CN111040228A - Surfactant, preparation method and application thereof, and polyurethane high-resilience foam - Google Patents

Surfactant, preparation method and application thereof, and polyurethane high-resilience foam Download PDF

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CN111040228A
CN111040228A CN201911373288.6A CN201911373288A CN111040228A CN 111040228 A CN111040228 A CN 111040228A CN 201911373288 A CN201911373288 A CN 201911373288A CN 111040228 A CN111040228 A CN 111040228A
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surfactant
value
silicone oil
hydrogen
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黄登登
王伟伟
唐雄峰
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Jiangsu Maysta Chemical Co ltd
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    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0042—Use of organic additives containing silicon
    • 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
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
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Abstract

The invention provides a surfactant, a preparation method and application thereof, and polyurethane high-resilience foam, and belongs to the technical field of surfactants. The raw material of the surfactant comprises a first component, a second component and a third component, wherein the first component accounts for 20-40 wt% of the raw material, the second component accounts for 20-40 wt% of the raw material, and the third component accounts for 20-60 wt% of the raw material. The structural formula of the first component is:
Figure DDA0002340262430000011
the structural formula of the second component is as follows:

Description

Surfactant, preparation method and application thereof, and polyurethane high-resilience foam
Technical Field
The invention relates to the technical field of surfactants, and particularly relates to a surfactant, a preparation method and application thereof, and a polyurethane high-resilience foam.
Background
The high resilience polyurethane foam plastic is also called HR foam, is a high-grade polyurethane soft foam variety, and has advanced processing performance and excellent physical performance through material and technological innovation on the basis of common soft foam, and may be cold cured, simple in preparation process, excellent in performance and wide in application. Compared with the common soft foam plastic, the high-resilience foam plastic has higher elasticity and better comfort performance, thereby quickly replacing the common soft foam in the fields of automobiles, furniture industry and the like as a high-grade cushion material.
Along with the expansion of high-resilience polyurethane foam in different application fields, various special performance requirements are generated, and along with the requirement of high-resilience foam on diversification in different products, a single active component cannot meet the special requirements of the high-resilience polyurethane foam on volume, ventilation, shearing, surface and dimensional stability.
In view of this, the present application is specifically made.
Disclosure of Invention
A first object of the present invention includes providing a surfactant which can improve not only the stability of a polyurethane high resilience foam but also the open-cell property of a polyurethane high resilience foam.
The second object of the present invention includes providing a method for preparing the above surfactant.
A third object of the present invention consists in providing the use of the above-mentioned surfactants, for example for the preparation of polyurethane high resilience foams.
A fourth object of the present invention includes providing a polyurethane resilient foam using the above surfactant in the manufacturing process.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the invention provides a surfactant, which comprises a first component, a second component and a third component. The first component accounts for 20-40 wt% of the raw materials, the second component accounts for 20-40 wt% of the raw materials, and the third component accounts for 20-60 wt% of the raw materials.
The structural formula of the first component is:
Figure BDA0002340262420000021
wherein m has a value of 0-20, n has a value of 0-15, and m + n has a value of 1-20; r and R1Independently of the structure of (A) is-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR2Wherein a has a value of 1-9, b has a value of 0-9, and a + b has a value of 1-15, R2Is an alkyl group having 1 to 4 carbon atoms.
The structural formula of the second component is as follows:
Figure BDA0002340262420000022
wherein m has a value of 0-25, n has a value of 0-15, and m + n has a value of 1-25; r and R1Independently of the structure of (A) is-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR2Wherein a has a value of 0-25, b has a value of 1-25, and a + b has a value of 1-25, R2Is an alkyl group having 1 to 4 carbon atoms.
And the first component and the second component have different structural formulas.
The third component is a copolymer with terminal hydroxyl groups derived from a polyol.
Optionally, the first component in the surfactant comprises R1-Si(CH3)2-O-[Si(CH3)2-O]5.2-[Si(CH3)R-O]2.3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)1.5CH3；
Or R1-Si(CH3)2-O-[Si(CH3)2-O]6.1-[Si(CH3)R-O]1.2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)1.5CH3；
Or R1-Si(CH3)2-O-[Si(CH3)2-O]5.5-[Si(CH3)R-O]1.2-Si(CH3)2-R1，R＝R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3；
Or R1-Si(CH3)2-O-[Si(CH3)2-O]7.2-[Si(CH3)R-O]2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3。
Optionally, the second component in the surfactant comprises Si (CH)3)3-O-[Si(CH3)2-O]8.3-[Si(CH3)R-O]3.5-Si(CH3)3Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)6CH3；
Or Si (CH)3)3-O-[Si(CH3)2-O]8.3-[Si(CH3)R-O]2.3-Si(CH3)3Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)6CH3；
Or R1-Si(CH3)2-O-[Si(CH3)2-O]9.3-[Si(CH3)R-O]3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)8CH3；
Or R1-Si(CH3)2-O-[Si(CH3)2-O]10.1-[Si(CH3)R-O]3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)8CH3。
Alternatively, the third component of the surfactant is a polyether polyol having a molecular weight of 2000 to 3000, the polyether polyol having propylene glycol as an initiator.
In addition, the invention also provides a preparation method of the surfactant, which comprises the following steps: mixing the raw materials according to the proportion.
In addition, the invention also provides application of the surfactant in preparation of polyurethane high-resilience foam.
In addition, the invention also provides a high resilience foam, and the surfactant used in the preparation process of the high resilience foam comprises the surfactant.
The surfactant, the preparation method and the application thereof, and the polyurethane high-resilience foam have the beneficial effects that:
the surfactant provided by the application combines the first component and the second component which belong to the polyether modified organic silicon substance and have different structures, so that the surfactant can have obvious effects on the aspects of adjustment of a foam cell structure, flowability during foaming, foam smell and the like, and particularly has obvious effects on the aspects of adjustment of the structure and the opening rate of cells. Further, the third component as a polyether polyol may improve the compatibility of the raw material system. Under the coordination of the three components, the surface and dimensional stability of the polyurethane foam can be effectively regulated and controlled.
The preparation method is simple, convenient and controllable. The surfactant is used for preparing high-resilience foam, and can effectively regulate and control the dimensional stability of the high-resilience polyurethane foam.
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 embodiment of the present application, the preparation method and the application thereof, and the polyurethane high resilience foam are specifically described below.
The surfactant provided by the application comprises a first component, a second component and a third component. The first component can comprise 20 to 40 wt% of the feedstock (e.g., 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, etc.), the second component can comprise 20 to 40 wt% of the feedstock (e.g., 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, etc.), and the third component can comprise 20 to 60 wt% of the feedstock (e.g., 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 50 wt%, 60 wt%, etc.). The sum of the weight percentages of the three components in the raw materials is 100 percent.
The main structural formulas of the first component and the second component are as follows:
Figure BDA0002340262420000051
for the first component, in the above-described main structural formula, m and n have values of 0 to 20 and 0 to 15, respectively, and m + n has a value of 1 to 20; r and R1Independently of the structure of (A) is-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR2Wherein a and b have values of 1-9 and 0-9, respectively, and a + b has a value of 1-15, R2Is an alkyl group having 1 to 4 carbon atoms. For the second component, in the above-described main structural formula, m and n have values of 0 to 25 and 0 to 15, respectively, and m + n has a value of 1 to 25; r and R1Independently of the structure of (A) is-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR2Wherein a and b have values of 0-25 and 1-25, respectively, and a + b has a value of 1-25, R2Is an alkyl group having 1 to 4 carbon atoms.
It should be noted that, in the present application, the specific structural formulas of the first component and the second component are different, that is, the first component and the second component are different substances.
The third component is a copolymer with terminal hydroxyl groups derived from a polyol. The polyol may include, among other things, a low molecular weight polyol such as at least one of ethylene glycol, 1, 3-butanediol, 1, 6-hexanediol, diethylene glycol, and dipropylene glycol. The third component may be, for example, a polyether polyol having a molecular weight of 2000-3000 with propylene glycol as an initiator.
The inventors found that the simultaneous use of the first component and the second component having different structures in the raw materials can significantly improve the open cell content and stability of the polyurethane foam as compared with the use of only one of them, and that the use of only the first component and the second component can provide superior effects as compared with the use of a larger amount of the polyether-modified silicone substance. In the present application, the first component and the second component mainly serve to improve the open cell content and the stability of the foam, respectively.
Alternatively, the first component in the surfactant may comprise, for example, R1-Si(CH3)2-O-[Si(CH3)2-O]5.2-[Si(CH3)R-O]2.3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)1.5CH3(ii) a Or comprises R1-Si(CH3)2-O-[Si(CH3)2-O]6.1-[Si(CH3)R-O]1.2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)1.5CH3(ii) a Or comprises R1-Si(CH3)2-O-[Si(CH3)2-O]5.5-[Si(CH3)R-O]1.2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3(ii) a Or comprises R1-Si(CH3)2-O-[Si(CH3)2-O]7.2-[Si(CH3)R-O]2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3。
The second component of the surfactant may include, for example, Si (CH)3)3-O-[Si(CH3)2-O]8.3-[Si(CH3)R-O]3.5-Si(CH3)3Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)6CH3(ii) a Or comprising Si (CH)3)3-O-[Si(CH3)2-O]8.3-[Si(CH3)R-O]2.3-Si(CH3)3Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)6CH3(ii) a Or comprises R1-Si(CH3)2-O-[Si(CH3)2-O]9.3-[Si(CH3)R-O]3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)8CH3(ii) a Or comprises R1-Si(CH3)2-O-[Si(CH3)2-O]10.1-[Si(CH3)R-O]3-Si(CH3)2-R1Wherein，R＝R1＝-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)8CH3。
In some embodiments, the first component has the formula R1-Si(CH3)2-O-[Si(CH3)2-O]5.2-[Si(CH3)R-O]2.3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)1.5CH3. The second component has the molecular formula of Si (CH)3)3-O-[Si(CH3)2-O]8.3-[Si(CH3)R-O]3.5-Si(CH3)3Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)6CH3. The third component is polyether polyol with propylene glycol as initiator and molecular weight of 2000.
In other embodiments, the first component has the formula R1-Si(CH3)2-O-[Si(CH3)2-O]6.1-[Si(CH3)R-O]1.2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)1.5CH3. The second component has the molecular formula of Si (CH)3)3-O-[Si(CH3)2-O]8.3-[Si(CH3)R-O]2.3-Si(CH3)3Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)6CH3. The third component is polyether polyol with propylene glycol as initiator and molecular weight of 2000.
In other embodiments, the first componentHas the molecular formula R1-Si(CH3)2-O-[Si(CH3)2-O]5.5-[Si(CH3)R-O]1.2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3. The second component has a molecular formula of R1-Si(CH3)2-O-[Si(CH3)2-O]9.3-[Si(CH3)R-O]3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)8CH3. The third component is polyether polyol with propylene glycol as initiator and molecular weight of 3000.
In other embodiments, the first component has the formula R1-Si(CH3)2-O-[Si(CH3)2-O]7.2-[Si(CH3)R-O]2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3. The second component has a molecular formula of R1-Si(CH3)2-O-[Si(CH3)2-O]10.1-[Si(CH3)R-O]3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)8CH3. The third component is polyether polyol with propylene glycol as initiator and molecular weight of 3000.
In the application, the first component and the second component with different structures are combined, so that the adjustment of the cell structure of the foam, the fluidity during foaming, the foam smell and the like can be obviously performed, and particularly, the structure and the opening rate of the cells can be adjusted. Further, the third component as a polyether polyol may improve the compatibility of the raw material system. Under the coordination of the three components, the surface and dimensional stability of the polyurethane foam can be effectively regulated and controlled.
In addition, the application also provides a preparation method of the surfactant, and the preparation method can comprise the following steps: mixing the raw materials according to the proportion.
Alternatively, the raw materials can be mixed and stirred for 1.8-2.2h (e.g., 1.8h, 2h, or 1.2h, etc.) at 38-42 deg.C (e.g., 38 deg.C, 40 deg.C, or 42 deg.C, etc.). Wherein, the stirring speed can be 200-500 r/min.
In some preferred embodiments, the raw materials are mixed and stirred at 40 ℃ for 2 h.
It is worth to be noted that the first component and the second component with different structures can be obtained by reacting hydrogen-containing silicone oil with allyl polyether according to different proportions in the presence of a catalyst and a cocatalyst, or the first component and the second component with different structures can be obtained by reacting allyl polyether with different hydrogen-containing silicone oils respectively in the presence of a catalyst and a cocatalyst. In addition, the number of kinds of hydrogen-containing silicone oil used in the production process of the first component is 1 or more, and similarly, the number of kinds of hydrogen-containing silicone oil used in the production process of the second component is 1 or more.
Alternatively, the hydrogen-containing silicone oil, the allyl polyether, the catalyst and the cocatalyst can be reacted for 2 to 8 hours (e.g., 2 hours, 4 hours, 5 hours, 6 hours or 8 hours, etc.) under the condition of 90 to 160 ℃ (e.g., 90 ℃, 100 ℃, 150 ℃, 160 ℃, etc.). The hydrogen-containing silicone oil, allyl polyether, catalyst, and co-catalyst are collectively defined herein as a first system.
Alternatively, the catalyst may include, for example, a platinum catalyst (e.g., chloroplatinic acid catalyst). The catalyst may be used, by reference, in an amount of 3-30ppm (e.g., 3ppm, 10ppm, 20ppm, 30ppm, etc.) of the total amount of the first system.
Alternatively, the co-catalyst may include, for example, at least one of diethanolamine, triethanolamine, acetamide, triethylamine, and N-butylethanolamine. The amount of cocatalyst can, by reference, be 3-300ppm (e.g., 3ppm, 10ppm, 50ppm, 100ppm, 200ppm, or 300ppm, etc.) of the total amount of the first system.
Further, the preparation method of the hydrogen-containing silicone oil in the application can comprise the following steps: reacting octamethylcyclotetrasiloxane, high hydrogen-containing silicone oil and a capping agent. Alternatively, the capping agent may comprise hexamethyldisiloxane or tetramethyldisiloxane, for example.
Wherein the chemical formula of the high hydrogen-containing silicone oil is C7H22O2Si3。
For reference, octamethylcyclotetrasiloxane, high hydrogen silicone oil and capping agent can be reacted for 5-8h (e.g. 5h, 6.5h or 8h, etc.) at 30-90 deg.C (e.g. 30 deg.C, 60 deg.C or 90 deg.C, etc.). The reaction is preferably carried out in the presence of a catalyst (e.g., an acidic catalyst), wherein the acidic acidulant can comprise at least one of acid clay, concentrated sulfuric acid, trifluoromethanesulfonic acid, and an acidic resin, preferably acid clay and/or concentrated sulfuric acid. The acidic catalyst may be used in an amount of 1 to 6 wt% (e.g., 1 wt%, 3 wt%, 6 wt%, etc.) of the total amount of octamethylcyclotetrasiloxane, high hydrogen silicone oil, and hexamethyldisiloxane.
Under the reaction conditions, the octamethylcyclotetrasiloxane, the high hydrogen-containing silicone oil and the end sealing agent are reacted in different proportions to generate different hydrogen-containing silicone oils.
In summary, the preparation method of the surfactant provided by the application is simple, easy to operate and controllable in process. Terminal hydrogen is introduced at the end of the hydrogen-containing silicone oil chain, and hydrogen-containing silicone oil with different structures is designed to be grafted with allyl polyether with different molecular weights, so that the effective regulation range of the openness and the stability of the polyurethane high-resilience foam is increased, and meanwhile, the polyurethane high-resilience foam plays a positive role in system compatibility and effective regulation of the surface and the dimensional stability of the polyurethane foam.
In addition, the invention also provides application of the surfactant in preparation of polyurethane high-resilience foam.
In addition, the invention also provides a polyurethane high resilience foam, which is prepared by taking the surfactant as the surfactant.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
(1) Synthesis of the first component
105.46g of octamethylcyclotetrasiloxane, 40.24g of high hydrogen silicone oil and 34.73g of tetramethyldisiloxane are reacted for 6 hours under the action of acid clay at 50 ℃ to obtain hydrogen silicone oil A.
50g of hydrogen-containing silicone oil A and 76.01g of allyl polyether are heated to 130 ℃ in a reactor under the conditions of 4ppm of chloroplatinic acid catalyst and 100ppm of diethanolamine cocatalyst to react for 4 hours to obtain the compound with the molecular formula R1-Si(CH3)2-O-[Si(CH3)2-O]5.2-[Si(CH3)R-O]2.3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)1.5CH3。
(2) Synthesis of the second component
115.38g of octamethylcyclotetrasiloxane, 41.97g of high hydrogen silicone oil and 23.09g of hexamethyldisiloxane are reacted for 6 hours under the action of acid clay at 80 ℃ to obtain hydrogen silicone oil B.
Under the conditions of 5ppm chloroplatinic acid catalyst and 200ppm diethanolamine cocatalyst, 35g of hydrogen-containing silicone oil B and 87.31g of allyl polyether are heated to 130 ℃ under normal pressure in a reactor to react for 5 hours to obtain Si (CH) with the molecular formula3)3-O-[Si(CH3)2-O]8.3-[Si(CH3)R-O]3.5-Si(CH3)3Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)6CH3。
(3) Preparation of the surfactant
According to the mixture ratio in the table 1, the first component, the second component and the third component (polyether polyol with the molecular weight of 2000 and taking propylene glycol as an initiator) are mixed and stirred for 2 hours in different proportions at 40 ℃ to obtain different high-resilience foam organosilicon surfactants.
The cell sizes of the resulting foams were compared using the different silicone surfactants described above under the same high resilience foam production conditions, and the results are shown in table 1.
TABLE 1 ratio and sample application evaluation results
Figure BDA0002340262420000111
Figure BDA0002340262420000121
Note: cell thickness is represented by "+", and an increase in "+" represents a thickening of the cells (the same applies below).
As can be seen from Table 1, in the above-mentioned blending ratio range, the larger the content of the first component is, the coarser the cells of the prepared foam sample of the corresponding surfactant are, without changing the content of the third component.
Example 2
(1) Synthesis of the first component
123.6g of octamethylcyclotetrasiloxane, 20.97g of high hydrogen silicone oil and 35.65g of tetramethyldisiloxane are reacted for 6 hours under the action of acid clay at 50 ℃ to obtain hydrogen silicone oil A.
50g of hydrogen-containing silicone oil A and 76.01g of allyl polyether are heated to 130 ℃ in a reactor under the conditions of 4ppm of chloroplatinic acid catalyst and 100ppm of diethanolamine cocatalyst to react for 4 hours to obtain the compound with the molecular formula R1-Si(CH3)2-O-[Si(CH3)2-O]6.1-[Si(CH3)R-O]1.2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)1.5CH3。
(2) Synthesis of the second component
124.75g of octamethylcyclotetrasiloxane, 29.82g of high hydrogen silicone oil and 25.74g of tetramethyldisiloxane are reacted for 6 hours under the action of acid clay at 80 ℃ to obtain hydrogen silicone oil B.
Under the conditions of 5ppm chloroplatinic acid catalyst and 200ppm diethanolamine cocatalyst, 35g of hydrogen-containing silicone oil B and 87.31g of allyl polyether are heated to 130 ℃ under normal pressure in a reactor to react for 5 hours to obtain Si (CH) with the molecular formula3)3-O-[Si(CH3)2-O]8.3-[Si(CH3)R-O]2.3-Si(CH3)3Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)6CH3。
(3) Preparation of the surfactant
According to the mixture ratio in the table 2, the first component, the second component and the third component (polyether polyol with the molecular weight of 2000 and taking propylene glycol as an initiator) are mixed and stirred for 2 hours in different proportions at the temperature of 40 ℃, so that different high-resilience foam organosilicon surfactants are obtained.
The cell sizes of the resulting foams were compared using the different silicone surfactants described above under the same high resilience foam production conditions, and the results are shown in table 2.
TABLE 2 ratio and sample application evaluation results
Figure BDA0002340262420000131
As can be seen from Table 2, in the above-mentioned blending ratio range, the larger the content of the first component is, the coarser the cells of the prepared foam sample of the corresponding surfactant are, without changing the content of the third component.
Example 3
(1) Synthesis of the first component
119.51g of octamethylcyclotetrasiloxane, 22.49g of high hydrogen silicone oil and 38.23g of tetramethyldisiloxane are reacted for 6 hours under the action of concentrated sulfuric acid at 30 ℃, and hydrogen silicone oil A is obtained after neutralization and filtration.
Under the conditions of 4ppm of chloroplatinic acid catalyst and 100ppm of diethanolamine cocatalyst, 40g of hydrogen-containing silicone oil A and 76.85g of allyl polyether are heated to 130 ℃ under normal pressure in a reactor to react for 4 hours to obtain a compound with a molecular formula of R1-Si(CH3)2-O-[Si(CH3)2-O]5.5-[Si(CH3)R-O]1.2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3。
(2) Synthesis of the second component
124.75g of octamethylcyclotetrasiloxane, 29.82g of high hydrogen silicone oil and 25.74g of tetramethyldisiloxane are reacted for 6 hours under the action of concentrated sulfuric acid at 30 ℃, and hydrogen silicone oil B is obtained after neutralization and filtration.
Heating 25g of hydrogen-containing silicone oil B and 93.87g of allyl polyether to 130 ℃ under normal pressure in a reactor under the conditions of 4ppm of chloroplatinic acid catalyst and 100ppm of diethanolamine cocatalyst to react for 5 hours to obtain the compound with the molecular formula R1-Si(CH3)2-O-[Si(CH3)2-O]9.3-[Si(CH3)R-O]3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)8CH3。
(3) Preparation of the surfactant
According to the mixture ratio in the table 3, the first component, the second component and the third component (polyether polyol with the molecular weight of 3000 and taking propylene glycol as an initiator) are mixed and stirred for 2 hours in different proportions at the temperature of 40 ℃ to obtain different high resilience foam organosilicon surfactants.
The cell sizes of the resulting foams were compared using the different silicone surfactants described above under the same high resilience foam production conditions, and the results are shown in table 3.
TABLE 3 ratio and sample application evaluation results
Figure BDA0002340262420000151
As can be seen from Table 3, in the above-mentioned blending ratio range, the larger the content of the first component is, the coarser the cells of the prepared foam sample of the corresponding surfactant are, without changing the content of the third component.
Example 4
(1) Synthesis of the first component
121.89g of octamethylcyclotetrasiloxane, 29.21g of high hydrogen silicone oil and 29.21g of tetramethyldisiloxane are reacted for 6 hours under the action of concentrated sulfuric acid at 30 ℃, and hydrogen silicone oil A is obtained after neutralization and filtration.
Under the conditions of 4ppm of chloroplatinic acid catalyst and 100ppm of diethanolamine cocatalyst, 40g of hydrogen-containing silicone oil A and 74.85g of allyl polyether are heated to 130 ℃ under normal pressure and reacted for 4 hours in a reactor to obtain a molecular formula R1-Si(CH3)2-O-[Si(CH3)2-O]7.2-[Si(CH3)R-O]2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3。
(2) Synthesis of the second component
126.75g of octamethylcyclotetrasiloxane, 32.48g of high hydrogen silicone oil and 21.12g of tetramethyldisiloxane are reacted for 6 hours under the action of concentrated sulfuric acid at 30 ℃, and hydrogen silicone oil B is obtained after neutralization and filtration.
Under the conditions of 4ppm of chloroplatinic acid catalyst and 100ppm of diethanolamine cocatalyst, 25g of hydrogen-containing silicone oil B and 95.76g of allyl polyether are heated to 130 ℃ under normal pressure in a reactor to react for 5 hours to obtain a molecular formula R1-Si(CH3)2-O-[Si(CH3)2-O]10.1-[Si(CH3)R-O]3-Si(CH3)2-R1The second component of (a) is,wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)8CH3。
(3) Preparation of the surfactant
According to the mixture ratio in the table 4, the first component, the second component and the third component (polyether polyol with the molecular weight of 3000 and taking propylene glycol as an initiator) are mixed and stirred for 2 hours in different proportions at the temperature of 40 ℃, so that different high-resilience foam organosilicon surfactants are obtained.
The cell sizes of the resulting foams were compared using the different silicone surfactants described above under the same high resilience foam production conditions, and the results are shown in table 4.
TABLE 4 ratio and sample application evaluation results
Figure BDA0002340262420000161
As can be seen from Table 4, in the above-mentioned blending ratio range, the larger the content of the first component is, the coarser the cells of the prepared foam sample of the corresponding surfactant are, without changing the content of the third component.
Therefore, from the application evaluation results, after hydrogen is introduced at the chain end of the hydrogen-containing silicone oil, the hydrogen-containing silicone oil with different structures is grafted with allyl polyether with different molecular weights, the proportion of different components is regulated, the effective regulation range of the openness and stability of the polyurethane high-resilience foam is increased, when the proportion of the component C is fixed, the effective regulation of larger range of the foam pore size can be realized by regulating the proportion of the component A and the component B, the proportion of active components has similar rules when different, and a research basis is provided for effectively regulating the size stability of the high-resilience polyurethane foam.
Test examples
Taking example 1 as an example, comparative examples 1-4 are set up;
comparative example 1 differs from example 1 in that: the first component has the following structural formula:
Figure BDA0002340262420000171
wherein m has a value of 22 and n has a value of 17; r has the structure of-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR2Wherein a has a value of 12, b has a value of 10, R2Is an alkyl group having 1 carbon atom; r1Has the structure of-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR2Wherein a has a value of 12, b has a value of 10, R2Is an alkyl group having 1 carbon atom.
Comparative example 2 differs from example 1 in that: the third component is polyether polyol with propylene glycol as initiator and molecular weight of 500.
Comparative example 3 differs from example 1 in that: the first component accounts for 60 wt% of the raw material, and the third component accounts for 40 wt% of the raw material.
Comparative example 4 differs from example 1 in that: the second component accounts for 60 wt% of the raw materials, and the third component accounts for 40 wt% of the raw materials.
Comparative examples 1 to 4 were prepared with the respective surfactants in the ratios shown in table 1, and the cell thicknesses of the resulting foams were compared under the same high resilience foam preparation conditions using the different surfactants described above, and the results showed that: when the structural formula of the first component, the substances corresponding to the third component, the using amount of the first component or the using amount of the second component in the sample components are regulated and controlled outside the range of the application, the openness and stability of the polyurethane high-resilience foam are correspondingly influenced, and the regulation tolerance of the thickness of the foam is narrowed.
To sum up, the surfactant provided by the application can effectively regulate and control the openness and stability of the polyurethane high-resilience foam. The preparation method is simple, easy to operate and controllable in process. The surfactant is used for preparing high-resilience foam, and can effectively regulate and control the dimensional stability of the high-resilience polyurethane foam.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by 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 in that a raw material of the surfactant comprises a first component, a second component and a third component, wherein the first component accounts for 20-40 wt% of the raw material, the second component accounts for 20-40 wt% of the raw material, and the third component accounts for 20-60 wt% of the raw material;
the structural formula of the first component is as follows:
Figure FDA0002340262410000011
wherein m has a value of 0-20, n has a value of 0-15, and m + n has a value of 1-20; r and R1Independently of the structure of (A) is-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR2Wherein a has a value of 1-9, b has a value of 0-9, and a + b has a value of 1-15, R2Is alkyl containing 1-4 carbon atoms;
the structural formula of the second component is as follows:
Figure FDA0002340262410000012
wherein m has a value of 0-25, n has a value of 0-15, and m + n has a value of 1-25; r and R1Independently of the structure of (A) is-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR2Wherein a has a value of 0-25, b has a value of 1-25, and a + b has a value of 1-25, R2Is alkyl containing 1-4 carbon atoms;
and the first component and the second component have different structural formulas;
the third component is a copolymer with terminal hydroxyl groups derived from a polyol;
preferably, the polyol comprises a low molecular weight polyol; more preferably, the low molecular weight polyol includes at least one of ethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, and dipropylene glycol.
2. The surfactant of claim 1 wherein said first component of said surfactant comprises R1-Si(CH3)2-O-[Si(CH3)2-O]5.2-[Si(CH3)R-O]2.3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)1.5CH3；
Or R1-Si(CH3)2-O-[Si(CH3)2-O]6.1-[Si(CH3)R-O]1.2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)2(CH2CH(CH3)O)1.5CH3；
Or R1-Si(CH3)2-O-[Si(CH3)2-O]5.5-[Si(CH3)R-O]1.2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3；
Or R1-Si(CH3)2-O-[Si(CH3)2-O]7.2-[Si(CH3)R-O]2-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)1CH3。
3. The surfactant of claim 1 wherein said second component of said surfactant comprises Si (CH)3)3-O-[Si(CH3)2-O]8.3-[Si(CH3)R-O]3.5-Si(CH3)3Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)6CH3；
Or Si (CH)3)3-O-[Si(CH3)2-O]8.3-[Si(CH3)R-O]2.3-Si(CH3)3Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)3(CH2CH(CH3)O)6CH3；
Or R1-Si(CH3)2-O-[Si(CH3)2-O]9.3-[Si(CH3)R-O]3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)8CH3；
Or R1-Si(CH3)2-O-[Si(CH3)2-O]10.1-[Si(CH3)R-O]3-Si(CH3)2-R1Wherein R ═ R1＝-CH2CH2CH2O(CH2CH2O)1(CH2CH(CH3)O)8CH3。
4. The surfactant of claim 1, wherein said third component of said surfactant is a polyether polyol having a molecular weight of 2000 to 3000;
preferably, the polyether polyol is initiated with propylene glycol.
5. A process for preparing a surfactant as claimed in any one of claims 1 to 4, comprising the steps of: mixing the raw materials according to the proportion.
6. The preparation method according to claim 5, characterized in that the raw materials are mixed and stirred for 1.8-2.2h at 38-42 ℃;
more preferably, the raw materials are mixed and stirred for 2 hours at the temperature of 40 ℃.
7. The preparation method according to claim 5, wherein the first component and the second component are obtained by reacting allyl polyether with different hydrogen-containing silicone oil in the presence of a catalyst and a cocatalyst; or the hydrogen-containing silicone oil and the allyl polyether react according to different proportions in the presence of a catalyst and a cocatalyst;
preferably, the hydrogen-containing silicone oil and the allyl polyether are reacted for 2 to 8 hours at 90 to 160 ℃ in the presence of the catalyst and the cocatalyst;
preferably, the catalyst comprises a platinum catalyst;
preferably, the co-catalyst comprises at least one of diethanolamine, triethanolamine, acetamide, triethylamine, and N-butyl ethanolamine.
8. The preparation method according to claim 7, wherein the hydrogen-containing silicone oil is obtained by reacting octamethylcyclotetrasiloxane, high hydrogen-containing silicone oil and end-capping reagent;
preferably, the capping agent comprises hexamethyldisiloxane or tetramethyldisiloxane;
preferably, the octamethylcyclotetrasiloxane, the high hydrogen-containing silicone oil and the end socket agent are reacted for 5-8 hours at 30-90 ℃ in the presence of an acidic catalyst;
preferably, the acidic catalyst comprises at least one of acid clay, concentrated sulfuric acid, trifluoromethanesulfonic acid, and an acidic resin, preferably acid clay and/or concentrated sulfuric acid.
9. Use of a surfactant according to any one of claims 1 to 5 in the preparation of a polyurethane high resilience foam.
10. A polyurethane high resilience foam, wherein the surfactant used in the preparation of the high resilience foam comprises the surfactant according to any one of claims 1 to 5.
CN201911373288.6A 2019-12-27 2019-12-27 Surfactant, preparation method and application thereof, and polyurethane high-resilience foam Pending CN111040228A (en)

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