Preparation method and application of composite polyurethane foam

Abstract

The invention discloses a preparation method and application of composite polyurethane foam. The preparation method comprises the following preparation steps of preparation of other foam materials, irradiation crosslinking (optional), foaming, buffing of the surfaces of the materials, corona treatment of the buffed surfaces and preparation of the other foam materials. Coating two-component polyurethane on release paper, a release film or a mold; attaching other foams (the buffing corona surface is in contact with the polyurethane); curing at high temperature; stripping the release paper, the release film or the mold; the adhesive has the beneficial effects that the maximum stripping force reaches 550N / 5cm, and the composite surface between materials cannot fall off or be stripped.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane foam preparation, and in particular to a method for preparing a block composite polyurethane foam and application thereof. Background Art

[0002] Foam material, also known as foam, is a widely used functional material; the composition of the material can be polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), thermoplastic polyurethane (TPU), thermoplastic elastomer (TPE), polyvinyl chloride (PVC), polystyrene (PS), silicone rubber, polyvinylidene fluoride (PVDF), polyimide (PI), microporous foamed thermoplastic polyester elastomer material (M-TPEE), microporous foamed thermoplastic polyamide material (M-PEBA) and two-component polyurethane foam material (PU), etc. Each foam material has its own advantages and disadvantages and corresponding application fields. For example, polyethylene foam material has the characteristics of low price and good sound absorption effect, and is widely used in the field of flooring; EVA foam material is used in yoga mats, soles and other fields; TPU foam material can be widely used in the field of sports shoe soles, etc.

[0003] Two-component polyurethane foam (PU) is obtained by chemical reaction after mixing polyol component and isocyanate component. The foam cells are mainly produced by carbon dioxide gas released by the reaction of water and isocyanate. By adjusting the ratio of polyol component to isocyanate component, foams of various hardness can be easily obtained, and the range of resilience and hardness can be particularly wide. Because the polyurethane material itself has the dual properties of plastic and rubber, the performance of polyurethane foam is excellent, and it has the characteristics of shock absorption, sound absorption, warmth retention, and good flame retardancy. Therefore, film-like polyurethane microporous foam is widely used in 3C, automobiles, home decoration, fashion bags and other fields.

[0004] However, PU foam has poor performance in high-hardness foams, and its thermal conductivity is still higher than that of some foam materials. In addition, its price is more expensive than that of most other foams, which greatly limits the application of PU foam. Furthermore, by using adhesives to combine other foams with PU foam, the composite materials can be given their own advantages and cover up their corresponding disadvantages. Therefore, this method is widely used.

[0005] However, this method has very high requirements for adhesives. If you are not careful, it is easy to cause debonding, resulting in failure of the composite material. In addition, the adhesive compounding method increases the manufacturing cost of the composite material and reduces the product grade rate. If you do not use adhesives and directly apply or laminate PU foam on other foams, you can solve the problem of using adhesives and greatly improve the production efficiency of composite foams.

[0006] However, polyurethane is a material with high polarity, which is quite different from other materials in polarity. Therefore, the interfacial tension between different materials is different, which will cause the problem of low adhesion between materials and affect the normal use of composite materials.

[0007] In order to solve the above problems, the present invention proposes a method for preparing a composite polyurethane foam and its application. The bonding force and compatibility of the two foams in the composite polyurethane foam prepared by the above method are effectively improved, thereby expanding the application field of the polyurethane foam. Summary of the invention

[0008] The present invention provides a preparation method of a composite polyurethane foam and application thereof. The bonding force and compatibility of two foams in the composite polyurethane foam prepared by the method are effectively improved, thereby expanding the application field of the polyurethane foam.

[0009] Specific:

[0010] 1) The present invention can greatly improve the bonding force between the two-component polyurethane and other foams by adding active hydrogen components, i.e., polyol components or polyamines, etc., during the manufacturing process of other foams;

[0011] 2) By adding the grinding and corona treatment processes in the production process, the contact area between the polyurethane and other foams is increased and the surface tension of other foams is increased, thereby further improving the bonding strength of the composite material.

[0012] 3) The present invention also points out the composition of active hydrogen components suitable for different foams;

[0013] To achieve the above object, the present invention is implemented by the following technical solutions:

[0014] A method for preparing a composite polyurethane foam comprises the following steps:

[0015] S1 Preparation of other foams, taking radiation cross-linked polyethylene as an example:

[0016] S11 radiation cross-linked polyethylene foam material extrusion

[0017] The mass fraction of the raw material is

[0018] Polyethylene: 70 parts

[0019] Foaming masterbatch: 15 parts

[0020] Sensitizer: 10 parts

[0021] Colorant: 3 parts

[0022] Antioxidants: 2 servings

[0023] S12 irradiation cross-linking

[0024] Only cross-linked polyethylene (IXPE) and cross-linked polypropylene (IXPP) need irradiation cross-linking, while other foaming materials do not need irradiation cross-linking;

[0025] After electron accelerator irradiation cross-linking, the cross-linking time is 10min;

[0026] S13 high temperature foaming

[0027] After high-temperature foaming, foam A is obtained, and foam A is radiation cross-linked polyethylene foam;

[0028] The general foaming temperature is 150℃ and the foaming time is 10min.

[0029] S14 for surface grinding of materials

[0030] Perform surface grinding on one side of foam A

[0031] S15 for microdermabrasion surface corona

[0032] The corona power is 4-8kw and the corona time is 1-5 seconds.

[0033] After the above operations, foam A which has been subjected to single-side grinding and corona treatment is obtained.

[0034] Preparation of S2 composite polyurethane foam

[0035] S21 coats the two-component polyurethane on the release paper, release film or mold;

[0036] Two-component polyurethane materials are composed of a polyol component and an isocyanate component;

[0037] Specifically,

[0038] The polyol component comprises the following components in parts by weight:

[0039] Polyol: 80~90

[0040] Cell regulator: 5-10

[0041] Catalyst: 0.1~0.3

[0042] Color paste: 3~8

[0043] Water: 0-2

[0044] Flame retardant: 0~80

[0045] The isocyanate component is isocyanate or a modified product or prepolymer of isocyanate;

[0046] The ratio of isocyanate component to polyol component is: the isocyanate group is 1% to 50% more than the active hydrogen component.

[0047] S22 and Foam A are laminated

[0048] Lay with the surface of foam A that has been polished and corona treated;

[0049] S23 high temperature curing

[0050] The temperature of high temperature curing is 80℃~120℃, and the time of high temperature curing is 3~10min;

[0051] S24 peels off the release paper, film or mold to obtain composite polyurethane foam.

[0052] As a further improvement,

[0053] The other foam materials include polyethylene (PE), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), thermoplastic polyurethane (TPU), thermoplastic elastomer (TPE), polyvinyl chloride (PVC), polystyrene (PS), silicone rubber, polyvinylidene fluoride (PVDF), polyimide (PI), microporous foamed thermoplastic polyester elastomer material (M-TPEE), and microporous foamed thermoplastic polyamide material (M-PEBA).

[0054] As a further improvement,

[0055] In the other foam material, active hydrogen components are added during the preparation process, and the content of the active hydrogen components is 0.5 to 30 parts by weight.

[0056] As a further improvement,

[0057] The active hydrogen component is polyester, polyether, polycarbonate, bio-based, polyacrylate or polyolefin polyol or polyamine, and other active hydrogen components that can react with isocyanate.

[0058] As a further improvement, in the S14 for grinding the surface of the material,

[0059] It includes two processes: coarse grinding and fine grinding. During coarse grinding, the mesh of sandpaper is 20-150 mesh, and all the pores on the surface of the foam are ground open.

[0060] When fine grinding, the mesh number of sandpaper is 150-600 mesh, which can make the pores on the foam surface fine.

[0061] As a further improvement, the two-component polyurethane comprises component A and component B.

[0062] Component A is an active hydrogen component, specifically including the following components:

[0063] A mixture of polyol or polyamine, a catalyst, a chain extender and water;

[0064] Polyol components:

[0065] Polyol: 80~90

[0066] Cell regulator: 5-10

[0067] Catalyst: 0.1~0.3

[0068] Color paste: 3~8

[0069] Water: 0-2

[0070] Flame retardant: 0~80

[0071] Component B is an isocyanate component, specifically comprising the following components:

[0072] Isocyanate or modified products or prepolymers of isocyanate;

[0073] The isocyanate group of the isocyanate component is in excess of the active hydrogen component by 1% to 50%.

[0074] Isocyanate component:

[0075] Isocyanate or modified products or prepolymers of isocyanate;

[0076] The ratio of isocyanate component to polyol component is: the isocyanate group is 1% to 50% more than the active hydrogen component.

[0077] The composite polyurethane foam preparation method of the present invention has the following beneficial effects:

[0078] 1) In the present invention, by adding active hydrogen components in the manufacturing process of other foams, on the one hand, it can play a certain plasticizing role in the foam, and on the other hand, it introduces active hydrogen components that can react with excess isocyanate groups in the two-component polyurethane, greatly improving the bonding force and compatibility of the two foams;

[0079] 2) The present invention also provides the most suitable active hydrogen component for the corresponding foam in the specific embodiment;

[0080] 3) In the present invention, the contact area between other foams and the two-component polyurethane is further increased by the grinding process; the polarity of the surface of other foams is increased by the corona process, and the number of active hydrogens on the surface is further increased; by laminating the two-component polyurethane before curing, that is, laminating when the two-component polyurethane has fluidity, the two-component polyurethane can fully combine with the pore surface of other foams, greatly increasing the contact area of ​​the two materials, thereby significantly improving the bonding force and compatibility of the two materials;

[0081] 4) Through high-temperature curing, the excess isocyanate components in the two-component polyurethane can quickly migrate to the inside of other foams, and then react and cross-link with the multi-active hydrogen components on the surface and inside of other foams, thereby further greatly improving the bonding force between the two materials, making the bonding surface of the two materials very strong. Compared with the solution of using adhesives to combine the two materials, this solution has low cost, high efficiency, and strong bonding between materials;

[0082] 4) In the present invention, the composite foam greatly expands the application field of polyurethane foam. For example, the polyurethane foam composited with irradiated cross-linked polyethylene foam can be applied to the field of high-end flooring, further improving the rebound and sound absorption performance of the floor; the polyurethane foam composited with supercritical foamed polypropylene can improve the hardness and flame retardant properties of the composite polyurethane foam, and can be applied to the field of new energy vehicle batteries or energy storage batteries; the composite with supercritical foamed TPU can significantly improve the temperature resistance of the composite material, and is applied to the fields of wear-resistant and heat-resistant sports shoes and mountaineering shoe soles; the polyurethane foam composited with EVA foam material can greatly improve the support, rebound and sound absorption effects of yoga mats, and is applied to the field of high-end yoga mats; the composite with PVDF foam can improve the flame retardant properties and significantly reduce the cost while ensuring the temperature resistance of the composite material. BRIEF DESCRIPTION OF THE DRAWINGS

[0083] Figure 1 It is a product diagram of EVA and polyurethane foam in Examples 2-4 of the composite polyurethane foam preparation method of the present invention;

[0084] Figure 2 The cross section of the EVA foam and the polyurethane foam in Examples 2-4 of the method for preparing the composite polyurethane foam of the present invention is one;

[0085] Figure 3 Cross-section 2 of the EVA foam and the polyurethane foam in Examples 2-4 of the method for preparing the composite polyurethane foam of the present invention. DETAILED DESCRIPTION

[0086] In order to make the purpose, technical solutions and advantages of the present invention more clear, the following embodiments and the accompanying drawings are combined to illustrate the present invention. Figure 1 , 2 The present invention will be further described:

[0087] Example 1

[0088] Combination Figures 1 to 3 , this embodiment 1 is described in detail.

[0089] Example 1

[0090] This embodiment uses radiation cross-linked polyethylene foam (IXPE) combined with polyurethane foam. The specific implementation process is as follows:

[0091] Preparation of radiation cross-linked polyethylene foam (IXPE) material - irradiation cross-linking (cross-linking by electron accelerator irradiation, cross-linking time 10min) - high temperature foaming (150℃, foaming time 10min) - grinding of material surface - corona of grinding surface - radiation cross-linked polyethylene foam (IXPE) material

[0092] Apply two-component polyurethane on release paper - attach the above foam (the grinding corona surface is in contact with the polyurethane) - high temperature curing (90℃5min) - peel off the release paper - polyethylene foam composite polyurethane foam

[0093] The radiation cross-linked polyethylene foam (IXPE) material is prepared by adding 8% by mass of active hydrogen components to the original formula;

[0094] The active hydrogen component is a hydroxyl-terminated polybutadiene polyol with a molecular weight of 1000;

[0095] The radiation cross-linking is to irradiate the material with high-energy rays;

[0096] The skin grinding process is divided into two processes: coarse grinding and fine grinding.

[0097] When coarse grinding, the mesh number of sandpaper is 20, which can grind open all the pores on the foam surface; when fine grinding, the mesh number of sandpaper is 400, which can make the pores on the foam surface fine.

[0098] In the corona process, the corona surface is a grinding surface; the corona power is 4kw and the corona time is 3 seconds

[0099] The two-component polyurethane has one component, which is an active hydrogen component, a mixture of polyol, catalyst, chain extender and water; and the other component is an isocyanate prepolymer. The isocyanate group of the isocyanate component is 15% more than that of the active hydrogen component.

[0100] Polyol components:

[0101] Polypropylene glycol, molecular weight 1000:90

[0102] Polyether modified silicone oil cell regulator: 5

[0103] Organotin catalyst: 0.2

[0104] Color paste: 3

[0105] Water: 1

[0106] Flame retardant: 0

[0107] Isocyanate component:

[0108] Isocyanate prepolymer (MDI and polypropylene glycol prepolymer);

[0109] The ratio of the isocyanate component to the polyol component is that the isocyanate group is 15% more than the active hydrogen component.

[0110] In this embodiment, hydroxy-terminated polybutadiene polyol is added to the original formula for preparing radiation cross-linked polyethylene foam (IXPE) material. This polyol has good compatibility with polyethylene, and its addition significantly improves the bonding strength between the radiation cross-linked polyethylene foam and the two-component polyurethane foam.

[0111] Irradiated cross-linked polyethylene foam composite polyurethane foam can be used in the field of high-end flooring, which further improves the floor rebound level. When the floor is subjected to a small impact, it can stably absorb the impact force and has excellent sound absorption performance; when the floor is subjected to a large impact, it can give a large rebound force and has excellent sound absorption performance;

[0112] Example 2-1

[0113] This embodiment uses ethylene-vinyl acetate copolymer (EVA) combined with polyurethane foam, and the specific implementation process is as follows:

[0114] EVA foam preparation - high temperature foaming (foaming temperature 160℃) - grinding the surface of the material - corona treatment of the grinding surface - EVA foam material

[0115] Apply two-component polyurethane on the release film - attach the above foam (the grinding corona surface is in contact with the polyurethane) - high temperature curing (80℃10min) - peel off the release film - polyethylene foam composite polyurethane foam

[0116] The EVA foam material is prepared by adding 30% by weight of active hydrogen component to the original formula;

[0117] The active hydrogen component is polyethylene adipate glycol diol polyol with a molecular weight of 500;

[0118] The grinding process is divided into two processes: coarse grinding and fine grinding. In the coarse grinding, the mesh number of the sandpaper is 80, and all the pores on the foam surface are ground open; in the fine grinding, the mesh number of the sandpaper is 200, and the pores on the foam surface are fine.

[0119] In the corona treatment process, the corona treatment surface is a polished surface;

[0120] The two-component polyurethane comprises one component of active hydrogen, which is a mixture of polyester polyol, catalyst, chain extender and water; and the other component is isocyanate prepolymer.

[0121] Polyol components:

[0122] Polyols mixed with polyether triol with a molecular weight of 1000 and polypropylene glycol with a molecular weight of 3000 in a ratio of 1:1: 80

[0123] Polyether modified silicone oil cell regulator: 10

[0124] Compound catalyst of cyclohexylmethyl tertiary amine and organotin Catalyst: 0.3

[0125] Color paste: 3

[0126] Water: 2

[0127] Flame retardant: 0

[0128] Isocyanate component:

[0129] TDI;

[0130] Among them, the ratio of isocyanate component to polyol component is: the isocyanate group is 30% more than the active hydrogen component

[0131] The composite foam obtained in this embodiment still showed separation between the interface of the two-component polyurethane foam and the EVA foam during the peeling test;

[0132] Example 2-2

[0133] This embodiment uses ethylene-vinyl acetate copolymer (EVA) combined with polyurethane foam, and the specific implementation process is as follows:

[0134] EVA foam preparation - high temperature foaming (foaming temperature 160℃) - grinding the surface of the material - corona treatment of the grinding surface - EVA foam material

[0135] Apply two-component polyurethane on the release film - attach the above foam (the grinding corona surface is in contact with the polyurethane) - high temperature curing (80℃10min) - peel off the release film - polyethylene foam composite polyurethane foam

[0136] The EVA foam material is prepared by adding 30% by weight of active hydrogen component to the original formula;

[0137] The active hydrogen component is a polymer polyol (POP) with a molecular weight of 1000;

[0138] The grinding process is divided into two processes: coarse grinding and fine grinding. In the coarse grinding, the mesh number of the sandpaper is 80, and all the pores on the foam surface are ground open; in the fine grinding, the mesh number of the sandpaper is 200, and the pores on the foam surface are fine.

[0139] In the corona treatment process, the corona treatment surface is a polished surface;

[0140] The two-component polyurethane comprises one component of active hydrogen, which is a mixture of polyester polyol, catalyst, chain extender and water; and the other component is isocyanate prepolymer.

[0141] Polyol components:

[0142] Polyols mixed with polyether triol with a molecular weight of 1000 and polypropylene glycol with a molecular weight of 3000 in a ratio of 1:1: 80

[0143] Polyether modified silicone oil cell regulator: 10

[0144] Compound catalyst of cyclohexylmethyl tertiary amine and organotin Catalyst: 0.3

[0145] Color paste: 3

[0146] Water: 2

[0147] Flame retardant: 0

[0148] Isocyanate component:

[0149] TDI;

[0150] Among them, the ratio of isocyanate component to polyol component is: the isocyanate group is 30% more than the active hydrogen component

[0151] The composite foam obtained in this example still showed separation at the interface between the two-component polyurethane foam and the EVA foam during the peeling test, but the peeling force was higher than that of Example 2-1;

[0152] Example 2-3

[0153] This embodiment uses ethylene-vinyl acetate copolymer (EVA) combined with polyurethane foam, and the specific implementation process is as follows:

[0154] EVA foam preparation - high temperature foaming (foaming temperature 160℃) - grinding the surface of the material - corona treatment of the grinding surface - EVA foam material

[0155] Apply two-component polyurethane on the release film - attach the above foam (the grinding corona surface is in contact with the polyurethane) - high temperature curing (80℃10min) - peel off the release film - polyethylene foam composite polyurethane foam

[0156] The EVA foam material is prepared by adding 30% by weight of active hydrogen component to the original formula;

[0157] The active hydrogen component is a 1:1 mixed polyol of a polymer polyol (POP) with a molecular weight of 1000 and a hydroxy-terminated polybutadiene polyol with a molecular weight of 1000;

[0158] The grinding process is divided into two processes: coarse grinding and fine grinding. In the coarse grinding, the mesh number of the sandpaper is 80, and all the pores on the foam surface are ground open; in the fine grinding, the mesh number of the sandpaper is 200, and the pores on the foam surface are fine.

[0159] In the corona treatment process, the corona treatment surface is a polished surface;

[0160] The two-component polyurethane comprises one component of active hydrogen, which is a mixture of polyester polyol, catalyst, chain extender and water; and the other component is isocyanate prepolymer.

[0161] Polyol components:

[0162] Polyols mixed with polyether triol with a molecular weight of 1000 and polypropylene glycol with a molecular weight of 3000 in a ratio of 1:1: 80

[0163] Polyether modified silicone oil cell regulator: 10

[0164] Compound catalyst of cyclohexylmethyl tertiary amine and organotin Catalyst: 0.3

[0165] Color paste: 3

[0166] Water: 2

[0167] Flame retardant: 0

[0168] Isocyanate component:

[0169] TDI;

[0170] Among them, the ratio of isocyanate component to polyol component is: the isocyanate group is 30% more than the active hydrogen component

[0171] In the peeling test of the composite foam obtained in this example, the foam interfaces of the two components were slightly separated; Example 2-4

[0172] This embodiment uses ethylene-vinyl acetate copolymer (EVA) combined with polyurethane foam, and the specific implementation process is as follows:

[0173] EVA foam preparation - high temperature foaming (foaming temperature 160℃) - grinding the surface of the material - corona treatment of the grinding surface - EVA foam material

[0174] Apply two-component polyurethane on the release film - attach the above foam (the grinding corona surface is in contact with the polyurethane) - high temperature curing (80℃10min) - peel off the release film - polyethylene foam composite polyurethane foam

[0175] The EVA foam material is prepared by adding 30% by weight of active hydrogen component to the original formula;

[0176] The active hydrogen component is a polymer polyol (POP) with a molecular weight of 1000, a hydroxy-terminated polybutadiene polyol with a molecular weight of 1000, and a polyether triol with a molecular weight of 1000 using glycerol as an initiator, the mixing ratio of which is 1:1:1;

[0177] The grinding process is divided into two processes: coarse grinding and fine grinding. In the coarse grinding, the mesh number of the sandpaper is 80, and all the pores on the foam surface are ground open; in the fine grinding, the mesh number of the sandpaper is 200, and the pores on the foam surface are fine.

[0178] In the corona treatment process, the corona treatment surface is a polished surface;

[0179] The two-component polyurethane comprises one component of active hydrogen, which is a mixture of polyester polyol, catalyst, chain extender and water; and the other component is isocyanate prepolymer.

[0180] Polyol components:

[0181] Polyols mixed with polyether triol with a molecular weight of 1000 and polypropylene glycol with a molecular weight of 3000 in a ratio of 1:1: 80

[0182] Polyether modified silicone oil cell regulator: 10

[0183] Compound catalyst of cyclohexylmethyl tertiary amine and organotin Catalyst: 0.3

[0184] Color paste: 3

[0185] Water: 2

[0186] Flame retardant: 0

[0187] Isocyanate component:

[0188] TDI;

[0189] Among them, the ratio of isocyanate component to polyol component is: the isocyanate group is 30% more than the active hydrogen component

[0190] In the peeling test, the composite foam obtained in this embodiment showed no separation at the interface of the two foams when the EVA foam was cut.

[0191] Figure 1 This is a product diagram of EVA and polyurethane foam in this embodiment;

[0192] Figure 2 This is a scanning electron microscope image of the interface between the EVA and polyurethane foam products of this embodiment. Figure 1 ;

[0193] Figure 3 This is a scanning electron microscope image of the interface between the EVA and polyurethane foam products of this embodiment. Figure 2 ;

[0194] Depend on Figure 2 , 3 The scanning electron microscope image shows that the EVA foam and the polyurethane foam are tightly combined;

[0195]

[0196] From the comparison of the test results in Table 1, it can be seen that the polyurethane foam composited with the EVA foam material prepared in Examples 2-4 can greatly improve the support, rebound and sound absorption effects of the yoga mat, and is applied to the field of high-end yoga mats.

[0197] Example 3

[0198] In this embodiment, the TPU foamed by supercritical carbon dioxide is combined with polyurethane foam. The specific implementation process is as follows:

[0199] Preparation of TPU material foamed by supercritical carbon dioxide - supercritical carbon dioxide foaming (foaming temperature 120℃) - grinding the surface of the material - corona on the grinding surface - TPU foam material foamed by supercritical carbon dioxide

[0200] Apply two-component polyurethane on the mold - attach the above foam (the grinding corona surface is in contact with the polyurethane) - high temperature curing (120℃3min) - peel off the mold - TPU foam composite polyurethane foam

[0201] The TPU foam material is prepared by adding 0.5% by weight of active hydrogen component to the original formula;

[0202] The active hydrogen component is polyoxypropylene triamine with a molecular weight of 1000 and glycerol as an initiator;

[0203] The grinding process is divided into two processes: coarse grinding and fine grinding. In the coarse grinding, the mesh number of the sandpaper is 30, and all the pores on the foam surface are ground open; in the fine grinding, the mesh number of the sandpaper is 150, and the pores on the foam surface are fine.

[0204] In the corona treatment process, the corona treatment surface is a polished surface;

[0205] The corona power is 4kw and the corona time is 5 seconds.

[0206] The two-component polyurethane has one component, which is an active hydrogen component, a mixture of polyol, catalyst, chain extender and water; and the other component is an isocyanate prepolymer. The isocyanate group of the isocyanate component is 10% more than that of the active hydrogen component.

[0207] Polyol components:

[0208] Polyols mixed with polyether triol with a molecular weight of 1000 and polypropylene glycol with a molecular weight of 3000 in a ratio of 1:1: 85

[0209] Polyether modified silicone oil cell regulator: 8

[0210] Organotin catalyst: 0.2

[0211] Color paste: 5

[0212] Water: 1

[0213] Flame retardant: 30

[0214] Isocyanate component:

[0215] MDI;

[0216] Among them, the ratio of isocyanate component to polyol component is: the isocyanate group is 10% more than the active hydrogen component

[0217] Supercritical carbon dioxide foamed TPU composites can significantly improve the temperature resistance of composite materials and are used in wear-resistant and heat-resistant sports shoes, mountaineering and labor protection shoe soles.

[0218] Example 4

[0219] This embodiment uses polyvinylidene fluoride (PVDF) foam and polyurethane foam in combination, and the specific implementation process is as follows:

[0220] Preparation of polyvinylidene fluoride (PVDF) foam material - supercritical carbon dioxide foaming - grinding of material surface - corona of grinding surface - PVDF foam material

[0221] Apply two-component polyurethane on the mold - attach the above foam (the grinding corona surface is in contact with the polyurethane) - high temperature curing (120℃8min) - peel off the mold - PVDF foam composite polyurethane foam

[0222] The PVDF foam material is prepared by adding 20% ​​by mass of active hydrogen component to the original formula;

[0223] The active hydrogen component is polycarbonate diol (PCDL) with a molecular weight of 800;

[0224] The radiation cross-linking is to irradiate the material with high-energy rays;

[0225] The grinding process is divided into two processes: coarse grinding and fine grinding. In the coarse grinding, the mesh number of the sandpaper is 30, and all the pores on the foam surface are ground open; in the fine grinding, the mesh number of the sandpaper is 200, and the pores on the foam surface are fine.

[0226] In the corona treatment process, the corona treatment surface is a polished surface;

[0227] The corona power is 8kw and the corona time is 4 seconds.

[0228] The two-component polyurethane has one component, which is an active hydrogen component, a mixture of polyol, catalyst, chain extender and water; and the other component is isocyanate. The isocyanate group of the isocyanate component is 50% more than that of the active hydrogen component.

[0229] Polyol components:

[0230] Polyol: 80

[0231] Cell regulator: 5

[0232] Catalyst: 0.3

[0233] Color paste: 8

[0234] Water: 0

[0235] Flame retardant: 80

[0236] Isocyanate component:

[0237] Isocyanate MDI;

[0238] Among them, the ratio of isocyanate component to polyol component is: the isocyanate group is 50% more than the active hydrogen component

[0239] PVDF foam composite can improve the flame retardant properties and significantly reduce costs while ensuring the temperature resistance of the composite material.

[0240] Comparative Example 1

[0241] This ratio uses radiation cross-linked polyethylene foam (IXPE) directly combined with polyurethane foam. The specific implementation process is as follows:

[0242] Preparation of radiation cross-linked polyethylene foam (IXPE) material - radiation cross-linking - high temperature foaming - radiation cross-linked polyethylene foam (IXPE) material

[0243] Apply two-component polyurethane on release paper - attach the above foam - high temperature curing - peel off release paper - polyethylene foam composite polyurethane foam

[0244] No active hydrogen components are added during the preparation of radiation cross-linked polyethylene foam (IXPE) materials;

[0245] Comparative Example 2

[0246] The TPU foam foamed by supercritical carbon dioxide in this ratio is bonded to the polyurethane foam by a conventional adhesive.

[0247] The test results of Examples 1 to 3 and Comparative Examples 1 to 2 are shown in Table 2.

[0248]

[0249] Compression set test method

[0250] Compression rate 2mm / min 0.002~8MPa Compression curve Sample size 50*50*2mm

[0251] The peeling state cutting means that the two foams are broken under the action of the peeling force, and the rupture position is not the bonding position of the two foams. In other words, the bonding force of the two foams is greater than the tearing force of the foams themselves, which proves that the two foams are tightly attached together.

[0252] It is implemented by combining polyurethane foam with different materials. Because the materials themselves are different, it is impossible to compare and evaluate which one is the best.

[0253] As can be seen from the above, in the embodiments, the present invention specifically provides that polyurethane foam can be combined with different materials to produce different products:

[0254] 1) Irradiation cross-linked polyethylene foam composite polyurethane foam can be used in the field of high-end flooring;

[0255] 2) EVA foam and polyurethane foam can greatly improve the support, rebound and sound absorption effects of yoga mats and are used in the field of high-end yoga mats;

[0256] 3) Supercritical carbon dioxide foamed TPU composite can significantly improve the temperature resistance of composite materials, and is used in the fields of wear-resistant and heat-resistant sports shoes, mountaineering and labor protection shoe soles;

[0257] 4) The combination of polyvinylidene fluoride (PVDF) foam and polyurethane foam can improve the flame retardant properties and significantly reduce costs while ensuring the temperature resistance of the composite material.

[0258] By adding active hydrogen components in the manufacturing process of other foams, on the one hand, it can play a certain plasticizing role in the foam, and on the other hand, it introduces active hydrogen components that can react with the excess isocyanate groups in the two-component polyurethane, greatly improving the bonding and compatibility of the two foams; through the skin grinding process, the contact area between other foams and the two-component polyurethane is further increased; through the corona process, the polarity of the surface of other foams is increased, and the number of active hydrogen on the surface is further increased; by bonding before the two-component polyurethane is cured, that is, bonding when the two-component polyurethane has fluidity, the two-component polyurethane can fully bond with the pore surface of other foams, greatly increasing the contact area of ​​the two materials, thereby significantly improving the bonding and compatibility of the two materials. Compared with the solution of using adhesives to combine the two materials, this solution has low cost, high efficiency, and strong bonding between materials.

[0259] The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. All equivalent changes made using the present invention are within the patent protection scope of the present invention.

Claims

1. A method for preparing a composite polyurethane foam, characterized in that: The composite polyurethane foam material is prepared by compounding material one and material two. in, 1) Material 1: Material 1 is other foam materials, and active hydrogen components are added to the other foam materials; 2) Material 2: Material 2 is a two-component polyurethane material; The other foam materials and the two-component polyurethane material are cured at high temperature to obtain the required composite polyurethane foam material.

2. The method for preparing composite polyurethane foam according to claim 1, characterized in that: The other foam materials include any one of polyethylene, polypropylene, ethylene-vinyl acetate copolymer, thermoplastic polyurethane, thermoplastic elastomer, polyvinyl chloride, polystyrene, silicone rubber, polyvinylidene fluoride, polyimide, microporous foamed thermoplastic polyester elastomer material, and microporous foamed thermoplastic polyamide material.

3. The method for preparing composite polyurethane foam according to claim 1, characterized in that: In the preparation of the other foam materials, an active hydrogen component is added in an amount of 0.5% to 30% by mass to the original formula.

4. The method for preparing composite polyurethane foam according to claim 1, characterized in that: The active hydrogen component is any one or more of polyester, polyether, polycarbonate, bio-based, polyacrylate, polyolefin polyol, and polyamine.

5. The method for preparing composite polyurethane foam according to claim 1, characterized in that: Other foam materials are prepared according to the following steps: S1 When other foam materials are cross-linked polyethylene and cross-linked polypropylene, radiation cross-linking is performed S11 radiation cross-linked foam extrusion S12 irradiation cross-linking S13 high temperature foaming S14 for surface grinding of materials S15 for microdermabrasion surface corona After the above operations, foam A which has been subjected to single-sided grinding and corona treatment is obtained; Preparation of S2 composite polyurethane foam S21 coats the two-component polyurethane on the release paper, release film or mold; Two-component polyurethane materials are composed of a polyol component and an isocyanate component; Specifically, The polyol component comprises the following components in parts by weight: Polyol: 80~90 Cell regulator: 5-10 Catalyst: 0.1~0.3 Color paste: 3~8 Water: 0-2 Flame retardant: 0~80 The isocyanate component is any one of isocyanate, modified isocyanate and prepolymer; Among them, the ratio of isocyanate component to polyol component is: The isocyanate group is 1% to 50% more than the active hydrogen component S22 and Foam A are laminated Lay with the surface of foam A that has been polished and corona treated; S23 high temperature curing The temperature of high temperature curing is 80℃~120℃, and the time of high temperature curing is 3~10min; S24 peels off the release paper, film or mold to obtain composite polyurethane foam.

6. The method for preparing composite polyurethane foam according to claim 5, characterized in that: When the other foam material is a cross-linked polyethylene foam material, The mass fractions of the raw materials are: Polyethylene: 70 parts; Foaming masterbatch: 15 parts; Sensitizer: 10 parts; Colorant: 3 parts; Antioxidants: 2 parts; The radiation cross-linked polyethylene foam material further comprises an active hydrogen component, and the content of the active hydrogen component is 0.5 to 30 parts by weight.

7. The method for preparing composite polyurethane foam according to claim 5, characterized in that: In the S14 process of grinding the surface of the material, It includes two processes: coarse grinding and fine grinding. During coarse grinding, the mesh of sandpaper is 20-150 mesh, and all the pores on the surface of the foam are ground open. When fine grinding, the mesh number of sandpaper is 150-600 mesh, which can make the pores on the foam surface fine.

8. The method for preparing composite polyurethane foam according to claim 5, characterized in that: The two-component polyurethane comprises component A and component B. Component A is an active hydrogen component, specifically including the following components: A mixture of polyol or polyamine, a catalyst, a chain extender and water; Polyol components: Polyol: 80~90 Cell regulator: 5-10 Catalyst: 0.1~0.3 Color paste: 3~8 Water: 0-2 Flame retardant: 0~80 Component B is an isocyanate component, specifically comprising the following components: Isocyanate or modified products or prepolymers of isocyanate; The isocyanate group of the isocyanate component is in excess of the active hydrogen component by 1% to 50%. Isocyanate component: Isocyanate or modified products or prepolymers of isocyanate; The ratio of the isocyanate component to the polyol component is as follows: the isocyanate group is 1% to 50% more than the active hydrogen component.

9. An application of a composite polyurethane foam, characterized in that: The composite polyurethane foam prepared by the composite polyurethane foam preparation method according to any one of claims 1 to 8 is applied to new energy vehicle batteries, energy storage batteries, yoga mats, and sports shoes.

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