CN114133529B - Aromatic polyurethane resin and preparation method and application thereof - Google Patents
Aromatic polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN114133529B CN114133529B CN202111526393.6A CN202111526393A CN114133529B CN 114133529 B CN114133529 B CN 114133529B CN 202111526393 A CN202111526393 A CN 202111526393A CN 114133529 B CN114133529 B CN 114133529B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/6715—Unsaturated monofunctional alcohols or amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/10—Properties of the materials having mechanical properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1664—Releasability
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
The invention provides an aromatic polyurethane resin, a preparation method and application thereof. The raw materials of the aromatic polyurethane resin comprise 40-88 parts by weight of polyether polyol, 5-70 parts by weight of cardanol, 7-25 parts by weight of aromatic isocyanate and 2-12 parts by weight of sealing agent; the cardanol comprises a combination of a first cardanol and a second cardanol; the first cardanol comprises any one or a combination of at least two of NX-9201, NX-9007 or NX-9008; the second cardanol comprises NX-2026. The aromatic polyurethane resin has good self-wetting leveling property by selecting the specific cardanol combination, polyether polyol, aromatic isocyanate and sealing agent, no additional leveling agent is needed, the adhesive force after curing is enhanced, and the material comprising the aromatic polyurethane resin has high peeling strength and good moisture and heat resistance.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, and particularly relates to aromatic polyurethane resin, a preparation method and application thereof.
Background
The main technical directions of the polyurethane synthetic leather industry are four main categories: solvent-type polyurethane, solvent-free two-component polyurethane, high-solid-content closed two-component polyurethane and water-based polyurethane. Solvent-based polyurethanes are prone to environmental pollution; the solvent-free double-component polyurethane is environment-friendly, but has poor storability, and the preparation process can be implemented only by a special pressure foaming machine, so that the operation difficulty is high; the high-solid-content closed double-component polyurethane has high viscosity, and a small amount of environment-friendly solvent is generally required to be introduced; the aqueous polyurethane product is environment-friendly, but the auxiliary agent is various, and meanwhile, the stability and physical properties of the product are relatively poor. The four types of polyurethane have the characteristics, but have the defects, so that the search for polyurethane products with simple process, environmental protection and high performance is always a hot spot for research in the industry.
For example, CN101812228A discloses an all-toluene solvent type polyurethane resin and a preparation method thereof. The polyurethane resin comprises polyurethane and toluene, and does not contain other components, so that the toluene can be recovered by using an activated carbon toluene recovery system, the defect that the solvent type polyurethane resin in the current market cannot recover the toluene by using the activated carbon toluene recovery system because of containing a plurality of solvent combinations instead of a single solvent is overcome, the economic benefit is improved, and the environment is protected. However, the above-mentioned problems can only be improved to some extent, and the problems cannot be completely avoided.
CN103772618A discloses an acrylic ester modified polyurethane resin for leather finishing and a preparation method thereof. The polyurethane resin comprises polyalcohol, solvent, chain extender micromolecular alcohol, antioxidant, isocyanate, catalyst, polymerization inhibitor, hydroxyl-containing acrylic ester, end-capping agent, initiator and acrylic monomer. The polyurethane resin is used as a base material, and the acrylic ester is used as a main modified material, so that the polyurethane resin has the advantages of two resins, the cost is low, and the solid content is improved to more than 50%. However, the modified polyurethane resin is disadvantageous for use at low temperatures.
CN107602802a discloses a solvent-free polyurethane resin for a sofa leather intermediate foaming layer and a preparation method thereof. The polyurethane resin comprises polyether polyester copolymer oligomer dihydric alcohol, a chain extender, a cross-linking agent, water, a catalyst, a foam stabilizer, a stabilizer, polypropylene oxide dihydric alcohol and isocyanate. The polyurethane resin does not contain any organic solvent, and the synthetic leather prepared by using the polyurethane resin as an intermediate layer has high peeling strength, good low-temperature folding endurance at-10 ℃, environment friendliness and soft hand feeling. However, the synthetic leather has a low peel retention rate and is disadvantageous for use at lower temperatures.
Therefore, development of a polyurethane resin which has strong adhesive force, high peel strength, excellent low-temperature folding endurance and wet heat resistance, low viscosity and environmental protection is a problem to be solved in the art.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the aromatic polyurethane resin, and the raw materials of the aromatic polyurethane resin are cardanol, specific polyether polyol, aromatic isocyanate and a sealing agent which are combined in a specific way, so that the polyurethane resin has low viscosity, high peel strength, good moisture and heat resistance, no solvent dilution and environmental protection; the material comprising the aromatic polyurethane resin has excellent mechanical properties.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an aromatic polyurethane resin, wherein the aromatic polyurethane resin comprises 40-88 parts by weight of polyether polyol, 5-70 parts by weight of cardanol, 7-25 parts by weight of aromatic isocyanate and 2-12 parts by weight of a sealing agent; the cardanol comprises a combination of a first cardanol and a second cardanol; the first cardanol comprises any one or a combination of at least two of NX-9201, NX-9007 or NX-9008; the second cardanol comprises NX-2026.
According to the invention, the cardanol is added, so that the aromatic polyurethane resin has good leveling property without adding a leveling agent; the aromatic polyurethane resin has excellent tensile property and good heat resistance by selecting the combination of specific cardanol and being matched with polyether polyol, aromatic isocyanate and a sealing agent; the synthetic leather comprising the aromatic polyurethane resin has high peel strength, good moisture and heat resistance and excellent low-temperature folding endurance.
In the invention, the second cardanol serves as a blocking agent for isocyanate groups.
Preferably, the raw materials of the aromatic polyurethane resin include 40 to 88 parts by weight of polyether polyol, for example, 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts, 72 parts, 74 parts, 78 parts, 80 parts, 82 parts, 84 parts, 86 parts, 88 parts, etc.
Preferably, the raw materials of the aromatic polyurethane resin include 5 to 70 parts by weight of cardanol, for example, 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, etc.
Preferably, the aromatic polyurethane resin comprises 7 to 25 parts by weight of aromatic isocyanate, for example, 7 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, etc.
Preferably, the raw material of the aromatic polyurethane resin includes 2 to 12 parts by weight of a blocking agent, for example, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, etc.
As a preferable technical scheme of the invention, the raw materials of the aromatic polyurethane resin comprise 50-85 parts by weight of polyether polyol, 5-35 parts by weight of cardanol, 10-21 parts by weight of aromatic isocyanate and 3-6 parts by weight of sealing agent.
Preferably, the polyether polyol has a functionality of 2 or 3.
The polyether polyol preferably has a number average molecular weight of 250 to 8000, and may be, for example, 250, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, or the like.
In the present invention, if the molecular weight of the polyether polyol is more than 8000, the reaction is incomplete due to low hydroxyl activity, so that the high-temperature curing and crosslinking are incomplete, the curing performance is poor, and when the molecular weight is too large, the reaction is difficult to occur.
Preferably, the polyether polyol comprises any one or a combination of at least two of polypropylene oxide ether polyol, polytetrahydrofuran ether glycol or polypropylene oxide tetrahydrofuran copolyether glycol.
Preferably, the polyether polyol comprises a polypropylene oxide ether polyol.
Preferably, the polypropylene oxide ether polyol comprises polypropylene oxide ether diol and/or polypropylene oxide ether triol.
Preferably, the polypropylene oxide ether polyol comprises polypropylene oxide ether diol and polypropylene oxide ether triol.
Preferably, the mass ratio of the polypropylene oxide ether glycol to the polypropylene oxide ether triol is (0.2-6): 1, for example, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, etc.
Preferably, the mass ratio of the first cardanol to the second cardanol is (0.3-6): 1, for example, may be 0.3:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 4:1, 5:1, 6:1, etc.
In the invention, if the mass ratio of the first cardanol to the second cardanol is too low, the softening temperature is low due to the too small amount of the first cardanol, and the hydrolysis resistance is insufficient in a 70 ℃/95% humidity test; if the mass ratio of the first cardanol to the second cardanol is too high, the product cost is too high.
Preferably, the aromatic isocyanate comprises any one or a combination of at least two of 2, 4-diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate, toluene-2, 4-diisocyanate or toluene-2, 6-diisocyanate.
Preferably, the blocking agent comprises N-methylacetamide.
In a second aspect, the present invention provides a method for producing the aromatic polyurethane resin according to the first aspect, the method comprising the steps of:
(1) Reacting polyether polyol, first cardanol and aromatic isocyanate to obtain polyurethane prepolymer;
(2) And (3) reacting the polyurethane prepolymer with second cardanol and a blocking agent to obtain the aromatic polyurethane resin.
In the present invention, the molar ratio of the isocyanate group in the aromatic isocyanate to the polyether polyol and the hydroxyl group in the first cardanol is 1.8 to 2.2, and may be, for example, 1.8, 1.9, 2, 2.1, 2.2, or the like.
As a preferred embodiment of the present invention, the reaction in the step (1) comprises a first stage reaction and a second stage reaction.
Preferably, the temperature of the first stage reaction is 65 to 80 ℃, and may be 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃,70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 78 ℃, 80 ℃ or the like, for example.
Preferably, the time of the first stage reaction is 2 to 7 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc.
Preferably, the first stage reaction comprises a first stage reaction with a first cardanol after pre-reacting a polyether polyol with an aromatic isocyanate; or, subjecting polyether polyol, first cardanol and aromatic isocyanate to a first stage reaction.
The polyether polyol and the aromatic isocyanate are preferably pre-reacted at a temperature of 70 to 80℃and may be, for example, 70℃71℃72℃73℃74℃75℃76℃77℃78℃79℃80 ℃.
Preferably, the polyether polyol is pre-reacted with the aromatic isocyanate for a period of 3 to 4 hours, for example, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, etc.
In the invention, after the pre-reaction, the raw materials for the first-stage reaction with the first cardanol also comprise other polyether polyols; the other polyether polyols include polypropylene oxide ether polyols.
In the invention, the step of pre-mixing the polyether polyol and the cardanol is further included before the first stage reaction of the polyether polyol, the first cardanol and the aromatic isocyanate.
Preferably, the temperature of the pre-mixing is 25 to 30 ℃, and may be, for example, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, or the like.
Preferably, the pre-mixing time is 5 to 20min, for example, 5min, 10min, 15min, 20min, etc.
Preferably, the temperature of the second stage reaction is 80 to 85 ℃, for example, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, and the like.
Preferably, the second stage reaction time is 2 to 6 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, etc.
Preferably, the mass percentage of isocyanate groups in the polyurethane prepolymer is less than or equal to 4.06%, for example, 2%, 2.68%, 2.7%, 2.79%, 2.80%, 3.03%, 3.35%, 4.06%, etc.
Preferably, the reaction in the step (2) is carried out at a temperature of 65 to 80℃and may be carried out at 66℃68℃70℃71℃72℃73℃74℃75℃76℃77℃78℃79℃80 ℃.
Preferably, the reaction time in the step (2) is 30 to 90min, for example, 30min, 40min, 50min, 60min, 70min, 80min, 90min, etc.
Preferably, the preparation method comprises the following steps:
(1) Pre-reacting polyether polyol with aromatic isocyanate for 3-4 hours at 70-80 ℃, adding first cardanol, and reacting for 2-7 hours at 65-80 ℃, or reacting polyether polyol, aromatic isocyanate and first cardanol for 2-7 hours at 65-80 ℃; then reacting for 2-6 hours at the temperature of 80-85 ℃ to obtain polyurethane prepolymer;
(2) And (3) reacting the polyurethane prepolymer with second cardanol and a sealing agent for 30-90 min at 65-80 ℃ to obtain the aromatic polyurethane resin.
In the present invention, after the polyether polyol and the aromatic isocyanate are pre-reacted at 70 to 80℃for 3 to 4 hours, the temperature is required to be reduced to 45 to 55℃when the first cardanol is added, and for example, 45℃46℃47℃48℃49℃50℃51℃52℃53℃54℃55 ℃.
In a third aspect, the present invention provides a polyurethane resin film comprising 90 to 100 parts by weight of the aromatic polyurethane resin of the first aspect and 4 to 17 parts by weight of a curing agent.
Preferably, the polyurethane resin film includes 90 to 100 parts by weight of the aromatic polyurethane resin according to the first aspect, and may be, for example, 90 parts, 92 parts, 94 parts, 96 parts, 98 parts, 100 parts, etc.
Preferably, the polyurethane resin film includes 4 to 17 parts by weight of the curing agent, for example, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, etc.
Preferably, the curing agent comprises an amine curing agent, further preferably 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane.
Preferably, the polyurethane resin film is prepared by a method comprising:
and mixing the aromatic polyurethane resin with a curing agent, defoaming, coating the mixture on a plate, and drying the plate after the first curing and the second curing to obtain the polyurethane resin film.
Preferably, the time for the deaeration is 20 to 40min, for example, 20min, 25min, 30min, 35min, 40min, etc.
Preferably, the temperature of the first curing is 95 to 100 ℃, and may be, for example, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, 100 ℃, or the like.
Preferably, the time of the first curing is 1 to 2 minutes, for example, 1 minute, 1.2 minutes, 1.4 minutes, 1.6 minutes, 1.8 minutes, 2 minutes, and the like may be used.
Preferably, the temperature of the second curing is 140 to 150 ℃, and for example, 140 ℃, 142 ℃, 144 ℃, 146 ℃, 148 ℃, 150 ℃ and the like can be used.
Preferably, the second curing time is 3 to 5 minutes, for example, 3 minutes, 4 minutes, 5 minutes, etc.
Preferably, the drying temperature is 60 to 70 ℃, and may be 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃,70 ℃ or the like, for example.
In the invention, when cardanol is not added into the polyurethane resin, a leveling agent is required to be added, and the cured polyurethane resin film has better leveling property.
In a fourth aspect, the present invention provides a synthetic leather comprising a top material layer, a polyurethane layer, a primer layer, and a base material laminated in this order; the polyurethane layer includes the aromatic polyurethane resin according to the first aspect and/or the polyurethane resin film according to the third aspect.
Preferably, the material of the fabric layer comprises 95 to 105 parts by weight of aliphatic polycarbonate resin JF-PDY-851MY, 0.4 to 0.6 part by weight of flatting agent, 3 to 5 parts by weight of color paste and 0.4 to 0.6 part by weight of thickener.
Preferably, the material of the fabric layer includes 95 to 105 parts by weight of an aliphatic polycarbonate resin JF-PDY-851MY, for example, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, 101 parts, 102 parts, 103 parts, 104 parts, 105 parts, etc.
Preferably, the material of the fabric layer includes 0.4 to 0.6 parts by weight of a leveling agent, for example, may be 0.4 parts, 0.5 parts, 0.6 parts, etc.
Preferably, the material of the fabric layer comprises 3-5 parts of color paste in parts by weight, for example, 3 parts, 4 parts, 5 parts and the like.
Preferably, the material of the facestock layer includes 0.4 to 0.6 parts by weight of a thickener, for example, may be 0.4 parts, 0.5 parts, 0.6 parts, etc.
Preferably, the material of the primer layer includes 95 to 105 parts by weight of an aromatic polyether resin JF-PDY-511H and 1 to 3 parts by weight of a thickener.
Preferably, the material of the primer layer comprises 95 to 105 parts by weight of an aromatic polyether resin JF-PDY-511H, for example, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, 101 parts, 102 parts, 103 parts, 104 parts, 105 parts and the like.
Preferably, the material of the primer layer includes 1 to 3 parts by weight of a thickener, for example, 1 part, 2 parts, 3 parts, etc.
Preferably, the substrate comprises imitation cotton linters.
In the invention, the synthetic leather is prepared by the following method, which comprises the following steps:
and sequentially stacking the fabric layer, the polyurethane layer, the primer layer and the base material, and drying to obtain the synthetic leather.
Preferably, the drying includes a first stage drying, a second stage drying, and a third stage drying.
Preferably, the temperature of the first stage drying is 85 to 95 ℃, and may be 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃ or the like, for example.
The temperature of the second-stage drying is preferably 105 to 115 ℃, and may be, for example, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, or the like.
The temperature of the third stage drying is preferably 125 to 135 ℃, and may be 125 ℃, 126 ℃, 127 ℃, 128 ℃, 129 ℃, 130 ℃, 131 ℃, 132 ℃, 133 ℃, 134 ℃, 135 ℃ or the like, for example.
Preferably, the time of the first stage drying, the second stage drying and the third stage drying each independently includes 2 to 4 minutes, and may be, for example, 2 minutes, 2.2 minutes, 2.4 minutes, 2.6 minutes, 2.8 minutes, 3 minutes, 3.2 minutes, 3.4 minutes, 3.6 minutes, 3.8 minutes, 4 minutes, and the like.
Preferably, the preparation method of the fabric layer comprises the following steps: dispersing and defoaming aliphatic polycarbonate resin JF-PDY-851MY, a flatting agent, a wetting agent, color paste and a thickening agent according to the formula amount, and carrying out first doctor blade coating, first drying, second doctor blade coating and second drying to obtain the fabric layer.
Preferably, the dispersing time is 20-40 min, for example, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40min, etc.
Preferably, the defoaming time is 20 to 40min, for example, 20min, 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, 40min, etc.
Preferably, the time of the first blade coating is 8 to 12s, for example, 8s, 9s, 10s, 11s, 12s, etc.
In the preparation method of the fabric layer, the first drying comprises the steps of respectively baking for 3min at the temperature of 80-90 ℃, 100-110 ℃ and 120-130 ℃.
Preferably, the second blade coating time is 10 to 15s, for example, 10s, 11s, 12s, 13s, 14s, 15s, etc.
In the preparation method of the fabric layer, the second drying comprises baking for 3min at 80-90 ℃, 100-110 ℃ and 120-130 ℃ respectively.
Preferably, the preparation method of the primer layer comprises the following steps: and mixing the aromatic polyether resin JF-PDY-511H and the thickener according to the formula amount, and coating the mixture on the surface of the polyurethane layer far away from the fabric layer to obtain the primer layer.
Preferably, the time of the coating is 10 to 30s, and may be, for example, 10s, 12s, 14s, 16s, 18s, 20s, 22s, 24s, 26s, 28s, 30s, etc.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the beneficial effects that:
according to the aromatic polyurethane resin provided by the invention, the viscosity of the aromatic polyurethane resin is less than or equal to 22000cp, and the modulus after curing is more than or equal to 3.4MPa by selecting the specific polyether polyol, the cardanol in the specific combination, the aromatic isocyanate and the sealing agent; the tensile strength is more than or equal to 25.1MPa, and the softening temperature is more than or equal to 185 ℃; the synthetic leather comprising the aromatic polyurethane resin has the peeling force of more than or equal to 9.3kg/3cm, the peeling force after 5 weeks under the conditions of 70 ℃/95% humidity of more than or equal to 8.2kg/3cm, the peeling force retention rate of more than or equal to 84.3%, and the anti-folding performance of more than or equal to 7 ten thousand times under the condition of minus 15 ℃, and has excellent mechanical properties and moisture resistance and heat resistance.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The various materials used in the examples and comparative examples of the present invention are commercially available or may be prepared according to conventional methods in the art unless specifically stated otherwise.
Example 1
This example provides an aromatic urethane resin whose raw materials include, in parts by weight, 70.5 parts of polypropylene oxide ether triol (number average molecular weight of 4800, functionality of 3), 11.8 parts of first cardanol (NX-9201 from Cardolite Co.), 4.2 parts of second cardanol (NX-2026 from Cardolite Co.), 10.3 parts of aromatic isocyanate (TDI-80) and 3.2 parts of N-methylacetamide.
The invention provides a preparation method of aromatic polyurethane resin, which comprises the following specific steps:
(1) Stirring polypropylene oxide ether triol and NX-9201 at 30 ℃ for 10min, rapidly adding TDI-80 at one time, slowly heating to 65 ℃, reacting for 3h, heating to 80 ℃ and reacting for 4h to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 2.68%);
(2) Reacting the polyurethane prepolymer with NX-2026 and N-methylacetamide for 1h at 65 ℃ to obtain the aromatic polyurethane resin.
Example 2
This example provides an aromatic polyurethane resin whose raw materials include 48 parts of polypropylene oxide ether triol (number average molecular weight of 6000, functionality of 3), 14.4 parts of polypropylene oxide ether diol (number average molecular weight of 2000, functionality of 2), 10.7 parts of first cardanol (NX-9201 from Cardolite company), 4.3 parts of second cardanol (NX-2026 from Cardolite company), 19.2 parts of aromatic isocyanate (TDI-80) and 3.4 parts of N-methylacetamide in parts by weight.
The invention provides a preparation method of aromatic polyurethane resin, which comprises the following specific steps:
(1) Reacting polypropylene oxide ether triol with TDI-80 at 75 ℃ for 3 hours, cooling to 55 ℃, adding polypropylene oxide ether diol and NX-9201 to react at 70 ℃ for 2 hours, and then heating to 80 ℃ to react for 3 hours to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 2.8%);
(2) Reacting the polyurethane prepolymer with NX-2026 and N-methylacetamide for 1h at 65 ℃ to obtain the aromatic polyurethane resin.
Example 3
This example provides an aromatic polyurethane resin whose raw materials include, in parts by weight, 13.4 parts of polypropylene oxide ether triol (number average molecular weight of 6000, functionality of 3), 40.1 parts of polypropylene oxide ether triol (number average molecular weight of 4800, functionality of 3), 26.7 parts of first cardanol (NX-9201 from Cardolite Co.), 4.7 parts of second cardanol (NX-2026 from Cardolite Co.), 11.5 parts of aromatic isocyanate (TDI-80) and 3.6 parts of N-methylacetamide.
The invention provides a preparation method of aromatic polyurethane resin, which comprises the following specific steps:
(1) Reacting polypropylene oxide ether triol with TDI-80 at 75 ℃ for 2 hours, cooling to 55 ℃, adding polypropylene oxide ether triol and NX-9201 to react at 70 ℃ for 3 hours, and then heating to 80 ℃ to react for 3 hours to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 3.03%);
(2) Reacting the polyurethane prepolymer with NX-2026 and N-methylacetamide for 1h at 65 ℃ to obtain the aromatic polyurethane resin.
Example 4
This example provides an aromatic polyurethane resin whose raw materials include, in parts by weight, 23.9 parts of polypropylene oxide ether triol (number average molecular weight of 3000, functionality of 3), 47.8 parts of polypropylene oxide ether diol (number average molecular weight of 2000, functionality of 2), 2.4 parts of first cardanol (NX-9008 from Cardolite Co.), 6.1 parts of second cardanol (NX-2026 from Cardolite Co.), 15.1 parts of aromatic isocyanate (TDI-65) and 4.7 parts of N-methylacetamide.
The invention provides a preparation method of aromatic polyurethane resin, which comprises the following specific steps:
(1) Stirring polypropylene oxide ether triol, polypropylene oxide ether diol and NX-9008 at 30 ℃ for 10min, rapidly adding TDI-65 at one time, slowly heating to 75 ℃, reacting for 5h, and heating to 80 ℃ for reacting for 3h to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 4.06%);
(2) Reacting the polyurethane prepolymer with NX-2026 and N-methylacetamide for 1h at 65 ℃ to obtain the aromatic polyurethane resin.
Example 5
This example provides an aromatic polyurethane resin whose raw materials include 16 parts by weight of polypropylene oxide ether triol (number average molecular weight of 3000, functionality of 3), 64.1 parts by weight of polypropylene oxide ether diol (number average molecular weight of 4000, functionality of 2), 1.9 parts by weight of first cardanol (NX-9008 from Cardolite Co.), 4.3 parts by weight of second cardanol (NX-2026 from Cardolite Co.), 10.4 parts by weight of aromatic isocyanate (TDI-65) and 3.3 parts by weight of N-methylacetamide.
The invention provides a preparation method of aromatic polyurethane resin, which comprises the following specific steps:
(1) Stirring polypropylene oxide ether triol, polypropylene oxide ether diol and NX-9008 at 30 ℃ for 10min, rapidly adding TDI-65 at one time, slowly heating to 75 ℃, reacting for 3h, heating to 80 ℃ and reacting for 4h to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 2.7%);
(2) Reacting the polyurethane prepolymer with NX-2026 and N-methylacetamide for 1h at 65 ℃ to obtain the aromatic polyurethane resin.
Example 6
This example provides an aromatic polyurethane resin whose raw materials include, in parts by weight, 63.5 parts of polypropylene oxide ether triol (number average molecular weight of 8000, functionality of 3), 9.1 parts of polypropylene oxide ether diol (number average molecular weight of 2000, functionality of 2), 9.1 parts of first cardanol (NX-9007 from Cardolite Co.), 4.3 parts of second cardanol (NX-2026 from Cardolite Co.), 10.7 parts of aromatic isocyanate (TDI-100), and 3.3 parts of N-methylacetamide.
The invention provides a preparation method of aromatic polyurethane resin, which comprises the following specific steps:
(1) Reacting polypropylene oxide ether triol with TDI-100 at 75 ℃ for 3 hours, cooling to 55 ℃, adding polypropylene oxide ether diol and NX-9007 to react at 70 ℃ for 4 hours, and then heating to 80 ℃ to react for 3 hours to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 2.79%);
(2) Reacting the polyurethane prepolymer with NX-2026 and N-methylacetamide for 1h at 65 ℃ to obtain the aromatic polyurethane resin.
Example 7
This example provides an aromatic polyurethane resin whose raw materials include, in parts by weight, 57.5 parts of polypropylene oxide ether triol (number average molecular weight of 4800, functionality of 3), 14.4 parts of polypropylene oxide ether diol (number average molecular weight of 2000, functionality of 2), 6.7 parts of first cardanol (NX-9007 from Cardolite Co.), 5.1 parts of second cardanol (NX-2026 from Cardolite Co.), 12.4 parts of aromatic isocyanate (TDI-100) and 3.9 parts of N-methylacetamide.
The invention provides a preparation method of aromatic polyurethane resin, which comprises the following specific steps:
(1) Stirring polypropylene oxide ether triol, polypropylene oxide ether diol and NX-9007 at 30 ℃ for 10min, rapidly adding TDI-100 at one time, slowly heating to 65 ℃, reacting for 5h, heating to 80 ℃ and reacting for 2h to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 3.29%);
(2) Reacting the polyurethane prepolymer with NX-2026 and N-methylacetamide for 1h at 65 ℃ to obtain the aromatic polyurethane resin.
Example 8
This example provides an aromatic polyurethane resin whose raw materials include, in parts by weight, 51.6 parts of polypropylene oxide ether triol (number average molecular weight 6000, functionality 3), 17.2 parts of polypropylene oxide ether diol (number average molecular weight 2000, functionality 2), 9.5 parts of first cardanol (NX-9007 from Cardolite Co.), 5.1 parts of second cardanol (NX-2026 from Cardolite Co.), 12.6 parts of aromatic isocyanate (TDI-100) and 4 parts of N-methylacetamide.
The invention provides a preparation method of aromatic polyurethane resin, which comprises the following specific steps:
(1) Reacting polypropylene oxide ether triol with TDI-100 at 75 ℃ for 3 hours, cooling to 55 ℃, adding polypropylene oxide ether diol and NX-9007 to react at 70 ℃ for 5 hours, and then heating to 80 ℃ to react for 2 hours to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 3.35%);
(2) Reacting the polyurethane prepolymer with NX-2026 and N-methylacetamide for 1h at 65 ℃ to obtain the aromatic polyurethane resin.
Example 9
This example provides an aromatic polyurethane resin differing from example 2 only in that the polypropylene oxide ether glycol was replaced with equal parts by weight of polyethylene oxide ether glycol (number average molecular weight: 2000), and the other raw materials and amounts were the same as in example 2.
This example provides a method for preparing the aromatic polyurethane resin, and the specific steps are the same as in example 2.
Example 10
This example provides an aromatic polyurethane resin differing from example 1 only in that polypropylene oxide ether triol, NX-9201 and NX-2026 are stirred at 30℃for 10min in step (1); in the step (2), NX-2026 was not added, and other raw materials, amounts and parameters were the same as in example 1.
Example 11
This example provides an aromatic polyurethane resin differing from example 1 only in that NX-9201 was replaced with 4.2 parts of NX-2026 in step (1), NX-2026 was replaced with 11.8 parts of NX-9201 in step (2), and other raw materials, amounts and parameters were the same as in example 1.
Comparative example 1
This comparative example provides an aromatic polyurethane resin whose raw materials include, in parts by weight, 55.1 parts of polypropylene oxide ether triol (number average molecular weight 6000, functionality 3), 18.4 parts of polypropylene oxide ether diol (number average molecular weight 2000, functionality 2), 10.1 parts of polypropylene oxide ether diol (number average molecular weight 1000, functionality 2), 11.5 parts of aromatic isocyanate (TDI-100) and 4.9 parts of N-methylacetamide.
The invention provides a preparation method of aromatic polyurethane resin, which comprises the following specific steps:
(1) Reacting polypropylene oxide ether triol (with the number average molecular weight of 6000 and the functionality of 3) with TDI-100 at 75 ℃ for 3 hours, cooling to 55 ℃, adding polypropylene oxide ether diol (with the number average molecular weight of 2000 and the functionality of 2) and polypropylene oxide ether diol (with the number average molecular weight of 1000 and the functionality of 2) to react for 5 hours at 70 ℃, and then heating to 80 ℃ to react for 2 hours to obtain a polyurethane prepolymer (the mass percentage of isocyanate groups is 3.35 percent);
(2) And (3) reacting the polyurethane prepolymer with N-methylacetamide at 65 ℃ for 1h to obtain the aromatic polyurethane resin.
Comparative example 2
This comparative example provides an aromatic urethane resin differing from example 1 only in that the second cardanol (NX-2026 available from Cardolite) was replaced with 0.5 times by mole of NX-9201, i.e., the molar ratio of isocyanate groups in the urethane prepolymer to hydroxyl groups in cardanol was kept unchanged, and the other raw materials and amounts were the same as in example 1.
This comparative example provides a method for preparing the aromatic polyurethane resin, and the specific procedure is the same as in example 1.
Comparative example 3
This comparative example provides an aromatic urethane resin differing from example 1 only in that the first cardanol (NX-9201 available from Cardolite) was replaced with 2-fold mol of NX-2026, that is, the molar ratio of isocyanate groups in aromatic isocyanate to hydroxyl groups in cardanol was kept unchanged, and the other raw materials and amounts were the same as in example 1.
This comparative example provides a method for preparing the aromatic polyurethane resin, and the specific procedure is the same as in example 1.
Comparative example 4
This comparative example provides an aromatic polyurethane resin differing from example 1 only in that the first cardanol was replaced with a polypropylene oxide ether glycol (number average molecular weight 1000, functionality 2) of equal molar ratio of hydroxyl groups, and other raw materials, amounts and preparation methods were the same as in example 1.
Application example 1
A polyurethane resin film comprising 100 parts of an aromatic polyurethane resin and a certain weight part of 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane; the aromatic polyurethane resin is the aromatic polyurethane resin provided in examples 1 to 11 and comparative examples 1 to 4; the weight parts of the 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane are shown in table 1; wherein comparative example 1 also requires the addition of 1 part of a leveling agent (BYK-333 from Pick chemical Co.); the specific preparation method of the polyurethane resin film comprises the following steps: mixing the aromatic polyurethane resin with a curing agent for 15min, defoaming for 30min, then knife-coating for 25s on a plate, pre-drying for 1min at 100 ℃, drying for 5min at 150 ℃, and then drying for 24h in a drying oven at 70 ℃ to obtain the polyurethane resin film. The results of the performance test of the polyurethane resin film are shown in table 2.
TABLE 1
Performance test of polyurethane resin film
(1) Polyurethane resin viscosity: a Brookfield company LVT dial viscometer, rotor number 4/64, and rotating speed 12r/min;
(2) 100% modulus (E): in the elastic deformation stage, the stress and the strain are in a proportional relation, the proportional coefficient is called elastic modulus, modulus for short, and the calculation formula is as follows, wherein the modulus tested by experiments is 100% modulus;
wherein: f is the stress (N) in the extending direction, S is the cross-sectional area (m 2 ) L is the length (m), ΔL is the elongation (m);
(3) Tensile strength: the strength (unit MPa) of the film after stretching and breaking is provided as an Instron 3367 electronic universal material tester.
(4) Softening temperature: polyurethane resin films including the aromatic polyurethane resins provided in examples 1 to 11 and comparative examples 1 to 4 were left to stand at 170 to 200℃respectively (gradient temperature rise, 5℃each time) for 10 minutes, and the softening temperature of the polyurethane resin films was observed.
The specific test results are shown in table 2:
TABLE 2
As can be seen from the table, the aromatic polyurethane resin provided by the invention has low viscosity, is environment-friendly and has good leveling property without adding a solvent and a leveling agent when in use by selecting polyether polyol, cardanol, aromatic isocyanate and a sealing agent with specific combinations and proportions. From examples 1 to 8, it is understood that the aromatic polyurethane resin has a viscosity of 8000 to 22000cp, the polyurethane resin film comprising the aromatic polyurethane resin has a modulus of 3.4 to 5.7MPa, a tensile strength of 25.1 to 36.8MPa, and a heat-resistant temperature of 185 to 195 ℃.
As is clear from a comparison between example 2 and example 9, when the polyether polyol is obtained by substituting polypropylene oxide ether glycol with polyethylene oxide ether glycol, the resin viscosity increases, the modulus and tensile strength of the polyurethane resin film decrease, and the heat resistance deteriorates; as is clear from comparison of example 1 with examples 10 and 11, the preparation method does not follow a specific procedure, i.e., the cardanol is not added in a specific order, the resin viscosity increases, and the modulus and tensile strength of the polyurethane resin film decreases; as is clear from comparison of example 1 with comparative examples 1 to 4, the polyurethane resin was increased in viscosity and deteriorated in performance when cardanol was not added or a combination of specific cardanol was not used in the polyurethane resin.
In summary, the polyurethane resin film has excellent mechanical properties and heat resistance by selecting polyether polyol, cardanol, aromatic isocyanate and a blocking agent in specific combinations and proportions.
Application example 2
The synthetic leather comprises a fabric layer, a polyurethane layer, a primer layer and a base material which are sequentially laminated; the polyurethane layer comprises the aromatic polyurethane resins provided in examples 1 to 11 and comparative examples 1 to 4; the specific preparation method of the synthetic leather comprises the following steps:
(1) Weighing 100 parts of aliphatic polycarbonate resin JF-PDY-851MY, adding 0.5 part of TEGO450 flatting agent, 1 part of graceful 328 wetting agent, 4 parts of dark blue BLPE 517 aqueous black paste and 0.5 part of BYK425 thickening agent, dispersing for 30min, filtering and defoaming for 30min, respectively baking for 3min at 90 ℃, 110 ℃ and 130 ℃ after 10s of doctor blade coating, and then secondarily doctor blade coating for 15s, respectively baking for 3min at 90 ℃, 110 ℃ and 130 ℃ to obtain the fabric layer;
(2) Weighing 100 parts of aromatic polyurethane resin, adding a certain part of 3, 3-dimethyl-4, 4-diamino dicyclohexyl methane, dispersing for 15min, defoaming for 30min, doctor-blading for 25s, pre-baking for 1min at 100 ℃, and then baking for 5min at 150 ℃ to obtain the polyurethane layer; the polyurethane resin is aromatic polyurethane resin provided in examples 1 to 11 and comparative examples 1 to 4; wherein, the aromatic polyurethane resin provided in the comparative example 1 is also added with 1 part of flatting agent; the weight parts of the 3, 3-dimethyl-4, 4-diamino dicyclohexylmethane are shown in table 1;
(3) Weighing 100 parts of aromatic polyether resin JF-PDY-511H, adding 2 parts of BYK425 thickening agent to thicken to about 15000cp, coating the mixture on the surface of the polyurethane layer far away from the fabric layer, doctor-blading for 20s, attaching a cotton-like velvet substrate (thickness 1 mm), and baking the mixture at 90 ℃, 110 ℃ and 130 ℃ for 3min to obtain the synthetic leather. The results of the performance test of the synthetic leather are shown in table 3.
Performance test of synthetic leather
(1) Peel force: testing by adopting a QB/T2888-2007 method;
(2) Peel force after 5 weeks at 70 ℃/95% humidity: testing by adopting a QB/T2888-2007 method;
(3) Peel force retention rate: the ratio of the peel force (2) to the peel force (1) after 5 weeks at 70 ℃/95% humidity;
(4) Low temperature folding endurance (-15 ℃): the test was performed using the GOTECH GT-7006-V50 method.
The specific test results are shown in table 3:
TABLE 3 Table 3
As can be seen from the table, the aromatic polyurethane resin provided by the invention has excellent mechanical properties and good moisture and heat resistance by selecting polyether polyol, cardanol, aromatic isocyanate and a sealing agent with specific combinations and proportions; as is clear from examples 1 to 8, the peel force of the synthetic leather was 9.3 to 13.5kg/3cm, the peel force after 5 weeks of standing at 70 ℃/95% humidity was 8.2 to 12.5kg/3cm, the peel retention rate was 84.3 to 93.9%, and the synthetic leather was resistant to folding at low temperature for 7 to 8 ten thousand times.
As is clear from a comparison of example 2 and example 9, when the polyether polyol is replaced with polyethylene oxide ether glycol, the synthetic leather has a reduced peel force and retention of peel force after 70 ℃/95% for 5 weeks; as is apparent from comparison of example 1 with examples 10 and 11, the peeling force and the peeling force retention rate were reduced after 70 ℃/95% for 5 weeks when the preparation method was not performed according to the specific procedure, i.e., the first cardanol and the second cardanol were not added in the specific order; as is clear from comparison of example 1 with comparative examples 1 to 4, when cardanol is not added to the aromatic urethane resin or a combination of specific cardanol is not used, the peeling force of the synthetic leather including the aromatic urethane resin is reduced and the moisture and heat resistance is deteriorated.
In summary, the aromatic polyurethane resin has low viscosity and self-leveling function by selecting the specific cardanol combination, the specific polyether polyol, the aromatic isocyanate and the sealing agent; the polyurethane resin film has high tensile strength and good heat resistance; the synthetic leather comprising the aromatic polyurethane resin has high peel strength, excellent moisture and heat resistance and good low-temperature folding resistance.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (17)
1. The aromatic polyurethane resin is characterized by comprising 40-88 parts by weight of polyether polyol, 5-70 parts by weight of cardanol, 7-25 parts by weight of aromatic isocyanate and 2-12 parts by weight of sealing agent;
the cardanol comprises a combination of a first cardanol and a second cardanol;
the first cardanol is any one or a combination of at least two of NX-9201, NX-9007 or NX-9008;
the second cardanol is NX-2026;
the polyether polyol comprises any one or a combination of at least two of polypropylene oxide ether polyol, polytetrahydrofuran ether glycol or polypropylene oxide tetrahydrofuran copolyether glycol;
the aromatic polyurethane resin is prepared by a method comprising the following steps:
(1) Reacting polyether polyol, first cardanol and aromatic isocyanate to obtain polyurethane prepolymer;
(2) Reacting the polyurethane prepolymer with second cardanol and a blocking agent to obtain the aromatic polyurethane resin;
the mass ratio of the first cardanol to the second cardanol is (0.3-6): 1.
2. The aromatic polyurethane resin according to claim 1, wherein the raw materials of the aromatic polyurethane resin comprise 50 to 85 parts by weight of polyether polyol, 5 to 35 parts by weight of cardanol, 10 to 21 parts by weight of aromatic isocyanate and 3 to 6 parts by weight of a blocking agent.
3. The aromatic polyurethane resin according to claim 1, wherein the polyether polyol has a functionality of 2 or 3;
the polyether polyol has a number average molecular weight of 250 to 8000.
4. The aromatic polyurethane resin according to claim 1, wherein the polypropylene oxide ether polyol comprises polypropylene oxide ether diol and/or polypropylene oxide ether triol.
5. The aromatic polyurethane resin according to claim 1, wherein the aromatic isocyanate comprises any one or a combination of at least two of 2,4 '-diphenylmethane diisocyanate, 4' -diphenylmethane diisocyanate, toluene-2, 4-diisocyanate, or toluene-2, 6-diisocyanate.
6. The aromatic polyurethane resin of claim 1, wherein the blocking agent comprises N-methylacetamide.
7. A method for producing the aromatic polyurethane resin according to any one of claims 1 to 6, comprising the steps of:
(1) Reacting polyether polyol, first cardanol and aromatic isocyanate to obtain polyurethane prepolymer;
(2) And (3) reacting the polyurethane prepolymer with second cardanol and a blocking agent to obtain the aromatic polyurethane resin.
8. The method of claim 7, wherein the reaction of step (1) comprises a first stage reaction and a second stage reaction;
the temperature of the first-stage reaction is 65-80 ℃;
the time of the first stage reaction is 2-7 h.
9. The method of claim 8, wherein the first stage reaction comprises pre-reacting a polyether polyol with an aromatic isocyanate followed by a first stage reaction with a first cardanol; or, carrying out a first stage reaction on polyether polyol, first cardanol and aromatic isocyanate;
the temperature of the pre-reaction of the polyether polyol and the aromatic isocyanate is 70-80 ℃;
the pre-reaction time of the polyether polyol and the aromatic isocyanate is 3-4 hours.
10. The method of claim 8, wherein the second stage reaction temperature is 80-85 ℃;
the second stage reaction time is 2-6 h.
11. The preparation method according to claim 7, wherein the mass percentage of isocyanate groups in the polyurethane prepolymer is less than or equal to 4.06%.
12. The method of claim 7, wherein the temperature of the reaction in step (2) is 65-80 ℃;
the reaction time in the step (2) is 30-90 min.
13. The preparation method according to claim 7, characterized in that the preparation method comprises the steps of:
(1) Pre-reacting polyether polyol with aromatic isocyanate for 3-4 hours at 70-80 ℃, adding first cardanol, and reacting for 2-7 hours at 65-80 ℃, or reacting polyether polyol, aromatic isocyanate and first cardanol for 2-7 hours at 65-80 ℃; then reacting for 2-6 hours at the temperature of 80-85 ℃ to obtain polyurethane prepolymer;
(2) And (3) reacting the polyurethane prepolymer with second cardanol and a sealing agent for 30-90 min at 65-80 ℃ to obtain the aromatic polyurethane resin.
14. A polyurethane resin film, characterized in that it comprises 90 to 100 parts by weight of the aromatic polyurethane resin according to any one of claims 1 to 6 and 4 to 17 parts by weight of a curing agent;
the curing agent comprises an amine curing agent which is 3,3 '-dimethyl-4, 4' -diamino dicyclohexylmethane.
15. The polyurethane resin film according to claim 14, wherein the polyurethane resin film is produced by a method comprising:
and mixing the aromatic polyurethane resin with a curing agent, defoaming, coating the mixture on a plate, and drying the plate after the first curing and the second curing to obtain the polyurethane resin film.
16. The polyurethane resin film according to claim 15, wherein the time for deaeration is 20 to 40 minutes;
the temperature of the first curing is 95-100 ℃;
the time of the first curing is 1-2 min;
the temperature of the second curing is 140-150 ℃;
the second curing time is 3-5 min;
the drying temperature is 60-70 ℃.
17. The synthetic leather is characterized by comprising a fabric layer, a polyurethane layer, a primer layer and a base material which are sequentially laminated;
the polyurethane layer comprises the aromatic polyurethane resin according to any one of claims 1 to 6 and/or the polyurethane resin film according to any one of claims 14 to 16.
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| CN109851753B (en) * | 2018-11-21 | 2021-09-24 | 上海华峰新材料研发科技有限公司 | Epoxy modified polymer modified polyurethane and preparation method and application thereof |
| CN111333809A (en) * | 2020-03-23 | 2020-06-26 | 宜兴市华夏化工材料有限公司 | Nonionic surfactant for hydrocarbon resin and preparation method thereof |
| EP3892659A1 (en) * | 2020-04-08 | 2021-10-13 | Covestro Deutschland AG | Low viscosity isocyanate prepolymers blocked with phenols obtainable from cashew nut shell oil, method for their preparation and their use |
| CN112625213B (en) * | 2020-12-04 | 2022-05-17 | 上海华峰新材料研发科技有限公司 | Solvent-free blocked polyurethane resin composition, polyurethane material and leather product |
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