Graphene / silicon dioxide modified polyurethane foam as well as preparation method and application thereof
By adding graphene/silica and amide monomers to polyurethane, and using aluminum sol method and surface modification technology, the problems of low strength, unresistance to high temperature and easy hydrolysis of ester groups of high-end foamed materials are solved, and the improvement of high mechanical strength, high temperature and anti-static properties are achieved.
Patent Information
- Application Number
- CN202411595365.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-11-08
- Publication Date
- 2025-03-04
AI Technical Summary
High-end polyurethane foaming materials have problems such as low strength, high temperature resistance, and easy hydrolysis of ester groups, and it is difficult to have comprehensive properties such as high temperature resistance, hydrolysis resistance and high elasticity.
By adding graphene/silica additives and amide monomers, the Al2O3 film on the surface of silica is coated by the aluminum sol method, and the dispersion and compatibility of graphene/silica in polyurethane are improved by surface modification of γ-glycidyl ether oxypropyl trimethoxysilane and cyclodextrin.
It significantly improves the mechanical strength, high temperature resistance and anti-static properties of polyurethane foam, can effectively derivate heat under high-temperature pressing, and improves the high-temperature peeling strength of polyurethane.
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Abstract
Description
Technical Field
[0001] The present application relates to a graphene / silicon dioxide modified polyurethane foam and a preparation method and application thereof, belonging to the field of new material technology. Background Art
[0002] Polyurethane (PU) is a widely used polymer (in light industry textiles, shoe soles, insoles, automobiles, building insulation materials, coatings and other fields, and has a broad application market.) Compared with other polymers, polyurethane has the advantages of a wide variety of raw materials, a wide range of adjustable formulas, and a rich variety of products (its products include polyurethane soft foam, polyurethane rigid foam, polyurethane elastomer, polyurethane coatings and waterproof materials, etc.). Polyurethane foam materials have developed rapidly in recent years, but due to the low strength of polyurethane foam materials, high temperature resistance, easy hydrolysis of ester groups in polyurethane, especially poor hydrolysis resistance under high temperature conditions, its application is limited. In particular, the key technology for the industrialization of high-end polyurethane foam materials with comprehensive properties such as high temperature resistance, hydrolysis resistance and high elasticity needs to be overcome. Graphene-modified polyurethane nanocomposites have attracted much attention due to their excellent comprehensive properties. Adding graphene or its derivatives to the polyurethane matrix can significantly improve the physical, mechanical, thermal, electromagnetic and other properties of polyurethane, meeting the special requirements of high performance and multi-function of polymer composites. Summary of the invention
[0003] In order to solve the problems existing in the prior art of high-end polyurethane foaming materials, such as low strength, low high temperature resistance, easy hydrolysis of ester groups, and difficulty in achieving comprehensive properties such as high temperature resistance, hydrolysis resistance and high elasticity, the present application provides a graphene / silicon dioxide modified polyurethane foam and a preparation method thereof. By adding graphene / silicon dioxide additives and amide monomers, the strength, high temperature resistance and antistatic properties of the polyurethane foam are improved.
[0004] This application adopts the following technical solutions:
[0005] According to one aspect of the present application, a method for preparing a graphene / silicon dioxide modified polyurethane foam is provided, comprising the following steps:
[0006] S1, adding an aqueous solution containing sodium carbonate to an aqueous solution containing aluminum nitrate to form an aluminum sol, adding silicon dioxide to the aluminum sol, reacting, and drying to obtain Al 2 O 3 Coated with silica;
[0007] S2, containing graphene oxide, Al 2 O 3A mixture of coated silica, stearic acid, γ-glycidyloxypropyltrimethoxysilane and cyclodextrin is ground in an inactive atmosphere, then allowed to stand in air with a humidity of 40% or more, dried, and laser reduced to obtain a graphene / silicon dioxide composite material;
[0008] S3. In a mixture containing polyether polyol and polymer polyol, amine catalyst A33, tin catalyst T9, water, pore opening agent, graphene / silicon dioxide, amide monomer, and mixed silicone oil are added, and after stirring, phenylmethane diisocyanate is added to obtain a raw material liquid, and the raw material liquid is poured into a mold to react to obtain the graphene / silicon dioxide modified polyurethane foam.
[0009] Optionally, in step S1, the weight ratio of aluminum nitrate to silicon dioxide is 1:5 to 50;
[0010] Optionally, in step S1, the weight ratio of aluminum nitrate to silicon dioxide is 1:8-15.
[0011] Optionally, in step S1, the reaction conditions include: pH value of 3.5-4.1, stirring at 15-45° C. for 4-48 hours.
[0012] Optionally, in step S1, the drying conditions include: drying at 200-300° C. for 1-5 hours.
[0013] The present invention uses an aluminum sol method to coat the surface of silicon dioxide with a dense and uniform nano-thickness Al 2 O 3 membrane.
[0014] Optionally, in step S2, A1 2 O 3 The weight ratio of coated silicon dioxide to graphene oxide, stearic acid, γ-glycidyloxypropyltrimethoxysilane and cyclodextrin is 1: (0.05-1.5): (0.05-1.5): (0.01-0.03): (0.05-1.5).
[0015] Optionally, in step S2, the grinding conditions include: a rotation speed of 300 to 600 r / min and a grinding time of 18 to 36 h.
[0016] Optionally, in step S2, the standing time is 8 to 24 hours.
[0017] Optionally, in step S2, the conditions for laser reduction include: power of 50 mW to 500 mW, and laser reduction time of 3 min to 20 min.
[0018] Optionally, in step S2, the drying conditions include: drying at 60-100° C. for 1-5 hours.
[0019] This application adopts laser reduction of graphene oxide reduction technology, which does not generate waste and is green and environmentally friendly. In order to overcome the problem of poor dispersibility of graphene / silicon dioxide in polyurethane, surface modification is performed by γ-glycidyloxypropyltrimethoxysilane and cyclodextrin to improve the dispersibility and compatibility of graphene / silicon dioxide in polyurethane.
[0020] Optionally, in step S3, the weight ratio of graphene / silicon dioxide to amide monomer is 5 to 20:1.
[0021] Optionally, in step S3, the weight ratio of phenylmethane diisocyanate to graphene / silicon dioxide is 20 to 200:1.
[0022] Optionally, in step S3, the weight ratio of phenylmethane diisocyanate to graphene / silicon dioxide is 45 to 90:1.
[0023] Optionally, in step S3, the amide monomer is selected from at least one of urea, N,N-dimethylformamide, N,N-dimethyloctanamide, succinimide, imide, nicotinamide, acrylamide, acetamide, butyramide, benzamide, p-nitrobenzamide, and N-methoxy-N-methylformamide.
[0024] Optionally, in step S3, the amide monomer is preferably N-methoxy-N-methylformamide.
[0025] In the present application, amide monomers are copolymerized with phenylmethane diisocyanate (MDI) to improve the mechanical properties of polyurethane foam. Amide monomers (containing O=CN bonds) are highly compatible with polyurethane (containing -NHCOO- bonds).
[0026] Optionally, in step S3, the conditions for the raw material liquid to be poured into the mold for reaction include: the mold temperature is 24.5° C. to 25.5° C., and the reaction time is 24 h to 72 h.
[0027] Optionally, in step S3, the stirring conditions include: stirring at a rotation speed of 1500 r / min for 2 to 3 min, and then stirring at a rotation speed of 2500 to 3000 r / min until uniform.
[0028] Optionally, in step S3, the raw material solution contains the following components in parts by weight:
[0029]
[0030] Optionally, in step S3, the polyether polyol is GLR2000.
[0031] Optionally, in step S3, the polymer polyol is POP.
[0032] Optionally, in step S3, the amine catalyst is triethylenediamine A33.
[0033] Optionally, in step S3, the tin catalyst is tin isooctanoate T9.
[0034] Optionally, in step S3, the pore opening agent is pore opening agent 1900h.
[0035] Optionally, in step S3, diphenylmethane diisocyanate is MDI8002.
[0036] According to another aspect of the present application, a graphene / silicon dioxide modified polyurethane foam prepared by the above preparation method is provided.
[0037] According to another aspect of the present application, there is also provided an application of the above-mentioned graphene / silicon dioxide modified polyurethane foam in shoe material processing.
[0038] The beneficial effects of this application include:
[0039] The graphene / silicon dioxide modified polyurethane foam and the preparation method thereof provided in the present application overcome the problem that the existing technology of high-end polyurethane foaming materials is difficult to have comprehensive properties such as high temperature resistance, hydrolysis resistance and high elasticity by adding graphene / silicon dioxide additives and amide monomers. Among them, the graphene / silicon dioxide additives can improve the mechanical strength, high temperature resistance and antistatic properties of the polyurethane foam; including effectively extracting the heat at the polyurethane pressing part under high temperature pressing, thereby improving the high temperature peeling strength of the polyurethane; the amide monomer is copolymerized with phenylmethane diisocyanate (MDI) to improve the mechanical properties of the polyurethane foam; the aluminum sol is coated with a dense and uniform Al on the surface of the silica. 2 O 3 membrane. DETAILED DESCRIPTION
[0040] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.
[0041] Unless otherwise specified, the raw materials in the examples of this application were purchased through Shanghai Aladdin Biochemical Technology Co., Ltd. or Sinopharm commercial channels.
[0042] Unless otherwise specified, conventional methods were used for testing and instrument settings were those recommended by the manufacturer.
[0043] Example 1 Preparation of graphene / silicon dioxide modified polyurethane foam
[0044] (1) Preparation of Al 2 O 3 Coated silica
[0045] 1g aluminum nitrate and 10g deionized water were prepared into liquid A, and 1g sodium carbonate and 10g deionized water were prepared into liquid B. Liquid B was slowly added to liquid A to prepare aluminum sol C, and then 10g silica was added, the pH value was adjusted to 4.0, stirred at 40℃ for 24h, and dried at 250℃ for 2h to prepare Al 2 O 3 Coated silica
[0046] (2) Preparation of graphene / silicon dioxide
[0047] 0.1 g of graphene oxide and 1 g of Al prepared in step (1) were added. 2 O 3 Coated silica, 0.1 g of stearic acid, 0.02 g of γ-glycidyloxypropyltrimethoxysilane, and 0.1 g of cyclodextrin were ball-milled in a high-speed ball mill at 400 r / min under nitrogen protection for 24 h, placed in air with a humidity of more than 40% for 12 h, and then dried at 80°C for 2 h, and laser reduced (power of 100 mW, reduction time of 30 min) to prepare graphene / silica.
[0048] (3) Preparation of graphene / silicon dioxide modified polyurethane foam
[0049] According to the formula in Table 1, first add polyether polyol and polymer polyol, then add amine catalyst A33, tin catalyst T9, water, pore opening agent, graphene / silica microspheres prepared in step (2), N-methoxy-N-methylformamide, and mixed silicone oil, and stir for 2 to 3 minutes in a stirrer at a speed of 1500 r / min; increase the speed to 2500 to 3000 r / min, add phenylmethane diisocyanate (MDI), pour into a mold, react at 25° C. for 48 hours, and then prepare a modified polyurethane foam.
[0050] Table 1 Graphene / silicon dioxide modified polyurethane foam raw material component formula
[0051] raw materials Added amount (parts by weight) Polyether polyols 50 Polymer polyols 38 Amine catalyst A33 0.02 Tin catalyst T9 0.03 water 2 Cell opener 3.55 Methylene diphenyl diisocyanate (MDI) 80 Mixed silicone oil 1.4 Graphene / silica microspheres 1 N-Methoxy-N-methylformamide 0.1 total 176
[0052] Example 2
[0053] The preparation of graphene / silicon dioxide modified polyurethane foam is the same as that in Example 1, except that N-methoxy-N-methylformamide is replaced by N,N-dimethylformamide.
[0054] Example 3
[0055] The preparation of graphene / silicon dioxide modified polyurethane foam is the same as that in Example 1, except that N-methoxy-N-methylformamide is replaced by p-nitrobenzamide.
[0056] Example 4
[0057] The preparation of graphene / silicon dioxide modified polyurethane foam is the same as that in Example 1, except that N-methoxy-N-methylformamide is replaced by urea.
[0058] Embodiments 5 to 10
[0059] The preparation of graphene / silica modified polyurethane foam is the same as that in Example 1, except that the amount of N-methoxy-N-methylformamide added is replaced by 0.1 parts by weight to 0.05 parts by weight, 0.08 parts by weight, 0.12 parts by weight, 0.15 parts by weight, 0.18 parts by weight, and 0.2 parts by weight, respectively.
[0060] Examples 11 to 21
[0061] The preparation of graphene / silicon dioxide modified polyurethane foam is the same as that in Example 1, except that the amount of graphene / silicon dioxide added is replaced by 1 part by weight to 0.5 parts by weight, 0.8 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2.0 parts by weight, 2.5 parts by weight, 3.0 parts by weight, 3.5 parts by weight, 4.0 parts by weight, and 4.5 parts by weight, respectively.
[0062] Comparative Example 1
[0063] According to the formula in Table 2, polyether polyol and polymer polyol were first added, and then amine catalyst A33, tin catalyst T9, water, pore opening agent and mixed silicone oil were added, and stirred for 2 to 3 minutes at a stirrer with a speed of 1500 r / min; the speed was increased to 2500 to 3000 r / min, phenylmethane diisocyanate (MDI) was added, and the mixture was poured into a mold and reacted for a period of time to prepare a polyurethane foam.
[0064] Table 2 Comparative Example 1 Polyurethane foam raw material formula
[0065]
[0066]
[0067] Comparative Example 2
[0068] The preparation of polyurethane foam is the same as that in Example 1, except that the addition amount of graphene / silicon dioxide is replaced from 1 part by weight to 0.1 part by weight respectively.
[0069] Comparative Example 3
[0070] The preparation of polyurethane foam is the same as that of Example 4, except that the amount of urea added is replaced from 1 part by weight to 0.001 part by weight.
[0071] Test Example 1
[0072] The polyurethane foams prepared in Examples 1 to 21 and Comparative Examples 1 to 3 were cut into different sizes, and the tensile strength and compression deformation rate of the sponge products were tested according to the requirements of national standards GBT6344-2008 "Determination of tensile strength and elongation at break of flexible foam polymeric materials", GBT 10807-2006 "Determination of hardness of flexible foam polymeric materials (indentation method)" and GB / T9640-2008 "GB / T 9640-2008 Accelerated aging test method for flexible and rigid foam polymeric materials". After the polyurethane foam material was pressed at a high temperature of 150°C, the high temperature peel strength was tested using a tensile machine. The test results of some embodiments and comparative examples are shown in Table 3.
[0073] Table 3 Properties of polyurethane
[0074]
[0075]
[0076] As can be seen from Table 3, the tensile strength, compression deformation rate, and peel strength after high-temperature pressing at 150°C of the modified polyurethane foam prepared by the methods of Examples 1-16 are significantly better than those of Comparative Examples 1-3, especially when the weight portion of N-methoxy-N-methylformamide in Examples 1, 5, and 6 is 0.05-0.1 parts, that is, the mass ratio of graphene / silicon dioxide: N-methoxy-N-methylformamide is 20:1-10:1, and the addition ratio of functionalized graphene in Examples 1, 11-14 is 0.5-1.5 parts, that is, the weight ratio of phenylmethane diisocyanate to graphene / silicon dioxide is 160:1-54:1, the tensile strength, compression deformation rate, and peel strength after high-temperature pressing at 150°C of the graphene-modified polyurethane foam are the best. The performance of the modified polyurethane foam prepared by Examples 16-21 is similar to that of Example 15.
[0077] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A method for preparing graphene / silicon dioxide modified polyurethane foam, characterized in that: The steps include: S1, adding an aqueous solution containing sodium carbonate dropwise to an aqueous solution containing aluminum nitrate to form an aluminum sol, adding silicon dioxide to the aluminum sol, reacting, and drying to obtain Al2O3-coated silicon dioxide; S2, grinding a mixture containing graphene oxide, Al2O3-coated silica, stearic acid, γ-glycidyloxypropyltrimethoxysilane, and cyclodextrin in an inactive atmosphere, and then standing in air with a humidity greater than or equal to 40%, drying, and laser reducing to obtain a graphene / silicon dioxide composite material; S3. In a mixture containing polyether polyol and polymer polyol, amine catalyst A33, tin catalyst T9, water, pore opening agent, graphene / silicon dioxide, amide monomer, and mixed silicone oil are added, and after stirring, phenylmethane diisocyanate is added to obtain a raw material liquid, and the raw material liquid is poured into a mold to react to obtain the graphene / silicon dioxide modified polyurethane foam.
2. The preparation method according to claim 1, characterized in that: In step S1, the weight ratio of aluminum nitrate to silicon dioxide is 1:5 to 1:50; Preferably, in step S1, the reaction conditions include: pH value of 3.5 to 4.1, stirring at 15 to 45° C. for 4 to 48 hours.
3. The preparation method according to claim 1, characterized in that: In step S2, the weight ratio of Al2O3-coated silicon dioxide to graphene oxide, stearic acid, γ-glycidyloxypropyltrimethoxysilane, and cyclodextrin is 1: (0.05-1.5): (0.05-1.5): (0.01-0.03): (0.05-1.5); Preferably, in step S2, the grinding conditions include: a rotation speed of 300 to 600 r / min, and a grinding time of 18 to 36 h; Preferably, in step S2, the standing time is 8 to 24 hours; Preferably, in step S2, the conditions for laser reduction include: power of 50 mW to 500 mW, and laser reduction time of 3 min to 20 min.
4. The preparation method according to claim 1, characterized in that: In step S3, the weight ratio of graphene / silicon dioxide to amide monomer is 5 to 20:
1.
5. The preparation method according to claim 1, characterized in that: In step S3, the weight ratio of phenylmethane diisocyanate to graphene / silicon dioxide is 20 to 200:
1.
6. The preparation method according to claim 1, characterized in that: In step S3, the amide monomer is selected from at least one of urea, N,N-dimethylformamide, N,N-dimethyloctanamide, succinimide, imide, nicotinamide, acrylamide, acetamide, butyramide, benzamide, p-nitrobenzamide, and N-methoxy-N-methylformamide.
7. The preparation method according to claim 1, characterized in that: In step S3, the stirring conditions include: stirring at a rotation speed of 1500 r / min for 2 to 3 minutes, and then stirring at a rotation speed of 2500 to 3000 r / min until uniform.
8. The preparation method according to claim 1, characterized in that: In step S3, the raw material liquid contains the following components in parts by weight:
9. The graphene / silicon dioxide modified polyurethane foam prepared by the preparation method according to any one of claims 1 to 8.
10. Application of the graphene / silicon dioxide modified polyurethane foam according to claim 9 in shoe material processing.