Slow-resilience memory sponge and preparation method thereof

Abstract

The invention discloses a slow-rebound memory sponge and a preparation method thereof, and belongs to the technical field of sponge material preparation, and the slow-rebound memory sponge comprises the following components by weight: 100 parts of diisocyanate, 100-150 parts of polyether polyol, 40-80 parts of slow-rebound polyether, 1-8 parts of organic silicon resin, 4-24 parts of modified resin, 3-20 parts of polycaprolactone resin, 1-3 parts of silicone oil, and 2-5 parts of an opening agent. The modified resin is a polymerization product obtained by taking 2-acrylic acid-2-[[(butylamino)-carbonyl] oxo] ethyl ester and butyl acrylate as blending monomers, and the modified resin is a polymerization product obtained by taking 2-acrylic acid-2-[[(butylamino)-carbonyl] oxo] ethyl ester and butyl acrylate as the blending monomers; through a blending strategy, the organic silicon resin, the modified resin and the polycaprolactone resin are added into the foamed polyurethane, so that the slow rebound resilience of the memory foam material is improved while the air permeability is kept.

Description

Technical Field

[0001] The present invention relates to the technical field of sponge material preparation, and in particular to a slow-rebound memory sponge and a preparation method thereof. Background Art

[0002] Slow rebound refers to a material's ability to slowly deform. After being deformed by an external force, it slowly returns to its original shape. This means the material possesses both viscous and elastic properties, absorbing impact energy and allowing repeated use without permanent deformation. Because polyurethane slow rebound memory foam is a prime example of a material with this characteristic, the term "slow rebound" often refers specifically to memory foam.

[0003] Slow-rebound memory foam is a polyurethane polymer with an open-cell structure. When subjected to external pressure, the (Open-Cell) molecules of this material will "flow" and shift and deform, fitting the contour of the contact surface of the pressure-applying object. Limited by the intermolecular van der Waals force, the rebound force is weak, thereby evenly distributing the pressure to the entire contact surface. When the pressure is removed, it will slowly return to its original shape. Its excellent performance in multiple application fields is also due to the material's special viscoelastic properties. When subjected to pressure shock, it undergoes both elastic deformation (energy storage deformation) that satisfies Hooke's law and irreversible plastic deformation (energy dissipation deformation). The deformation of memory foam is an organic combination of these two deformations. The plastic deformation will consume most of the impact energy, while the energy stored in the elastic deformation part can allow the memory foam material to slowly return to its pre-compression shape after the external force is removed. This characteristic makes the memory foam material exhibit a strong impact energy absorption ability.

[0004] Currently, the slow-rebound memory foam based on polyurethane materials mainly has the problems of too short rebound time or poor breathability. Generally speaking, the material density has a great influence on the performance of memory foam. High density can obtain good slow-rebound performance, but high density is also prone to cause poor air circulation and poor breathability. Too low density will have the problem of too short rebound time and poor mechanical properties. Summary of the Invention

[0005] In view of the above problems, the present invention provides a slow-rebound memory foam and a preparation method thereof.

[0006] The purpose of the present invention is achieved by adopting the following technical solutions:

[0007] A slow rebound memory foam, comprising the following components in parts by weight:

[0008] 100 parts of diisocyanate, 100-150 parts of polyether polyol, 40-80 parts of slow rebound polyether, 1-8 parts of silicone resin, 4-24 parts of modified resin, 3-20 parts of polycaprolactone resin, 1-3 parts of silicone oil, 2-5 parts of pore opener, 0.5-3 parts of catalyst, and 1-5 parts of deionized water;

[0009] The preparation method of the modified resin comprises the following steps:

[0010] 2-[[(butylamino)-carbonyl]oxy]ethyl 2-propenoate and butyl acrylate are weighed separately and dissolved in dimethylformamide solvent, an initiator is added, nitrogen is passed through to deoxygenate, and the mixture is stirred and kept warm at 60-80°C for 16-24 hours. After the reaction is completed, deionized water is added to dilute the reaction system, the precipitate is separated and dissolved in ethyl acetate, and then added to hexane solvent for precipitation, the precipitate is separated, and vacuum dried to obtain the product.

[0011] In some preferred embodiments, the initiator is one or more of azobisisobutyl cyanide, azobisisoheptanenitrile, dimethyl azobisisobutyrate, and dibenzoyl peroxide.

[0012] In some preferred embodiments, the mass ratio of the 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate to the butyl acrylate and the initiator is 10:(2.4-3.5):(0.01-0.04).

[0013] In some preferred embodiments, the diisocyanate is any one or more of diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, biphenyl diisocyanate, and benzyl diisocyanate.

[0014] In some preferred embodiments, the polyether polyol is any one of models DL-1000D, DL-2000D, DL-3000D, DL-4000D, or a combination of two thereof.

[0015] In some preferred embodiments, the slow rebound polyether is a first slow rebound polyether or a second slow rebound polyether; wherein, the first slow rebound polyether is obtained by polymerizing propylene oxide with glycerol as an initiator, and has a molecular weight of 550; the second slow rebound polyether is obtained by polymerizing propylene oxide with glycerol as an initiator, and has a molecular weight of 700.

[0016] In some preferred embodiments, the silicone resin is Dow Corning DOW790, Dow Corning DOW995 or 3M540.

[0017] In some preferred embodiments, the number average molecular weight of the polycaprolactone resin is 70,000-90,000.

[0018] In some preferred embodiments, the silicone oil is polyether-modified silicone oil, including one or more of models H-204, MSD-9103, MSD-9102, and OFX-0190.

[0019] In some preferred embodiments, the cell opener is any one of polyurethane cell opener GS-28, polyurethane cell opener M-9955, and polyurethane cell opener Y-1900.

[0020] In some preferred embodiments, the catalyst includes tin catalyst T9, amine catalyst A33 and amine catalyst A1; wherein the mass ratio of the tin catalyst T9 to the amine catalyst A33 and the amine catalyst A1 is (1-2): (8-10): 1.

[0021] The second aspect of the present invention is to provide a method for preparing the slow rebound memory foam, comprising the following steps:

[0022] Polyether polyol, slow-rebound polyether, silicone resin, modified resin, polycaprolactone resin, silicone oil, pore-opening agent, catalyst and deionized water are weighed in proportion and added to a stirrer, and stirred at 30-50°C until uniformly mixed, with a stirring speed of preferably 600 r / min; diisocyanate is added to the mixed system, stirred at high speed at 30-50°C, and then transferred to a preheated mold at a temperature of 50-70°C, kept warm for 5-10 minutes, and demolded to obtain the slow-rebound memory foam.

[0023] In some preferred embodiments, the high-speed stirring has a stirring speed of 1200 r / min and a stirring time of 10-20 s.

[0024] The beneficial effects of the present invention are:

[0025] In response to the problem that existing polyurethane memory foams are difficult to balance slow rebound performance and breathability, the present invention adopts a blending strategy. On the basis of the memory foam material prepared by slow rebound polyether in the existing technology, silicone resin, modified resin and polycaprolactone resin are added to the foamed polyurethane, so as to improve the slow rebound performance of the memory foam material while maintaining breathability. Specifically, the silicone resin is a single-component silicone resin, which can improve the elasticity of the material; the modified resin is a polymerization product with 2-acrylate-2-[[(butylamino)-carbonyl]oxy]ethyl ester and butyl acrylate as blending monomers. By introducing a semi-interpenetrating polymer network into the polyurethane polymerization system, the chain segment movement ability of the polymerization system is improved, and the flexibility is improved. At the same time, its carbamate side chain can establish a hydrogen bond system with the polyurethane polymerization chain, improve the interaction between the gaps under external force, and thus improve the rebound time; the semi-crystalline thermoplastic polycaprolactone resin is evenly dispersed in the system as tiny crystals, which inhibits the expansion of microcracks during stretching, improves the toughness of the material, and forms a physical cross-linked network to improve the memory performance. DETAILED DESCRIPTION

[0026] The present invention is further described with reference to the following examples.

[0027] Example 1

[0028] A slow rebound memory foam, comprising the following components in parts by weight:

[0029] 100 parts of diisocyanate, 120 parts of polyether polyol, 55 parts of slow rebound polyether, 5 parts of silicone resin, 16 parts of modified resin, 11 parts of polycaprolactone resin, 2 parts of silicone oil, 3.5 parts of pore opener, 2 parts of catalyst, and 3.5 parts of deionized water;

[0030] The diisocyanate is a mixture of isophorone diisocyanate and dicyclohexylmethane-4,4'-diisocyanate in equal molar ratios;

[0031] The polyether polyol is a mixture of models DL-1000D and DL-3000D, with a mass ratio of 1:2;

[0032] The slow-rebound polyether is a first slow-rebound polyether, which is obtained by polymerizing propylene oxide with glycerol as an initiator and has a molecular weight of 550;

[0033] The silicone resin is Dow Corning DOW790;

[0034] The modified resin is prepared by the following preparation method:

[0035] 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate (CAS No.: 63225-53-6) and butyl acrylate were respectively weighed and dissolved in dimethylformamide solvent, an initiator was added, nitrogen was passed through to deoxygenate, and the mixture was stirred at 70°C for 20 hours. After the reaction was completed, deionized water was added to dilute the reaction system, the precipitate was separated and dissolved in ethyl acetate, and then added to hexane solvent for precipitation. The precipitate was separated and vacuum dried to obtain the product; the initiator was azobisisobutylcyanide; the mass ratio of 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate to butyl acrylate and the initiator was 10:2.9:0.015;

[0036] The number average molecular weight of the polycaprolactone resin is 80,000;

[0037] The silicone oil is polyether modified silicone oil, model H-204;

[0038] The cell opener is polyurethane cell opener GS-28;

[0039] The catalyst is a mixture of the tin catalyst T9, the amine catalyst A33, and the amine catalyst A1, with a mass ratio of 1:9:1;

[0040] The preparation method of the slow rebound memory foam comprises the following steps:

[0041] Polyether polyol, slow-rebound polyether, silicone resin, modified resin, polycaprolactone resin, silicone oil, pore opener, catalyst and deionized water are weighed in proportion and added to a stirrer. The mixture is stirred at a speed of 600 r / min at 45°C until uniformly mixed. Diisocyanate is added to the mixed system, stirred at a high speed at 50°C, and then transferred to a preheated mold at a preheating temperature of 65°C. The mixture is kept warm for 5 minutes and demolded to obtain the slow-rebound memory foam. The stirring speed of the high-speed stirring is 1200 r / min and the stirring time is 14 seconds.

[0042] Example 2

[0043] A slow rebound memory foam, comprising the following components in parts by weight:

[0044] 100 parts of diisocyanate, 120 parts of polyether polyol, 55 parts of slow rebound polyether, 5 parts of silicone resin, 16 parts of modified resin, 11 parts of polycaprolactone resin, 2 parts of silicone oil, 3.5 parts of pore opener, 2 parts of catalyst, and 3.5 parts of deionized water;

[0045] The diisocyanate is a mixture of diphenylmethane diisocyanate and dicyclohexylmethane-4,4'-diisocyanate in equal molar ratios;

[0046] The polyether polyol is a mixture of models DL-2000D and DL-4000D, with a mass ratio of 1:2;

[0047] The slow-rebound polyether is a second slow-rebound polyether, which is obtained by polymerizing propylene oxide with glycerol as an initiator and has a molecular weight of 700;

[0048] The silicone resin is 3M540 (3M Company);

[0049] The modified resin is prepared by the following preparation method:

[0050] 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate and butyl acrylate were weighed separately and dissolved in dimethylformamide solvent, an initiator was added, nitrogen was passed through to deoxygenate, and the mixture was stirred at 70°C for 20 hours. After the reaction was completed, deionized water was added to dilute the reaction system, the precipitate was separated and dissolved in ethyl acetate, and then added to hexane solvent for precipitation. The precipitate was separated and dried in vacuo to obtain the product; the initiator was azobisisobutylcyanide; the mass ratio of 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate to butyl acrylate and the initiator was 10:2.4:0.04;

[0051] The number average molecular weight of the polycaprolactone resin is 80,000;

[0052] The silicone oil is polyether modified silicone oil, model number is MSD-9103;

[0053] The cell opener is polyurethane cell opener M-9955;

[0054] The catalyst is a mixture of the tin catalyst T9, the amine catalyst A33, and the amine catalyst A1, with a mass ratio of 1:9:1;

[0055] The preparation method of the slow rebound memory foam is the same as that in Example 1.

[0056] Example 3

[0057] A slow rebound memory foam, comprising the following components in parts by weight:

[0058] 100 parts of diisocyanate, 120 parts of polyether polyol, 55 parts of slow rebound polyether, 16 parts of modified resin, 11 parts of polycaprolactone resin, 2 parts of silicone oil, 3.5 parts of pore opener, 2 parts of catalyst, 3.5 parts of deionized water;

[0059] The diisocyanate is a mixture of isophorone diisocyanate and dicyclohexylmethane-4,4'-diisocyanate in equal molar ratios;

[0060] The polyether polyol is a mixture of models DL-1000D and DL-3000D, with a mass ratio of 1:2;

[0061] The slow-rebound polyether is a first slow-rebound polyether, which is obtained by polymerizing propylene oxide with glycerol as an initiator and has a molecular weight of 550;

[0062] The modified resin is prepared by the following preparation method:

[0063] 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate (CAS No.: 63225-53-6) and butyl acrylate were respectively weighed and dissolved in dimethylformamide solvent, an initiator was added, nitrogen was passed through to deoxygenate, and the mixture was stirred at 70°C for 20 hours. After the reaction was completed, deionized water was added to dilute the reaction system, the precipitate was separated and dissolved in ethyl acetate, and then added to hexane solvent for precipitation. The precipitate was separated and vacuum dried to obtain the product; the initiator was azobisisobutylcyanide; the mass ratio of 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate to butyl acrylate and the initiator was 10:2.9:0.015;

[0064] The number average molecular weight of the polycaprolactone resin is 80,000;

[0065] The silicone oil is polyether modified silicone oil, model H-204;

[0066] The cell opener is polyurethane cell opener GS-28;

[0067] The catalyst is a mixture of the tin catalyst T9, the amine catalyst A33, and the amine catalyst A1, with a mass ratio of 1:9:1;

[0068] The preparation method of the slow rebound memory foam is the same as that in Example 1.

[0069] Example 4

[0070] A slow rebound memory foam, comprising the following components in parts by weight:

[0071] 100 parts of diisocyanate, 120 parts of polyether polyol, 55 parts of slow rebound polyether, 5 parts of silicone resin, 11 parts of polycaprolactone resin, 2 parts of silicone oil, 3.5 parts of pore opener, 2 parts of catalyst, 3.5 parts of deionized water;

[0072] The diisocyanate is a mixture of isophorone diisocyanate and dicyclohexylmethane-4,4'-diisocyanate in equal molar ratios;

[0073] The polyether polyol is a mixture of models DL-1000D and DL-3000D, with a mass ratio of 1:2;

[0074] The slow-rebound polyether is a first slow-rebound polyether, which is obtained by polymerizing propylene oxide with glycerol as an initiator and has a molecular weight of 550;

[0075] The silicone resin is Dow Corning DOW790;

[0076] The number average molecular weight of the polycaprolactone resin is 80,000;

[0077] The silicone oil is polyether modified silicone oil, model H-204;

[0078] The cell opener is polyurethane cell opener GS-28;

[0079] The catalyst is a mixture of the tin catalyst T9, the amine catalyst A33, and the amine catalyst A1, with a mass ratio of 1:9:1;

[0080] The preparation method of the slow rebound memory foam is the same as that in Example 1.

[0081] Example 5

[0082] A slow rebound memory foam, comprising the following components in parts by weight:

[0083] 100 parts of diisocyanate, 120 parts of polyether polyol, 55 parts of slow rebound polyether, 5 parts of silicone resin, 16 parts of modified resin, 2 parts of silicone oil, 3.5 parts of pore opener, 2 parts of catalyst, 3.5 parts of deionized water;

[0084] The diisocyanate is a mixture of isophorone diisocyanate and dicyclohexylmethane-4,4'-diisocyanate in equal molar ratios;

[0085] The polyether polyol is a mixture of models DL-1000D and DL-3000D, with a mass ratio of 1:2;

[0086] The slow-rebound polyether is a first slow-rebound polyether, which is obtained by polymerizing propylene oxide with glycerol as an initiator and has a molecular weight of 550;

[0087] The silicone resin is Dow Corning DOW790;

[0088] The modified resin is prepared by the following preparation method:

[0089] 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate (CAS No.: 63225-53-6) and butyl acrylate were respectively weighed and dissolved in dimethylformamide solvent, an initiator was added, nitrogen was passed through to deoxygenate, and the mixture was stirred at 70°C for 20 hours. After the reaction was completed, deionized water was added to dilute the reaction system, the precipitate was separated and dissolved in ethyl acetate, and then added to hexane solvent for precipitation. The precipitate was separated and vacuum dried to obtain the product; the initiator was azobisisobutylcyanide; the mass ratio of 2-[[(butylamino)-carbonyl]oxy]ethyl 2-acrylate to butyl acrylate and the initiator was 10:2.9:0.015;

[0090] The silicone oil is polyether modified silicone oil, model H-204;

[0091] The cell opener is polyurethane cell opener GS-28;

[0092] The catalyst is a mixture of the tin catalyst T9, the amine catalyst A33, and the amine catalyst A1, with a mass ratio of 1:9:1;

[0093] The preparation method of the slow rebound memory foam is the same as that in Example 1.

[0094] Example 6

[0095] A slow rebound memory foam, comprising the following components in parts by weight:

[0096] 100 parts of diisocyanate, 120 parts of polyether polyol, 55 parts of slow rebound polyether, 2 parts of silicone oil, 3.5 parts of cell opener, 2 parts of catalyst, 3.5 parts of deionized water;

[0097] The diisocyanate is a mixture of isophorone diisocyanate and dicyclohexylmethane-4,4'-diisocyanate in equal molar ratios;

[0098] The polyether polyol is a mixture of models DL-1000D and DL-3000D, with a mass ratio of 1:2;

[0099] The slow-rebound polyether is a first slow-rebound polyether, which is obtained by polymerizing propylene oxide with glycerol as an initiator and has a molecular weight of 550;

[0100] The silicone oil is polyether modified silicone oil, model H-204;

[0101] The cell opener is polyurethane cell opener GS-28;

[0102] The catalyst is a mixture of the tin catalyst T9, the amine catalyst A33, and the amine catalyst A1, with a mass ratio of 1:9:1;

[0103] The preparation method of the slow rebound memory foam is the same as that in Example 1.

[0104] The slow rebound memory foam prepared in Examples 1-6 was tested and compared in terms of performance. The tensile strength was measured according to GB / T 6344-2008, the rebound rate was measured according to GB / T 6670-2008, the tear strength was measured according to GB / T 10808-2006, and the hardness was measured according to ISO 2439-2008. The test conditions were (normal temperature 25°C / low temperature -10°C) + 50% RH). The air permeability was measured according to JIS K6400-1 7B method. The test results are shown in the following table:

[0105]

[0106]

[0107] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A slow rebound memory foam, characterized in that: The composition is composed of the following components in parts by weight: 100 parts of diisocyanate, 100-150 parts of polyether polyol, 40-80 parts of slow rebound polyether, 1-8 parts of silicone resin, 4-24 parts of modified resin, 3-20 parts of polycaprolactone resin, 1-3 parts of silicone oil, 2-5 parts of pore opener, 0.5-3 parts of catalyst, and 1-5 parts of deionized water; The preparation method of the modified resin comprises the following steps: 2-[[(butylamino)-carbonyl]oxy]ethyl 2-propenoate and butyl acrylate are weighed separately and dissolved in dimethylformamide solvent, an initiator is added, nitrogen is passed through to deoxygenate, and the mixture is stirred and kept warm at 60-80°C for 16-24 hours. After the reaction is completed, deionized water is added to dilute the reaction system, the precipitate is separated and dissolved in ethyl acetate, and then added to hexane solvent for precipitation, the precipitate is separated, and vacuum dried to obtain the product.

2. The slow rebound memory foam according to claim 1, characterized in that: The mass ratio of the 2-acrylic acid-2-[[(butylamino)-carbonyl]oxy]ethyl ester to the butyl acrylate and the initiator is 10:(2.4-3.5):(0.01-0.04).

3. The slow rebound memory foam according to claim 1, characterized in that: The diisocyanate is any one or more of diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, biphenyl diisocyanate, and benzyl diisocyanate.

4. The slow rebound memory foam according to claim 1, characterized in that: The polyether polyol is any one of models DL-1000D, DL-2000D, DL-3000D, and DL-4000D, or a combination of two of them.

5. The slow rebound memory foam according to claim 1, characterized in that: The slow-rebound polyether is a first slow-rebound polyether or a second slow-rebound polyether; wherein, the first slow-rebound polyether is obtained by polymerizing propylene oxide with glycerol as an initiator, and has a molecular weight of 550; the second slow-rebound polyether is obtained by polymerizing propylene oxide with glycerol as an initiator, and has a molecular weight of 700.

6. The slow rebound memory foam according to claim 1, characterized in that: The organic silicone resin is Dow Corning DOW790, Dow Corning DOW995 or 3M540.

7. The slow rebound memory foam according to claim 1, characterized in that: The number average molecular weight of the polycaprolactone resin is 70,000-90,000.

8. The slow rebound memory foam according to claim 1, characterized in that: The cell opener is any one of polyurethane cell opener GS-28, polyurethane cell opener M-9955, and polyurethane cell opener Y-1900.

9. The slow rebound memory foam according to claim 1, characterized in that: The catalyst includes a tin catalyst T9, an amine catalyst A33, and an amine catalyst A1; wherein the mass ratio of the tin catalyst T9 to the amine catalyst A33 and the amine catalyst A1 is (1-2): (8-10):

1.

10. The method for preparing a slow rebound memory foam according to any one of claims 1 to 9, characterized in that: The following steps are involved: Polyether polyol, slow-rebound polyether, silicone resin, modified resin, polycaprolactone resin, silicone oil, pore-opening agent, catalyst and deionized water are weighed in proportion and added to a stirrer, and stirred at 30-50° C. until uniformly mixed; diisocyanate is added to the mixed system, stirred at high speed at 30-50° C., and then transferred to a preheated mold at a temperature of 50-70° C. and kept warm for 5-10 minutes. After demolding, the slow-rebound memory foam is obtained.

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