Antistatic polyurethane

Abstract

The invention discloses an antistatic polyurethane, which is obtained by molding polyurethane resin, and the polyurethane resin comprises 1, 8-diazabicyclo [5.4. 0]-7-undecylene and / or a phenate of the 1, 8-diazabicyclo [5.4. 0]-7-undecylene. According to the invention, the process problem caused by adding a conductive material and / or an antistatic agent and the reduction in product performance can be avoided, a polyurethane product with excellent antistatic performance can be obtained under the condition of not additionally introducing the conductive material and / or the antistatic agent, and the resistance can be reduced to 106-108 omega.

Description

Technical Field

[0001] This invention relates to the field of polyurethane, specifically to an antistatic polyurethane and the application of 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salts in improving the conductivity and antistatic properties of polyurethane. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Polyurethane and its microporous elastomers have advantages such as superior physical properties, wide range of hardness and density, good production adjustability, and chemical resistance, and are increasingly being used.

[0004] Ordinary polyurethane has a high surface resistivity (10). 14 Polyurethane (Ω) materials, which cannot meet the standards for antistatic materials, often generate static electricity on their surfaces due to friction during application. This static electricity cannot be eliminated in time through conduction or leakage, leading to the accumulation of static charge on the material surface and causing various problems and hazards. Polyurethane and its microporous elastomers with antistatic properties are of particular significance in scenarios requiring antistatic properties and are of great importance for safety in production sites.

[0005] Currently, antistatic technologies are all implemented by adding conductive materials and / or antistatic agents to reduce resistivity and improve conductivity. Conductive materials include carbon nanotubes, graphene, carbon black, metal powders, and metal oxide powders, while antistatic agents include quaternary ammonium salts and alkali metal salts.

[0006] The patent specification with publication number CN101962473A discloses a method for preparing a wear-resistant, hydrolysis-resistant, and antistatic polyurethane material and the shoe material made from it. The preparation method of this wear-resistant, hydrolysis-resistant, and antistatic polyurethane material includes the following steps: (1) baking the prepared polyol and isocyanate in an oven for later use; (2) adding a chain extender, catalyst, foaming agent, foam stabilizer, antioxidant, antistatic agent, and inorganic filler to the baked polyol and mixing them evenly to form material A; (3) mixing material A and the baked isocyanate material B to form a wear-resistant, hydrolysis-resistant, and antistatic polyurethane material. The antistatic agent is one of the following: quaternary ammonium salt cationic surfactant, polyether polymeric permanent antistatic agent, or nonionic surfactant.

[0007] Patent specification CN101974219A discloses a method for preparing a wear-resistant and antistatic polyurethane material and the shoe material made from it. This wear-resistant and antistatic polyurethane material is formed by mixing and casting raw material A and raw material B. Raw material A includes 30%-45% polyol, 3%-9% chain extender, 0.5%-0.9% catalyst, 0.05%-0.2% foaming agent, 0.05%-0.1% foam stabilizer, 0.5%-1% antioxidant, and 1%-10% inorganic conductive powder by mass. Raw material B is 40%-55% isocyanate by mass. The inorganic conductive powder is one or more of conductive titanium dioxide powder, conductive barium sulfate powder, and conductive mica powder.

[0008] However, the addition of conductive materials or antistatic agents increases the dispersion process in the production of polyurethane resins. At the same time, the production process of microporous elastomers is more difficult to control and will also reduce the physical properties of the material. Summary of the Invention

[0009] To address the aforementioned technical problems and shortcomings in the field, this invention provides an antistatic polyurethane that avoids the processing difficulties and performance degradation caused by adding conductive materials and / or antistatic agents. It can obtain a polyurethane product with excellent antistatic properties without introducing additional conductive materials and / or antistatic agents.

[0010] The specific technical solution is as follows: An antistatic polyurethane is obtained by molding a polyurethane resin, wherein the polyurethane resin comprises 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salt. The phenolic salt of 1,8-diazabicyclo[5.4.0]-7-undecene has a better effect on improving the conductivity and antistatic properties of the polyurethane than 1,8-diazabicyclo[5.4.0]-7-undecene itself. 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salt can act as a catalyst in the polyurethane production process.

[0011] In the polyurethane resin, the mass percentage of 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salt is preferably 0.1% or more, for example 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 3%, 4%, 5%, etc., and may further be 0.1% to 5%, and even further may be 0.4% to 1%.

[0012] Phenolic salts of 1,8-diazabicyclo[5.4.0]-7-undecene can be obtained by direct addition and / or reaction of 1,8-diazabicyclo[5.4.0]-7-undecene with phenolic antioxidants. Direct addition is preferred, as it is more beneficial to improving the conductivity and antistatic properties of polyurethane.

[0013] In this invention, the phenolic antioxidant can be any antioxidant with a phenolic structure known in the art, such as 2,6-di-tert-butyl-p-cresol.

[0014] The phenolic salts of 1,8-diazabicyclo[5.4.0]-7-undecene can be phenolic salts or products obtained by reacting 1,8-diazabicyclo[5.4.0]-7-undecene with phenolic antioxidants.

[0015] The phenolic salt of 1,8-diazabicyclo[5.4.0]-7-undecene can be prepared in advance before the preparation of polyurethane (prepared by referring to existing technology or obtained through commercial means, etc.), or it can be formed in the polyurethane product through a reaction during the preparation of the polyurethane product. The reaction can be the reaction of 1,8-diazabicyclo[5.4.0]-7-undecene and phenolic antioxidants, etc.

[0016] In some preferred embodiments, the polyurethane resin further comprises a phenolic antioxidant. 1,8-diazabicyclo[5.4.0]-7-undecene can react with the phenolic antioxidant to form a phenolic salt of 1,8-diazabicyclo[5.4.0]-7-undecene, thereby further improving the conductivity and antistatic properties of the polyurethane.

[0017] In the polyurethane resin, the phenolic antioxidant preferably accounts for more than 0.01% by mass, for example, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 3%, 4%, 5%, etc., and may further be 0.01% to 5%, and even more preferably 0.08% to 1%.

[0018] As a general inventive concept, this invention also provides the application of 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salts in improving the conductivity and antistatic properties of polyurethane. Furthermore, the phenolic salts of 1,8-diazabicyclo[5.4.0]-7-undecene can be obtained by direct addition and / or by reacting 1,8-diazabicyclo[5.4.0]-7-undecene with phenolic antioxidants; direct addition is preferred, as it is more beneficial for improving the conductivity and antistatic properties of polyurethane.

[0019] This invention does not impose any particular limitation on the preparation process of polyurethane (resin), and methods commonly used in the art can be employed. If foaming is involved in the preparation process, the foaming process can also employ conventional techniques existing in the art, such as pouring polyurethane resin into a mold for foaming, wherein the temperature of the mold can be set to 30~80℃, for example, 60℃.

[0020] In addition to the composition and dosage of polyurethane (resin) explicitly defined in this invention, other components and dosages of polyurethane (resin) are not particularly limited and can adopt commonly used raw material formulations and proportions in the art, such as polyisocyanates, polyols, etc. In some embodiments, chain extenders, catalysts, surfactants, foaming agents, fillers, antioxidants, etc., may also be included. In this invention, chain extenders should be interpreted broadly, that is, they include crosslinking agents. The introduction of foaming agents can make the resulting antistatic polyurethane a microporous elastomer, which can then be used to make shoe soles, insoles, etc. In addition to the phenolic antioxidants mentioned above, the antistatic polyurethane of this invention may not contain other antioxidants or may contain other types of antioxidants. The other types of antioxidants are not particularly limited and can be varieties and substances commonly used in the art.

[0021] For example, the mass content of isocyanate groups (-NCO) in the polyisocyanate may be 3%-24%.

[0022] For example, the polyisocyanate may include at least one of diphenylmethane diisocyanate, hexamethylene diisocyanate (HDI), HDI polymers (e.g., trimers), toluene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, etc.

[0023] For example, the polyol may include at least one of diols, triols, etc.

[0024] For example, the polyol may include at least one of polyether polyols (such as polypropylene glycol PPG), polyester polyols, polycarbonate polyols, polyether ester polyols, polycaprolactone polyols, etc.

[0025] For example, the number-average molecular weight of the polyol may be 300-6000 g / mol, such as 2000 g / mol.

[0026] For example, the chain extender may include at least one of ethylene glycol, pentanediol, 1,3-propanediol, 1,4-butanediol, hexanediol, triethanolamine, diethanolamine, hydroxyethyldiamine, glycerol, trimethylolpropane, etc.

[0027] For example, the catalyst may include at least one of a foaming catalyst, a gel catalyst, etc.

[0028] For example, the catalyst may include amine catalysts, or amine catalysts and metal catalysts, etc.

[0029] For example, the amine catalyst may include at least one of tertiary amine catalysts, secondary amine catalysts, and primary amine catalysts, specifically including N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, triethylenediamine, tetramethylalkylene diamine, pentamethyldiethylenetriamine, triethylamine, N,N-dimethylbenzylamine, N,N-dimethylhexadecanamine, 2-hydroxy-N,N,N-trimethyl-1-propylaminocarbamate, and 2,2-bismorpholinodiethyl ether. At least one of the following: 2-[[2-[2-(dimethoxy)ethylchloroethyl]methylamino]-ethanol-hydroxybenzoic acid-N,N,N,N'tetramethyl-2,2-oxydi(ethylamine)-tertiary amine, N,N-dialkylaminoalkylamine, tertiary amine-2(dimethyl)ethanol-carboxylic acid-cyclic amine, ethylene glycol-cyclic amine-tertiary amine, tertiary amine-2((2-dialkylaminoalkoxy)alkyl)alkylamino)alkylol-2,2-oxydi(N,N-dimethylethylamine).

[0030] For example, the metal catalyst may include at least one of the following: stannous neodecanoate, stannous octanoate, dibutyltin dilaurate, stannous isooctanoate, dimethyltin, trimethyltin, methyltin mercaptan, octyltin, bismuth isooctanoate, bismuth caprylate, zinc isooctanoate, zinc caprylate, potassium isooctanoate, potassium oleate, potassium acetate, etc.

[0031] For example, the surfactant may include at least one of DC-193, L1507, L1568, SI4203, B8002, B8962, B8905, B8915, B8930, B8935, and B8946PF. DC-193, L1507, and L1568 are available from Momentive Advanced Materials Group; SI4203, B8002, B8962, B8905, B8915, B8930, B8935, and B8946PF are available from Evonik Specialty Chemicals (Shanghai) Co., Ltd.

[0032] For example, the foaming agent may include at least one of water, physical foaming agents, etc.

[0033] For example, the filler may include at least one of bentonite, wollastonite, calcium carbonate, magnesium oxide, titanium dioxide, fumed silica, etc.

[0034] The present invention does not particularly limit the form of polyurethane (resin), which can be any common form in the art, can be liquid, can be solid, can be various types of profiles, can be foamed or not, can be elastomer or non-elastomer, can be thermoplastic or thermosetting, etc.

[0035] In some embodiments, the polyurethane resin includes component A and component B. The raw material composition of component A may include polyols, and may also include one or more of catalysts, surfactants, foaming agents (e.g., water), fillers, chain extenders, antioxidants, etc. The raw material composition of component B may include polyisocyanates, and may also include one or more of polyols, antioxidants, etc.

[0036] For example, by weight, the polyurethane resin may include 100 parts of component A, 50 to 90 parts (more likely 65 to 75 parts, such as 70 parts, etc.) of component B, and 0.1 to 5 parts (such as 0.8 parts, etc.) of 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salts.

[0037] For example, by mass, component A may include 100 parts of polyol, and may also include any one or a combination of the following: 0.2 to 3 parts of surfactant, chain extender not exceeding 20% ​​of the total mass of component A (e.g., 1%, 5%, 7%, 8%, 10%, 15%, etc.), foaming agent (e.g., water, etc.) not exceeding 15% of the mass of polyol in component A (e.g., 0.1%, 0.5%, 1%, 5%, 10%, etc.), filler not exceeding 45% of the mass of polyol in component A, phenolic antioxidant, etc. not exceeding 10% of the mass of polyol in component A.

[0038] For example, by weight, component B may include 100 to 200 parts (e.g., 150 parts, etc.) of polyisocyanate, and may also include any one or a combination of the following: 100 parts of polyol, phenolic antioxidants not exceeding 10% by weight of the polyol in component B, etc.

[0039] The introduction of 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salts into polyurethane resin can be selected from any one or a combination of the following: 1) added as one of the raw material components during the preparation of component A; 2) forming an independent component C for mixing with component A. In addition to containing 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salts, component C may also contain diluents, dispersants, etc., to ensure uniform dispersion of 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salts.

[0040] The introduction of phenolic antioxidants into polyurethane resins can be selected from any one or a combination of the following: 1) added as one of the raw materials during the preparation of component A; 2) added as one of the raw materials during the preparation of component B.

[0041] Polyurethane resin can be obtained by mixing components A and B, or by mixing components A, B, and C. Furthermore, the mixing order of components A, B, and C can be that component A is mixed with component C first, and then with component B.

[0042] In some cases, component A can be obtained by mixing the raw materials of component A.

[0043] In some cases, the temperature for preparing component A can be room temperature to 90°C, such as 40°C, 50°C, 65°C, etc.

[0044] In some cases, component A can be kept at a certain temperature, such as 65~95℃, before or during mixing with other components.

[0045] In some cases, when a polyol is used in component B, the polyol can be preheated and vacuum-dehydrated.

[0046] In some cases, prepolymerization can be carried out at an appropriate temperature during the preparation of component B. Furthermore, the prepolymerization temperature can be 65-95°C. Prepolymerization is preferably carried out under an inert atmosphere. The inert atmosphere described in this invention refers to an atmosphere that does not participate in the reaction, such as a nitrogen atmosphere or a rare gas atmosphere.

[0047] Compared with the prior art, the beneficial effects of this invention are as follows: This invention uses the catalyst 1,8-diazabicyclo[5.4.0]-7-undecene, and / or, the reaction of 1,8-diazabicyclo[5.4.0]-7-undecene with phenolic antioxidants to produce phenolates, and / or, directly using the phenolate catalyst of 1,8-diazabicyclo[5.4.0]-7-undecene. 1,8-diazabicyclo[5.4.0]-7-undecene and its phenolates, while acting as catalysts, can also significantly improve the conductivity of polyurethane, thereby achieving the production of polyurethane products with excellent antistatic effects without the addition of additional antistatic additives, with resistance reduced to 10 Ω·cm. 6 ~10 8 Ω.

[0048] This invention eliminates the need for additional antistatic agents, reduces the dispersion process of antistatic agents, and solves the process adjustment problems caused by adding external antistatic agents.

[0049] The preparation method of this invention is simple, practical, and easy to promote. Antistatic polyurethane has a wide range of applications and can be used in electronics, clothing, home furnishings, medical, transportation, packaging and other fields. Detailed Implementation

[0050] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Operating methods not specifically specified in the following embodiments are generally performed under conventional conditions or as recommended by the manufacturer.

[0051] Unless otherwise specified, the material usage "parts" in the following examples refer to parts by mass.

[0052] Example 1: Preparation of Component A: 100 parts of polyester polyol P1320A1 from Meirui New Materials Co., Ltd., 8 parts of ethylene glycol, 0.7 parts of water, 0.7 parts of surfactant B8905, and 2 parts of trimethylolpropane (TMP) were added to a reaction vessel, stirred, and heated to 65°C. The mixture was stirred at a constant temperature for 1.5 hours to obtain Component A.

[0053] Preparation of Component B: 100 parts of polyester polyol P1320A1 from Meirui New Materials Co., Ltd. were added to a reaction vessel and stirred evenly. The mixture was heated to 125°C and degassed under vacuum for 1.5 hours at a vacuum degree of -0.1 MPa. Then the mixture was cooled to 65°C, and 150 parts of diphenylmethane diisocyanate (MDI) were added. The mixture was reacted for 2.5 hours and then cooled to 50°C. The mixture was then discharged to obtain Component B.

[0054] Add 1,8-diazabicyclo[5.4.0]-7-undecenephenol salt (component C) to component A and mix evenly. Then mix it evenly with component B at a weight ratio of A:B=100:70. Pour the mixture into a mold at 50℃ for foaming to obtain polyurethane microporous elastomer.

[0055] The amount of component C is 0.8 parts of 1,8-diazabicyclo[5.4.0]-7-undecenephenol salt added to every 100 parts of polyester polyol in component A.

[0056] Example 2: The preparation of component A is the same as in Example 1.

[0057] Preparation of component B: The only difference from Example 1 is that 100 parts of polyester polyol P1320A1 from Meirui New Materials Co., Ltd. and 0.5 parts of phenolic antioxidant 2,6-di-tert-butyl-p-cresol were added to the reaction vessel and stirred evenly. All other aspects are the same.

[0058] 1,8-diazabicyclo[5.4.0]-7-undecene (component C) is added to component A and mixed evenly. Then, it is mixed evenly with component B at a weight ratio of A:B=100:70. The mixture is then poured into a mold at 50°C for foaming to obtain polyurethane microporous elastomer.

[0059] The amount of component C is 0.8 parts of 1,8-diazabicyclo[5.4.0]-7-undecene added per 100 parts of polyester polyol in component A.

[0060] Example 3: The only difference from Example 2 is that in the preparation of component B, the same amount of the non-phenolic antioxidant tris(2,4-di-tert-butylphenyl) phosphite is used instead of the phenolic antioxidant; all other aspects are the same.

[0061] Example 4: The only difference from Example 2 is that 1,8-diazabicyclo[5.4.0]-7-undecene is replaced by an equal amount of catalyst A33 in component C; all other aspects are the same.

[0062] Table 1 shows the resistance of the polyurethane microporous elastomers obtained in Examples 1-4.

[0063] Table 1 Furthermore, it should be understood that after reading the above description of the present invention, those skilled in the art can make various alterations or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims.

Claims

1. An antistatic polyurethane, obtained by molding polyurethane resin, characterized in that, The polyurethane resin comprises 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salts.

2. The antistatic polyurethane according to claim 1, characterized in that, In the polyurethane resin, the mass percentage of 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salt is 0.1% or more.

3. The antistatic polyurethane according to claim 2, characterized in that, In the polyurethane resin, the mass percentage of 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salt is 0.1% to 5%.

4. The antistatic polyurethane according to claim 3, characterized in that, In the polyurethane resin, the mass percentage of 1,8-diazabicyclo[5.4.0]-7-undecene and / or its phenolic salt is 0.4% to 1%.

5. The antistatic polyurethane according to any one of claims 1 to 4, characterized in that, The polyurethane resin also contains phenolic antioxidants.

6. The antistatic polyurethane according to claim 5, characterized in that, In the polyurethane resin, the phenolic antioxidant accounts for more than 0.01% by mass.

7. The antistatic polyurethane according to claim 6, characterized in that, In the polyurethane resin, the phenolic antioxidant accounts for 0.01% to 5% by mass.

8. The antistatic polyurethane according to claim 7, characterized in that, In the polyurethane resin, the phenolic antioxidant accounts for 0.08% to 1% of the total mass. 9.1,8-Diazabicyclo[5.4.0]-7-undecene and / or its phenolic salts in improving the conductivity and antistatic properties of polyurethane.

10. The application according to claim 9, characterized in that, Phenolates of 1,8-diazabicyclo[5.4.0]-7-undecene are obtained by direct addition and / or reaction of 1,8-diazabicyclo[5.4.0]-7-undecene with phenolic antioxidants.

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