CN113527623B - Solvent-free polyurethane resin and preparation method and application thereof - Google Patents
Solvent-free polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN113527623B CN113527623B CN202110873297.2A CN202110873297A CN113527623B CN 113527623 B CN113527623 B CN 113527623B CN 202110873297 A CN202110873297 A CN 202110873297A CN 113527623 B CN113527623 B CN 113527623B
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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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
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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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
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- 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
- D06N3/145—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 two or more layers of polyurethanes
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- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention provides a solvent-free polyurethane resin and a preparation method and application thereof, wherein the solvent-free polyurethane resin comprises a component A and a component B; the component A comprises polyether polyol and tall oil diol with specific parts; the component B comprises a polyurethane prepolymer; according to the solvent-free polyurethane resin, the tall oil diol containing a larger side chain is added into the component A to replace the traditional micromolecular diol to serve as a chain extender, so that the compatibility among the components is effectively improved, the lubricating property of a molecular chain is also improved, the finally obtained finished synthetic leather is soft and plump in hand feeling, and the grade of a synthetic leather product is improved.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a solvent-free polyurethane resin and a preparation method and application thereof.
Background
With the enhancement of human environmental awareness and the increasing improvement of environmental protection restrictions of countries in the world, the environmental protection problem of the polyurethane synthetic leather industry is more and more emphasized by each link of the industry chain, and the use of the traditional solvent type polyurethane is more and more restricted, so that the organic solvent removal production technology of the polyurethane synthetic leather industry is urgent.
In view of the characteristics of superior environmental protection performance, low production energy consumption, excellent physical properties of finished leather, high cost performance and the like, the solvent-free polyurethane synthetic leather production technology gradually enters the visual field of polyurethane synthetic leather production enterprises in two years. Through the development of recent years, certain effect is achieved.
CN110066373A discloses a solvent-free polyurethane resin for synthetic leather, a preparation method thereof and application thereof in water-based/solvent-free polyurethane synthetic leather; the paint is prepared by mixing and reacting a component A and a component B according to the mass ratio of 1; wherein the component A comprises polyalcohol, a micromolecular chain extender, a cross-linking agent, water, a catalyst and a foam stabilizer; the component B comprises polyol, isocyanate and dimethylolpropionic acid. The solvent-free polyurethane resin for synthetic leather provided by the invention does not contain any organic solvent, is low in energy consumption and high in production efficiency, and when the solvent-free polyurethane resin is used for water-based/solvent-free polyurethane synthetic leather, the obtained water-based/solvent-free polyurethane synthetic leather product is green and environment-friendly, soft in hand feeling, plump and high in peel strength.
CN108467472A discloses a solvent-free polyurethane resin and an application thereof in high-peeling aqueous/solvent-free polyurethane synthetic leather, wherein the solvent-free polyurethane resin comprises, by weight, 40-60 parts of polytetrahydrofuran diol, 10-20 parts of 1, 4-butanediol, 2-5 parts of hydroxyethyl acrylate, 5-10 parts of double bond-containing polymer diol, 0.05 part of a delayed catalyst, 0.5-1 part of water and 2-5 parts of a photoinitiator, the component B is an oligomer diol modified diphenylmethane diisocyanate prepolymer, and the weight ratio of A to B is 100. The polymer diol containing double bonds is one or a mixture of more of hydroxyl-terminated polybutadiene, hydroxyl-terminated hydrogenated polybutadiene, hydroxyl-terminated epoxidized polybutadiene resin, hydroxyl-terminated polyisoprene and the like. The solvent-free polyurethane resin contains double bonds, is used as foaming layer slurry of water-based/solvent-free synthetic leather, and can be used for preparing the synthetic leather with high peel strength through ultraviolet curing.
CN112961307A discloses a solvent-free polyurethane resin, an impregnation slurry, a preparation method and an application thereof, wherein the preparation raw material of the solvent-free polyurethane resin comprises a combination of polyol, diisocyanate, linear amino silicone oil and a blocking agent; the impregnation slurry comprises: the solvent-free polyurethane resin, a curing agent, a wetting agent and a foaming agent; the solvent-free polyurethane resin is prepared by introducing linear amino silicone oil into a preparation raw material, wherein the linear amino silicone oil has excellent flexibility, and a tertiary amino side group in the linear amino silicone oil can form firm adsorption and orientation with fibers, so that the superfine fiber base fabric prepared by preparing impregnation slurry by using the solvent-free polyurethane is soft and full in hand feeling and not stiff; the impregnation slurry has low viscosity, can realize the coating of the superfine fiber base cloth through the conventional roller coating operation, has no discharge of DMF and other solvents in the coating process, has little harm to the environment and human bodies, and is beneficial to industrial production.
However, the molecular structure of the solvent-free polyurethane resin used in the solvent-free polyurethane synthetic leather is a highly cross-linked alternative structure, the lubrication among molecular chains is insufficient, the manufactured finished leather has a slightly flat and thin stiff hand feeling, the manufactured finished leather is more applied to the field of sofa leather with low softness requirement, and the application of the finished leather in the field of clothing leather with high hand feeling requirement is slightly insufficient.
Therefore, the development of a solvent-free polyurethane resin with good softness is a technical problem which needs to be solved urgently in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a solvent-free polyurethane resin and a preparation method and application thereof; the solvent-free polyurethane resin comprises a component A and a component B; the component A comprises polyether polyol and tall oil diol with specific parts; the component B comprises a polyurethane prepolymer; by adding tall oil diol with a larger side chain into the component A as a chain extender to replace the traditional micromolecular chain extender, the compatibility among the components and the hand feeling softness of the finally obtained synthetic leather are effectively improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a solvent-free polyurethane resin comprising an a-component and a B-component;
the component A comprises the following components in parts by weight: 20-30 parts of polyether glycol and 5-8 parts of tall oil glycol;
the component B comprises polyurethane prepolymer.
The solvent-free polyurethane resin provided by the invention comprises a component A and a component B; tall oil diol containing a larger side chain is added into the component A to replace the traditional micromolecular diol to be used as a chain extender, the regular arrangement of hard segments in the molecular structure of polyurethane is destroyed, and the micromolecular diol is not required to be added as the chain extender, so that the molecular chain is smoother, and the elastic elongation of the coating is obviously improved; due to the introduction of the tall oil glycol, the compatibility among all the components of the solvent-free polyurethane resin is improved, the material bubble distribution of the component A and the material bubble distribution of the component B are finer and more uniform, and the obtained finished leather is softer and fuller in hand feeling and fine and smooth in crease; and the introduction of the tall oil diol also has certain lubricity on molecular chains of finished product coatings, so that the finished leather has soft and plump hand feeling, the product grade is improved, the application of the solvent-free polyurethane resin in the field of clothing leather is further met, a new thought is provided for desolvation products of the polyurethane resin for the clothing leather, and the method has important research significance.
The polyether polyol comprises 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, or the like.
The tall oil diol may be 5.3 parts by weight, 5.6 parts by weight, 5.9 parts by weight, 6.3 parts by weight, 6.6 parts by weight, 6.9 parts by weight, 7.3 parts by weight, 7.6 parts by weight, 7.9 parts by weight, or the like.
Preferably, the mass ratio of the component A to the component B is (55-100) such as 95.
Preferably, the tall oil diol is prepared by a process comprising the steps of:
(A1) Reacting tall oil with thionyl chloride to obtain tall oil acyl chloride;
(A2) And (2) reacting the tall oil acyl chloride obtained in the step (A1) with dopamine to obtain the tall oil diol.
As a preferred technical scheme, the tall oil diol provided by the invention is prepared by reacting tall oil with thionyl chloride to obtain tall oil acyl chloride; then reacting the tall oil acyl chloride with dopamine to obtain the tall oil diamine; the preparation method mainly utilizes the reaction of acyl chloride in tall oil acyl chloride and primary amine in dopamine; compared with the tall oil diol prepared by a conventional one-step method of directly adopting tall oil and alcohol amine, the tall oil diol prepared by the preparation method provided by the invention has higher yield and better quality, can obviously improve the hand feeling when being added into polyurethane, and also has certain improvement on the peel strength.
Preferably, in step (A1), the molar ratio of the thionyl chloride to the carboxyl groups in the tall oil is (2-3) from 1, 2.1.
Preferably, the temperature of the reaction in step (A1) is 70 to 100 ℃, such as 73 ℃, 76 ℃, 79 ℃, 83 ℃, 86 ℃, 89 ℃, 93 ℃, 96 ℃ or 99 ℃, etc.
Preferably, the reaction time in step (A1) is 4 to 6 hours, such as 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, or 5.8 hours, etc.
Preferably, the reaction in step (A1) further comprises separation and purification steps after the reaction is completed.
Preferably, in step (A2), the molar ratio of acid chloride groups in dopamine and tall oil acid chloride is (1-1.2) 1, such as 1.02.
Preferably, the dopamine in step (A2) is dopamine dissolved in an organic solvent.
Preferably, the organic solvent comprises N, N-dimethylformamide.
Preferably, the reaction in step (A2) further comprises a mixing step before the reaction.
Preferably, the mixing is performed by means of dropwise addition.
Preferably, the method also comprises a step of continuing mixing after the dropwise addition is finished.
Preferably, the mixing and mixing are both continued under ice bath conditions.
Because the reaction is violent, the mixing is carried out in an ice bath in a dropwise manner, and the step of continuously mixing in the ice bath is further included after the dropwise addition is finished, so that the subsequent reaction activity can be effectively reduced.
Preferably, the time for said further mixing is 20-40 min, such as 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min or 38min, etc.
Preferably, the reaction temperature in the step (A2) is 70-90 ℃,72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃ or 88 ℃, etc.
Preferably, the reaction time in step (A2) is 3 to 5 hours, such as 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, or 4.8 hours, etc.
As a preferable technical method, the preparation method comprises the following steps:
(A1) Reacting tall oil with thionyl chloride at 70-100 ℃ for 4-60 h, separating and purifying to obtain tall oil acyl chloride;
(A2) And (2) dropwise adding the tall oil acyl chloride obtained in the step (A1) into a DMF (dimethyl formamide) solution of dopamine in an ice bath, continuously mixing for 20-40 min in the ice bath, and reacting for 3-5 h at 70-90 ℃ to obtain the tall oil diol.
Preferably, the polyether polyol has a molecular weight of 500 to 7000, for example 1000, 2000, 3000, 4000, 5000 or 6000, etc., preferably 4000 to 7000.
Preferably, the polyether polyol comprises any one of, or a combination of at least two of, a polyoxypropylene polyol, a polyoxyethylene polyol, a polyoxypropylene-oxyethylene co-polyol or a polytetramethylene ether polyol.
Preferably, the polyether polyol has a ring energy reading of 2 to 3.
Preferably, the component A also comprises any one of or a combination of at least two of a catalyst, water or a leveling agent.
Preferably, the catalyst is contained in the a component in an amount of 0.03 to 0.08 parts by weight, for example, 0.035 parts by weight, 0.04 parts by weight, 0.045 parts by weight, 0.05 parts by weight, 0.055 parts by weight, 0.06 parts by weight, 0.065 parts by weight, 0.07 parts by weight, or 0.075 parts by weight, or the like.
The catalyst can be selected from amine catalysts and/or metal catalysts.
Preferably, the water is present in the A component in an amount of 0.4 to 1 part by weight, such as 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, or 0.95 parts by weight, and the like.
Preferably, the leveling agent is present in the a component in an amount of 0.1 to 0.3 parts by weight, such as 0.12 parts by weight, 0.14 parts by weight, 0.16 parts by weight, 0.18 parts by weight, 0.2 parts by weight, 0.22 parts by weight, 0.24 parts by weight, 0.26 parts by weight, or 0.28 parts by weight.
The leveling agent can be polyether modified siloxane and/or polyester modified siloxane.
Preferably, the polyurethane prepolymer is obtained by reacting polyether polyol and isocyanate.
Preferably, the isocyanate comprises any one of toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone isocyanate or hexamethylene diisocyanate or a combination of at least two thereof.
Preferably, the NCO group content in the polyurethane prepolymer is 8-20% by mass, such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 19%.
In a second aspect, the present invention provides a method for preparing a solvent-free polyurethane resin according to the first aspect, the method comprising the steps of:
(1) Mixing a polyether polyol, tall oil diol, optionally water, optionally a leveling agent, and optionally a catalyst to provide the a component;
(2) And (2) mixing the component A and the component B obtained in the step (1) to obtain the solvent-free polyurethane resin.
In a third aspect, the invention provides a solvent-free polyurethane synthetic leather, which comprises a base cloth, a solvent-free polyurethane intermediate layer and a polyurethane surface layer which are sequentially arranged;
the solvent-free polyurethane intermediate layer is prepared from a raw material comprising the solvent-free polyurethane resin according to the first aspect.
In a fourth aspect, the present invention provides a method for preparing the solvent-free polyurethane synthetic leather according to the third aspect, wherein the method comprises the following steps:
(B1) Coating the preparation raw material of the polyurethane surface layer on the surface of release paper, and drying to obtain a polyurethane surface layer coating;
(B2) And (3) coating the solvent-free polyurethane resin in the first aspect on the surface of the polyurethane surface layer coating obtained in the step (B1), pre-reacting, adhering base cloth, and curing to obtain the solvent-free polyurethane synthetic leather.
Preferably, the temperature of the pre-reaction in step (B2) is 85 to 115 ℃, such as 87 ℃, 89 ℃, 91 ℃, 93 ℃, 95 ℃, 97 ℃, 99 ℃, 103 ℃, 105 ℃, 107 ℃, 110 ℃ or 113 ℃, etc.
Preferably, the pre-reaction time in step (B2) is 50-70 s, such as 52s, 54s, 56s, 58s, 60s, 62s, 64s or 68 s.
Preferably, the curing time in step (B2) is 4-7 min, such as 4.3min, 4.6min, 4.9min, 5.3min, 5.6min, 5.9min, 6.3min, 6.6min or 6.9 min.
Preferably, the temperature of the aging in the step (B2) is 95 to 114 ℃, for example 96 ℃, 97 ℃, 98 ℃, 99 ℃,100 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, 110 ℃ or 112 ℃, etc.
Compared with the prior art, the invention has the following beneficial effects:
the solvent-free polyurethane resin provided by the invention has the advantages that the tall oil diol is added into the component A of the raw material preparation, the tall oil diol containing a larger side chain replaces the traditional small molecular diol to be used as a chain extender, the regular arrangement of hard segments in the molecular structure of polyurethane is destroyed, the molecular chain is smoother, the elastic elongation of the coating is obviously improved, and due to the introduction of the tall oil diol, the material compatibility is improved, so that the foam pore distribution of the component A and the component B layers is finer and more uniform, the finished leather has soft and plump hand feeling and fine creases, the application of clothing leather is further met, the product grade is improved, a new thought is provided for desolvation products of the polyurethane resin for clothing leather, and the solvent-free polyurethane resin has important research value.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Preparation example 1
A tall oil diol, the preparation method of which comprises the following steps:
(1) Reacting tall oil with thionyl chloride at 80 ℃ for 5 hours, separating and purifying to obtain tall oil acyl chloride; the molar ratio of the carboxyl groups in the thionyl chloride and tall oil is 2.5
(2) Slowly and dropwise adding the tall oil acyl chloride obtained in the step (1) into a DMF (dimethyl formamide) solution of dopamine under an ice bath condition (the molar ratio of acyl chloride groups in the dopamine to the tall oil acyl chloride is 1.1).
Preparation example 2
A tall oil diol, the preparation method of which comprises the following steps:
(1) Reacting tall oil with thionyl chloride at 70 ℃ for 6 hours, separating and purifying to obtain tall oil acyl chloride; the molar ratio of the carboxyl groups in the thionyl chloride and tall oil is 3
(2) Slowly and dropwise adding the tall oil acyl chloride obtained in the step (1) into a DMF (dimethyl formamide) solution of dopamine under an ice bath condition (the molar ratio of acyl chloride groups in the dopamine to the tall oil acyl chloride is 1.2).
Preparation example 3
A tall oil diol, the preparation method of which comprises the following steps:
(1) Reacting tall oil with thionyl chloride at 100 ℃ for 4 hours, separating and purifying to obtain tall oil acyl chloride; the molar ratio of the carboxyl groups in the thionyl chloride and tall oil is 2
(2) Slowly dropwise adding the tall oil acyl chloride obtained in the step (1) into a DMF (dimethyl formamide) solution of dopamine under an ice bath condition (the molar ratio of acyl chloride groups in the dopamine to the tall oil acyl chloride is 1).
Preparation example 4
A tall oil diol, which is prepared by a method comprising: weighing tall oil in a reaction bottle, protecting by inert gas, heating to 150 ℃, adding diethanolamine according to the molar ratio of the diethanolamine to the tall oil of 1 to react with the tall oil, and distilling under reduced pressure to remove water generated in the reaction to obtain the tall oil diol.
Preparation example 5
A tall oil polyol, the method of making comprising: weighing tall oil in a reaction bottle, protecting by inert gas, heating to 150 ℃, then adding triethanolamine according to the molar ratio of the triethanolamine to the tall oil being 1.
Example 1
A solvent-free polyurethane resin comprising an a-component and a B-component in a mass ratio of 80;
the component A comprises the following components in parts by weight:
the component B is polyurethane prepolymer (the preparation method comprises the steps of quantitatively putting polyoxypropylene polyol (Chinese petrochemical engineering, TED-28) and toluene diisocyanate into a reaction kettle, charging nitrogen, heating to 80 ℃ for reaction for 2.5h, and measuring the NCO mass content to be 10% to obtain the polyurethane prepolymer)
The preparation method of the solvent-free polyurethane resin provided by the embodiment comprises the following steps:
(1) Mixing polyoxypropylene polyol, tall oil diol (preparation example 1), water, a leveling agent (Yingchuang, B8629) and a catalyst (Air Products, polycat DBU) to obtain a component A;
(2) And mixing the component A and the component B to obtain the solvent-free polyurethane resin.
Example 2
A solvent-free polyurethane resin comprising an a-component and a B-component in a mass ratio of 90;
the component A comprises the following components in parts by weight:
the component B is a polyurethane prepolymer (the preparation method comprises the steps of quantitatively putting polyoxyethylene polyol (Arch, 21-77) and diphenylmethane diisocyanate into a reaction kettle, filling nitrogen, heating to 70 ℃ for reaction for 3 hours, measuring the NCO mass content to be 10 percent, and obtaining the polyurethane prepolymer)
The preparation method of the solvent-free polyurethane resin provided by the embodiment comprises the following steps:
(1) Mixing polyoxypropylene polyol, tall oil diol (preparation example 2), water, a leveling agent (Yingchuang, B8629) and a catalyst (Air Products, polycat DBU) to obtain a component A;
(2) And mixing the component A and the component B to obtain the solvent-free polyurethane resin.
Example 3
A solvent-free polyurethane resin comprising an a-component and a B-component in a mass ratio of 70;
the component A comprises the following components in parts by weight:
the component B is polyurethane prepolymer (the preparation method comprises the steps of quantitatively putting polytetramethylene ether glycol (PTMEG-2000, korea PTG company) and isophorone isocyanate into a reaction kettle, charging nitrogen, heating to 90 ℃ for reaction for 2 hours, measuring the NCO mass content to be 10 percent, and obtaining the polyurethane prepolymer)
The preparation method of the solvent-free polyurethane resin provided by the embodiment comprises the following steps:
(1) Mixing polyoxypropylene polyol, tall oil diol (preparation example 3), water, a leveling agent (Yingchuang, B8629) and a catalyst (Air Products, polycat DBU) to obtain the component A;
(2) And mixing the component A and the component B to obtain the solvent-free polyurethane resin.
Example 4
A solvent-free polyurethane resin which differs from example 1 only in that the tall oil diol obtained in production example 4 is used instead of the tall oil diol obtained in production example 1, and the other components, amounts and production methods are the same as in example 1.
Example 5
A solvent-free polyurethane resin which differs from example 1 only in that the tall oil polyol obtained in production example 5 was used in place of the tall oil diol obtained in production example 1, and the other components, amounts and production methods were the same as in example 1.
Comparative example 1
A solvent-free polyurethane resin was distinguished from example 1 only in that 1, 4-butanediol (Sichuan Tianhua Co., ltd.) was used in place of the tall oil diol obtained in preparation example 1, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 2
A solvent-free polyurethane resin was distinguished from example 1 only in that a polyester polyol (Nicotiana, CMA-44) was used in place of the polyoxypropylene polyol, and the other components, amounts and preparation methods were the same as in example 1.
Application example 1
A solvent-free polyurethane synthetic leather comprises base cloth, a solvent-free polyurethane middle layer and a polyurethane surface layer which are sequentially arranged;
the preparation method comprises the following steps:
(1) Coating a preparation raw material (JF-NS-8016F) of the polyurethane surface layer on the surface of release paper, and drying to obtain a polyurethane surface layer coating;
(2) And (2) coating solvent-free polyurethane resin (example 1) on the surface of the polyurethane surface layer coating obtained in the step (1), pre-reacting for 60s at 100 ℃, adhering base cloth, curing for 5min at 120 ℃, and removing release paper to obtain the solvent-free polyurethane synthetic leather.
Application example 2
A solvent-free polyurethane synthetic leather which is different from application example 1 only in that the solvent-free polyurethane resin obtained in example 1 is replaced with the solvent-free polyurethane resin obtained in example 2, and other components, the use amounts and the preparation method are the same as those of application example 1.
Application example 3
A solvent-free polyurethane synthetic leather which is different from application example 1 only in that the solvent-free polyurethane resin obtained in example 3 is used instead of the solvent-free polyurethane resin obtained in example 1, and other components, the use amounts and the preparation method are the same as those of application example 1.
Application example 4
A solvent-free polyurethane synthetic leather which is different from application example 1 only in that the solvent-free polyurethane resin obtained in example 4 is used instead of the solvent-free polyurethane resin obtained in example 1, and other components, the use amounts and the preparation method are the same as those of application example 1.
Application example 5
A solvent-free polyurethane synthetic leather which is different from application example 1 only in that the solvent-free polyurethane resin obtained in example 5 is used instead of the solvent-free polyurethane resin obtained in example 1, and other components, the use amounts and the preparation method are the same as those of application example 1.
Comparative application example 1
A solvent-free polyurethane synthetic leather is different from application example 1 only in that the solvent-free polyurethane resin obtained in comparative example 1 is used instead of the solvent-free polyurethane resin obtained in example 1, and other components, the use amounts and the preparation method are the same as those of application example 1.
Comparative application example 2
A solvent-free polyurethane synthetic leather which differs from application example 1 only in that the solvent-free polyurethane resin obtained in comparative example 2 was used instead of the solvent-free polyurethane resin obtained in example 1, and the other components, the amounts and the preparation method were the same as in application example 1.
And (3) performance testing:
(1) Softness: testing according to the test method provided in QB/T4870;
(2) Peeling strength: the test was carried out according to the test method provided in GB/T279.
The solvent-free polyurethane synthetic leathers obtained according to the above test methods in the corresponding examples 1 to 5 and the comparative application examples 1 to 2 were tested, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in table 1: synthetic leather prepared by the solvent-free polyurethane resin provided by the invention has good softness and higher peel strength.
Comparing application example 1 with comparative application examples 1-2, it can be found that the introduction of tall oil diol molecules into a solvent-free polyurethane system can significantly improve the softness of synthetic leather prepared from the tall oil diol molecules and reduce the plastic feeling of the synthetic leather. Further comparing application examples 1 and 4-5, it can be found that the introduction of tall oil prepared by the method of the present invention as a chain extender in a solvent-free polyurethane system significantly improves the softness and peel strength of synthetic leather finally obtained.
The applicant states that the present invention is illustrated by the above examples to a solvent-free polyurethane resin, its preparation and application, but the present invention is not limited to the above examples, i.e. it is not meant that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (31)
1. A solvent-free polyurethane resin for synthetic leather is characterized by comprising a component A and a component B;
the component A comprises the following components in parts by weight: 20-30 parts of polyether glycol and 5-8 parts of tall oil glycol;
the component B comprises a polyurethane prepolymer;
the tall oil diol is prepared by a method comprising the following steps:
(A1) Reacting tall oil with thionyl chloride to obtain tall oil acyl chloride;
(A2) Reacting the tall oil acyl chloride obtained in the step (A1) with dopamine to obtain the tall oil diol;
the mass ratio of the component A to the component B is (55-100) to 100;
the molar ratio of the thionyl chloride to the carboxyl in the tall oil in the step (A1) is (2-3) to 1;
the molar ratio of acyl chloride groups in dopamine and tall oil acyl chloride in the step (A2) is (1-1.2): 1;
the molecular weight of the polyether polyol is 500-7000;
the polyether polyol has a functionality of 2 to 3.
2. The solvent-free polyurethane resin according to claim 1, wherein the reaction temperature in the step (A1) is 70 to 100 ℃.
3. The solvent-free polyurethane resin according to claim 1, wherein the reaction time of the step (A1) is 4 to 6 hours.
4. The solvent-free polyurethane resin according to claim 1, wherein the reaction of step (A1) is further followed by separation and purification.
5. The solvent-free polyurethane resin according to claim 1, wherein the dopamine in the step (A2) is dopamine dissolved in an organic solvent.
6. The solventless polyurethane resin of claim 5 wherein the organic solvent comprises N, N-dimethylformamide.
7. The solvent-free polyurethane resin according to claim 1, wherein the step (A2) further comprises a mixing step before the reaction.
8. The solvent-free polyurethane resin according to claim 7, wherein the mixing is performed by a dropwise manner.
9. The solvent-free polyurethane resin according to claim 8, further comprising a step of continuing the mixing after the completion of the dropping.
10. The solventless polyurethane resin of claim 9 wherein the continuing mixing and mixing are performed under ice bath conditions.
11. The solventless polyurethane resin of claim 9 wherein the mixing is continued for a period of 20 to 40 minutes.
12. The solvent-free polyurethane resin according to claim 1, wherein the reaction temperature in the step (A2) is 70 to 90 ℃.
13. The solvent-free polyurethane resin according to claim 1, wherein the reaction time of the step (A2) is 3 to 5 hours.
14. The solvent-free polyurethane resin according to claim 1, wherein the polyether polyol has a molecular weight of 4000 to 7000.
15. The solventless polyurethane resin of claim 1 wherein the polyether polyol comprises any one of a polyoxypropylene polyol, a polyoxyethylene polyol, a polyoxypropylene-oxyethylene copolyol or a polytetramethylene ether polyol or a combination of at least two thereof.
16. The solvent-free polyurethane resin of claim 1, wherein the a component further comprises any one of a catalyst, water or a leveling agent or a combination of at least two thereof.
17. The solvent-free polyurethane resin of claim 16, wherein the catalyst is contained in the a component in an amount of 0.03 to 0.08 parts by weight.
18. The solvent-free polyurethane resin of claim 16, wherein the water content of the a component is 0.4 to 1 part by weight.
19. The solvent-free polyurethane resin of claim 16, wherein the leveling agent is contained in the component a in an amount of 0.1 to 0.3 parts by weight.
20. The solvent-free polyurethane resin of claim 1, wherein the polyurethane prepolymer is obtained by reacting a polyether polyol with an isocyanate.
21. The solvent-free polyurethane resin according to claim 20, wherein the reaction temperature is 70 to 90 ℃.
22. The solventless polyurethane resin of claim 20 wherein the reaction time is 2 to 3 hours.
23. A solvent-free polyurethane resin according to claim 20 wherein the isocyanate comprises any one of toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, isophorone isocyanate or hexamethylene diisocyanate or a combination of at least two thereof.
24. The solvent-free polyurethane resin as claimed in claim 1, wherein the NCO group content in the polyurethane prepolymer is 8-20% by mass.
25. A method for preparing a solvent-free polyurethane resin according to any one of claims 1 to 24, comprising the steps of:
(1) Mixing polyether polyol, tall oil diol, optional water, an optional leveling agent and an optional catalyst to obtain the component A;
(2) And (2) mixing the component A and the component B obtained in the step (1) to obtain the solvent-free polyurethane resin.
26. The solvent-free polyurethane synthetic leather is characterized by comprising base cloth, a solvent-free polyurethane middle layer and a polyurethane surface layer which are sequentially arranged;
a raw material for producing the solvent-free polyurethane intermediate layer comprises the solvent-free polyurethane resin according to any one of claims 1 to 23.
27. A method of preparing the solvent-free polyurethane synthetic leather of claim 26, wherein the method comprises the steps of:
(B1) Coating the preparation raw material of the polyurethane surface layer on the surface of release paper, and drying to obtain a polyurethane surface layer coating;
(B2) Coating the solvent-free polyurethane resin as described in any one of claims 1 to 24 on the surface of the polyurethane surface coating obtained in the step (B1), pre-reacting, attaching a base fabric, curing, and removing the release film to obtain the solvent-free polyurethane synthetic leather.
28. The method according to claim 27, wherein the pre-reaction temperature in the step (B2) is 85 to 115 ℃.
29. The method according to claim 27, wherein the pre-reaction time in the step (B2) is 50 to 70 seconds.
30. The method of claim 27, wherein the aging time in step (B2) is 4 to 7min.
31. The method according to claim 27, wherein the curing in the step (B2) is carried out at a temperature of 95 to 114 ℃.
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