CN111040229A - Open-cell type organic silicon surfactant, preparation method and application thereof, and high-resilience foam - Google Patents
Open-cell type organic silicon surfactant, preparation method and application thereof, and high-resilience foam Download PDFInfo
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Abstract
The application provides an open-cell silicone surfactant, a preparation method and application thereof, and high-resilience foam, and belongs to the technical field of surfactants. The raw material of the open-cell silicone surfactant comprises, by weight, 5-20% of a component A, 5-20% of a component B, 1-10% of a component C, 30-59% of a component D and 30-50% of a component E. The component A has the following structural formula:
the component B has the following structural formula:
the component C has the following structural formula:
Description
Technical Field
The application relates to the technical field of surfactants, in particular to an open-cell type organosilicon surfactant, a preparation method and application thereof, and high-resilience foam.
Background
The polyurethane high-resilience foam plastic is a kind of foam plastic with excellent performance, and compared with the common foam plastic, the high-resilience foam plastic has higher elasticity, better comfort performance and longer performance durability. While ordinary polyurethane flexible foams remain the leading product in the market, high resilience foams are also becoming more and more widely used, not only for automotive and motorcycle, aircraft seating, but also for high-end furniture.
The production of polyurethane high resilience foam is usually that polyether polyol, water, catalyst, organosilicon surfactant, foaming agent, other auxiliary agent and isocyanate are stirred and mixed at high speed, and the reaction is carried out rapidly under the action of catalyst to form the foam with a net structure, the forming process of the foam is carried out simultaneously with the foaming and gel reaction, especially MDI system foam, because the gel reaction is rapid, the gas generated by the reaction is easily closed in the cell structure to cause the product to expand the mould, which is not beneficial to demoulding, and the subsequent process easily causes the foam to break, thus affecting the production efficiency and quality of the product. Therefore, the role of the surfactant in the overall process is of particular importance.
At present, the surfactant used by the polyurethane high-resilience foam has poor effect of regulating and controlling the thickness degree of foam cells.
In view of this, the present application is specifically made.
Disclosure of Invention
One of the objects of the present application includes providing an open-cell silicone surfactant that is capable of effectively regulating the openability and stability of polyurethane high resilience foams.
The second purpose of the application is to provide a preparation method of the open-cell type organosilicon surfactant, which is simple, easy to operate and suitable for industrial production.
It is a further object of the present invention to provide a use of the above open-cell silicone surfactant in the preparation of a high resilience foam.
The fourth object of the present application includes providing a high resilience foam having a better and stable cell size, using the above open-cell silicone surfactant in the preparation process.
The following technical scheme can be adopted to solve the technical problems:
the application provides an open-cell type organosilicon surfactant, which comprises, by weight, 5-20% of a component A, 5-20% of a component B, 1-10% of a component C, 30-59% of a component D and 30-50% of a component E.
The component A has the following structural formula:
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 has the structure of-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR1Wherein a has a value of 1-9, b has a value of 0-9, and a + b has a value of 1-15, R1Is an alkyl group having 1 to 4 carbon atoms.
The component B has the following structural formula:
wherein m has a value of 1-25, n has a value of 1-15, and m + n has a value of 2-35; r has the structure of-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 1-30, R2Is an alkyl group having 1 to 4 carbon atoms.
The component A and the component B have different structural formulas.
The component C has the following structural formula:
wherein m has a value of 5 to 10.
The component D and the component E are both copolymers with terminal hydroxyl groups derived from polyhydroxy compounds, and the component D and the component E have different structural formulas.
Alternatively, m in the structural formula of the component A is 3.2, n is 1.9, a in the structural formula of R is 2, and b is 1.5; or m is 4.2, n is 2.5, a in the structural formula of R is 2, and b is 1.5; or m is 2.5, n is 1.5, a in the structural formula of R is 3, and b is 1; or m is 3, n is 1.7, a in the structural formula of R is 3, and b is 1. In the above structural formula R1Are all methyl.
Alternatively, m in the structural formula of the component B is 8.3, n is 3.1, a in the structural formula of R is 3, and B is 6; or m is 10.1, n is 4.6, a in the structural formula of R is 3, and b is 6; or m is 6.5, n is 3.2, a in the structural formula of R is 1, and b is 8; or m is 7.2, n is 3.5, a in the structural formula of R is 1, and b is 8. In the above structural formula R2Are all methyl.
Alternatively, the C component comprises Si (CH)3)3-O-[Si(CH3)2-O]5-Si(CH3)3、Si(CH3)3-O-[Si(CH3)7-O]5-Si(CH3)3、Si(CH3)3-O-[Si(CH3)8-O]5-Si(CH3)3、Si(CH3)3-O-[Si(CH3)7-O]9-Si(CH3)3And Si (CH)3)3-O-[Si(CH3)7-O]10-Si(CH3)3At least one of (1).
In addition, the application also provides a preparation method of the open-cell type organosilicon surfactant, which comprises the following steps: mixing the component A, the component B, the component C, the component D and the component E.
In addition, the application also provides an application of the open-cell type organosilicon surfactant in preparation of high-resilience foam.
In addition, the application also provides a high-resilience foam, and the preparation process of the high-resilience foam uses the open-cell type organosilicon surfactant.
The open-cell silicone surfactant, the preparation method and the application thereof, and the high-resilience foam have the beneficial effects that:
through the matching of the component A and the component B which have different structures and are used as polyether modified organic silicon substances, the surface tension of a foam wall is adjusted in the foam forming process, so that the open cell ratio of polyurethane foam is improved, and the problems of foam product shrinkage and the like caused by closed cells are solved. The compatibility of the starting systems can be improved by using two copolymers (D-component and E-component) which have terminal hydroxyl groups derived from polyhydroxy compounds. In addition, the dimethyl silicone oil (component C) is introduced into the raw material system, so that the open porosity and stability of the polyurethane high-resilience foam can be effectively regulated, positive effects on system compatibility and effective regulation of the surface and dimensional stability of the polyurethane foam are achieved, the special requirements of the high-resilience polyurethane foam on volume, ventilation, shearing, surface and dimensional stability are met, and the problems of the system compatibility and effective regulation of the size and surface stability of the polyurethane foam are effectively solved.
The preparation method of the surfactant is simple, easy to operate and suitable for industrial production. The preparation method is used for preparing the high-resilience foam, and can effectively regulate and control the stability of the foam size.
Detailed Description
The following is a detailed description.
The raw material of the open-cell silicone surfactant provided by the application comprises, by weight, 5-20% of a component A, 5-20% of a component B, 1-10% of a component C, 30-59% of a component D and 30-50% of a component E.
Wherein, the component A has the following structural formula:
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 has the structure of-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR1Wherein a has a value of 1-9, b has a value of 0-9, and a + b has a value of 1-15, R1Is an alkyl group having 1 to 4 carbon atoms.
The component B has the following structural formula:
wherein m has a value of 1-25, n has a value of 1-15, and m + n has a value of 2-35. R has the structure of-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 1-30, R2Is an alkyl group having 1 to 4 carbon atoms.
It is worth noting that the A component and the B component have different structural formulas, namely, the A component and the B component are not the same substance.
The component C has the following structural formula:
wherein m has a value of 5 to 10.
Both component D and component E are copolymers having terminal hydroxyl groups derived from polyhydroxy compounds. It is worth noting that the D component and the E component have different structural formulas, that is, the D component and the E component are not the same substance.
Alternatively, the polyol comprises a low molecular weight polyol, such as at least one of ethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, and dipropylene glycol.
Further, the D component may be a low molecular weight polyether polyol, which may have a molecular weight of 100 to 500. The E component may be a high molecular weight polyether polyol, which may have a molecular weight of 2000 to 4000.
It is worth noting that alternatively, the starting material for the open-cell silicone surfactant contains only 5 components from component a to component E, in which case the sum of the weight percentages of the 5 components is 100%.
As can be seen, one of the a-component and the B-component is mainly used to improve the open cell content of the foam, and the other is mainly used to maintain the stability of the foam. In still other embodiments, the starting material for the open-cell silicone surfactant may further contain a polyether-modified silicone material other than the a-component and the B-component.
Alternatively, the A component of the open cell silicone surfactant can include, for example, the first formula wherein m is 3.2, n is 1.5, R has a formula wherein a is 2, and b is 1.9; m in the structural formula of the second is 4.2, n is 2.5, a in the structural formula of R is 2, and b is 1.5; m in the third structural formula is 2.5, n is 1.5, a in the structural formula of R is 3, and b is 1; in the fourth structural formula, m is 3, n is 1.7, a in the structural formula of R is 3, and b is 1. In the above structural formula R1Are all methyl.
The component B in the open-cell organosilicon surfactant can comprise the following components, for example, m in the structural formula of the first component is 8.3, n is 3.1, a in the structural formula of R is 3, and B is 6; m in the structural formula of the second is 10.1, n is 4.6, a in the structural formula of R is 3, and b is 6; m in the third structural formula is 6.5, n is 3.2, a in the structural formula of R is 1, and b is 8; the fourth formula has m of 7.2, n of 3.5, and R has a of 1 and b of 8. In the above structural formula R2Are all methyl.
The C component of the open-cell silicone surfactant may include, for example, Si (CH)3)3-O-[Si(CH3)2-O]5-Si(CH3)3、Si(CH3)3-O-[Si(CH3)7-O]5-Si(CH3)3、Si(CH3)3-O-[Si(CH3)8-O]5-Si(CH3)3、Si(CH3)3-O-[Si(CH3)7-O]9-Si(CH3)3And Si (CH)3)3-O-[Si(CH3)7-O]10-Si(CH3)3At least one of (1).
The component D in the open-cell type organosilicon surfactant is polyether polyol taking propylene glycol as an initiator, and the molecular weight of the polyether polyol can be 300 or 500. The component E is polyether polyol taking 1, 4-butanediol as an initiator, and the molecular weight of the polyether polyol can be 2000 or 3000.
In some embodiments herein, m of the structural formula of component a is 3.2, n is 1.9, a of the structural formula of R is 2, and b is 1.9. M in the structural formula of the component B is 8.3, n is 3.1, a in the structural formula of R is 3, and B is 6. The molecular formula of the C component is Si (CH)3)3-O-[Si(CH3)2-O]5-Si(CH3)3. The component D is polyether polyol which takes propylene glycol as an initiator and has the molecular weight of 300. The component E is polyether polyol which takes 1, 4-butanediol as an initiator and has the molecular weight of 2000.
In some embodiments herein, m is 4.2, n is 2.5, R is 2, and b is 1.5. In the structural formula of the component B, m is 10.1, n is 4.6, a in the structural formula of R is 3, and B is 6. The C component comprises at least one of a C1 component and a C2 component, namely the C component can only comprise (is) a C1 component, can only comprise (is) a C2 component, and can also simultaneously contain a C1 component and a C2 component. Wherein the molecular formula of the C1 component is Si (CH)3)3-O-[Si(CH3)5-O]5-Si(CH3)3The molecular formula of the C2 component is Si (CH)3)3-O-[Si(CH3)7-O]5-Si(CH3)3. The component D is polyether polyol which takes propylene glycol as an initiator and has the molecular weight of 300. The component E is polyether polyol which takes 1, 4-butanediol as an initiator and has the molecular weight of 2000.
In some embodiments herein, m is 2.5, n is 1.5, R is 3, and b is 1. In the structural formula of the component B, m is 6.5, n is 3.2, a in the structural formula of R is 1, and B is 8. The molecular formula of the C component is Si (CH)3)3-O-[Si(CH3)8-O]5-Si(CH3)3. The component D is polyether polyol which takes propylene glycol as an initiator and has the molecular weight of 500. The component E is polyether polyol which takes 1, 4-butanediol as an initiator and has a molecular weight of 3000.
In some embodiments herein, m of the structural formula of component a is 3, n is 1.7, a of the structural formula of R is 3, and b is 1. M of the structural formula of the component B is 7.2, n is 3.5, a of the structural formula of R is 1, and B is 8. The C component comprises at least one of a C3 component, a C4 component and a C5 component, namely the C component can only comprise (is) a C3 component, can only comprise (is) a C4 component, can only comprise (is) a C5 component, and can also simultaneously contain a C3 component, a C4 component and a C5 component. Wherein the molecular formula of the C3 component is Si (CH)3)3-O-[Si(CH3)8-O]5-Si(CH3)3The molecular formula of the C4 component is Si (CH)3)3-O-[Si(CH3)7-O]9-Si(CH3)3The molecular formula of the C5 component is Si (CH)3)3-O-[Si(CH3)7-O]10-Si(CH3)3. The component D is polyether polyol which takes propylene glycol as an initiator and has the molecular weight of 500. The component E is polyether polyol with molecular weight of 3000 and 1, 4-butanediol as initiator.
It is worth to say that the inventor finds that, in the application, the simultaneous use of at least two polyether modified organosilicon substances with different structures in the raw materials of the open-cell type organosilicon surfactant can obviously improve the open-cell rate and stability of the polyurethane foam compared with the use of only one polyether modified organosilicon substance, and the improvement effect of the open-cell rate and stability of the polyurethane foam can be better by using only two polyether modified organosilicon substances with different structures compared with the use of three or more polyether modified organosilicon substances with different structures.
Furthermore, the inventors have found that the simultaneous use of two copolymers having terminal hydroxyl groups derived from a polyhydroxy compound in the starting materials of the open-cell silicone surfactants in the present application can significantly improve the compatibility of the starting material system over the use of only one copolymer, and that the use of only two copolymers having terminal hydroxyl groups derived from a polyhydroxy compound can provide better compatibility of the starting material system than the use of three or more copolymers having terminal hydroxyl groups derived from a polyhydroxy compound.
In the application, the polyether modified organic silicon substances (the component A and the component B) with different structures are matched to adjust the surface tension of the foam wall in the foam forming process, so that the open cell ratio of the polyurethane foam is improved, and the problems of shrinkage and the like of a foam product caused by closed cells are solved. The compatibility of the starting systems can be improved by using two copolymers (D-component and E-component) which have terminal hydroxyl groups derived from polyhydroxy compounds. On the basis, the dimethyl silicone oil (component C) is introduced, so that the effective regulation and control of the openness and the stability of the polyurethane high-resilience foam body can be realized, the positive effects on the system compatibility and the effective regulation and control of the surface and the dimensional stability of the polyurethane foam are achieved, the special requirements of the high-resilience polyurethane foam on the volume, ventilation, shearing, surface and dimensional stability are met, and the problems of the system compatibility and the effective regulation and control of the surface and the dimensional stability of the polyurethane foam are effectively solved.
Further, the application also provides a preparation method of the open-cell type organosilicon surfactant, which comprises the following steps: mixing the component A, the component B, the component C, the component D and the component E.
Optionally, at least three components are already mixed prior to mixing with the C component. The mixing in the sequence can lead the mixed system to have better compatibility, and is beneficial to improving the regulation and control effect of the surfactant on foam cells.
For reference, the component A, the component B, the component C, the component D and the component E can be stirred and mixed for 0.8 to 1.2 hours (such as 0.8 hour, 1 hour or 1.2 hours and the like) under the condition of 45 to 55 ℃ (such as 45 ℃, 50 ℃ or 55 ℃ and the like). The stirring speed can be 200-500 r/min.
In the application, the component A and the component B can be obtained by reacting hydrogen-containing silicone oil, allyl polyether, a catalyst and a cocatalyst according to different proportions, namely, the hydrogen-containing silicone oil, the allyl polyether, the catalyst and the cocatalyst react with each other according to different proportions to respectively generate the component A and the component B. In addition, the catalyst can be obtained by reacting allyl polyether, a catalyst and a cocatalyst with different hydrogen-containing silicone oil, namely, the A component and the B component can be respectively generated by reacting the allyl polyether, the catalyst and the cocatalyst with different hydrogen-containing silicone oil.
It is worth noting that the type of the hydrogen-containing silicone oil used for preparing the component A or the component B can be one or more, namely, at least one hydrogen-containing silicone oil is used in the process of preparing the component A, and at least one hydrogen-containing silicone oil is used in the process of preparing the component B.
Alternatively, the reaction of the hydrogen-containing silicone oil, the allyl polyether, the catalyst, and the cocatalyst can be carried out at 80-160 ℃ (e.g., 80 ℃, 100 ℃, 120 ℃, 150 ℃, 160 ℃, etc.) for 2-8h (e.g., 2h, 4h, 5h, 6h, 8h, etc.).
The above-mentioned catalyst may, for example, be a platinum catalyst including chloroplatinic acid as a catalyst. The catalyst may be used in an amount of 3 to 30ppm (e.g., 3ppm, 10ppm, 15ppm, 20ppm, 25ppm, 30ppm, etc.) based on the total amount of hydrogen-containing silicone oil, allyl polyether, catalyst, and cocatalyst.
The cocatalyst may include, for example, at least one of N-butylethanolamine, diethanolamine, acetamide, triethanolamine and triethylamine. Alternatively, the promoter may be used in an amount of 3 to 300ppm (e.g., 3ppm, 10ppm, 50ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, etc.) of the total amount of hydrogen-containing silicone oil, allyl polyether, catalyst, and promoter.
By reference, the preparation of hydrogen-containing silicone oil may comprise: reacting octamethylcyclotetrasiloxane, hexamethyldisiloxane and high hydrogen-containing silicone oil (the mixed system of the three is defined as Y system) at 30-90 deg.C (such as 30 deg.C, 50 deg.C, 60 deg.C, 80 deg.C or 90 deg.C) for 5-8h (such as 5h, 6h, 7h or 8 h). It is worth to be noted that different hydrogen-containing silicone oils can be generated by the reaction of the three substances in different proportions.
The Y system is, by reference, carried out in the presence of a catalyst. The catalyst may, for example, comprise an acidic catalyst, such as at least one of acid clay (preferred), concentrated sulfuric acid (preferred), trifluoromethanesulfonic acid, and an acidic resin. Alternatively, the acidic catalyst can be used in an amount of 1 to 6 wt% (e.g., 1 wt%, 2 wt%, 4 wt%, 5 wt%, or 6 wt%, etc.) of the total Y system.
In conclusion, the preparation method is simple and suitable for industrialization. The hydrogen-containing silicone oil with different structures is grafted with allyl polyether with different molecular weights, the proportion of different components is regulated, and particularly, the effective regulation of the openness and the stability of the polyurethane high-resilience foam body can be realized by introducing dimethyl silicone oil with different structures and different contents.
In addition, the application also provides application of the open-cell type organosilicon surfactant, such as application in preparing high-resilience foam, particularly polyurethane high-resilience foam.
In addition, the application also provides a high resilience foam, and the surfactant used in the preparation process of the high resilience foam comprises the open-cell type organosilicon surfactant. The high resilience foam has excellent openness and stability.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
(1) Synthesis of component A
83.12g of octamethylcyclotetrasiloxane, 42.57g of high hydrogen silicone oil and 54.31g of hexamethyldisiloxane are reacted for 6 hours at 80 ℃ under the action of acid clay to obtain first hydrogen silicone oil.
Adding 50g of first hydrogen-containing silicone oil and 64.32g of allyl polyether into a reactor, heating to 130 ℃ under normal pressure and reacting for 5h under the conditions of 5ppm of chloroplatinic acid catalyst and 200ppm of diethanolamine cocatalyst to obtain a component A, wherein m is 3.2, n is 1.9, a in a molecular formula of R is 2, b is 1.5, R is in a structural formula of R1Is methyl.
(2) Synthesis of component B
114.9g of octamethylcyclotetrasiloxane, 37.01g of high hydrogen silicone oil and 28.09g of hexamethyldisiloxane are reacted under the action of acid clay at 80 ℃ for 6 hours to obtain second hydrogen silicone oil.
Adding 35g of second hydrogen-containing silicone oil and 87.31g of allyl polyether into a reactor, heating to 130 ℃ under normal pressure and reacting for 5h under the conditions of 5ppm of chloroplatinic acid catalyst and 200ppm of diethanolamine cocatalyst to obtain a component B, wherein m in the molecular formula is 8.3, n is 3.1, a in the structural formula of R is 3, B is 6, R is2Is methyl.
(3) Preparation of organosilicon surfactant for high resilience foam
Mixing the component A, the component B, the component C, the component D and the component E according to different proportions in the mixture ratio in the table 1, and stirring for 1h at the temperature of 50 ℃ to obtain different organosilicon surfactant samples for high-resilience foam.
Wherein the structural formula of the component C is as follows:
wherein m has a value of 5. The component D is polyether polyol with the molecular weight of 300 and taking propylene glycol as an initiator, and the component E is polyether polyol with the molecular weight of 2000 and taking 1, 4-butanediol as an initiator.
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
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 compounding ratio range, the larger the content of the component C, the coarser the cells of the foam produced from the corresponding surfactant, without changing the contents of the components A, B and E.
Example 2
(1) Synthesis of component A
89.83g of octamethylcyclotetrasiloxane, 46.12g of high hydrogen-containing silicone oil and 44.06g of hexamethyldisiloxane are reacted for 6 hours at 80 ℃ under the action of acid clay to obtain first hydrogen-containing silicone oil.
Adding 50g of first hydrogen-containing silicone oil and 69.68g of allyl polyether into a reactor, heating to 130 ℃ under normal pressure and reacting for 6h under the conditions of 6ppm of chloroplatinic acid catalyst and 200ppm of triethanolamine cocatalyst to obtain a component A, wherein the molecular formula m is 4.2, n is 2.5, a in the structural formula of R is 2, b is 1.5, R is 21Is methyl.
(2) Synthesis of component B
113.9g of octamethylcyclotetrasiloxane, 44.58g of high hydrogen silicone oil and 21.93g of hexamethyldisiloxane are reacted at 80 ℃ for 6 hours under the action of acid clay to obtain second hydrogen silicone oil.
Adding 28g of second hydrogen-containing silicone oil and 84.13g of allyl polyether into a reactor, heating to 130 ℃ under normal pressure and reacting for 6h under the conditions of 6ppm of chloroplatinic acid catalyst and 200ppm of triethanolamine cocatalyst to obtain a component B, wherein m in a molecular formula is 10.1, n is 4.6, a in a structural formula of R is 3, B is 6, R is 62Is methyl.
(3) Preparation of organosilicon surfactant for high resilience foam
Mixing the component A, the component B, the component C, the component D and the component E according to different proportions in the following table 2, and stirring for 1h at the temperature of 50 ℃ to obtain different organosilicon surfactant samples for high resilience foam.
Wherein the structural formula of the component C is as follows:
wherein m has a value of 5. The component D is polyether polyol with the molecular weight of 300 and taking propylene glycol as an initiator, and the component E is polyether polyol with the molecular weight of 2000 and taking 1, 4-butanediol as an initiator.
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
As can be seen from Table 2, in the above compounding ratio ranges, the larger the content of the component C, the coarser the cells of the resulting foam from its corresponding surfactant, without changing the contents of the components A, B and E.
In addition, the above C component was changed as follows:
changing one: the value of m in the structural formula of the component C is 7.
Changing two: the C component comprises a C component 1 and a C component 2, wherein m in the structural formula of the C component 1 is 5; the value of m in the structural formula of the C component 2 is 7.
Similarly, silicone surfactants were prepared according to the formulation shown in Table 2, and the different silicone surfactants were used under the same high resilience foam preparation conditions to compare the cell sizes of the foams obtained, and the results still show: in the case of the same contents of the A component, the B component and the E component, the larger the content of the C component, the coarser the cells of the foam produced from the corresponding surfactant.
Example 3
(1) Synthesis of component A
76.20g of octamethylcyclotetrasiloxane, 39.43g of high hydrogen-containing silicone oil and 64.36g of hexamethyldisiloxane are reacted for 6 hours at 30 ℃ under the action of concentrated sulfuric acid to obtain first hydrogen-containing silicone oil.
Adding 50g of first hydrogen-containing silicone oil and 63.18g of allyl polyether into a reactor, heating to 120 ℃ under normal pressure and reacting for 7h under the conditions of 6ppm of chloroplatinic acid catalyst and 100ppm of diethanolamine cocatalyst to obtain a component A, wherein m in a molecular formula is 2.5, n is 1.5, a in a structural formula of R is 3, b is 1, R is1Is methyl.
(2) Synthesis of component B
103.69g of octamethylcyclotetrasiloxane, 44.03g of high hydrogen-containing silicone oil and 32.28g of hexamethyldisiloxane are reacted for 6 hours at 30 ℃ under the action of concentrated sulfuric acid to obtain second hydrogen-containing silicone oil.
Adding 29g of second hydrogen-containing silicone oil and 90.39g of allyl polyether into a reactor, heating to 130 ℃ under normal pressure and reacting for 6h under the conditions of 6ppm of chloroplatinic acid catalyst and 100ppm of diethanolamine cocatalyst to obtain a component B3, wherein m in the molecular formula is 6.5, n is 3.2, a in the structural formula of R is 1, B is 8, and R2 is methyl.
(3) Preparation of organosilicon surfactant for high resilience foam
Mixing the component A, the component B, the component C, the component D and the component E according to different proportions in the table 3, and stirring for 1h at the temperature of 50 ℃ to obtain different organosilicon surfactant samples for high resilience foam.
Wherein m in the structural formula of the component C is 8. The component D is polyether polyol with the molecular weight of 500 and taking propylene glycol as an initiator, and the component E is polyether polyol with the molecular weight of 3000 and taking 1, 4-butanediol as an initiator.
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
As can be seen from Table 3, in the above compounding ratio ranges, the larger the content of the component C, the coarser the cells of the resulting foam from its corresponding surfactant, without changing the contents of the components A, D and E.
Example 4
(1) Synthesis of component A
82.22g of octamethylcyclotetrasiloxane, 40.19g of high hydrogen-containing silicone oil and 57.59g of hexamethyldisiloxane are reacted for 6 hours at 30 ℃ under the action of concentrated sulfuric acid to obtain first hydrogen-containing silicone oil.
Adding 52g of first hydrogen-containing silicone oil and 66.97g of allyl polyether into a reactor, heating to 120 ℃ under normal pressure and reacting for 7h under the conditions of 6ppm of chloroplatinic acid catalyst and 100ppm of diethanolamine cocatalyst to obtain a component A4, wherein m in a molecular formula is 3, n is 1.7, a in a structural formula of R is 3, b is 1, R is1Is methyl.
(2) Synthesis of component B
105.99g of octamethylcyclotetrasiloxane, 44.44g of high hydrogen silicone oil and 29.57g of hexamethyldisiloxane are reacted for 6 hours at 30 ℃ under the action of concentrated sulfuric acid to obtain second hydrogen silicone oil.
29g of a second hydrogen-containing silicone oil, 91.24g of allyl polyether, were charged to a reactor at 6ppm of chloroplatinic acid catalyst and 100ppm of diethanolamine cocatalystHeating to 130 deg.C under normal pressure, reacting for 6h to obtain component B, wherein m in molecular formula is 7.2, n is 3.5, a in structural formula of R is 1, B is 8, and R is2Is methyl.
(3) Preparation of organosilicon surfactant for high resilience foam
Mixing the component A, the component B, the component C, the component D and the component E according to different proportions in the table 4, and stirring for 1h at the temperature of 50 ℃ to obtain different organosilicon surfactant samples for high resilience foam.
Wherein m in the structural formula of the component C is 8. The component D is polyether polyol with the molecular weight of 500 and taking propylene glycol as an initiator, and the component E is polyether polyol with the molecular weight of 3000 and taking 1, 4-butanediol as an initiator.
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
As can be seen from Table 4, in the above compounding ratio ranges, the larger the content of the component C, the coarser the cells of the resulting foam from its corresponding surfactant, without changing the contents of the components B, D and E.
In addition, the above C component was changed as follows:
changing one: the value of m in the structural formula of the component C is 9.
Changing two: the value of m in the structural formula of the component C is 10.
Changing three steps: the C component comprises a C component 1 and a C component 2, wherein m in the structural formula of the C component 1 is 8; the value of m in the structural formula of the C component 2 is 9.
Changing four: the C component comprises a C component 1 and a C component 2, wherein m in the structural formula of the C component 1 is 8; the value of m in the structural formula of the C component 2 is 10.
And V, changing: the C component comprises a C component 1 and a C component 2, wherein m in the structural formula of the C component 1 is 9; the value of m in the structural formula of the C component 2 is 10.
Changing six: the C component comprises a C component 1, a C component 2 and a C component 3, wherein in the structural formula of the C component 1, the value of m is 8; the value of m in the structural formula of the C component 2 is 9, and the value of m in the structural formula of the C component 3 is 10.
Similarly, silicone surfactants were prepared according to the formulation shown in Table 4, and the different silicone surfactants were used under the same high resilience foam preparation conditions to compare the cell sizes of the resulting foams, and the results still show: in the case of constant contents of the B, D and E components, the greater the content of the C component, the coarser the cells of the foam produced from its corresponding surfactant.
Therefore, the application evaluation results show that the introduction of the dimethyl silicone oil with different structures and different contents can realize the effective regulation and control of the openness and the stability of the polyurethane high-resilience foam, and the dimethyl silicone oil has similar rules in siloxane polyether systems with different structures, thereby providing a research basis for effectively regulating and controlling the dimensional stability of the high-resilience polyurethane foam.
Test examples
Taking example 1 as an example, comparative examples 1-8 are set up;
comparative examples 1 to 3 differ from example 1 in that: the raw materials do not contain a component C, a component A and a component B in sequence.
Comparative example 4 differs from example 1 in that: in the structural formula of the component A, m is 30, and n is 18; r has the structure that a is 10, b is 10, R1Is an alkyl group having 1 carbon atom.
Comparative example 5 differs from example 1 in that: the value of m in the C component is 3.
Comparative example 6 differs from example 1 in that: the value of m in the C component is 12.
Comparative example 7 differs from example 1 in that: the raw material comprises 15 percent of component A, 10 percent of component B, 20 percent of component C, 20 percent of component D and 35 percent of component E in percentage by weight.
Comparative example 8 differs from example 1 in that: the raw material consists of 15 percent of component A, 10 percent of component B, 0.5 percent of component C, 39.5 percent of component D and 35 percent of component E in percentage by weight.
The silicone surfactants of comparative examples 1 to 8 were prepared separately under the same preparation conditions in the proportions shown in Table 1, and the cell thicknesses of foams obtained using the different silicone surfactants described above were compared.
The following are found: when one of A, B, C is absent in the components, or the structures of A and C and the dosage of C are regulated and controlled outside the application range, 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 suitable for industrial production. The open-cell silicone surfactant is used for preparing high-resilience foam, and can effectively regulate and control the dimensional stability of the high-resilience polyurethane foam.
Claims (10)
1. An open-cell silicone surfactant is characterized in that raw materials of the open-cell silicone surfactant comprise, by weight, 5-20% of a component A, 5-20% of a component B, 1-10% of a component C, 30-59% of a component D and 30-50% of a component E;
the component A has the following structural formula:
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 has the structure of-CH2CH2CH2O(CH2CH2O)a(CH2CH(CH3)O)bR1Wherein a has a value of 1-9, b has a value of 0-9, and a + b has a value of 1-15, R1Is alkyl containing 1-4 carbon atoms;
the component B has the following structural formula:
wherein m has a value of 1-25, n has a value of 1-15, and m + n has a value of 2-35; r has the structure of-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 1-30, R2Is alkyl containing 1-4 carbon atoms;
and the component A and the component B have different structural formulas;
the C component has the following structural formula:
wherein m has a value of 5 to 10;
the D component and the E component are both copolymers with terminal hydroxyl derived from polyhydroxy compounds, and the D component and the E component have different structural formulas;
preferably, the polyol comprises a low molecular weight polyol; more optionally, the low molecular weight polyol comprises at least one of ethylene glycol, propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, and dipropylene glycol;
preferably, the D component is a low molecular weight polyether polyol; more alternatively, the molecular weight of the D component is from 100 to 500;
preferably, the E component is a high molecular weight polyether polyol; more alternatively, the E component has a molecular weight of 2000 to 4000.
2. The open-cell silicone surfactant of claim 1 wherein m in the structural formula of component a in the open-cell silicone surfactant is 3.2, n is 1.9, a in the structural formula of R is 2, b is 1.5; or m is 4.2, n is 2.5, a in the structural formula of R is 2, and b is 1.5; or m is 2.5, n is 1.5, a in the structural formula of R is 3, and b is 1; or m is 3, n is 1.7, a in the structural formula of R is 3, and b is 1.
3. The open-cell silicone surfactant of claim 1 wherein m in the structural formula of component B in the open-cell silicone surfactant is 8.3, n is 3.1, a in the structural formula of R is 3, B is 6; or m is 10.1, n is 4.6, a in the structural formula of R is 3, and b is 6; or m is 6.5, n is 3.2, a in the structural formula of R is 1, and b is 8; or m is 7.2, n is 3.5, a in the structural formula of R is 1, and b is 8.
4. The open-cell silicone surfactant of claim 1 wherein said C component of said open-cell silicone surfactant comprises Si (CH)3)3-O-[Si(CH3)2-O]5-Si(CH3)3、Si(CH3)3-O-[Si(CH3)7-O]5-Si(CH3)3、Si(CH3)3-O-[Si(CH3)8-O]5-Si(CH3)3、Si(CH3)3-O-[Si(CH3)7-O]9-Si(CH3)3And Si (CH)3)3-O-[Si(CH3)7-O]10-Si(CH3)3At least one of (1).
5. An open-cell silicone surfactant according to claim 1, wherein said D-component of said open-cell silicone surfactant is a polyether polyol with propylene glycol as an initiator, preferably said D-component has a molecular weight of 300 or 500;
the E component is polyether polyol taking 1, 4-butanediol as an initiator, and preferably the molecular weight of the E component is 2000 or 3000.
6. A method for preparing an open-cell silicone surfactant according to any of claims 1-5, comprising the steps of: mixing said A part, said B part, said C part, said D part, and said E part;
preferably, the component A, the component B, the component C, the component D and the component E are stirred and mixed for 0.8 to 1.2 hours at the temperature of between 45 and 55 ℃;
preferably, the A component, the B component, the C component, the D component and the E component are stirred and mixed for 1h at the temperature of 50 ℃;
preferably, the stirring speed is 200-500 r/min.
7. The preparation method of claim 6, wherein the component A and the component B are obtained by reacting hydrogen-containing silicone oil, allyl polyether, a catalyst and a cocatalyst according to different proportions, or by reacting allyl polyether, a catalyst and a cocatalyst with different hydrogen-containing silicone oil;
preferably, the reaction is carried out at 80-160 ℃ for 2-8 h.
8. The production method according to claim 7, wherein the catalyst comprises a platinum catalyst;
preferably, the catalyst comprises a chloroplatinic acid catalyst;
preferably, the amount of the catalyst is 3-30ppm of the total amount of the hydrogen-containing silicone oil, the allyl polyether, the catalyst and the cocatalyst;
preferably, the cocatalyst comprises at least one of diethanolamine, triethanolamine, acetamide, triethylamine and N-butylethanolamine;
preferably, the amount of the cocatalyst is 3-300ppm of the total amount of the hydrogen-containing silicone oil, the allyl polyether, the catalyst and the cocatalyst.
9. Use of an open-cell silicone surfactant according to any of claims 1 to 5 for the preparation of a high resilience foam.
10. A high resilience foam, wherein the surfactant used in the production of said high resilience foam comprises the open-celled silicone surfactant of any one of claims 1 to 5.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111518306A (en) * | 2020-05-11 | 2020-08-11 | 江西麦豪化工科技有限公司 | Cell opening agent, thermoplastic polyurethane foam and preparation method thereof |
| CN112724452A (en) * | 2020-12-29 | 2021-04-30 | 南京美思德新材料有限公司 | Surfactant, preparation method and application thereof |
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| CN115505095A (en) * | 2022-10-21 | 2022-12-23 | 江苏美思德化学股份有限公司 | Open-cell single-component polyurethane foam joint mixture and preparation method thereof |
| CN115505095B (en) * | 2022-10-21 | 2023-09-29 | 江苏美思德化学股份有限公司 | Open-cell type single-component polyurethane foam joint mixture and preparation method thereof |
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