CN114106280B - Aliphatic polyurethane resin and preparation method and application thereof - Google Patents
Aliphatic polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN114106280B CN114106280B CN202111526774.4A CN202111526774A CN114106280B CN 114106280 B CN114106280 B CN 114106280B CN 202111526774 A CN202111526774 A CN 202111526774A CN 114106280 B CN114106280 B CN 114106280B
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having 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
- C08G18/28—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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- 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
Abstract
The invention provides an aliphatic polyurethane resin, a preparation method and application thereof. The raw materials of the aliphatic polyurethane resin comprise 40-88 parts by weight of polyether polyol, 4-70 parts by weight of cardanol, 7-25 parts by weight of aliphatic 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 aliphatic polyurethane resin has good self-wetting leveling property by selecting the specific cardanol combination, polyether polyol, aliphatic isocyanate and sealing agent, no additional leveling agent is needed, the adhesive force after curing is enhanced, and the material comprising the aliphatic 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 an aliphatic 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 aliphatic polyurethane resin, and the raw materials of the aliphatic polyurethane resin are cardanol, specific polyether polyol, aliphatic isocyanate and a sealing agent which are combined in a specific way, so that the aliphatic polyurethane resin has low viscosity, high peel strength, good moisture and heat resistance, no solvent dilution and environmental protection; the material comprising the aliphatic 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 aliphatic polyurethane resin, wherein the raw materials of the aliphatic polyurethane resin comprise 40-88 parts by weight of polyether polyol, 4-70 parts by weight of cardanol, 7-25 parts by weight of aliphatic isocyanate and 2-12 parts by weight of blocking 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 aliphatic polyurethane resin has good leveling property without adding a leveling agent; the specific cardanol combination is selected to be matched with polyether polyol, aliphatic isocyanate and a sealing agent for use, so that the aliphatic polyurethane resin has excellent tensile property and good heat resistance; the synthetic leather comprising the aliphatic polyurethane resin has high peel strength, good moisture and heat resistance and excellent low-temperature folding endurance.
Preferably, the raw materials of the aliphatic 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 aliphatic polyurethane resin include 4 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 raw materials of the aliphatic polyurethane resin include 7 to 25 parts by weight of aliphatic 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 materials of the aliphatic polyurethane resin include 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 aliphatic polyurethane resin comprise 50-85 parts by weight of polyether polyol, 4-35 parts by weight of cardanol, 10-21 parts by weight of aliphatic 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 (0.05-1): 1, for example, may be 0.05:1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 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 aliphatic isocyanate comprises any one or a combination of at least two of isophorone diisocyanate (IPDI), 4' -dicyclohexylmethane diisocyanate (HMDI), hexamethylene Diisocyanate (HDI).
Preferably, the blocking agent comprises 3, 5-dimethylpyrazole.
In a second aspect, the present invention provides a method for producing the aliphatic polyurethane resin according to the first aspect, the method comprising the steps of:
(1) Reacting polyether polyol, first cardanol and aliphatic isocyanate to obtain polyurethane prepolymer;
(2) And (3) reacting the polyurethane prepolymer with second cardanol and a blocking agent to obtain the aliphatic polyurethane resin.
In the present invention, the molar ratio of the isocyanate group in the aliphatic 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 70 to 90℃and may be, for example, 70℃72℃74℃76℃78℃80℃82℃84℃86℃88℃90 ℃.
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, 7 hours, etc.
Preferably, the first stage reaction comprises a first stage reaction with a first cardanol after pre-reacting a polyether polyol with an aliphatic isocyanate; or, subjecting polyether polyol, first cardanol and aliphatic isocyanate to a first stage reaction.
The polyether polyol is preferably pre-reacted with the aliphatic isocyanate at a temperature of 80 to 90℃and may be, for example, 80℃82℃84℃86℃88℃90 ℃.
Preferably, the polyether polyol is pre-reacted with the aliphatic isocyanate for a period of time ranging from 2 to 4 hours, and may be, for example, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 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 aliphatic 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 second stage reaction is carried out in the presence of a catalyst.
In the present invention, the catalyst includes SA-8 catalyst (polycat SA-8, shanghai, yingzhang specialty chemical Co., ltd.), which may be added by dilution with polypropylene oxide polyether polyol.
In the present invention, the amount of the catalyst used in the polyurethane system is 5 to 20ppm, and for example, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 14ppm, 16ppm, 18ppm, etc. can be used.
Preferably, the temperature of the second stage reaction is 85 to 95℃and may be, for example, 85℃86℃87℃88℃89℃90℃91℃92℃93℃94℃95 ℃.
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%, for example, 2%, 2.68%, 2.7%, 2.79%, 2.80%, 3.03%, 3.35% and the like.
Preferably, the temperature of the reaction in the step (2) is 70 to 90℃and may be, for example, 70℃72℃74℃76℃78℃80℃82℃84℃86℃88℃90 ℃.
Preferably, the reaction time in step (2) is 1 to 5 hours, and may be, for example, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, etc.
Preferably, the preparation method comprises the following steps:
(1) Pre-reacting polyether polyol and aliphatic isocyanate for 2-4 hours at the temperature of 80-90 ℃, adding first cardanol, and reacting for 2-7 hours at the temperature of 70-90 ℃; or, reacting polyether polyol, aliphatic isocyanate and first cardanol for 2-7 h at 70-90 ℃; then adding a catalyst, and reacting for 2-6 hours at the temperature of 85-95 ℃ to obtain a polyurethane prepolymer;
(2) And (3) reacting the polyurethane prepolymer with second cardanol and a sealing agent for 1-5 hours at 70-90 ℃ to obtain the aliphatic polyurethane resin.
In a third aspect, the present invention provides a polyurethane resin film comprising 90 to 100 parts by weight of the aliphatic 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 aliphatic polyurethane resin according to the first aspect, 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:
mixing the aliphatic polyurethane resin with a curing agent, defoaming, coating the mixture on a plate, and drying the plate after primary curing and secondary 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 aliphatic polyurethane resin, a leveling agent is required to be added, and the polyurethane resin film obtained by curing 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 aliphatic 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 JF-PDY-851MY emulsion (aliphatic polycarbonate resin), 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 comprises 95-105 parts by weight of JF-PDY-851MY emulsion, and for example, 95 parts by weight, 96 parts by weight, 97 parts by weight, 98 parts by weight, 99 parts by weight, 100 parts by weight, 101 parts by weight, 102 parts by weight, 103 parts by weight, 104 parts by weight, 105 parts by weight and the like.
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 base material layer comprises 95 to 105 parts by weight of JF-PDY-511H emulsion (aromatic polyether resin) and 1 to 3 parts by weight of thickener.
Preferably, the material of the primer layer comprises 95-105 parts by weight of JF-PDY-511H emulsion, 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 JF-PDY-851MY emulsion, a flatting agent, a wetting agent, color paste and a thickening agent according to the formula amount, and carrying out first doctor-blading, first drying, second doctor-blading 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 JF-PDY-511H emulsion and a thickening agent 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 aliphatic polyurethane resin provided by the invention, the viscosity of the aliphatic polyurethane resin is less than or equal to 18000cp, and the modulus after curing is more than or equal to 3MPa by selecting the specific polyether polyol, the cardanol in the specific combination, the aliphatic isocyanate and the sealing agent; the tensile strength is more than or equal to 24.3MPa; the softening temperature is more than or equal to 180 ℃; the peel force of the synthetic leather comprising the aliphatic polyurethane resin is more than or equal to 8.3kg/3cm, the peel force after 5 weeks under the conditions of 70 ℃/95% humidity is more than or equal to 7.0kg/3cm, the peel force retention rate is more than or equal to 81.4%, and the synthetic leather has excellent mechanical properties, moisture resistance and heat resistance, and can resist folding times at-15 ℃ for more than or equal to 6 ten thousand times.
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 aliphatic urethane resin whose raw materials include 60.1 parts by weight of polypropylene oxide ether triol (number average molecular weight of 6000, functionality of 3), 15 parts by weight of polypropylene oxide ether diol (number average molecular weight of 1000, functionality of 2), 1.8 parts by weight of first cardanol (NX-9201 from Cardolite Co.), 4.7 parts by weight of second cardanol (NX-2026 from Cardolite Co.), 13.9 parts by weight of isophorone diisocyanate (IPDI) and 4.5 parts by weight of 3, 5-dimethylpyrazole.
The embodiment provides a preparation method of the aliphatic polyurethane resin, which comprises the following specific steps:
(1) Stirring polypropylene oxide ether triol, polypropylene oxide ether glycol and NX-9201 at 30 ℃ for 10min, adding IPDI at one time, slowly heating to 80 ℃, reacting for 2h, cooling to below 65 ℃, adding 10ppm SA-8 (poly cat SA-8, shanghai Yingchuang special chemical Co., ltd.), heating to 90 ℃ and reacting for 5h to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 2.89%);
(2) Reacting the polyurethane prepolymer with NX-2026 and 3, 5-dimethylpyrazole for 1h at the temperature of 75 ℃ to obtain the aliphatic polyurethane resin.
Example 2
This example provides an aliphatic urethane resin whose raw materials include, in parts by weight, 57.2 parts of polypropylene oxide ether triol (number average molecular weight of 4800, functionality of 3), 19.1 parts of polypropylene oxide ether diol (number average molecular weight of 2000, functionality of 2), 2.3 parts of first cardanol (NX-9201 from Cardolite Co.), 4.4 parts of second cardanol (NX-2026 from Cardolite Co.), 12.8 parts of IPDI and 4.2 parts of 3, 5-dimethylpyrazole.
The embodiment provides a preparation method of the aliphatic polyurethane resin, which comprises the following specific steps:
(1) Stirring polypropylene oxide ether triol, polypropylene oxide ether diol and NX-9201 at 30 ℃ for 10min, adding IPDI at one time, slowly heating to 80 ℃, reacting for 2h, cooling to 65 ℃ and then adding 10ppm SA-8, heating to 90 ℃ and reacting for 4h to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 2.65%);
(2) Reacting the polyurethane prepolymer with NX-2026 and 3, 5-dimethylpyrazole for 1h at the temperature of 75 ℃ to obtain the aliphatic polyurethane resin.
Example 3
This example provides an aliphatic polyurethane resin whose raw materials include, in parts by weight, 18 parts of polypropylene oxide ether triol (number average molecular weight of 8000, functionality of 3), 36 parts of polypropylene oxide ether triol (number average molecular weight of 4800, functionality of 3), 18 parts of polypropylene oxide ether diol (number average molecular weight of 1000, functionality of 2), 2.7 parts of first cardanol (NX-9201 from Cardolite company), 5.2 parts of second cardanol (NX-2026 from Cardolite company), 15.3 parts of IPDI and 4.9 parts of 3, 5-dimethylpyrazole.
The embodiment provides a preparation method of the aliphatic polyurethane resin, which comprises the following specific steps:
(1) Firstly adding polypropylene oxide ether triol, stirring for 10min at 30 ℃, then adding IPDI once again, gradually heating to 80 ℃ for reaction for 2h, continuously adding polypropylene oxide ether diol and NX-9201, reacting for 2h at 80 ℃, cooling to below 65 ℃, adding 10ppm SA-8, heating to 90 ℃ for reaction for 6h, and obtaining polyurethane prepolymer (the mass percentage of isocyanate groups is 3.21%);
(2) Reacting the polyurethane prepolymer with NX-2026 and 3, 5-dimethylpyrazole for 1h at the temperature of 75 ℃ to obtain the aliphatic polyurethane resin.
Example 4
This example provides an aliphatic urethane resin whose raw materials include, in parts by weight, 49.9 parts of polypropylene oxide ether triol (number average molecular weight 6000, functionality 3), 29.9 parts of polypropylene oxide ether diol (number average molecular weight 3000, functionality 2), 1 part of first cardanol (NX-9008 from Cardolite Co.), 3.8 parts of second cardanol (NX-2026 from Cardolite Co.), 9.1 parts of IPDI, 2.7 parts of 4,4' -dicyclohexylmethane diisocyanate (HMDI) and 3.7 parts of 3, 5-dimethylpyrazole.
The embodiment provides a preparation method of the aliphatic polyurethane resin, which comprises the following specific steps:
(1) Firstly adding IPDI and HMDI, stirring and mixing for 10min, then adding polypropylene oxide ether triol, gradually heating to 80 ℃ for reaction for 2h, continuously adding polypropylene oxide ether diol and NX-9008, reacting for 2h at 80 ℃, cooling to below 65 ℃, then adding 10ppm SA-8, heating to 90 ℃ for reaction for 5h, and obtaining a polyurethane prepolymer (the mass percentage of isocyanate groups is 2.31%);
(2) Reacting the polyurethane prepolymer with NX-2026 and 3, 5-dimethylpyrazole for 1h at the temperature of 75 ℃ to obtain the aliphatic polyurethane resin.
Example 5
This example provides an aliphatic urethane 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), 0.4 parts of first cardanol (NX-9008 from Cardolite Co.), 5.6 parts of second cardanol (NX-2026 from Cardolite Co.), 13.1 parts of IPDI, 3.9 parts of HMDI and 5.3 parts of 3, 5-dimethylpyrazole.
The embodiment provides a preparation method of the aliphatic polyurethane resin, which comprises the following specific steps:
(1) Firstly adding IPDI and HMDI, stirring and mixing for 10min, then adding polypropylene oxide ether triol, polypropylene oxide ether diol and NX-9008, reacting for 2h at 80 ℃, cooling to below 65 ℃, then adding 10ppm SA-8, heating to 90 ℃ and reacting for 4h to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 3.48%);
(2) Reacting the polyurethane prepolymer with NX-2026 and 3, 5-dimethylpyrazole for 1h at the temperature of 75 ℃ to obtain the aliphatic polyurethane resin.
Example 6
This example provides an aliphatic urethane resin whose raw materials include, in parts by weight, 48.1 parts of polypropylene oxide ether triol (number average molecular weight 6000, functionality 3), 28.8 parts of polypropylene oxide ether diol (number average molecular weight 2000, functionality 2), 1.6 parts of first cardanol (NX-9007 from Cardolite Co.), 4.4 parts of second cardanol (NX-2026 from Cardolite Co.), 12.9 parts of IPDI and 4.2 parts of 3, 5-dimethylpyrazole.
The embodiment provides a preparation method of the aliphatic 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, adding IPDI at one time, slowly heating to 80 ℃, reacting for 2h, cooling to 65 ℃ and then adding 10ppm SA-8, heating to 90 ℃ and reacting for 4h to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 2.66%);
(2) Reacting the polyurethane prepolymer with NX-2026 and 3, 5-dimethylpyrazole for 1h at the temperature of 75 ℃ to obtain the aliphatic polyurethane resin.
Example 7
This example provides an aliphatic urethane resin whose raw materials include, in parts by weight, 50.6 parts of polypropylene oxide ether triol (number average molecular weight of 4800, functionality of 3), 25.3 parts of polypropylene oxide ether diol (number average molecular weight of 3000, functionality of 2), 3.2 parts of first cardanol (NX-9007 from Cardolite Co.), 4.4 parts of second cardanol (NX-2026 from Cardolite Co.), 10.4 parts of IPDI, 2 parts of Hexamethylene Diisocyanate (HDI), and 4.2 parts of 3, 5-dimethylpyrazole.
The embodiment provides a preparation method of the aliphatic polyurethane resin, which comprises the following specific steps:
(1) Firstly adding IPDI and HDI, stirring and mixing for 10min, then adding polypropylene oxide ether triol, gradually heating to 80 ℃ for reaction for 2h, continuously adding polypropylene oxide ether diol and NX-9007, reacting for 2h at 80 ℃, cooling to below 65 ℃, then adding 10ppm SA-8, heating to 90 ℃ for reaction for 4h, and obtaining a polyurethane prepolymer (the mass percentage of isocyanate groups is 2.68%);
(2) Reacting the polyurethane prepolymer with NX-2026 and 3, 5-dimethylpyrazole for 1h at the temperature of 75 ℃ to obtain the aliphatic polyurethane resin.
Example 8
This example provides an aliphatic urethane resin whose raw materials include, in parts by weight, 41.5 parts of polypropylene oxide ether triol (number average molecular weight of 4800, functionality of 3), 29.7 parts of polypropylene oxide ether diol (number average molecular weight of 2000, functionality of 2), 4.2 parts of first cardanol (NX-9007 from Cardolite Co.), 5.2 parts of second cardanol (NX-2026 from Cardolite Co.), 12.2 parts of IPDI, 2.3 parts of HDI and 4.9 parts of 3, 5-dimethylpyrazole.
The embodiment provides a preparation method of the aliphatic polyurethane resin, which comprises the following specific steps:
(1) Firstly adding IPDI and HDI, stirring and mixing for 10min, then adding polypropylene oxide ether triol, gradually heating to 80 ℃ for reaction for 2h, continuously adding polypropylene oxide ether diol and NX-9007, reacting for 2h at 80 ℃, cooling to below 65 ℃, then adding 10ppm SA-8, heating to 90 ℃ for reaction for 4h, and obtaining a polyurethane prepolymer (the mass percentage of isocyanate groups is 3.21%);
(2) Reacting the polyurethane prepolymer with NX-2026 and 3, 5-dimethylpyrazole for 1h at the temperature of 75 ℃ to obtain the aliphatic polyurethane resin.
Example 9
This example provides an aliphatic polyurethane resin differing from example 1 only in that the polypropylene oxide ether glycol was replaced with equal parts by weight of polyethylene oxide ether glycol (number average molecular weight 1000), and other raw materials and amounts were the same as in example 1.
This example provides a method for preparing the aliphatic polyurethane resin, and the specific steps are the same as in example 1.
Example 10
This example provides an aliphatic polyurethane resin differing from example 1 only in that in step (1), polypropylene oxide ether triol, polypropylene oxide ether diol, NX-9201 and NX-2026 are stirred at 30℃for 10min; in the step (2), NX-2026 was not added, and other raw materials, amounts and preparation methods were the same as in example 1.
Example 11
This example provides an aliphatic polyurethane resin differing from example 1 only in that NX-9201 was replaced with 4.7 parts of NX-2026 in step (1), NX-2026 was replaced with 1.8 parts of NX-9201 in step (2), and other raw materials, amounts and preparation methods were the same as in example 1.
Comparative example 1
This comparative example provides an aliphatic polyurethane resin whose raw materials include, in parts by weight, 63.8 parts of polypropylene oxide ether triol (number average molecular weight of 6000, functionality of 3), 15.9 parts of polypropylene oxide ether diol (number average molecular weight of 1000, functionality of 2), 14.2 parts of IPDI and 6.1 parts of 3, 5-dimethylpyrazole.
The comparative example provides a preparation method of the aliphatic polyurethane resin, which comprises the following specific steps:
(1) Stirring polypropylene oxide ether triol and polypropylene oxide ether diol at 30 ℃ for 10min, adding IPDI at one time, slowly heating to 80 ℃, reacting for 2h, cooling to 65 ℃ and then adding 10ppm SA-8, heating to 90 ℃ and reacting for 5h to obtain polyurethane prepolymer (the mass percentage of isocyanate groups is 2.86%);
(2) And (3) reacting the polyurethane prepolymer with 3, 5-dimethylpyrazole at the temperature of 75 ℃ for 1h to obtain the aliphatic polyurethane resin.
Comparative example 2
This comparative example provides an aliphatic 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 aliphatic polyurethane resin, and the specific procedure is the same as in example 1.
Comparative example 3
This comparative example provides an aliphatic 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 aliphatic 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 aliphatic polyurethane resin, and the specific procedure is the same as in example 1.
Comparative example 4
This comparative example provides an aliphatic polyurethane resin differing from example 1 only in that the first cardanol (NX-9201 from Cardolite) was replaced with polypropylene oxide ether glycol (number average molecular weight: 1000, functionality: 2), and the other raw materials and amounts were the same as in example 1.
This comparative example provides a method for preparing the aliphatic polyurethane resin, and the specific procedure is the same as in example 1.
Application example 1
A polyurethane resin film comprising 100 parts of an aliphatic polyurethane resin and a certain weight part of 3, 3-dimethyl-4, 4-diaminodicyclohexylmethane; the polyurethane resin is the aliphatic 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 aliphatic 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) 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 shown as follows, wherein the modulus tested by experiments is 100% modulus.
Wherein: f is stress (N) in the extending direction; s is the cross-sectional area (m) 2 ) The method comprises the steps of carrying out a first treatment on the surface of the L is the length (m); Δl is elongation (m);
(3) Tensile strength: the strength (unit MPa) of the film after stretching and breaking is provided with an Instron 3367 electronic universal material tester;
(4) Softening temperature: the polyurethane resin films including the aliphatic 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 temperatures of the polyurethane resin films were observed.
The specific test results are shown in table 2:
TABLE 2
As can be seen from the table, the aliphatic 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 the polyether polyol, the cardanol, the aliphatic isocyanate and the blocking agent with specific combinations and proportions. From examples 1 to 8, it is understood that the viscosity of the polyurethane resin is 8000 to 18000cp, the modulus of the polyurethane resin film including the aliphatic polyurethane resin is 3 to 4.3MPa, the tensile strength is 24.3 to 37.6MPa, and the heat-resistant temperature is 180 to 185 ℃.
As is clear from a comparison between example 1 and example 9, when the polyether polyol is not selected from the polypropylene oxide ether polyol and the polyethylene oxide ether polyol is used, the viscosity of the resin increases, the modulus and tensile strength of the polyurethane resin film decrease, and the heat resistance is poor; as is apparent from comparison of example 1 with examples 10 and 11, the preparation method was not carried out in a specific procedure, i.e., when the cardanol was not added in a specific order, or the first cardanol and the second cardanol were not added in a specific ratio, the resin viscosity was increased, and the modulus and tensile strength of the polyurethane resin film were decreased; 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, aliphatic 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 aliphatic polyurethane resins provided in examples 1-11 and comparative examples 1-4; the specific preparation method of the synthetic leather comprises the following steps:
(1) Weighing 100 parts of JF-PDY-851MY emulsion, adding 0.5 part of TEGO450 flatting agent, 1 part of graceful 328 wetting agent, 4 parts of deep 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 ℃ and 110 ℃ and 130 ℃ after 10s doctor blading, and then secondarily doctor blading for 15s, respectively baking for 3min at 90 ℃ and 110 ℃ and 130 ℃ to obtain the fabric layer;
(2) Weighing 100 parts of aliphatic 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 aliphatic polyurethane resin is the aliphatic polyurethane resin provided in examples 1 to 11 and comparative examples 1 to 4; wherein, the aliphatic 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 JF-PDY-511H emulsion, adding 2 parts of BYK425 thickening agent to thicken to about 15000cp, coating 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 for 3min at 90 ℃, 110 ℃ and 130 ℃ respectively 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 aliphatic polyurethane resin provided by the invention has the advantages that the peeling force of the synthetic leather comprising the aliphatic polyurethane resin is 8.3-10.7 kg/3cm through selecting polyether polyol, cardanol, aliphatic isocyanate and a sealing agent with specific combination and proportion, the peeling force is 7-9.7 kg/3cm after the synthetic leather is placed for 5 weeks under the condition of 70 ℃/95% humidity, the peeling retention rate is 81.4-90.7%, and the synthetic leather is resistant to folding for 6-7 ten thousands of times at the temperature of minus 15 ℃.
As is clear from a comparison of example 1 and example 9, when the polyether polyol is not selected from the polypropylene oxide ether polyol and the polyethylene oxide ether polyol is used, the peel force and the retention rate of the peel force of the synthetic leather after 70 ℃/95% for 5 weeks are reduced; as is apparent from comparison of example 1 with examples 10 and 11, the preparation method was not carried out in accordance with a specific procedure, i.e., when the cardanol was not added in a specific order, or when the first cardanol and the second cardanol were not added in a specific ratio, the peeling force and the peeling force retention rate were reduced after 70 ℃/95% for 5 weeks of the synthetic leather; as is clear from comparison of example 1 with comparative examples 1 to 4, when cardanol is not added to the urethane resin or a combination of specific cardanol is not used, the peeling force of the synthetic leather including the urethane resin is reduced and the moisture-resistant and heat-resistant properties are deteriorated.
In summary, the aliphatic polyurethane resin has low viscosity and self-leveling function by selecting the specific cardanol combination, the specific polyether polyol, the aliphatic isocyanate and the blocking agent; the polyurethane resin film has high tensile strength and good heat resistance; the synthetic leather comprising the aliphatic 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 (33)
1. The aliphatic polyurethane resin is characterized in that the raw materials of the aliphatic polyurethane resin comprise 40-88 parts by weight of polyether polyol, 4-70 parts by weight of cardanol, 7-25 parts by weight of aliphatic 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 mass ratio of the first cardanol to the second cardanol is (0.05-1): 1;
the aliphatic polyurethane resin is prepared by the following method:
(1) Reacting polyether polyol, first cardanol and aliphatic isocyanate to obtain polyurethane prepolymer;
(2) And (3) reacting the polyurethane prepolymer with second cardanol and a blocking agent to obtain the aliphatic polyurethane resin.
2. The aliphatic polyurethane resin according to claim 1, wherein the raw materials of the aliphatic polyurethane resin comprise 50 to 85 parts by weight of polyether polyol, 4 to 35 parts by weight of cardanol, 10 to 21 parts by weight of aliphatic isocyanate and 3 to 6 parts by weight of blocking agent.
3. The aliphatic polyurethane resin according to claim 1, wherein the polyether polyol has a functionality of 2 or 3.
4. The aliphatic polyurethane resin according to claim 1, wherein the polyether polyol has a number average molecular weight of 250 to 8000.
5. The aliphatic polyurethane resin according to claim 1, wherein the polyether polyol comprises a polypropylene oxide ether polyol.
6. The aliphatic polyurethane resin according to claim 5, wherein the polypropylene oxide ether polyol comprises polypropylene oxide ether diol and/or polypropylene oxide ether triol.
7. The aliphatic polyurethane resin according to claim 1, wherein the aliphatic isocyanate comprises any one or a combination of at least two of isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, or hexamethylene diisocyanate.
8. The aliphatic polyurethane resin according to claim 1, wherein the blocking agent comprises 3, 5-dimethylpyrazole.
9. A method for producing the aliphatic polyurethane resin according to any one of claims 1 to 8, characterized by comprising the steps of:
(1) Reacting polyether polyol, first cardanol and aliphatic isocyanate to obtain polyurethane prepolymer;
(2) And (3) reacting the polyurethane prepolymer with second cardanol and a blocking agent to obtain the aliphatic polyurethane resin.
10. The method of claim 9, wherein the reaction of step (1) comprises a first stage reaction and a second stage reaction.
11. The process of claim 10, wherein the temperature of the first stage reaction is 70-90 ℃.
12. The method of claim 10, wherein the first reaction time is 2 to 7 hours.
13. The method of claim 10, wherein the first stage reaction comprises pre-reacting a polyether polyol with an aliphatic isocyanate followed by a first stage reaction with a first cardanol; or, subjecting polyether polyol, first cardanol and aliphatic isocyanate to a first stage reaction.
14. The process of claim 13, wherein the polyether polyol is pre-reacted with the aliphatic isocyanate at a temperature of 80 to 90 ℃.
15. The method of claim 13, wherein the polyether polyol is pre-reacted with the aliphatic isocyanate for a period of 2 to 4 hours.
16. The process of claim 10 wherein the second stage reaction is carried out in the presence of a catalyst.
17. The process of claim 10, wherein the second stage reaction is at a temperature of 85 to 95 ℃.
18. The method according to claim 10, wherein the second stage reaction time is 2 to 6 hours.
19. The preparation method according to claim 9, wherein the mass percentage of isocyanate groups in the polyurethane prepolymer is less than or equal to 4%.
20. The process according to claim 9, wherein the temperature of the reaction in step (2) is 70 to 90 ℃.
21. The process according to claim 9, wherein the reaction time in step (2) is 1 to 5 hours.
22. The preparation method according to claim 9, characterized in that the preparation method comprises the steps of:
(1) Pre-reacting polyether polyol and aliphatic isocyanate for 2-4 hours at the temperature of 80-90 ℃, adding first cardanol, and reacting for 2-7 hours at the temperature of 70-90 ℃; or, reacting polyether polyol, aliphatic isocyanate and first cardanol for 2-7 h at 70-90 ℃; then adding a catalyst, and reacting for 2-6 hours at the temperature of 85-95 ℃ to obtain a polyurethane prepolymer;
(2) And (3) reacting the polyurethane prepolymer with second cardanol and a sealing agent for 1-5 hours at 70-90 ℃ to obtain the aliphatic polyurethane resin.
23. A polyurethane resin film, characterized in that it comprises 90 to 100 parts by weight of the aliphatic polyurethane resin according to any one of claims 1 to 8 and 4 to 17 parts by weight of a curing agent.
24. The polyurethane resin film according to claim 23, wherein the curing agent comprises an amine-based curing agent.
25. The polyurethane resin film according to claim 24, wherein the curing agent is 3,3 '-dimethyl-4, 4' -diaminodicyclohexylmethane.
26. The polyurethane resin film according to claim 24, wherein the polyurethane resin film is produced by a method comprising:
mixing the aliphatic polyurethane resin with a curing agent, defoaming, coating the mixture on a plate, and drying the plate after primary curing and secondary curing to obtain the polyurethane resin film.
27. The polyurethane resin film according to claim 26, wherein the time for deaeration is 20 to 40 minutes.
28. The polyurethane resin film according to claim 26, wherein the temperature of the first curing is 95 to 100 ℃.
29. The polyurethane resin film according to claim 26, wherein the time for the first curing is 1 to 2 minutes.
30. The polyurethane resin film according to claim 26, wherein the temperature of the second curing is 140 to 150 ℃.
31. The polyurethane resin film according to claim 26, wherein the time for the second curing is 3 to 5 minutes.
32. The polyurethane resin film according to claim 26, wherein the drying temperature is 60 to 70 ℃.
33. 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 aliphatic polyurethane resin according to any one of claims 1 to 8 and/or the polyurethane resin film according to any one of claims 23 to 32.
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| US7244772B2 (en) * | 2004-06-30 | 2007-07-17 | Council Of Scientific And Industrial Research | Process for preparing polyurethane polyol and rigid foams therefrom |
| KR20120102408A (en) * | 2011-03-08 | 2012-09-18 | 현대자동차주식회사 | Composition of antimicrobial bio polyyrethane foam |
| US10144845B2 (en) * | 2013-11-27 | 2018-12-04 | Dow Global Technologies Llc | Cardanol modified epoxy polyol |
| CN104086743B (en) * | 2014-06-30 | 2016-04-06 | 江西科技师范大学 | The preparation method of cardanol polylol and urethane thereof |
| CN106977694B (en) * | 2017-03-14 | 2019-09-17 | 中科院广州化学有限公司南雄材料生产基地 | The cured urethane acrylate photosensitive resin of ultraviolet light and its preparation method and purposes |
| KR20200047610A (en) * | 2017-08-31 | 2020-05-07 | 허큘레스 엘엘씨 | Urethane acrylate hybrid structure adhesive |
| KR20200131267A (en) * | 2018-03-11 | 2020-11-23 | 에보니크 오퍼레이션즈 게엠베하 | Cardanol Blocked Isocyanate Adhesion Accelerator for PVC Plastisols |
| 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 |
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