyl silicone oil B4 has a structural formula
The simethicone b7, wherein the q of the simethicone b7 is 5.
The copolymer C1 with terminal hydroxyl groups derived from polyols was a polyether polyol with 1, 4-butanediol as initiator and a molecular weight of 500.
Test examples
The surfactant obtained in the above examples 1 to 4 is used for preparing polyurethane high resilience foam, specifically, the high resilience polyurethane foam is prepared by the reaction of an X component and a Y component, and the preparation method is as follows:
preparation of the X component material: the weighed polyols, catalysts, foaming agents and surfactants are mixed and stirred for 20s at normal temperature according to the formula amount in the table 1 in parts by weight.
TABLE 1 formulation
| Raw materials | Formulation of |
| ZSN-330 | 100 |
| The surfactant provided by the embodiment of the application | 2 |
| Methylene dichloride | 15 |
| Water (W) | 5 |
| Triethylene diamine | 0.4 |
| Stannous octoate | 0.4 |
The Y component material is toluene diisocyanate (TDI-80).
When in use, X, Y component materials are mixed according to the proportion of X: y is 100: 35, stirring for 5s under the stirring condition of 2000r/min, and pouring the mixture into a standard mould (the mould temperature is 25 ℃) on the premise of not freely foaming the foam, thus preparing the polyurethane high-resilience foam.
The thickness of cells in the obtained foams was compared, and the results are shown in tables 2 to 5.
TABLE 2 compounding ratios and results
Note: in the table, cell size is represented by "+", and increasing "+" indicates that the cells are coarser, as follows.
TABLE 3 compounding ratios and results
TABLE 4 compounding ratios and results
TABLE 5 compounding ratios and results
It can be seen from tables 2 to 5 that, on the basis of a single polyether modified silicone oil, allyl chloride derivatives with different structures are introduced to obtain co-modified silicone oil, the co-modified silicone oil and dimethyl silicone oil are prepared in different proportions, the effective regulation and control range of the porosity and the foam stability of the polyurethane high resilience foam is increased, and when the proportion of the component B is fixed, the effective regulation of the foam pore size to a greater extent can be realized by regulating the proportion of the component A, so that a research basis is provided for effectively regulating and controlling the size stability of the high resilience polyurethane foam.
In conclusion, the surfactant contains the modified silicone oil with the specific structural formula provided by the application, so that the strength of the polyurethane foam is improved, and the opening property and the stability of the polyurethane high-resilience foam are adjusted. The preparation method of the surfactant is simple and easy to operate. The surfactant is used for preparing polyurethane foam, and the product performance of the polyurethane foam can be effectively improved.
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 modified silicone oil is characterized in that the structural formula of the modified silicone oil is
Wherein m has a value of 1-20, n has a value of 1-15, p has a value of 1-15, and m + n + p has a value of 3-20, R1Is R2Or R3；
Wherein R is2Has the structure simple formula of-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR4A has a value of 1-10, b has a value of 0-10, and a + b has a value of 1-15, R4Is an alkyl group having 1 to 4 carbon atoms;
R3has the structural formula
Wherein R is5Selected from hydrogen atom, C2-C10 alkyl, C3-C10 cycloalkyl and C6-C10 aryl or substituted aryl, R6And R7Each independently selected from an ester group, a nitrile group, a ketone group, an aldehyde group, a sulfone group or a hydrogen atom.
2. The modified silicone oil according to claim 1, wherein R is5Selected from phenyl, n-heptyl, furyl, 4-tolyl, alpha-naphthyl, 4-chlorophenyl2-chlorobenzene or a hydrogen atom;
preferably, said R is6And R7Each independently selected from-CO2Me、-CO2Et、-CO2n-Bu、-CN、-COCH3、-CH3or-H.
3. The method for preparing modified silicone oil according to claim 1 or 2, comprising the steps of: reacting hydrogen-containing silicone oil with allyl polyether, an allyl chloride derivative, a first catalyst and a cocatalyst, wherein the hydrogen-containing silicone oil is obtained by reacting octamethylcyclotetrasiloxane, high hydrogen-containing silicone oil and hexamethyldisiloxane or reacting octamethylcyclotetrasiloxane, high hydrogen-containing silicone oil and 1,1,3, 3-tetramethyldisiloxane under the action of a second catalyst;
preferably, the reaction temperature for preparing the hydrogen-containing silicone oil is 30-90 ℃, and the reaction time is 5-8 h;
preferably, the reaction temperature for preparing the modified silicone oil is 70-150 ℃, and the reaction time is 2-10 h.
4. The production method according to claim 3, wherein the second catalyst is an acid catalyst;
preferably, the acidic catalyst comprises at least one of acid clay, sulfuric acid, trifluoromethanesulfonic acid, and an acid resin;
preferably, the acidic catalyst is an acid clay;
preferably, the acid catalyst accounts for 3-6 wt% of the total mass of the raw materials for preparing the hydrogen-containing silicone oil;
preferably, the first catalyst is a platinum-containing catalyst;
preferably, the first catalyst is a chloroplatinic acid catalyst;
preferably, the first catalyst accounts for 3-20ppm of the total amount of raw materials for preparing the modified silicone oil;
preferably, the cocatalyst comprises at least one of acetamide, diethanolamine, N-butylethanolamine, triethanolamine and triethylamine;
preferably, the cocatalyst accounts for 50-2000ppm of the total amount of raw materials for preparing the modified silicone oil.
5. The use of a modified silicone oil according to claim 1 or 2, wherein the modified silicone oil is used for the preparation of a surfactant.
6. A surfactant comprising the modified silicone oil according to claim 1 or 2;
preferably, the modified silicone oil accounts for 5-30% of the surfactant by weight.
7. The surfactant of claim 6 further comprising a surfactant of the formula
The dimethylsilicone fluid of (1), wherein q has a value of 5 to 10;
preferably, the weight percentage of the simethicone in the surfactant is 1-10%.
8. The surfactant of claim 7 further comprising a copolymer having terminal hydroxyl groups derived from a polyol, wherein the polyol comprises a low molecular weight polyol;
preferably, the low molecular weight polyol comprises ethylene glycol, 1, 2-propylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, glycerol, or n-butanol;
preferably, the molecular weight of the copolymer is 300-;
preferably, the weight percentage of the copolymer in the surfactant is 60-90%.
9. A process for preparing a surfactant as claimed in any one of claims 6 to 8, comprising the steps of: preparing the surfactant from the modified silicone oil;
preferably, when the raw material of the surfactant further contains the dimethylsilicone oil and the copolymer having a terminal hydroxyl group derived from a polyhydric compound, the modified silicone oil, the dimethylsilicone oil and the copolymer having a terminal hydroxyl group derived from a polyhydric compound are mixed.
10. A polyurethane foam, characterized in that a surfactant according to any one of claims 6 to 8 is added during the preparation of the polyurethane foam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011576227.2A CN112694617B (en) | 2020-12-28 | 2020-12-28 | Modified silicone oil, surfactant, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011576227.2A CN112694617B (en) | 2020-12-28 | 2020-12-28 | Modified silicone oil, surfactant, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112694617A true CN112694617A (en) | 2021-04-23 |
| CN112694617B CN112694617B (en) | 2022-04-15 |
Family
ID=75511754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011576227.2A Active CN112694617B (en) | 2020-12-28 | 2020-12-28 | Modified silicone oil, surfactant, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112694617B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929959A (en) * | 2021-11-25 | 2022-01-14 | 南京美思德新材料有限公司 | Foam surfactant, preparation method thereof and foam |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000056805A1 (en) * | 1999-03-24 | 2000-09-28 | Ck Witco Corporation | Polyurethane foam stabilizers |
| CN102295771A (en) * | 2011-05-13 | 2011-12-28 | 华东理工大学 | Hyperbranched polymer as well as modified substance thereof and application of modified substance |
| CN105199108A (en) * | 2015-08-20 | 2015-12-30 | 江苏奥斯佳材料科技有限公司 | Foam stabilizer and preparation method and application thereof in synthesizing polyurethane foaming material |
| CN109867808A (en) * | 2018-12-24 | 2019-06-11 | 南京美思德新材料有限公司 | A kind of high rebound foam organic silicon surfactant and preparation method |
-
2020
- 2020-12-28 CN CN202011576227.2A patent/CN112694617B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000056805A1 (en) * | 1999-03-24 | 2000-09-28 | Ck Witco Corporation | Polyurethane foam stabilizers |
| CN102295771A (en) * | 2011-05-13 | 2011-12-28 | 华东理工大学 | Hyperbranched polymer as well as modified substance thereof and application of modified substance |
| CN105199108A (en) * | 2015-08-20 | 2015-12-30 | 江苏奥斯佳材料科技有限公司 | Foam stabilizer and preparation method and application thereof in synthesizing polyurethane foaming material |
| CN109867808A (en) * | 2018-12-24 | 2019-06-11 | 南京美思德新材料有限公司 | A kind of high rebound foam organic silicon surfactant and preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929959A (en) * | 2021-11-25 | 2022-01-14 | 南京美思德新材料有限公司 | Foam surfactant, preparation method thereof and foam |
| CN113929959B (en) * | 2021-11-25 | 2022-11-22 | 南京美思德新材料有限公司 | Foam surfactant, preparation method thereof and foam |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112694617B (en) | 2022-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5739173A (en) | Preparation of flame-resistant soft polyurethane foams of reduced smoke density, and melamine/expandable graphite/polyether-polyol dispersions for this purpose | |
| EP1080671B1 (en) | Seat cushion pad | |
| CN107857865B (en) | Full-water environment-friendly flame-retardant flatulence memory polyurethane foam for automobile seat and preparation method thereof | |
| TWI242569B (en) | Description composition for flame-retardant flexible polyurethane foam | |
| CA1171600A (en) | Siloxane copolymer mixtures useful as foam stabilizers in high resilience polyurethane foam | |
| CN109867808A (en) | A kind of high rebound foam organic silicon surfactant and preparation method | |
| JP2005500417A (en) | Process for the production of polyurethane products using polymer polyols in which the carrier polyol is a polyol based on tertiary amines | |
| US4607064A (en) | Polyurethane and urethane-modified isocyanurate foams and a polyol composition useful in their preparation | |
| CN112694617B (en) | Modified silicone oil, surfactant, preparation method and application thereof | |
| CA1326938C (en) | Open celled polyurethane foams | |
| US4031044A (en) | Polyether based, high resilient polyurethane foam | |
| CN111040229A (en) | Open-cell type organic silicon surfactant, preparation method and application thereof, and high-resilience foam | |
| CN109942823A (en) | With the polyether silicones copolymer and synthetic method of good emulsifiability and application | |
| JPS60245623A (en) | Production of flexible polyether-urethane foam of low gas permeability | |
| JPS6140249B2 (en) | ||
| JPS6032639B2 (en) | Morpholino-containing polyalkylsiloxane | |
| JP3880699B2 (en) | Method for producing flexible polyurethane foam | |
| JP2000290344A (en) | Energy absorbing soft polyurethane foamed article and manufacture thereof | |
| CN111040228A (en) | Surfactant, preparation method and application thereof, and polyurethane high-resilience foam | |
| JPS6411204B2 (en) | ||
| WO2018235515A1 (en) | Composition for soft polyurethane foam, soft polyurethane foam, and vehicle seat pad | |
| WO1993024552A1 (en) | Flexible, combustion-modified, polyurethane foams | |
| JP3610138B2 (en) | Method for producing low-density high-elasticity flexible polyurethane foam | |
| JP7204650B2 (en) | Polyol blends useful for making viscoelastic foams | |
| JP3955119B2 (en) | Method for producing low density high elastic polyurethane foam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |