CN112646116A - Two-component solvent-free polyurethane resin and preparation method and application thereof - Google Patents

Two-component solvent-free polyurethane resin and preparation method and application thereof Download PDF

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Publication number
CN112646116A
CN112646116A CN202011566205.8A CN202011566205A CN112646116A CN 112646116 A CN112646116 A CN 112646116A CN 202011566205 A CN202011566205 A CN 202011566205A CN 112646116 A CN112646116 A CN 112646116A
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component
catalyst
hydroxyl
isocyanate
solvent
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林涤非
田明翰
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DONGGUAN RUIAN POLYMER RESIN CO LTD
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DONGGUAN RUIAN POLYMER RESIN CO LTD
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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
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833—Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2018—Heterocyclic amines; Salts thereof containing one heterocyclic ring having one nitrogen atom in the ring
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/4808—Mixtures of two or more polyetherdiols
    • 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
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • 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
    • D06N3/146—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 characterised by the macromolecular diols used
    • 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
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/068—Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the technical field of polyurethane, in particular to a bi-component solvent-free polyurethane resin and a preparation method and application thereof, wherein no organic solvent is added in the production process, so the production process is environment-friendly and operator-friendly, compared with a solvent type process, the solvent is not required to be heated and evaporated and a solvent recovery tank is not required to be built, and the production process is energy-saving; the tertiary amine catalyst and the heat-sensitive catalyst are added in the resin formula to be matched with the hydroxyl A component and the isocyanate B component, so that the early-stage opening time can be increased, resin caking and coating equipment blockage are avoided, the production efficiency is improved, the post-curing speed is high, the energy consumption is reduced, the effects of slow before and fast after are achieved, and the high peel strength is realized.

Description

Two-component solvent-free polyurethane resin and preparation method and application thereof
Technical Field
The invention relates to the technical field of polyurethane, in particular to a two-component solvent-free polyurethane resin and a preparation method and application thereof.
Background
The polyurethane synthetic leather has excellent performances of scraping resistance, wear resistance, folding fastness, solvent resistance and the like, has the same soft hand feeling and appearance as natural leather, and is an ideal substitute for the natural leather. Solvent type polyurethane resins are currently used in the market, and the production process thereof is divided into a dry method and a wet method. The wet process is developed after the dry process and is characterized in that a multilayer structure with a continuous porous layer is obtained by adopting an in-water film forming method, the process is that DMF and other auxiliary agents are added into polyurethane resin to prepare mixed liquid, the mixed liquid is coated on base cloth, then the mixed liquid is put into water to replace the DMF, the polyurethane resin is gradually solidified to form a microporous polyurethane grain surface layer, and then dry process veneering and subsequent surface treatment are further carried out, thus obtaining the finished product of the polyurethane synthetic leather. As a large amount of organic solvents such as DMF, toluene, butanone and the like are used, the solvents not only cause serious environmental pollution in production, but also harm the health of operators.
In recent years, a two-component solvent-free polyurethane resin intermediate layer, which is a substitute of a solvent-based polyurethane resin intermediate layer, has been researched by related patents, but the two-component solvent-free polyurethane resin applied to the synthetic leather intermediate layer has short opening time, is easy to cause resin caking, is easy to block coating equipment, and has poor production efficiency.
Disclosure of Invention
The invention aims to provide a two-component solvent-free polyurethane resin with long open time in the early development stage, high post-curing speed and high peel strength, a preparation method and application thereof aiming at the defects in the prior art.
The purpose of the invention is realized by the following technical scheme:
a two-component solvent-free polyurethane resin comprises a hydroxyl A component, an isocyanate B component and a catalyst C component in a mass ratio of (95-105) to (80-90) to (0.1-1):
the hydroxyl A component consists of the following raw materials in parts by weight:
80-95 parts of polyether glycol
Chain extender 5-20 parts
0.5-5 parts of cross-linking agent
0.05 to 0.5 portion of surfactant
The isocyanate B component consists of the following raw materials in parts by weight:
40-50 parts of diisocyanate
50-60 parts of polyether glycol
0.01-0.1 part of stabilizer
The catalyst C component consists of the following raw materials in parts by weight:
0.1-0.5 part of tertiary amine type catalyst
0.01 to 0.05 portion of heat-sensitive catalyst
Preferably, the polyether diol of the hydroxyl A component is one or two of polyoxypropylene-oxyethylene copolymer diol with the molecular weight of 1000-3000 and polytetrahydrofuran diol with the molecular weight of 1000-2000;
preferably, the chain extender of the hydroxyl A component is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, diethylene glycol, neopentyl glycol and 1, 6-hexanediol;
preferably, the cross-linking agent of the hydroxyl A component is one or two of glycerol and trihydroxy methyl propane;
preferably, the surfactant of the hydroxyl A component is a polyether modified silicone surfactant.
Preferably, the polyether modified organosilicon surfactant is one or more of DC-193, DC-3042, L-580 and B8715.
Preferably, the diisocyanate of the isocyanate B component is one or more of diphenylmethane diisocyanate, toluene-2, 4-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and carbodiimide modified isocyanate;
preferably, the polyether diol of the isocyanate B component is one or two of polyoxypropylene-oxyethylene copolymer diol with the molecular weight of 1000-3000 and polytetrahydrofuran diol with the molecular weight of 1000-2000;
preferably, the stabilizer of the isocyanate B component is an antioxidant.
More preferably, the antioxidant is one or more of 245, 264, 1010, 1076 and phosphite.
Preferably, the tertiary amine catalyst of the catalyst C component is one or more of triethylene diamine, dimethylethanolamine, bis (dimethylaminoethyl) ether and N-ethylmorpholine;
preferably, the thermosensitive catalyst of the catalyst C component is one of 1, 8-diazabicyclo [5.4.0] undec-7-ene and N-methyl-N' -hydroxyethyl piperazine.
A preparation method of two-component solvent-free polyurethane resin comprises the following steps:
step one, respectively preparing a hydroxyl A component, an isocyanate B component and a catalyst C component, specifically:
preparing a hydroxyl A component, namely putting polyether diol, a chain extender, a cross-linking agent and a surfactant into a reaction kettle, heating to 60 +/-2 ℃, and uniformly stirring to obtain the hydroxyl A component;
adding diisocyanate, polyether diol and stabilizer into a reaction kettle, stirring and heating to 75 +/-2 ℃, and stirring and reacting until the difference between the detection value of a-NCO group and the theoretical value is +/-0.5 percent to obtain an isocyanate B component;
preparing a catalyst C component, namely mixing a tertiary amine catalyst and a heat-sensitive catalyst and then uniformly stirring;
step two, fully mixing the hydroxyl A component, the isocyanate B component and the catalyst C component according to the mass ratio of (95-105): (80-90): 0.1-1, then coating the mixture on release paper with a surface layer, semi-drying the mixture at the temperature of 100-.
The application of the two-component solvent-free polyurethane resin is characterized in that the two-component solvent-free polyurethane resin is applied to a synthetic leather intermediate layer.
The invention has the beneficial effects that: the invention does not add any organic solvent in the production process, is friendly to the environment and operators, does not need to heat and evaporate the solvent and build a solvent recovery tank compared with a solvent type process, is an energy-saving production process, adds the tertiary amine type catalyst and the heat-sensitive type catalyst in the resin formula to be matched with the hydroxyl A component and the isocyanate B component, can increase the early-stage opening time, avoids resin caking and coating equipment blockage, improves the production efficiency, has high post-curing speed, reduces energy consumption, achieves the effect of slowing down the front and speeding up the back, and realizes high peeling strength.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A two-component solvent-free polyurethane resin is composed of a hydroxyl A component, an isocyanate B component and a catalyst C component:
the hydroxyl A component consists of the following raw materials in parts by weight:
80 parts of polyether glycol
Chain extender 5 parts
0.5 part of cross-linking agent
0.05 part of surfactant
The isocyanate B component consists of the following raw materials in parts by weight:
40 parts of diisocyanate
50 parts of polyether glycol
0.01 part of stabilizer
The catalyst C component consists of the following raw materials in parts by weight:
0.1 part of tertiary amine type catalyst
0.01 part of heat-sensitive catalyst
In the embodiment, the polyether diol of the hydroxyl A component is polyoxypropylene-ethylene oxide copolymerized diol with the molecular weight of 2000;
the chain extender of the hydroxyl A component is ethylene glycol;
the cross-linking agent of the hydroxyl A component is glycerol;
the surfactant of the hydroxyl A component is polyether modified organosilicon surfactant.
In this example, the polyether-modified silicone surfactant was DC-193.
In this example, the diisocyanate of the isocyanate B component is diphenylmethane diisocyanate;
the polyether diol of the isocyanate component B is polyoxypropylene-ethylene oxide copolymerized diol with the molecular weight of 2000;
the stabilizer of the isocyanate B component is an antioxidant.
In this embodiment, the antioxidant is antioxidant 245.
In the embodiment, the tertiary amine catalyst of the catalyst component C is triethylene diamine;
the thermosensitive catalyst of the catalyst C component is 1, 8-diazabicyclo [5.4.0] undec-7-ene.
A preparation method of two-component solvent-free polyurethane resin comprises the following steps:
step one, respectively preparing a hydroxyl A component, an isocyanate B component and a catalyst C component, specifically:
preparing a hydroxyl A component, namely putting polyether diol, a chain extender, a cross-linking agent and a surfactant into a reaction kettle, heating to 60 +/-2 ℃, and uniformly stirring to obtain the hydroxyl A component;
adding diisocyanate, polyether diol and stabilizer into a reaction kettle, stirring and heating to 75 +/-2 ℃, and stirring and reacting until the difference between the detection value of a-NCO group and the theoretical value is +/-0.5 percent to obtain an isocyanate B component;
preparing a catalyst C component, namely mixing a tertiary amine catalyst and a heat-sensitive catalyst and then uniformly stirring;
step two, fully mixing the hydroxyl A component, the isocyanate B component and the catalyst C component according to the mass ratio of 95:80: 0.4, uniformly coating the mixture on release paper with a surface layer, semi-drying the mixture at 120 ℃ for 30 seconds, then adhering base cloth, continuing to react at 120 ℃ for 10 minutes, and curing and molding the mixture to obtain the bi-component solvent-free polyurethane resin.
Example 2
A two-component solvent-free polyurethane resin is composed of a hydroxyl A component, an isocyanate B component and a catalyst C component:
the hydroxyl A component consists of the following raw materials in parts by weight:
90 parts of polyether glycol
15 portions of chain extender
2 portions of cross-linking agent
0.2 portion of surfactant
The isocyanate B component consists of the following raw materials in parts by weight:
diisocyanate 45 parts
55 parts of polyether glycol
0.05 part of stabilizer
The catalyst C component consists of the following raw materials in parts by weight:
0.3 part of tertiary amine type catalyst
0.03 part of thermosensitive catalyst
In the embodiment, the polyether diol of the hydroxyl A component is polytetrahydrofuran diol with molecular weight of 2000;
the chain extender of the hydroxyl A component is neopentyl glycol;
the cross-linking agent of the hydroxyl A component is trihydroxy methyl propane;
the surfactant of the hydroxyl A component is polyether modified organosilicon surfactant.
In this embodiment, the polyether-modified silicone surfactant is DC-3042.
In the embodiment, the diisocyanate of the isocyanate B component is diphenylmethane diisocyanate;
the polyether diol of the isocyanate component B is polytetrahydrofuran diol with molecular weight of 2000;
the stabilizer of the isocyanate B component is an antioxidant.
In this example, the antioxidant was 1010.
In this example, the tertiary amine catalyst of catalyst C component is bis (dimethylaminoethyl) ether;
the thermosensitive catalyst of the catalyst C component is N-methyl-N' -hydroxyethyl piperazine.
A preparation method of two-component solvent-free polyurethane resin comprises the following steps:
step one, respectively preparing a hydroxyl A component, an isocyanate B component and a catalyst C component, specifically:
preparing a hydroxyl A component, namely putting polyether diol, a chain extender, a cross-linking agent and a surfactant into a reaction kettle, heating to 60 +/-2 ℃, and uniformly stirring to obtain the hydroxyl A component;
adding diisocyanate, polyether diol and stabilizer into a reaction kettle, stirring and heating to 75 +/-2 ℃, and stirring and reacting until the difference between the detection value of a-NCO group and the theoretical value is +/-0.5 percent to obtain an isocyanate B component;
preparing a catalyst C component, namely mixing a tertiary amine catalyst and a heat-sensitive catalyst and then uniformly stirring;
and step two, fully mixing the hydroxyl A component, the isocyanate B component and the catalyst C component according to the mass ratio of 100:85:0.5, uniformly coating the mixture on release paper with a surface layer, semi-drying the mixture at 120 ℃ for 60 seconds, then adhering base cloth, continuing to react at 120 ℃ for 8 minutes, and curing and molding the mixture to obtain the bi-component solvent-free polyurethane resin.
Example 3
A two-component solvent-free polyurethane resin is composed of a hydroxyl A component, an isocyanate B component and a catalyst C component:
the hydroxyl A component consists of the following raw materials in parts by weight:
95 parts of polyether glycol
20 portions of chain extender
5 portions of cross-linking agent
0.5 part of surfactant
The isocyanate B component consists of the following raw materials in parts by weight:
50 parts of diisocyanate
Polyether glycol 60 parts
0.1 portion of stabilizer
The catalyst C component consists of the following raw materials in parts by weight:
0.5 part of tertiary amine type catalyst
0.05 part of heat-sensitive catalyst
In the embodiment, the polyether diol of the hydroxyl A component is polyoxypropylene-ethylene oxide copolymerized diol with the molecular weight of 3000;
the chain extender 1, 2-propanediol of the hydroxyl A component;
the cross-linking agent of the hydroxyl A component is trihydroxy methyl propane;
the surfactant of the hydroxyl A component is polyether modified organosilicon surfactant.
In this example, the polyether-modified silicone surfactant was L-580.
In the embodiment, the diisocyanate of the isocyanate B component is diphenylmethane diisocyanate;
the polyether diol of the isocyanate component B is polyoxypropylene-ethylene oxide copolymerized diol with the molecular weight of 3000;
the stabilizer of the isocyanate B component is an antioxidant.
In this example, the antioxidant was 1076.
In this example, the tertiary amine catalyst of catalyst C component is bis (dimethylaminoethyl) ether;
the thermosensitive catalyst of the catalyst C component is 1, 8-diazabicyclo [5.4.0] undec-7-ene.
A preparation method of two-component solvent-free polyurethane resin comprises the following steps:
step one, respectively preparing a hydroxyl A component, an isocyanate B component and a catalyst C component, specifically:
preparing a hydroxyl A component, namely putting polyether diol, a chain extender, a cross-linking agent and a surfactant into a reaction kettle, heating to 60 +/-2 ℃, and uniformly stirring to obtain the hydroxyl A component;
adding diisocyanate, polyether diol and stabilizer into a reaction kettle, stirring and heating to 75 +/-2 ℃, and stirring and reacting until the difference between the detection value of a-NCO group and the theoretical value is +/-0.5 percent to obtain an isocyanate B component;
preparing a catalyst C component, namely mixing a tertiary amine catalyst and a heat-sensitive catalyst and then uniformly stirring;
step two, fully mixing the hydroxyl A component, the isocyanate B component and the catalyst C component according to the mass ratio of 105:90: 0.4, uniformly coating the mixture on release paper with a surface layer, semi-drying the mixture at 130 ℃ for 30 seconds, then adhering base cloth, continuing to react at 130 ℃ for 7 minutes, and curing and molding the mixture to obtain the bi-component solvent-free polyurethane resin.
Example 4
A two-component solvent-free polyurethane resin is composed of a hydroxyl A component, an isocyanate B component and a catalyst C component:
the hydroxyl A component consists of the following raw materials in parts by weight:
85 parts of polyether glycol
15 portions of chain extender
5 portions of cross-linking agent
0.5 part of surfactant
The isocyanate B component consists of the following raw materials in parts by weight:
diisocyanate 45 parts
Polyether glycol 60 parts
0.1 portion of stabilizer
The catalyst C component consists of the following raw materials in parts by weight:
0.4 part of tertiary amine type catalyst
0.02 part of heat-sensitive catalyst
In this embodiment, the polyether diol of the hydroxyl group a component is polytetrahydrofuran diol with a molecular weight of 2000;
the chain extender of the hydroxyl A component is ethylene glycol and 1, 2-propylene glycol in a mass ratio of 1: 1;
the cross-linking agent of the hydroxyl A component is glycerol and trihydroxy methyl propane with the mass ratio of 1: 1;
the surfactant of the hydroxyl A component is polyether modified organosilicon surfactant.
In the embodiment, the polyether modified organosilicon surfactant is DC-193 and L-580 with the mass ratio of 1: 1.
In the embodiment, the diisocyanate of the isocyanate B component is diphenylmethane diisocyanate and carbodiimide modified isocyanate with a mass ratio of 4: 1;
the polyether diol of the isocyanate component B is polytetrahydrofuran diol with the molecular weight of 2000;
the stabilizer of the isocyanate B component is an antioxidant.
In this example, the antioxidant is 245 and 1010 in a mass ratio of 1: 1.
In the embodiment, the tertiary amine catalyst of the catalyst component C is triethylene diamine and N-ethyl morpholine with the mass ratio of 1: 1;
the thermosensitive catalyst of the catalyst C component is 1, 8-diazabicyclo [5.4.0] undec-7-ene and N-methyl-N' -hydroxyethyl piperazine in a mass ratio of 1: 1.
A preparation method of two-component solvent-free polyurethane resin comprises the following steps:
step one, respectively preparing a hydroxyl A component, an isocyanate B component and a catalyst C component, specifically:
preparing a hydroxyl A component, namely putting polyether diol, a chain extender, a cross-linking agent and a surfactant into a reaction kettle, heating to 60 +/-2 ℃, and uniformly stirring to obtain the hydroxyl A component;
adding diisocyanate, polyether diol and stabilizer into a reaction kettle, stirring and heating to 75 +/-2 ℃, and stirring and reacting until the difference between the detection value of a-NCO group and the theoretical value is +/-0.5 percent to obtain an isocyanate B component;
preparing a catalyst C component, namely mixing a tertiary amine catalyst and a heat-sensitive catalyst and then uniformly stirring;
and step two, fully mixing the hydroxyl A component, the isocyanate B component and the catalyst C component according to the mass ratio of 100:85:0.5, uniformly coating the mixture on release paper with a surface layer, semi-drying the mixture at 130 ℃ for 30 seconds, then attaching base cloth, continuing to react at 130 ℃ for 7 minutes, and curing and molding the mixture to obtain the bi-component solvent-free polyurethane resin.
Example 5
A two-component solvent-free polyurethane resin is composed of a hydroxyl A component, an isocyanate B component and a catalyst C component:
the hydroxyl A component consists of the following raw materials in parts by weight:
90 parts of polyether glycol
Chain extender 5 parts
5 portions of cross-linking agent
0.5 part of surfactant
The isocyanate B component consists of the following raw materials in parts by weight:
50 parts of diisocyanate
50 parts of polyether glycol
0.1 portion of stabilizer
The catalyst C component consists of the following raw materials in parts by weight:
0.5 part of tertiary amine type catalyst
0.05 part of heat-sensitive catalyst
In the embodiment, the polyether diol of the hydroxyl A component is polyoxypropylene-ethylene oxide copolymerized diol and polytetrahydrofuran diol with the mass ratio of 1: 3;
the chain extender of the hydroxyl A component is ethylene glycol, 1, 2-propylene glycol and 1, 6-hexanediol with the mass ratio of 1:1: 1;
the cross-linking agent of the hydroxyl A component is glycerol and trihydroxy methyl propane with the mass ratio of 2: 1;
the surfactant of the hydroxyl A component is polyether modified organosilicon surfactant.
In the embodiment, the mass ratio of the polyether modified organosilicon surfactant is DC-193 to L-580 of 2: 1.
In the embodiment, the diisocyanate of the isocyanate B component is diphenylmethane diisocyanate and carbodiimide modified isocyanate with the mass ratio of 5: 1;
the polyether diol of the isocyanate component B is polytetrahydrofuran diol with the molecular weight of 1500;
the stabilizer of the isocyanate B component is an antioxidant.
In the embodiment, the antioxidant is 245 and 1076 in a mass ratio of 2: 1.
In the embodiment, the tertiary amine catalyst of the catalyst component C is triethylene diamine and N-ethylmorpholine with the mass ratio of 2: 1;
the thermosensitive catalyst of the catalyst C component is 1, 8-diazabicyclo [5.4.0] undec-7-ene and N-methyl-N' -hydroxyethyl piperazine in a mass ratio of 2: 1.
A preparation method of two-component solvent-free polyurethane resin comprises the following steps:
step one, respectively preparing a hydroxyl A component, an isocyanate B component and a catalyst C component, specifically:
preparing a hydroxyl A component, namely putting polyether diol, a chain extender, a cross-linking agent and a surfactant into a reaction kettle, heating to 60 +/-2 ℃, and uniformly stirring to obtain the hydroxyl A component;
adding diisocyanate, polyether diol and stabilizer into a reaction kettle, stirring and heating to 75 +/-2 ℃, and stirring and reacting until the difference between the detection value of a-NCO group and the theoretical value is +/-0.5 percent to obtain an isocyanate B component;
preparing a catalyst C component, namely mixing a tertiary amine catalyst and a heat-sensitive catalyst and then uniformly stirring;
step two, fully mixing the hydroxyl A component, the isocyanate B component and the catalyst C component according to the mass ratio of 95:80: 0.4, then uniformly coating the mixture on release paper with a surface layer, semi-dry-pasting the mixture for 90 seconds at 100 ℃, then pasting the mixture on base cloth, continuously reacting for 10 minutes at 100 ℃, and curing and forming the mixture to obtain the bi-component solvent-free polyurethane resin.
Figure 57568DEST_PATH_IMAGE002
。
The open time of the two-component solvent-free intermediate layer polyurethane resin on the market is 7-10 minutes, and the embodiment of the invention can find that the open time of the two-component solvent-free intermediate layer polyurethane resin prepared by the invention can reach 25-30 minutes, which is obviously superior to that of a comparative example on the market.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (8)

1. A two-component solvent-free polyurethane resin, characterized in that: the catalyst consists of a hydroxyl A component, an isocyanate B component and a catalyst C component in a mass ratio of (95-105) to (80-90) to (0.1-1):
the hydroxyl A component consists of the following raw materials in parts by weight:
80-95 parts of polyether glycol
Chain extender 5-20 parts
0.5-5 parts of cross-linking agent
0.05 to 0.5 portion of surfactant
The isocyanate B component consists of the following raw materials in parts by weight:
40-50 parts of diisocyanate
50-60 parts of polyether glycol
0.01-0.1 part of stabilizer
The catalyst C component consists of the following raw materials in parts by weight:
0.1-0.5 part of tertiary amine type catalyst
0.01-0.05 part of heat-sensitive catalyst.
2. The two-component solvent-free polyurethane resin of claim 1, wherein:
the polyether diol of the hydroxyl A component is one or two of polyoxypropylene-ethylene oxide copolymerized diol with the molecular weight of 1000-3000 and polytetrahydrofuran diol with the molecular weight of 1000-2000;
the chain extender of the hydroxyl A component is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 4-butanediol, diethylene glycol, neopentyl glycol and 1, 6-hexanediol;
the cross-linking agent of the hydroxyl A component is one or two of glycerol and trihydroxy methyl propane;
the surfactant of the hydroxyl A component is polyether modified organosilicon surfactant.
3. The two-component solvent-free polyurethane resin of claim 2, wherein: the polyether modified organosilicon surfactant is one or more of DC-193, DC-3042, L-580 and B8715.
4. The two-component solvent-free polyurethane resin of claim 1, wherein:
the diisocyanate of the isocyanate B component is one or more of diphenylmethane diisocyanate, toluene-2, 4-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and carbodiimide modified isocyanate;
the polyether diol of the isocyanate B component is one or two of polyoxypropylene-oxyethylene copolymerized diol with the molecular weight of 1000-3000 and polytetrahydrofuran diol with the molecular weight of 1000-2000;
the stabilizer of the isocyanate B component is an antioxidant.
5. The two-component solvent-free polyurethane resin of claim 4, wherein: the antioxidant is one or more of 245, 264, 1010, 1076 and phosphite esters.
6. The two-component solvent-free polyurethane resin of claim 1, wherein:
the tertiary amine catalyst of the catalyst C component is one or more of triethylene diamine, dimethylethanolamine, bis (dimethylaminoethyl) ether and N-ethylmorpholine;
the thermosensitive catalyst of the catalyst C component is one of 1, 8-diazabicyclo [5.4.0] undec-7-ene and N-methyl-N' -hydroxyethyl piperazine.
7. A preparation method of two-component solvent-free polyurethane resin is characterized by comprising the following steps: the method comprises the following steps:
step one, respectively preparing a hydroxyl A component, an isocyanate B component and a catalyst C component, specifically:
preparing a hydroxyl A component, namely putting polyether diol, a chain extender, a cross-linking agent and a surfactant into a reaction kettle, heating to 60 +/-2 ℃, and uniformly stirring to obtain the hydroxyl A component;
adding diisocyanate, polyether diol and stabilizer into a reaction kettle, stirring and heating to 75 +/-2 ℃, and stirring and reacting until the difference between the detection value of a-NCO group and the theoretical value is +/-0.5 percent to obtain an isocyanate B component;
preparing a catalyst C component, namely mixing a tertiary amine catalyst and a heat-sensitive catalyst and then uniformly stirring;
step two, fully mixing the hydroxyl A component, the isocyanate B component and the catalyst C component according to the mass ratio of (95-105): (80-90): 0.1-1, then coating the mixture on release paper with a surface layer, semi-drying the mixture at the temperature of 100-.
8. Use of the two-component solvent-free polyurethane resin according to claim 1, wherein the two-component solvent-free polyurethane resin is applied to a synthetic leather intermediate layer.
CN202011566205.8A 2020-12-25 2020-12-25 Two-component solvent-free polyurethane resin and preparation method and application thereof Pending CN112646116A (en)

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CN112011027A (en) * 2019-05-31 2020-12-01 万华化学（北京）有限公司 Preparation method of polyurethane composite material
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