CN107226894B - Solvent-free middle layer polyurethane resin for soft mirror synthetic leather and preparation method and application thereof - Google Patents
Solvent-free middle layer polyurethane resin for soft mirror synthetic leather and preparation method and application thereof Download PDFInfo
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- CN107226894B CN107226894B CN201710604887.9A CN201710604887A CN107226894B CN 107226894 B CN107226894 B CN 107226894B CN 201710604887 A CN201710604887 A CN 201710604887A CN 107226894 B CN107226894 B CN 107226894B
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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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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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
- D06N3/146—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
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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
- D06N3/147—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 isocyanates used
- D06N3/148—(cyclo)aliphatic polyisocyanates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- D06N2209/00—Properties of the materials
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- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
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Abstract
The invention discloses a solvent-free middle layer polyurethane resin for soft mirror synthetic leather and a preparation method and application thereof, wherein the solvent-free middle layer polyurethane resin for soft mirror synthetic leather is obtained by mixing and drying a component A and a component B according to the mass ratio of 1:2-1: 1. The solvent-free soft mirror synthetic leather prepared by the invention does not contain any organic solvent, is green and environment-friendly, has soft hand feeling and no crease, has physical properties of no cracking after being bent for 10 ten thousand times at normal temperature, no cracking after being bent for 8 ten thousand times at minus 20 ℃, peel strength of more than 60N/3cm, and peel strength retention rate of 75 percent after 5 to 8 weeks under the conditions of constant temperature and constant humidity of 70 ℃, 95 percent of humidity.
Description
Technical Field
The invention relates to a solvent-free middle layer polyurethane resin for soft mirror synthetic leather, a preparation method and application thereof, belonging to the field of functional polyurethane synthetic leather.
Background
The polyurethane synthetic leather is widely applied to various fields such as clothes, eating and housing, and along with the continuous development and progress of the synthetic leather industry, people have wider and higher requirements on synthetic leather products. The polyurethane synthetic leather is required to have basic physical properties such as peel strength, hydrolysis resistance, yellowing resistance, bending resistance and the like, and is required to meet the requirements of aesthetic feeling, comfort and some special functions. The polyurethane mirror surface synthetic leather is a representative branch of the synthetic leather, has the effects of smooth mirror surface on the surface, smooth hand feeling and no trace after being folded, is well pursued by people, and is widely applied to the product fields of bags, shoe materials, decoration and the like.
Synthetic leather with traditional polyurethane mirror effect is mostly prepared by two production processes: one is a wet-dry veneering process, and due to the special performance of mirror-surface polyurethane synthetic leather, the wet-process polyurethane resin is required to have the characteristics of no foam hole, moderate solidification speed and high washing speed. In the process, a large amount of toxic and harmful solvents such as DMF are used, and the prepared wet-process Bess DMF has serious residue. The other is a moisture curing process, wherein the polyurethane used for moisture curing contains active isocyanate groups, and can react with trace moisture in the air to generate a urea bond structure when exposed to the air with constant temperature and humidity, so that the finally generated polymer of the moisture curing polyurethane is a polyurethane-polyurea structure, and the chemical structure has the characteristics of excellent wear resistance, adhesive force, durability, smoothness, transparency and the like. The mirror surface leather produced by the moisture curing process has much better flatness and brightness than the mirror surface leather produced by the common wet process. However, the moisture curing production process also has obvious defects, such as high constant temperature and humidity conditions required for curing, common requirement of airing in a factory building, large occupied space, low production efficiency, large solvent volatilization in the production process, great harm to operators, and flammability and explosiveness. The mirror surface leather produced by moisture curing has certain defects on the performance, such as poor low-temperature flex resistance, and cannot be applied to products such as shoe materials and the like with high requirements on low-temperature flex.
Most of polyurethane mirror surface leathers in the market have hard handfeel, the used resin is polyurethane resin with medium and high modulus, and the low-modulus wet-process polyurethane resin used for the mirror surface leathers with soft handfeel is rare, mainly because the low-modulus polyurethane resin has low strength, poor stripping and weak supporting force, and the effect of no crease is difficult to achieve.
With the increasing attention of people to low carbon, green and environment protection, the stricter laws and regulations on environmental protection of synthetic leather products, and the restriction of import measures of solvent-based polyurethane resins in developed countries such as europe and the united states, the conventional solvent-based polyurethane resins face huge examination. The development of the crease-free mirror synthetic leather which does not contain any organic solvent, has low energy consumption, high production efficiency and good physical property and has soft hand feeling has very important significance.
Disclosure of Invention
The invention aims to provide a solvent-free middle layer polyurethane resin for soft mirror synthetic leather, and a preparation method and application thereof. The polyurethane resin does not contain any organic solvent, has low energy consumption and high production efficiency, and can meet the requirements of downstream customers and consumers on the hand feeling, the appearance, the performance and the like of the mirror synthetic leather.
The solvent-free middle layer polyurethane resin for the soft mirror synthetic leather is obtained by mixing and drying a component A and a component B according to the mass ratio of 1:2-1: 1.
The component A comprises the following raw materials in parts by weight:
the component B comprises the following raw materials in parts by weight:
40-50 parts of polyether polycarbonate copolymer type oligomer dihydric alcohol
50-60 parts of isocyanate
0.5-1.0 part of light/heat stabilizer.
The polyether polycarbonate copolymerization type oligomer dihydric alcohol is prepared from diethyl carbonate and polyether dihydric alcohol through an ester exchange process, and has the molecular weight of 500-3000.
The preparation raw materials of the polyether polycarbonate copolymerization type oligomer dihydric alcohol comprise the following components in parts by mass:
2-25 parts of diethyl carbonate
75-98 parts of polyether glycol
0.02-0.06 part of catalyst.
The polyether diol is polypropylene oxide diol with the molecular weight of 200-2000 and/or polytetrahydrofuran diol with the molecular weight of 200-2000.
The chain extender is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol hydroquinone bis (2-hydroxyethyl) ether.
The cross-linking agent is one or two of glycerol and trimethylolpropane.
The catalyst used in the component A is a delayed catalyst, and is selected from BiCAT 8106, BiCAT 8108, BiCAT8124, BiCAT 3228, Borchi Kat 22, Borchi Kat 24, BiCAT 4130, BiCAT 4232, MB20 and one of phenate, formate and hydrochloride of the organometallic catalysts.
The light/heat stabilizer is an ultraviolet absorbent, a hindered amine light stabilizer or an antioxidant; wherein the ultraviolet absorbent is UV-1, UV-320, UV-1130, UV-P, UV-1164 or UV-234; the hindered amine light stabilizer is 292, 622, 770, 944, 5050, 5060 or 5151; the antioxidant is 245, 1010, 1035, 1076, 1098 or 3114.
The isocyanate is one or more of 4,4 '-diphenylmethane diisocyanate (MDI-100), a mixture of 2, 4-diphenylmethane diisocyanate and 4, 4' -diphenylmethane diisocyanate (MDI-50) and a mixture of diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate (polymeric MDI). The isocyanates may be modified by introducing uretdione, urethane, isocyanurate, carbodiimide or allophanate groups, or may be used in the form of prepolymers by reacting the isocyanates with active hydrogen-containing compounds.
The catalyst used in the raw material of the polyether polycarbonate copolymer oligomer diol is tetrabutyl titanate or tetraisopropyl titanate.
The polyurethane resin system components of the present invention do not contain organic solvents; more particularly, the polyurethane resin system components do not contain ethers or glycol ethers, ketones, esters, nitrogen compounds, sulfur compounds, nitro compounds, halogenated hydrocarbons, hydrocarbons having a boiling point above 60 ℃.
The preparation method of the solvent-free middle layer polyurethane resin for the soft mirror synthetic leather comprises the following steps:
step 1: preparation of polyether polycarbonate copolymer type oligomer dihydric alcohol
Will be equipped with a magnetic stirrer, a constant pressure burette, a thermometer and N2The four-mouth flask with inlet pipe and air-cooling condenser pipe is arranged in a jacketed resistance heater, polyether glycol and catalyst are filled in the flask, the mouth of a constant pressure titration pipe extends below the liquid level of the polyether glycol, diethyl carbonate is filled in the constant pressure titration pipe, and N is introduced2Exhausting air in a reaction bottle, gradually increasing the temperature of a reaction system to 120-130 ℃ under normal pressure, dropwise adding diethyl carbonate into the reaction bottle, reacting for 30min, then allowing liquid to flow down at a branch opening of a distillation column, controlling the discharge temperature of the branch opening of the distillation column to be below 78 ℃, gradually increasing the temperature of the reaction system to 240 ℃ when the discharge rate is slowed down after 2h of reaction, continuing the reaction for 2h, vacuumizing under reduced pressure when the discharge liquid does not flow out any more, keeping the system at 240 ℃, keeping the vacuum degree to be more than or equal to 0.095MPa, continuously reacting for 3h, measuring the hydroxyl value, controlling the hydroxyl value to be 28-224mg KOH/g, and preparing the polyether polycarbonate copolymer oligomer dihydric alcohol with the molecular weight of 500-4000;
step 2: preparation of component A
Dehydrating polyether polycarbonate copolymer oligomer dihydric alcohol for 3-5h at 90-110 ℃ and-0.08 MPa to-0.1 MPa to reduce the occurrence of side reaction for later use; adding the dehydrated polyether polycarbonate copolymerization type oligomer dihydric alcohol into a reaction kettle, sequentially adding a chain extender, a cross-linking agent, a catalyst and a light/heat stabilizer, heating to 60-80 ℃, stirring and reacting for 4-6h to obtain a component A, and sealing and packaging for later use;
and step 3: preparation of component B
Putting isocyanate and a light/heat stabilizer into a reaction kettle, stirring and mixing uniformly, then adding dehydrated polyether polycarbonate copolymerization type oligomer dihydric alcohol, heating to 65-90 ℃, stirring and reacting for 2-4h until the difference between the detection value of-NCO group and the theoretical value is +/-0.2% (the theoretical design value-NCO content is 5-20%), obtaining a component B, and sealing and packaging for later use;
and 4, step 4: preparation of solvent-free middle layer polyurethane resin for soft mirror synthetic leather
Coating mirror surface resin slurry LT-150 produced by polyurethane new material Co-Safei Anli on mirror surface paper, drying and molding at 130 ℃ to obtain a mirror surface layer; and (3) placing the component A and the component B in a low-pressure casting machine according to the mass ratio of 1:2-1:1, fully mixing, casting and coating on the mirror surface layer after uniform mixing, and drying at the temperature of 100-.
The solvent-free middle layer polyurethane resin for the soft mirror synthetic leather is suitable for the mirror synthetic leather, and when the solvent-free middle layer polyurethane resin for the soft mirror synthetic leather is used, the solvent-free middle layer polyurethane resin for the soft mirror synthetic leather is pre-reacted for 30-90 seconds at the temperature of 100-150 ℃, base cloth is attached after the pre-reaction is finished, and then the reaction is continued for 5-10 minutes at the temperature of 100-150 ℃ so as to be crosslinked, cured and molded; and (4) after curing and forming, rolling and stripping the mirror surface paper to obtain the solvent-free soft crease-free mirror surface synthetic leather.
The production process can achieve complete curing and shaping within 3-5 minutes, and the production efficiency is greatly improved compared with the production efficiency of the traditional wet method. The solvent-free soft mirror synthetic leather prepared by the invention does not contain any organic solvent, is green and environment-friendly, has soft hand feeling and no crease, has physical properties of no cracking after being bent for 10 ten thousand times at normal temperature, no cracking after being bent for 8 ten thousand times at minus 20 ℃, peel strength of more than 60N/3cm, and peel strength retention rate of 75 percent after 5 to 8 weeks under the conditions of constant temperature and constant humidity of 70 ℃, 95 percent of humidity.
Compared with the prior art, the invention has the beneficial effects that:
1. the self-made polyether polycarbonate copolymer oligomer dihydric alcohol is adopted, so that the self-made polyether polycarbonate copolymer oligomer dihydric alcohol not only has the soft and low-temperature-resistant flexibility of polyether, but also has excellent supporting performance and weather resistance after a polycarbonate structure is introduced, and the prepared solvent-free mirror surface leather is ensured to be soft in hand feeling and has a crease-free effect.
2. The polyether polycarbonate copolymer oligomer dihydric alcohol synthesized by the method destroys the original crystallinity of polytetrahydrofuran dihydric alcohol, the viscosity is less than or equal to 1500cp at 25 ℃, and the viscosity of the prepared component A and the component B is less than 1500cp at 25 ℃. The materials can not form bubbles when the cutter head rolls in the production process, the solvent-free middle layer polyurethane resin coated on the cutter head is ensured not to contain dark bubbles, and the finished leather has a good mirror effect.
3. The resin is composed of a polyhydroxy component A and an isocyanate-terminated prepolymer component B, does not contain any organic solvent, and releases heat in the reaction process; the energy consumption required by production and processing is low, and the production efficiency is high; the prepared solvent-free soft mirror surface leather is a clean low-carbon environment-friendly product, accords with the development trend of the synthetic leather industry, and better accords with the requirements of green consumption, environmental protection and health of consumers.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be noted that the specific material ratios, process conditions, results, etc. described in the examples of the present invention are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Example 1: preparation of polytetrahydrofuran polycarbonate copolymer type oligomer dihydric alcohol
Will be equipped with a magnetic stirrer, a constant pressure burette, a thermometer and N2A four-necked flask with an inlet tube and an air-cooled condenser tube was set in a jacketed resistance heater, 600 parts by mass of polytetrahydrofuran diol (PTMG, molecular weight 300) was charged into the flask, a constant pressure burette port was extended below the level of the polytetrahydrofuran diol, 130 parts by mass of diethyl carbonate was charged into the constant pressure burette, 0.1 part by mass of tetraisopropyl titanate was added, and N was introduced2The air in a reaction bottle is exhausted, the temperature of a reaction system is gradually raised to 120-130 ℃ under normal pressure, diethyl carbonate is dripped into the reaction bottle, after 30min of reaction, liquid flows down at a branch opening of a distillation column, the discharge temperature of the branch opening of the distillation column is controlled to be below 78 ℃, after 2h of reaction, the temperature of the reaction system is gradually increased to 240 ℃ when the discharge rate is slowed down, the reaction is continued for 2h, when the discharge liquid does not discharge any more, vacuum pumping is carried out under reduced pressure, the system is kept at 240 ℃, the vacuum degree is more than or equal to 0.095MPa, after 3h of continuous reaction, the product is separated by cooling, and the polytetrahydrofuran polycarbonate with the hydroxyl value of 185mg KOH/g (molecular weight of 606)A polymeric oligomeric diol.
Example 2: preparation of polypropylene oxide polycarbonate copolymer oligomer dihydric alcohol
The procedure of this example was conducted in accordance with example 1 except that 600 parts by mass of 300 molecular weight polytetrahydrofuran diol was replaced with 600 parts by mass of 300 molecular weight polypropylene oxide diol. A polypropylene oxide polycarbonate copolymeric oligomer diol with a hydroxyl number of 185mg KOH/g (molecular weight 606) was prepared.
Example 3: preparation of polypropylene oxide polytetrahydrofuran polycarbonate copolymer oligomer dihydric alcohol
The procedure of this example was conducted in accordance with example 1 except that 600 parts by mass of polytetrahydrofuran diol having a molecular weight of 300 was replaced with 400 parts by mass of polypropylene oxide diol having a molecular weight of 1000 and 200 parts by mass of polytetrahydrofuran diol having a molecular weight of 500, diethyl carbonate was added in an amount of 52 parts by mass, and tetraisopropyl titanate was added in an amount of 0.12 part by mass. A polypropylene oxide polytetrahydrofuran polycarbonate copolymeric oligomer diol with a hydroxyl number of 47mg KOH/g (molecular weight 2387) was prepared.
Example 4: preparation of solvent-free middle layer polyurethane resin for soft mirror synthetic leather
The preparation process of the solvent-free middle layer polyurethane resin for the soft mirror synthetic leather in the embodiment is as follows:
1. preparation of component A
Dehydrating the polytetrahydrofuran polycarbonate copolymerization oligomer dihydric alcohol prepared in the example 1 at the temperature of 100 ℃, and under the pressure of-0.08 MPa to-0.1 MPa for 5 hours, cooling to 30 ℃, adding chain extender 1, 2-propylene glycol, catalyst BiCAT 3228, light/heat stabilizer Chisorb P and Chisorb 944, heating to 60 ℃, stirring and reacting for 4 hours to obtain a component A, and sealing and packaging for later use;
the raw materials in the step 1 comprise the following components in parts by mass:
2. preparation of component B
Putting isocyanate Wannate MDI-100 into a reaction kettle, uniformly stirring, then putting dehydrated polytetrahydrofuran polycarbonate copolymerization type oligomer dihydric alcohol (prepared in example 1) and a light/heat stabilizer Chinox 1010, heating to 80 ℃, stirring and reacting for 2 hours until the detection value of-NCO groups is (9.9 +/-0.2)%, obtaining a component B, and sealing and packaging for later use;
in the step 2, the raw materials comprise the following components in parts by mass:
50 parts of polytetrahydrofuran polycarbonate copolymerized oligomer dihydric alcohol
Isocyanate (Wannate MDI-100) 50 parts
0.5 part of light/heat stabilizer (Chinox 1010).
3. Preparation of solvent-free middle layer polyurethane resin for soft mirror synthetic leather
Coating mirror surface resin slurry LT-150 produced by polyurethane new material Co-Safei Anli on mirror surface paper, drying at 130 ℃ for 2 minutes and forming to obtain a mirror surface layer; mixing the component A and the component B according to the mass ratio of 100: 165 in a low-pressure casting machine, uniformly mixing, casting and coating the mixture on the mirror surface layer, and drying at 110 ℃ to obtain the solvent-free intermediate layer polyurethane resin for the soft mirror surface synthetic leather.
4. Applications of
Pre-reacting the solvent-free middle layer polyurethane resin for the soft mirror synthetic leather prepared in the step 3 at 110 ℃ for 60 seconds, attaching the base cloth after the pre-reaction is finished, and then continuously reacting at 100-150 ℃ for 7 minutes to crosslink, solidify and mold the soft mirror synthetic leather; and (4) after curing and forming, rolling and stripping the mirror surface paper to obtain the solvent-free soft crease-free mirror surface synthetic leather. The physical properties of the material can reach no cracking after being bent for 10 ten thousand times at normal temperature, no cracking after being bent for 8 ten thousand times at-20 ℃, the peel strength of the material is 80N/3cm, and the peel strength of the material is 70N/3cm after being peeled for 5 weeks under the conditions of constant temperature and humidity of 70 ℃ and 95 percent.
The raw materials used in this example:
polytetrahydrofuran polycarbonate copolymerized oligomer diol is oligomer diol with molecular weight of 606 prepared in example 1; 1,2-PG is a commercial product; BiCAT 3228 is an organic bismuth catalyst from leading Chemicals, USA; chisorb P, Chisorb 944 and Chinox 1010 are respectively an ultraviolet absorbent, a light stabilizer and an antioxidant of Taiwan double bond chemical industry Co., Ltd; wannate MDI-100 is a pure diphenylmethylene diisocyanate produced by Nicotiana Tenwamura.
Example 5: preparation of solvent-free middle layer polyurethane resin for soft mirror synthetic leather
The preparation process of the solvent-free middle layer polyurethane resin for the soft mirror synthetic leather in the embodiment is as follows:
1. preparation of component A
Dehydrating the polypropylene oxide polycarbonate copolymer oligomer dihydric alcohol prepared in the embodiment 2 for 5 hours at the temperature of 100 ℃, and under the pressure of-0.08 MPa to-0.1 MPa, cooling to 30 ℃, adding a chain extender 1, 4-butanediol, a catalyst Borchi Kat 24, a light/heat stabilizer Chisorb 234 and a Chisorb 944, heating to 60 ℃, stirring for reaction for 4 hours to obtain a component A, and sealing and packaging for later use;
the raw materials in the step 1 comprise the following components in parts by mass:
2. preparation of component B
Putting isocyanate Wannate MDI-100 into a reaction kettle, uniformly stirring, then putting dehydrated polypropylene oxide polycarbonate copolymerization type oligomer dihydric alcohol (prepared in example 2) and a light/heat stabilizer Chinox 1010, heating to 80 ℃, stirring and reacting for 2 hours until the detection value of-NCO groups is (14.7 +/-0.2)%, obtaining a component B, and sealing and packaging for later use;
in the step 2, the raw materials comprise the following components in parts by mass:
40 parts of polypropylene oxide polycarbonate copolymer oligomer dihydric alcohol
Isocyanate (Wannate MDI-100) 60 parts
0.5 part of light/heat stabilizer (Chinox 1010).
3. Preparation of solvent-free middle layer polyurethane resin for soft mirror synthetic leather
Coating mirror surface resin slurry LT-150 produced by polyurethane new material Co-Safei Anli on mirror surface paper, drying at 130 ℃ for 2 minutes and forming to obtain a mirror surface layer; mixing the component A and the component B according to the mass ratio of 100: and the mixture is poured and coated on the mirror surface layer after being uniformly mixed, and the solvent-free intermediate layer polyurethane resin for the soft mirror surface synthetic leather can be obtained after drying at 110 ℃.
4. Applications of
Pre-reacting the solvent-free middle layer polyurethane resin for the soft mirror synthetic leather prepared in the step 3 at 110 ℃ for 70 seconds, attaching base cloth after the pre-reaction is finished, and then continuously reacting at 150 ℃ for 8 minutes to crosslink, solidify and mold the soft mirror synthetic leather; and (4) after curing and forming, rolling and stripping the mirror surface paper to obtain the solvent-free soft crease-free mirror surface synthetic leather. The physical properties of the material can reach no cracking after being bent for 10 ten thousand times at normal temperature, no cracking after being bent for 8 ten thousand times at-20 ℃, the peel strength of the material is 75N/3cm, and the peel strength of the material is 68N/3cm after being bent for 6 weeks under the conditions of constant temperature and humidity of 70 ℃ and 95 percent.
The raw materials used in this example:
the polypropylene oxide polycarbonate copolymer oligomer diol was the oligomer diol with a molecular weight of 606 prepared in example 2; 1, 4-butanediol is a commercial product; borchi Kat 24 is a metallate catalyst from OMG Borchers, Inc.; chisorb 234, Chisorb 944 and Chinox 1010 are ultraviolet absorbent, light stabilizer and antioxidant of Taiwan double bond chemical industry Co.Ltd; wannate MDI-100 is pure diphenylmethylene diisocyanate produced by Nicotiana Tenwawa;
example 6: preparation of solvent-free middle layer polyurethane resin for soft mirror synthetic leather
The preparation process of the solvent-free middle layer polyurethane resin for the soft mirror synthetic leather in the embodiment is as follows:
1. preparation of component A
Dehydrating the polypropylene oxide polytetrahydrofuran polycarbonate copolymer oligomer dihydric alcohol prepared in the embodiment 3 for 5h at the temperature of 100 ℃ and under the pressure of-0.08 MPa to-0.1 MPa, cooling to 30 ℃, adding chain extender 1, 4-butanediol, cross-linking agent glycerol, catalyst MB20, light/heat stabilizer Tinuvin 1130 and Chisorb292, heating to 60 ℃, stirring and reacting for 4h to obtain a component A, and sealing and packaging for later use;
the raw materials in the step 1 comprise the following components in parts by mass:
2. preparation of component B
Putting isocyanate Wannate MDI-100 and Wannate MDI-50 into a reaction kettle, uniformly stirring, then putting dehydrated polytetrahydrofuran polycarbonate copolymerization oligomer dihydric alcohol (prepared in example 1) and a light/heat stabilizer Chinox 1010, heating to 80 ℃, stirring and reacting for 2 hours until the detection value of-NCO groups is (9.9 +/-0.2)%, obtaining a component B, and sealing and packaging for later use;
in the step 2, the raw materials comprise the following components in parts by mass:
3. preparation of solvent-free middle layer polyurethane resin for soft mirror synthetic leather
Coating mirror surface resin slurry LT-150 produced by polyurethane new material Co-Safei Anli on mirror surface paper, drying at 130 ℃ for 2 minutes and forming to obtain a mirror surface layer; mixing the component A and the component B according to the mass ratio of 100: 105, placing the mixture in a low-pressure casting machine, fully mixing, casting and coating the mixture on the mirror surface layer after uniform mixing, and drying at 110 ℃ to obtain the solvent-free middle layer polyurethane resin for the soft mirror surface synthetic leather.
4. Applications of
Pre-reacting the solvent-free middle layer polyurethane resin for the soft mirror synthetic leather prepared in the step 3 at 110 ℃ for 40 seconds, attaching base cloth after the pre-reaction is finished, and then continuously reacting at 150 ℃ for 6 minutes to crosslink, solidify and mold the soft mirror synthetic leather; and (4) after curing and forming, rolling and stripping the mirror surface paper to obtain the solvent-free soft crease-free mirror surface synthetic leather. The physical properties of the material can reach no cracking after being bent for 10 ten thousand times at normal temperature, no cracking after being bent for 8 ten thousand times at-20 ℃ when being cold-resistant, the peel strength is 70N/3cm, and the peel strength is 62N/3cm after being peeled for 8 weeks under the conditions of constant temperature and humidity of 70 ℃ and 95 percent.
The raw materials used in this example:
in the component A, polypropylene oxide polytetrahydrofuran polycarbonate copolymer oligomer dihydric alcohol is oligomer dihydric alcohol with the molecular weight of 2387 synthesized in example 3, glycerol and 1, 4-butanediol are commercially available products, MB20 is an organic bismuth catalyst produced by American air chemical products company, Tinuvin 1130 is an ultraviolet absorbent produced by Germany BASF company, and Chisorb292 is a light stabilizer produced by Taiwan double bond chemical industry Co., Ltd;
in the component B, Wannate MDI-100 and Wannate MDI-50 are diisocyanate produced by Nitinol Corp, polytetrahydrofuran polycarbonate copolymerized oligomer dihydric alcohol is oligomer dihydric alcohol with the molecular weight of 606 synthesized in example 1, and Chinox 1010 is an antioxidant of Taiwan double bond chemical company Limited.
Claims (5)
1. A solvent-free middle layer polyurethane resin for soft mirror synthetic leather is characterized in that: the composition is obtained by mixing and drying a component A and a component B according to the mass ratio of 1:2-1: 1;
the component A comprises the following raw materials in parts by weight:
the component B comprises the following raw materials in parts by weight:
40-50 parts of polyether polycarbonate copolymer type oligomer dihydric alcohol
50-60 parts of isocyanate
0.5-1.0 part of light/heat stabilizer;
the polyether polycarbonate copolymerization type oligomer dihydric alcohol is prepared from diethyl carbonate and polyether dihydric alcohol through an ester exchange process, and the molecular weight is 500-3000;
the polyether polycarbonate copolymer oligomer dihydric alcohol comprises the following raw materials in parts by mass:
2-25 parts of diethyl carbonate
75-98 parts of polyether glycol
0.02-0.06 part of catalyst;
the polyether diol is polypropylene oxide diol with the molecular weight of 200-2000 and/or polytetrahydrofuran diol with the molecular weight of 200-2000; the catalyst is tetrabutyl titanate or tetraisopropyl titanate;
the preparation of the polyether polycarbonate copolymerized oligomer diol comprises the following steps:
will be equipped with a magnetic stirrer, a constant pressure burette, a thermometer and N2The four-mouth flask with inlet pipe and air-cooling condenser pipe is arranged in a jacketed resistance heater, polyether glycol and catalyst are filled in the flask, the mouth of a constant pressure titration pipe extends below the liquid level of the polyether glycol, diethyl carbonate is filled in the constant pressure titration pipe, and N is introduced2The air in the reaction bottle is exhausted, the temperature of the reaction system is gradually raised to 120-130 ℃ under normal pressure, diethyl carbonate is dripped into the reaction bottle, after 30min of reaction, liquid flows down at the branch opening of the distillation column, the discharge temperature of the branch opening of the distillation column is controlled to be below 78 ℃, after 2h of reaction, the temperature of the reaction system is gradually increased to 240 ℃ when the discharge rate is slowed down, the reaction is continued for 2h, when the discharge liquid does not discharge any more, the vacuum pumping is carried out under reduced pressure, the system is kept at 240 ℃ and the vacuum degree is more than or equal to 0.095MPa, after 3h of continuous reaction, the hydroxyl value is measured, the hydroxyl value is controlled to be 28-224mg KOH/g, and the polyether polycarbonate copolymer oligomer dihydric alcohol with the molecular weight of 500.
2. The solvent-free intermediate layer polyurethane resin for soft mirror synthetic leather according to claim 1, characterized in that:
the chain extender is one or more of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol hydroquinone bis (2-hydroxyethyl) ether;
the cross-linking agent is one or two of glycerol and trimethylolpropane;
the catalyst used in the component A is a delayed catalyst, and is selected from BiCAT 8106, BiCAT 8108, BiCAT8124, BiCAT 3228, Borchi Kat 22, Borchi Kat 24, BiCAT 4130, BiCAT 4232, MB20 and one of phenate, formate and hydrochloride of the organometallic catalysts;
the light/heat stabilizer is an ultraviolet absorbent, a hindered amine light stabilizer or an antioxidant; wherein the ultraviolet absorbent is UV-1, UV-320, UV-1130, UV-P, UV-1164 or UV-234; the hindered amine light stabilizer is 292, 622, 770, 944, 5050, 5060 or 5151; the antioxidant is 245, 1010, 1035, 1076, 1098 or 3114;
the isocyanate is one or more of 4,4 '-diphenylmethane diisocyanate, a mixture of 2, 4-diphenylmethane diisocyanate and 4, 4' -diphenylmethane diisocyanate, and a mixture of diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate.
3. The method for preparing the solvent-free intermediate layer polyurethane resin for soft mirror synthetic leather according to claim 1, characterized by comprising the steps of:
step 1: preparation of component A
Dehydrating polyether polycarbonate copolymer oligomer dihydric alcohol for 3-5h at 90-110 ℃ and-0.08 MPa to-0.1 MPa to reduce the occurrence of side reaction for later use; adding the dehydrated polyether polycarbonate copolymerization type oligomer dihydric alcohol into a reaction kettle, sequentially adding a chain extender, a cross-linking agent, a catalyst and a light/heat stabilizer, heating to 60-80 ℃, stirring and reacting for 4-6h to obtain a component A, and sealing and packaging for later use;
step 2: preparation of component B
Putting isocyanate and a light/heat stabilizer into a reaction kettle, stirring and mixing uniformly, then adding dehydrated polyether polycarbonate copolymerization type oligomer dihydric alcohol, heating to 65-90 ℃, stirring and reacting until the difference between the-NCO group detection value and the theoretical value is +/-0.2 percent to obtain a component B, and sealing and packaging for later use;
and step 3: preparation of solvent-free middle layer polyurethane resin for soft mirror synthetic leather
Coating mirror resin slurry LT-150 on mirror paper, drying and molding at 130 ℃ to obtain a mirror surface layer; and (3) placing the component A and the component B in a low-pressure casting machine according to the mass ratio of 1:2-1:1, fully mixing, casting and coating on the mirror surface layer after uniform mixing, and drying at the temperature of 100-.
4. The use of the solvent-free intermediate layer polyurethane resin for soft mirror synthetic leather according to claim 1, characterized in that: the solvent-free middle layer polyurethane resin for the soft mirror synthetic leather is used for preparing the mirror synthetic leather.
5. Use according to claim 4, characterized in that it comprises the following steps:
when in use, the solvent-free middle layer polyurethane resin for the soft mirror synthetic leather is pre-reacted for 30 to 90 seconds at the temperature of 100-150 ℃, the base cloth is attached after the pre-reaction is finished, and then the reaction is continued for 5 to 10 minutes at the temperature of 100-150 ℃ so as to be crosslinked, cured and molded; and (4) after curing and forming, rolling and stripping the mirror surface paper to obtain the solvent-free soft crease-free mirror surface synthetic leather.
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| CN109705299A (en) * | 2018-08-29 | 2019-05-03 | 旭川化学（苏州）有限公司 | A kind of mirror surface leather waterborne polyurethane resin and preparation method thereof |
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| WO2021059884A1 (en) * | 2019-09-25 | 2021-04-01 | 三菱瓦斯化学株式会社 | Polycarbonate resin |
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| CN111704709B (en) * | 2020-06-29 | 2022-01-28 | 上海华峰新材料研发科技有限公司 | Low-modulus solvent-free polyurethane resin for synthetic leather and preparation method thereof |
| CN113493563A (en) * | 2021-07-14 | 2021-10-12 | 扬州工业职业技术学院 | Polyether polyol and preparation method and application thereof |
| CN114541151A (en) * | 2022-02-16 | 2022-05-27 | 世联汽车内饰（苏州）有限公司 | Low-temperature-resistant synthetic leather for vehicles and preparation method thereof |
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