Low-density high-elasticity antistatic polyurethane foam material and preparation method thereof

Abstract

The invention discloses a low-density high-elasticity antistatic polyurethane foam material and a preparation method thereof, and relates to the technical field of static electricity resistance. The invention comprises a white material and a black material, and is characterized in that the white material comprises polyether polyol, polyester polyol, sulfonate polyester polyol and a functional aid, and the black material comprises polyester polyol, polyether polyol, sulfonate polyester polyol and diisocyanate; according to the sulfonate polyester polyol, dicarboxylic acid, alkali metal sulfonate and dihydric alcohol are subjected to dehydration condensation to form hydroxyl-terminated macromolecules; the purpose that polyurethane has excellent mechanical property, light weight and permanent antistatic property is achieved.

Description

Technical Field

[0001] The invention relates to the field of antistatic technology, in particular to a low-density high-elasticity antistatic polyurethane foam material and a preparation method thereof. Background Art

[0002] Static electricity is a static charge or a non-flowing charge. Static electricity is formed when charges accumulate on an object or surface. If the accumulated static electricity cannot be transferred in time, it will cause static electricity hazards.

[0003] Polyurethane is a widely used polymer material. Like other polymers, it has electrical insulation properties. During transportation and use, it will generate greater static electricity hazards due to friction.

[0004] Static electricity hazards are caused by static electricity charges or static electricity fields. The relative movement, contact and separation of materials lead to the accumulation of relatively static positive and negative charges, which generates static electricity. Polyurethane materials have good electrical insulation properties, and static electricity generated by friction is not easy to disappear. The accumulation of static electricity will cause many problems and even become a disaster.

[0005] The way to eliminate the harm of static electricity is to reduce the resistance of polyurethane through antistatic agents. Different types of antistatic agents have different mechanisms of action.

[0006] (1) Antistatic agent with conductive filler added Carbon black, graphite, carbon nanotubes, metal oxides, metals, etc. are materials with electronic conductivity. Electronic conductor materials can be used as conductive fillers to prepare polyurethane antistatic materials. The advantage of conductive fillers is that the polyurethane materials added have good antistatic properties and low cost, but the disadvantage is that the addition amount is large. Generally, the addition amount must reach about 30% to achieve the desired effect, and it has a greater impact on the mechanical properties of the material.

[0007] (2) External coating surfactant type antistatic agent Water, alcohol or other organic solvents are usually used as solvents or dispersants. When the polyurethane material is soaked with an antistatic agent, the lipophilic groups in the antistatic agent molecules will be adsorbed on the surface of the polyurethane material. After the impregnation and drying, after the polyurethane material surface is dehydrated, the hydrophilic groups in the antistatic agent molecules are arranged on the air side, which is easy to absorb environmental water, or combine with water in the air through hydrogen bonds to form a monomolecular conductive layer, so that the static charge leaks quickly, achieving the purpose of antistatic.

[0008] (3) Add surfactant-type antistatic agent During the molding process of polyurethane materials, antistatic agents are added and mixed evenly. After the resin is cured, the hydrophilic groups on the antistatic agent molecules are arranged on the air side, absorbing water molecules in the air to form a monomolecular conductive layer. During processing and use, stretching, friction and cleaning will cause defects in the antistatic agent molecular layer on the surface of the material, reducing the antistatic performance. However, unlike the external coating antistatic agent, after a period of time, the antistatic molecules in the material will continue to migrate to the surface, restore the defective parts, and re-display the antistatic effect.

[0009] (4) Add conductive polymer antistatic agent Conductive polymer antistatic agents are a class of substances with electronic conductivity, mainly polyacetylene, polythiophene, polypyrrole, polyaniline, etc. and their derivatives. The conductive principle mainly comes from the conjugated π bonds in its molecules. Each carbon atom provides a π orbital, which overlaps with the π orbitals of two adjacent carbon atoms to form a conjugated π bond that runs through the entire polymer chain. This structure allows electrons to move freely in the entire conjugated system, thereby giving it conductive properties and achieving conductive and antistatic effects. After this type of antistatic agent is treated and modified by a special method, its compatibility with the matrix material can be improved, so that the blended material can have a good antistatic effect while maintaining mechanical properties. Summary of the invention

[0010] The purpose of the present invention is to provide a low-density, high-elasticity antistatic polyurethane foam material and a preparation method thereof, so as to achieve the purpose of polyurethane having excellent mechanical properties, light weight and permanent antistatic.

[0011] In order to achieve the above object, the present invention adopts the following technical means: A low-density, high-elasticity, antistatic polyurethane foam material, comprising a white material and a black material, wherein the white material comprises polyether polyol, polyester polyol, sulfonate polyester polyol and a functional additive, and the black material comprises polyester polyol, polyether polyol, sulfonate polyester polyol and diisocyanate; The sulfonate polyester polyol is a hydroxyl-terminated macromolecule formed by dehydration condensation of dicarboxylic acid, alkali metal sulfonate and diol.

[0012] Among them, the sulfonate polyester polyol prepared by using alkali metal sulfonate, after being introduced into the polyurethane system, not only provides excellent physical and mechanical properties as the polyurethane soft segment, but also can cooperate with the moisture in the air to form a conductive channel on the surface of the material, thereby quickly and effectively transferring static charge.

[0013] At the same time, the introduced sulfonate polyester polyol forms an ester-bonded system with the material system in the polyester chain segment, thereby ensuring that the antistatic property of the material will not be lost due to long-term use.

[0014] Furthermore, the sulfonate polyester polyol introduced in the solvent-free system of the present application, in addition to providing excellent physical and mechanical properties and antistatic properties, also acts as a pore opener during the polymerization reaction, and the main body of the material will not shrink at low density, thereby greatly reducing the weight of the material under the same volume, so that it can be better used in the sole material as a lightweight antistatic material.

[0015] Preferably, the sulfonate polyester polyol has a number average molecular weight of 500-5000 g / mol, an acid value of 0.2-0.6 mgKOH / g, and a sulfonate content of 0.3-0.5 mol per kilogram.

[0016] Furthermore, the alkali metal sulfonate is lithium 5-sulfoisophthalate.

[0017] In this way, when introducing sulfonate polyester polyol into the polyester system, the benzene ring in lithium 5-sulfonate isophthalic acid is used to allow the polyester chain segments to be wrapped around the benzene ring during the entanglement of the polyester chain segments. Not only can the rigidity of the benzene ring be used to improve the mechanical properties of the material, but it can also greatly improve the elasticity of the polyester foam material, giving it excellent cushioning properties. Moreover, based on the combined alkali metal lithium ions, the electron transfer capacity to the point channel can be improved. Thereby improving the material's anti-charge performance.

[0018] Furthermore, the polyester polyol is a hydroxyl-terminated macromolecule formed by dehydration condensation of dicarboxylic acid and diol, and the number average molecular weight of the polyester polyol is 500-5000 g / mol, and the acid value is 0.2-0.6 mgKOH / g.

[0019] Furthermore, the polyether polyol includes one or more of polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene-oxypropylene polyol, and polytetramethylene ether polyol, and the number average molecular weight of the polyether polyol is 1000 to 8000 g / mol.

[0020] Furthermore, the diisocyanate includes one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate, naphthalene diisocyanate and isomers and / or derivatives and / or modified polymers thereof.

[0021] Furthermore, the NCO content in the black material is 15wt.%~25wt.% based on the diisocyanate.

[0022] Furthermore, the functional additives include chain extenders, cross-linking agents, foaming agents, foam stabilizers and catalysts.

[0023] Furthermore, a method for preparing the aforementioned low-density, high-elasticity, antistatic polyurethane foam material comprises the following steps: S100. Dispose the white material and the black material separately; S200. The white material and the black material are mixed and then aged to obtain the foaming material.

[0024] Furthermore, in the step S100, the mixing temperature is 40-60°C, the reaction temperature is 70-80°C, and the reaction time is 2-3h; In the step S200, the mass ratio of the hydroxyl equivalent of the white material to the diisocyanate equivalent of the black material is 100:95-105, the aging temperature is 90-120° C., and the aging time is 20-60 min.

[0025] During use, the present invention has the following beneficial effects: The present invention introduces water-soluble sulfonate polyester polyol into the polyurethane system, which, as the polyurethane soft segment, not only provides excellent physical and mechanical properties, but also, due to the water absorption of the sulfonate, absorbs moisture in the air on the surface of the material to form a conductive channel that can quickly and effectively transfer static charge. The sulfonate functional group blocked in the polyester chain segment is linked to the material system by an ester bond, and will not migrate out of the system due to water washing, evaporation, friction, etc., resulting in loss of antistatic properties. In addition, in the solvent-free system of the present application, the sulfonate polyester polyol also plays the role of a pore opener, ensuring that the material has the characteristics of being lightweight. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments.

[0027] Therefore, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features of the embodiments may be combined with each other.

[0029] A low-density, high-elasticity, antistatic polyurethane foam material, comprising a white material and a black material, wherein the white material comprises polyether polyol, polyester polyol, sulfonate polyester polyol and a functional additive, and the black material comprises polyester polyol, polyether polyol, sulfonate polyester polyol and diisocyanate; The sulfonate polyester polyol is a hydroxyl-terminated macromolecule formed by dehydration condensation of dicarboxylic acid, alkali metal sulfonate and diol.

[0030] The dicarboxylic acid here can be one or more of succinic acid, glutaric acid, adipic acid, pimelic acid, and sebacic acid, preferably adipic acid.

[0031] The diol here can be one or more of ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, hexanediol, cyclohexanedimethanol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-propanediol, preferably 2-methyl-1,3-propanediol.

[0032] The number average molecular weight of the sulfonate polyester polyol is 500-5000 g / mol, the acid value is 0.2-0.6 mgKOH / g, and the sulfonate content per kilogram is 0.3-0.5 mol.

[0033] Furthermore, the alkali metal sulfonate is lithium 5-sulfoisophthalate.

[0034] Furthermore, the polyester polyol is a hydroxyl-terminated macromolecule formed by dehydration condensation of dicarboxylic acid and diol, and the number average molecular weight of the polyester polyol is 500-5000 g / mol, and the acid value is 0.2-0.6 mgKOH / g.

[0035] The dicarboxylic acid in the polyester polyol is one or more of succinic acid, glutaric acid, adipic acid, pimelic acid and sebacic acid, preferably adipic acid.

[0036] The diol in the polyester polyol may be one or more of ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, hexanediol, cyclohexanedimethanol, 2-methyl-1,3-propanediol, and 3-methyl-1,5-propanediol, preferably ethylene glycol.

[0037] Furthermore, the polyether polyol includes one or more of polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene-oxypropylene polyol, and polytetramethylene ether polyol, and the number average molecular weight of the polyether polyol is 1000-8000 g / mol.

[0038] Furthermore, the diisocyanate includes one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate, naphthalene diisocyanate, and isomers and / or derivatives and / or modified polymers thereof.

[0039] Meanwhile, the NCO content in the black material is 15wt.% to 25wt.% based on the diisocyanate.

[0040] Furthermore, the functional additives include chain extenders, cross-linking agents, foaming agents, foam stabilizers and catalysts.

[0041] The chain extending crosslinking agent here can be any one of ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, hexylene glycol, cyclohexanedimethanol, diethanolamine, trimethylolpropane, glycerol, ethylenediamine, propylenediamine, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-methylenebis(2-chloroaniline) or triethanolamine, or a combination of at least two thereof.

[0042] The blowing agent here can be one of water, ethylene dichloride or cyclopentane or a mixture of more than one of them.

[0043] The foam stabilizer here can be hydroxy silicone oil and / or amino silicone oil, and its number average molecular weight is 2500~5000g / mol.

[0044] The catalyst here can be any one of 1,4-diazo (2,2,2-cyclooctane), triethylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,N-dimethylbenzylamine, N,N'-tetramethylethylenediamine, dimethylaminopropylamine, N,N-dimethylethanolamine, 2,4,6-tris (dimethylaminomethyl) phenol, N-ethylmorpholine, bis-N,N'-dimethylaminoethyl ether, potassium isooctanoate, potassium acetate, organic bismuth, and organic zinc, or a combination of at least two thereof.

[0045] The following is a detailed description in conjunction with specific implementation methods. Example

[0046] Mix 10 parts of sulfonate polyester polyol, 10 parts of polyester polyol, 10 parts of polyether polyol, 2 parts of chain extender cross-linking agent, 1 part of foaming agent, 0.1 parts of foam stabilizer and 0.1 parts of catalyst to obtain a white material component; react 10 parts of sulfonate polyester polyol, 10 parts of polyester polyol, 10 parts of polyether polyol and 10 parts of diisocyanate to obtain a black material component.

[0047] The sulfonate polyester polyol uses lithium 5-sulfonate of isophthalic acid as the alkali metal sulfonate. The mixing temperature of the white material component and the black material component is 40-60°C, the reaction temperature is 70-80°C, and the reaction time is 2-3h.

[0048] Then the white material component and the black material component obtained above are mixed and aged to obtain the polyurethane antistatic material.

[0049] When the white material component and the black material component are mixed, the mass ratio of the hydroxyl equivalent of the white material component to the isocyanate equivalent of the black material component is controlled to be 100: 95-105; the aging temperature is 90-120° C., and the aging time is 20-60 min. Example

[0050] Compared with Example 1, the changes are that 90 parts of sulfonate polyester polyol, 90 parts of polyester polyol, 90 parts of polyether polyol, 30 parts of chain extender cross-linking agent, 5 parts of foaming agent, 2 parts of foam stabilizer and 5 parts of catalyst are mixed to obtain a white material component; 90 parts of sulfonate polyester polyol, 90 parts of polyester polyol, 90 parts of polyether polyol and 90 parts of diisocyanate are reacted to obtain a black material component.

[0051] Other conditions are the same as in Example 1. Example

[0052] Compared with Example 1, the changes are that 50 parts of sulfonate polyester polyol, 50 parts of polyester polyol, 50 parts of polyether polyol, 16 parts of chain extender cross-linking agent, 3 parts of foaming agent, 1 part of foam stabilizer and 3 parts of catalyst are mixed to obtain a white material component; 50 parts of sulfonate polyester polyol, 50 parts of polyester polyol, 50 parts of polyether polyol and 50 parts of diisocyanate are reacted to obtain a black material component.

[0053] Other conditions are the same as in Example 1. Example

[0054] Compared with Example 3, the difference is that when the white material component and the black material component are mixed, the mass ratio of the hydroxyl equivalent of the white material component to the isocyanate equivalent of the black material component is controlled to be 100:95.

[0055] The remaining conditions are the same as those in Example 3. Example

[0056] Compared with Example 3, the difference is that when the white material component and the black material component are mixed, the mass ratio of the hydroxyl equivalent of the white material component to the isocyanate equivalent of the black material component is controlled to be 100:100.

[0057] The remaining conditions are the same as those in Example 3. Example

[0058] Compared with Example 3, the difference is that when the white material component and the black material component are mixed, the mass ratio of the hydroxyl equivalent of the white material component to the isocyanate equivalent of the black material component is controlled to be 100:105.

[0059] The remaining conditions are the same as those in Example 3. Example

[0060] Compared with Example 3, the difference is that the sulfonate polyester polyol uses sodium 5-sulfoisophthalic acid as the alkali metal sulfonate.

[0061] The remaining conditions are the same as those in Example 3. Example

[0062] Compared with Example 3, the difference is that the sulfonate polyester polyol uses potassium 5-sulfoisophthalate as the alkali metal sulfonate.

[0063] The remaining conditions are the same as those in Example 3.

[0064] Comparative Example 1 Compared with Example 3, the difference is that the sulfonate polyester polyol uses lithium dodecylbenzenesulfonate as the alkali metal sulfonate.

[0065] The remaining conditions are the same as those in Example 3.

[0066] Comparative Example 2 Compared with Example 3, the difference is that the sulfonate polyester polyol uses copper methanesulfonate as the metal sulfonate.

[0067] Comparative Example 3 Compared with Example 5, the difference is that when the white material component and the black material component are mixed, the mass ratio of the hydroxyl equivalent of the white material component to the isocyanate equivalent of the black material component is controlled to be 100:110.

[0068] Comparative Example 4 Compared with Example 5, the difference is that when the white material component and the black material component are mixed, the mass ratio of the hydroxyl equivalent of the white material component to the isocyanate equivalent of the black material component is controlled to be 100:90.

[0069] Based on the aforementioned embodiments and comparative examples, Embodiment 3 is taken as the optimal embodiment. Compared with Comparative Example 1, since lithium dodecylbenzenesulfonate is used as the alkali metal salt of the sulfonate polyester polyol in Comparative Example 1, the benzene ring is para-substituted. Thus, when the polyester chain segments wrap around the benzene ring functional groups, the asymmetric wrapping forces the chain segments near the benzene ring functional groups to form a cluster and entangle, thereby improving the elasticity of the material and reducing the negative impact on the elasticity of the material when the rigidity of the material is increased by introducing the benzene ring functional groups.

[0070] In Comparative Example 2, copper methanesulfonate is used as the metal sulfonate of sulfonate polyester polyol. Although copper ions have better electron transfer efficiency, during the application of soles, due to the strong complexing property of copper ions, they are easily complexed with external impurities, resulting in a decrease in the anti-fouling ability of the soles. However, the present application uses lithium 5-sulfonate isophthalic acid as the metal sulfonate of sulfonate polyester polyol, which cannot guarantee the efficiency of electron transfer. At the same time, the stability of lithium ions can also be used to allow the sole material to have certain self-cleaning properties. At the same time, compared with copper ions with too large ionic radius, lithium ions have a smaller ionic radius, which can be better coated by polyester segments, and the material stability is stronger. Compared with other metal sulfonates, the antistatic property is more difficult to be destroyed.

[0071] Compared with Example 3, Example 7 and Example 8. Different alkali metal sulfonates are used to form sulfonate polyester polyols. Compared with sodium ions and potassium ions, lithium ions have a smaller ion radius, which makes the material itself more polarizable. Combined with the stronger electron transport properties of lithium ions compared with sodium ions and potassium ions, when Example 3 of the present application uses lithium 5-sulfonate of isophthalic acid as the alkali metal salt, the polyurethane sole material can have excellent anti-fouling self-cleaning and antistatic properties.

[0072] Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A low-density, high-elasticity, antistatic polyurethane foam material, comprising white material and black material, characterized in that: The white material includes polyether polyol, polyester polyol, sulfonate polyester polyol and functional additives, and the black material includes polyester polyol, polyether polyol, sulfonate polyester polyol and diisocyanate; The sulfonate polyester polyol is a hydroxyl-terminated macromolecule formed by dehydration condensation of dicarboxylic acid, alkali metal sulfonate and diol.

2. The low-density, high-elasticity, antistatic polyurethane foam material according to claim 1, characterized in that: The sulfonate polyester polyol has a number average molecular weight of 500-5000 g / mol, an acid value of 0.2-0.6 mgKOH / g, and a sulfonate content of 0.3-0.5 mol per kilogram.

3. The low-density, high-elasticity, antistatic polyurethane foam material according to claim 1, characterized in that: The alkali metal sulfonate is lithium 5-sulfoisophthalate.

4. The low-density, high-elasticity, antistatic polyurethane foam material according to claim 1, characterized in that: The polyester polyol is a hydroxyl-terminated macromolecule formed by dehydration condensation of dicarboxylic acid and diol. The number average molecular weight of the polyester polyol is 500-5000 g / mol and the acid value is 0.2-0.6 mgKOH / g.

5. The low-density, high-elasticity, antistatic polyurethane foam material according to claim 1, characterized in that: The polyether polyol includes one or more of polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene-oxypropylene polyol, and polytetramethylene ether polyol. The number average molecular weight of the polyether polyol is 1000-8000 g / mol.

6. The low-density, high-elasticity, antistatic polyurethane foam material according to claim 1, characterized in that: The diisocyanate includes one or more of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate, naphthalene diisocyanate, and isomers and / or derivatives and / or modified polymers thereof.

7. The low-density, high-elasticity, antistatic polyurethane foam material according to claim 1, characterized in that: The NCO content of the black material is 15 wt.% to 25 wt.% based on the diisocyanate.

8. The low-density, high-elasticity, antistatic polyurethane foam material according to claim 1, characterized in that: The functional additives include a chain extender, a cross-linking agent, a foaming agent, a foam stabilizer and a catalyst.

9. A method for preparing the low-density, high-elasticity, antistatic polyurethane foam material according to any one of claims 1 to 8, characterized in that: The following steps are involved: S100. Dispose the white material and the black material separately; S200. The white material and the black material are mixed and then aged to obtain the foaming material.

10. The preparation method according to claim 9, characterized in that: In the step S100, the mixing temperature is 40-60°C, the reaction temperature is 70-80°C, and the reaction time is 2-3h; In the step S200, the mass ratio of the hydroxyl equivalent of the white material to the diisocyanate equivalent of the black material is 100:95-105, the aging temperature is 90-120° C., and the aging time is 20-60 min.