CN113527694A - Preparation method of solvent-free polyurethane resin and application of solvent-free polyurethane resin in textile coating - Google Patents

Preparation method of solvent-free polyurethane resin and application of solvent-free polyurethane resin in textile coating Download PDF

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CN113527694A
CN113527694A CN202110890098.2A CN202110890098A CN113527694A CN 113527694 A CN113527694 A CN 113527694A CN 202110890098 A CN202110890098 A CN 202110890098A CN 113527694 A CN113527694 A CN 113527694A
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solvent
free polyurethane
polycarbonate diol
component
polyurethane resin
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CN113527694B (en
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王海峰
王燕武
吴伟杰
李晓飞
李嘉晋
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Hefei Anli Polyurethane New Material Co ltd
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Hefei Anli Polyurethane New Material 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The invention discloses a preparation method of solvent-free polyurethane resin and application thereof in textile coating, which comprises the steps of firstly preparing acrylic polycarbonate diol ester by reacting polycarbonate diol with acryloyl chloride; preparing polycarbonate diol modified isocyanate prepolymer, and then reacting the polycarbonate diol modified isocyanate prepolymer with the prepared acetoacetic acid monohydroxy diol ester to prepare carbamate containing active methylene; and finally, under the action of DBU organic acid salt, performing a Michael addition reaction on the component A and the component B to prepare the solvent-free polyurethane resin. The solvent-free polyurethane resin prepared by the invention can be applied to the field of synthetic leather, and can be used as a surface resin coating or a middle resin coating for bonding synthetic leather base materials. The solvent-free polyurethane resin prepared by the invention does not need a solvent-free polyurethane casting machine in the application process, so that the dependence of the solvent-free polyurethane resin on the solvent-free polyurethane casting machine can be avoided, and the application universality of the solvent-free polyurethane resin is further improved by equipment removal.

Description

Preparation method of solvent-free polyurethane resin and application of solvent-free polyurethane resin in textile coating
Technical Field
The invention belongs to the field of preparation of polyurethane resin, and particularly relates to a preparation method of solvent-free polyurethane resin and application of the solvent-free polyurethane resin in a textile coating.
Background
The environmental protection trend of the polyurethane synthetic leather industry is more mature after basic development of more than ten years, the aqueous polyurethane synthetic leather technology and the solvent-free polyurethane synthetic leather technology have obvious technical advantages, and particularly the solvent-free polyurethane synthetic leather technology has excellent environmental protection performance, durability and other mechanical properties better than those of solvent-based polyurethane synthetic leather. Therefore, the yield of the solvent-free polyurethane synthetic leather product is on the trend of increasing year by year, and the application field is gradually extended to various fields such as massage chairs, automobile interiors, sports and leisure shoes, football, electronic packaging and the like from the initial sofa furniture field. However, although the solvent-free polyurethane synthetic leather process technology has obvious advantages, the technology has pain points in the processing and manufacturing links, namely the technology can mix, pour and coat the solvent-free polyurethane A component resin and the solvent-free polyurethane B component resin only by attaching to a solvent-free polyurethane casting machine, so that the solvent-free polyurethane resin is converted into a solvent-free polyurethane coating, and the solvent-free polyurethane synthetic leather is manufactured. Because the existing solvent-free component A is a polyalcohol component and is in a terminal OH structure, the solvent-free component B is an isocyanate component and is in a terminal NCO structure, if a pouring machine is not relied on, the components can quickly react and tackify under normal temperature conditions, so that the viscosity is increased until the components are solidified, and the coating at a cutter head of a production line cannot be realized. The reason why the link is called as a pain point is that when solvent-free polyurethane casting machine equipment is used for production and processing, the problems of material change of different types of solvent-free polyurethane resin materials, regular cleaning, maintenance, part replacement and the like of the solvent-free polyurethane casting machine equipment can be met, the manufacturing efficiency of solvent-free polyurethane synthetic leather products is greatly influenced, the capacity of the solvent-free polyurethane synthetic leather products is influenced, the production and manufacturing cost of the products is increased to a certain extent, and the market competitiveness is not favorably improved.
Therefore, whether to develop a solvent-free polyurethane synthetic leather manufacturing technology without using a solvent-free polyurethane casting machine, namely a solvent-free polyurethane synthetic leather manufacturing technology without equipment, has important practical significance for greatly improving the production efficiency of solvent-free polyurethane synthetic leather products, reducing the manufacturing cost, popularizing and applying the coverage and the like. In order to realize the equipment removal of the technology, the dependence of the solvent-free polyurethane A component resin and the solvent-free polyurethane B component resin on a solvent-free polyurethane casting machine is mainly solved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of solvent-free polyurethane resin and application of the solvent-free polyurethane resin in a textile coating, so as to realize equipment removal of the solvent-free polyurethane resin and apply the solvent-free polyurethane resin to processing application of solvent-free polyurethane synthetic leather.
The preparation method of the solvent-free polyurethane resin comprises the following steps:
step 1: preparation of acrylic polycarbonate diol ester (A component)
Adding polycarbonate diol and acryloyl chloride into a reactor, and reacting under the action of triethylamine until hydroxyl groups disappear through infrared detection to prepare acrylic polycarbonate diol ester, namely the component A;
the structural formula of the acrylic polycarbonate diol ester is as follows:
Figure BDA0003195634160000021
step 2: preparation of Carbamate (B component)
2a preparation of polycarbonate diol modified isocyanate prepolymer
Adding polycarbonate diol and isocyanate components into a reactor according to the molar ratio of 1:2.02-2.1, and reacting until hydroxyl groups disappear through infrared detection to obtain a polycarbonate diol modified isocyanate prepolymer, wherein the structural formula is shown as follows:
Figure BDA0003195634160000022
wherein R is1Is the portion of the isocyanate component from which the NCO groups have been removed.
2b preparation of monohydroxydiol acetoacetate
Adding ethyl acetoacetate and a dihydric alcohol chain extender into a reactor according to the molar ratio of 1:1.05-1.1, then adding 5-10 mass percent of sodium methoxide into the ethyl acetoacetate, heating to react and evaporate ethanol, detecting the hydroxyl value of a product, and obtaining the acetoacetic acid monohydroxy diol ester after the product is qualified, wherein the structural formula is shown as follows:
Figure BDA0003195634160000023
wherein R is2Is a part of the glycol chain extender from which OH groups are removed.
2c preparation of Carbamates (B component)
Adding the isocyanate prepolymer prepared by the step 2a and the acetoacetic acid monohydroxy diol ester prepared by the step 2B into a reactor according to the molar ratio of 1:2.01-2.05, heating for reaction, and performing infrared detection until NCO groups disappear to obtain carbamate, namely a component B, wherein the structural formula is as follows:
Figure BDA0003195634160000024
and step 3: preparation of solvent-free polyurethane resin
Mixing the component A prepared in the step 1 and the component B prepared in the step 2 according to the molar ratio of 1:1.01-1.05, adding DBU organic acid salt accounting for 0.1-0.2% of the total mass of the mixture of the component A and the component B, heating to 110-130 ℃, reacting for 5-10min, and fully drying to obtain the solvent-free polyurethane resin.
In the step 1, the polycarbonate diol is dehydrated for 2 to 3 hours under the conditions of 100-110 ℃ and-0.09 to-0.095 MPa in advance, then is cooled to the room temperature, acryloyl chloride is added, a reflux condenser tube is installed, nitrogen is filled for protection, and a balloon is used for sealing; and slowly dropwise adding triethylamine with the molar quantity equal to that of the polycarbonate diol while fully stirring, after dropwise adding, heating to 40-50 ℃, reacting for 3-5h, and reacting until hydroxyl groups disappear by infrared detection to obtain acrylic polycarbonate diol ester (component A).
In the step 1, the molar ratio of the polycarbonate diol to the acryloyl chloride is 1: 2.02-2.1.
In step 2a, the temperature of a reaction bottle is raised to 55-65 ℃ in advance, then the weighed isocyanate component is added into the reaction container, then the dehydrated polycarbonate diol is added into the reaction bottle, and the temperature is raised to a set temperature (when the isocyanate component is aromatic isocyanate such as MDI, carbodiimide modified MDI and the like, the set temperature is 75-85 ℃), and when the isocyanate component is H12And (3) when aliphatic isocyanates such as MDI, IPDI, HDI and the like are used, the temperature is set to be 85-95 ℃, the reaction is carried out for 2-4h, and the hydroxyl groups are eliminated through infrared detection, so that the polycarbonate diol modified isocyanate prepolymer is prepared.
In step 1 and step 2a, the polycarbonate diol is a bio-based diol, specifically a polycarbonate diol prepared by condensing carbon dioxide and propylene oxide, and has a functionality of 2 and a molecular weight of 2000-3000.
In the step 2b, adding ethyl acetoacetate and a dihydric alcohol chain extender into a reactor, then adding a sodium methoxide catalyst, heating to 100-. The dihydric alcohol chain extender is one of ethylene glycol, 1, 4-butanediol, 1, 2-propanediol and 1, 3-propanediol, and the hydroxyl value of the prepared corresponding acetoacetic acid monohydroxy diol ester is 310-400mg KOH/g.
In the step 2c, the isocyanate prepolymer prepared in the step 2a and the acetoacetic acid monohydroxy diol ester prepared in the step 2B are respectively added into a reactor, the temperature is gradually increased to 80-90 ℃ under the condition of full stirring, the reaction is carried out for 2-4h, and the carbamate (component B) is prepared after infrared detection until NCO groups disappear.
In step 3, the DBU organic acid salt is one of DBU phenate, DBU formate and DBU isooctanoate.
The solvent-free polyurethane resin prepared by the invention is applied to the field of synthetic leather, is used as a surface resin coating or a middle resin coating, and is used for bonding synthetic leather base materials. The method specifically comprises the following steps:
mixing the acrylic polycarbonate diol ester (component A) prepared in the step 1 and the carbamate (component B) prepared in the step 2, adding DBU organic acid salt, fully and uniformly stirring, coating on a surface layer resin coating on release paper or directly coating on the release paper, baking for 2-3min at the temperature of 60-80 ℃, attaching a synthetic leather base material, and baking for 5-8min at the temperature of 110-130 ℃ to obtain the solvent-free polyurethane synthetic leather product.
The principle of formation of the solvent-free polyurethane resin of the present invention is illustrated below:
the prepared component A and component B are heated to above 60 ℃ under the catalytic action of DBU organic acid salt, and the following reactions can occur: when the temperature is raised to be above 60 ℃, the DBU organic acid salt catalyst can be dissociated for deacidification, namely formic acid, phenol or isooctanoic acid are removed, and DBU organic base compounds with catalytic activity are released; the DBU organic alkali can capture hydrogen ions in active methylene in the component B, so that the component B generates carbanions with nucleophilic action, and double bonds in an acrylic ester structure of the component A can be attacked to generate Michael addition reaction; after the catalytic reaction is finished, the DBU organic base is released again, so that the component B and the component A can be further continuously catalyzed to carry out polymerization addition reaction, and finally the macromolecular solvent-free polyurethane resin with a cyclic structure is generated.
Figure BDA0003195634160000041
The invention has the beneficial effects that:
1. compared with the solvent-free polyurethane resin technology in the existing market, the solvent-free polyurethane resin casting method does not rely on solvent-free polyurethane casting equipment for casting and coating, can reduce the time-consuming influence of maintenance of the solvent-free polyurethane casting equipment and replacement of different types of solvent-free polyurethane resin materials on the production of leather products, realizes the equipment removal of solvent-free polyurethane resin processing and use, and effectively improves the application universality of the solvent-free polyurethane resin and the production efficiency of the solvent-free polyurethane synthetic leather products;
2. the invention only needs to adopt ammonium salt catalyst-DBU organic acid salt, and the catalyst can only catalyze the Michael addition reaction of the component B and the component A after releasing the organic acid under the high temperature condition; no organic metal catalyst is used, so that the condition that the component B and the component A are basically not reacted with each other at room temperature after being mixed on the premise of not using solvent-free polyurethane casting equipment is ensured, and the mixed A, B component still has enough flowing viscosity (namely the viscosity cannot rise rapidly to cause the blockage of a cutter head during coating and cannot be used), so that the room-temperature processing continuous processing production becomes possible;
3. the polycarbonate polyol is polypropylene carbonate dihydric alcohol prepared by carbon dioxide synthesis, so that the prepared solvent-free polyurethane resin does not contain any organic solvent and is ecological and environment-friendly, and the raw material polycarbonate polyol is bio-based series polyol, so that the ecological and environment-friendly property of the invention is ensured from the source; meanwhile, the reasonable utilization of the carbon dioxide is also beneficial to reducing the greenhouse effect and improving the atmospheric environment.
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.
The raw materials used in the present invention are illustrated below:
PPCD 221 is a 2 functionality, molecular weight 2000 polycarbonate diol, PPCD 222 is a 2 functionality, molecular weight
2000, PPCD 236 is a 2 functionality, molecular weight 3000 polycarbonate diol, all three of which are products of fine chemical industry, inc, gulf da, huizhou; acryloyl chloride, triethylamine, ethyl acetoacetate, ethylene glycol, 1, 4-butanediol, 1, 2-propanediol and the like are all commercial products; 1, 3-propanediol is a bio-based chain extender product from dupont, usa; catalysts such as DBU phenate, DBU formate and DBU isooctanoate are products of Shanghai Deyin chemical Co., Ltd; MDI, carbodiimide modified MDI, H12Isocyanates such as MDI, IPDI, HDI and the like are all products of Wanhua chemical company.
Example 1:
the preparation method of the solvent-free polyurethane resin in the embodiment comprises the following steps:
1. preparation of polycarbonate diol acrylate (A component):
dehydrating polycarbonate diol PPCD 221 at 100 ℃ and-0.095 MPa for 2h, cooling to room temperature, adding acryloyl chloride into a reaction bottle at a molar ratio of 1:2.02 to PPCD 221, installing a reflux condenser tube, introducing nitrogen for protection, and sealing with a balloon. Slowly dripping triethylamine with the same molar weight as that of the PPCD 221 under full stirring, after dripping is finished, heating to 40 ℃, reacting for 5 hours until hydroxyl groups disappear by infrared detection, and preparing acrylic polycarbonate diol ester (A component);
2. preparation of carbamate (B component):
preparing a polycarbonate diol modified isocyanate prepolymer:
heating a reaction bottle to 55 ℃ in advance, adding weighed MDI-100 into the reaction container, adding the dehydrated polycarbonate diol PPCD 221 with the molar ratio of 1:2.02 to the MDI-100 into the reaction bottle, heating to 75 ℃, reacting for 3h, and performing infrared detection until hydroxyl groups disappear to obtain the polycarbonate diol modified isocyanate prepolymer.
Preparing acetoacetic acid monohydroxy glycol ester:
adding ethyl acetoacetate and ethylene glycol into a reaction bottle according to the molar ratio of 1:1.05, then adding 5 mass percent of sodium methoxide of ethyl acetoacetate, heating to 100 ℃ for reaction for 4 hours, evaporating ethanol, detecting the hydroxyl value of a product, and obtaining the mono-hydroxy glycol acetoacetate after the product is qualified; the hydroxyl value of the prepared corresponding acetoacetic acid monohydroxyethylene glycol ester is 370-400mg KOH/g.
Preparing carbamate (component B):
adding the isocyanate prepolymer prepared in the step I and the acetoacetic acid monohydroxy glycol ester prepared in the step II into a reaction bottle according to the molar ratio of 1:2.01, gradually heating to 80 ℃, reacting for 4 hours, and performing infrared detection until NCO groups disappear to prepare carbamate (component B);
3. preparation of solvent-free polyurethane resin:
and (2) mixing the component A prepared in the step (1) and the component B prepared in the step (2) according to a molar ratio of 1:1.01, adding DBU (diethylene glycol diphenyl oxide) phenolate accounting for 0.1% of the total mass of the mixture of the component A and the component B, heating to 110 ℃, reacting for 10min, and fully drying to obtain the solvent-free polyurethane resin.
4. The solvent-free polyurethane resin can be applied to the field of synthetic leather, and can be used as a surface resin coating or a middle resin coating for bonding synthetic leather substrates.
And (2) mixing the acrylic polycarbonate diol ester (component A) prepared in the step (1) and the carbamate (component B) prepared in the step (2), adding DBU (diethylene glycol diphenyl ether) phenolate, fully and uniformly stirring, coating the mixture on a surface resin coating on release paper or directly coating the mixture on the release paper, baking the mixture at the temperature of 60 ℃ for 3min, attaching a synthetic leather base material, and baking the mixture at the temperature of 110 ℃ for 8min to obtain a solvent-free polyurethane synthetic leather product.
Example 2:
the preparation method of the solvent-free polyurethane resin in the embodiment comprises the following steps:
1. preparation of polycarbonate diol acrylate (A component):
dehydrating polycarbonate diol PPCD 222 at 110 ℃ and under the pressure of-0.09 MPa for 3h in advance, cooling to room temperature, adding acryloyl chloride into a reaction bottle, wherein the molar ratio of the acryloyl chloride to the PPCD 222 is 1:2.1, installing a reflux condensation tube, filling nitrogen for protection, and sealing by using a balloon. And slowly dropwise adding triethylamine with the molar quantity equal to that of the PPCD 222 under full stirring, after dropwise adding, heating to 50 ℃, and reacting for 3 hours until hydroxyl groups disappear through infrared detection, thereby obtaining the acrylic polycarbonate diol ester (A component).
2. Preparation of carbamate (B component):
preparing a polycarbonate diol modified isocyanate prepolymer:
the temperature of the reaction bottle is raised to 65 ℃ in advance, and then the weighed H is added into the reaction container12MDI, then adding the dehydrated and H into a reaction bottle12Heating polycarbonate diol PPCD 222 with the molar ratio of MDI of 1:2.1 to 85 ℃, reacting for 4h, and detecting by infrared until hydroxyl groups disappear to prepare the polycarbonate diol modified isocyanate prepolymer.
Preparing acetoacetic acid monohydroxy-1, 4-butanediol ester:
adding ethyl acetoacetate and 1, 4-butanediol into a reaction bottle according to the molar ratio of 1:1.1, then adding 10 mass percent of sodium methoxide into the ethyl acetoacetate, heating to 120 ℃ for reaction for 3h, evaporating ethanol, detecting the hydroxyl value of a product, and obtaining mono-hydroxy-1, 4-butanediol acetoacetate after the product is qualified; the hydroxyl value of the prepared corresponding acetoacetic acid monohydroxy-1, 4-butanediol ester is 310-330mg KOH/g.
Preparing carbamate (component B):
adding the isocyanate prepolymer prepared in the step I and the acetoacetic acid monohydroxy-1, 4-butanediol ester prepared in the step II into a reaction bottle according to the molar ratio of 1:2.05, gradually heating to 90 ℃ for reaction for 2 hours, and performing infrared detection until NCO groups disappear to prepare carbamate (component B);
3. preparation of solvent-free polyurethane resin:
and (2) mixing the component A prepared in the step (1) and the component B prepared in the step (2) according to a molar ratio of 1:1.05, adding DBU formate accounting for 0.2% of the total mass of the mixture of the component A and the component B, heating to 130 ℃, reacting for 5min, and fully drying to obtain the solvent-free polyurethane resin.
4. The solvent-free polyurethane resin can be applied to the field of synthetic leather, and can be used as a surface resin coating or a middle resin coating for bonding synthetic leather substrates. Mixing the acrylic polycarbonate diol ester (component A) prepared in the step 1 and the carbamate (component B) prepared in the step 2, adding DBU formate, fully and uniformly stirring, coating on a surface resin coating on release paper or directly coating on the release paper, baking for 2min at the temperature of 80 ℃, attaching a synthetic leather base material, and baking for 5min at the temperature of 130 ℃ to obtain a solvent-free polyurethane synthetic leather product.
Example 3:
the preparation method of the solvent-free polyurethane resin in the embodiment comprises the following steps:
1. preparation of polycarbonate diol acrylate (A component):
dehydrating the polycarbonate diol PPCD 236 at 105 ℃ and under the pressure of-0.092 MPa for 2.5h in advance, cooling to room temperature, adding acryloyl chloride into a reaction bottle, wherein the molar ratio of the acryloyl chloride to the PPCD 236 is 1:2.05, installing a reflux condenser tube, introducing nitrogen for protection, and sealing by using a balloon. Slowly dripping triethylamine with the same molar weight as that of the PPCD 236 under full stirring, after dripping is finished, heating to 45 ℃, reacting for 4 hours until hydroxyl groups disappear through infrared detection, and preparing acrylic polycarbonate diol ester (A component);
2. preparation of carbamate (B component):
preparing a polycarbonate diol modified isocyanate prepolymer:
heating a reaction bottle to 60 ℃ in advance, adding weighed IPDI into the reaction container, adding the dehydrated polycarbonate diol PPCD 236 with the mole ratio of 1:2.05 to the IPDI into the reaction bottle, heating to 95 ℃, reacting for 2h, and performing infrared detection until hydroxyl groups disappear to obtain the polycarbonate diol modified isocyanate prepolymer.
Preparing acetoacetic acid monohydroxy-1, 2-propylene glycol ester:
adding ethyl acetoacetate and 1, 2-propylene glycol into a reaction bottle according to the molar ratio of 1:1.08, then adding 8 mass percent of sodium methoxide into the ethyl acetoacetate, heating to 110 ℃ for reaction for 3.5 hours, evaporating ethanol, detecting the hydroxyl value of a product, and obtaining monoacetyl acetate-1, 2-propylene glycol ester after the product is qualified; the hydroxyl value of the prepared corresponding acetoacetic acid monohydroxy-1, 2-propylene glycol ester is 340-360mg KOH/g.
Preparing carbamate (component B):
adding the isocyanate prepolymer prepared in the step I and the acetoacetic acid monohydroxy-1, 2-propylene glycol ester prepared in the step II into a reaction bottle according to the molar ratio of 1:2.03, gradually heating to 85 ℃ for reaction for 3 hours, and performing infrared detection until NCO groups disappear to prepare carbamate (component B);
3. preparation of solvent-free polyurethane resin:
and (3) mixing the component A prepared in the step (1) and the component B prepared in the step (2) according to a molar ratio of 1:1.03, adding DBU isooctanoate accounting for 0.15% of the total mass of the mixture of the component A and the component B, heating to 120 ℃, reacting for 8min, and fully drying to obtain the solvent-free polyurethane resin.
4. The solvent-free polyurethane resin can be applied to the field of synthetic leather, and can be used as a surface resin coating or a middle resin coating for bonding synthetic leather substrates. And (2) mixing the acrylic polycarbonate diol ester (component A) prepared in the step (1) and the carbamate (component B) prepared in the step (2), adding DBU (dibutyl phthalate) isooctoate, fully and uniformly stirring, coating the mixture on a surface resin coating on release paper or directly coating the mixture on the release paper, baking the mixture at the temperature of 70 ℃ for 2.5min, attaching a synthetic leather base material, and baking the mixture at the temperature of 120 ℃ for 6min to obtain a solvent-free polyurethane synthetic leather product.
Comparative example:
example 1 in patent CN 106220817B was applied to the solvent-free automotive interior leather obtained in example 4.
The solvent-free polyurethane resin prepared by the invention is used as the middle layer resin in the field of automobile interior leather, and is compared with example 1 in the invention patent 'a solvent-free middle layer polyurethane resin for automobile interior leather and a preparation method thereof' (CN 106220817B) to verify the actual effect of the solvent-free polyurethane resin on the mechanical properties such as peel strength, hydrolysis resistance and the like when being applied to the field of automobile interior leather. The specific data are shown in the following table:
Figure BDA0003195634160000091
note: the peel strength is detected according to the GB/T8949 method; hydrolysis resistance (jungle test) was tested by QB/T4671.
As can be seen from the data in the above table, the solvent-free polyurethane resin without solvent-free polyurethane casting machine is applied to the field of automobile interior leather, and the mechanical properties similar to those of the comparative example can be obtained no matter the initial peel strength (reaching 105N/3cm or above and far higher than the peel strength requirement required by the automobile interior leather) or the hydrolysis resistance level (the peel strength retention rate exceeds 90% after ten weeks of jungle tests) is obtained. Therefore, the method has practical feasibility when being applied to synthetic leather products such as solvent-free automobile interior leather and the like on the premise of not using professional solvent-free polyurethane pouring equipment and using bio-based polycarbonate diol as a main raw material; has important practical significance and economic benefit for improving the production efficiency of the solvent-free polyurethane synthetic leather.

Claims (10)

1. A preparation method of solvent-free polyurethane resin is characterized by comprising the following steps:
step 1: preparation of acrylic polycarbonate diol ester
Adding polycarbonate diol and acryloyl chloride into a reactor, and reacting under the action of triethylamine until hydroxyl groups disappear through infrared detection to prepare acrylic polycarbonate diol ester, namely the component A;
the structural formula of the acrylic polycarbonate diol ester is as follows:
Figure FDA0003195634150000011
step 2: preparation of carbamates
2a preparation of polycarbonate diol modified isocyanate prepolymer
Adding polycarbonate diol and isocyanate into a reactor, and reacting until hydroxyl groups disappear through infrared detection to prepare a polycarbonate diol modified isocyanate prepolymer, wherein the structural formula is shown as follows:
Figure FDA0003195634150000012
wherein R is1Is a portion of the isocyanate component from which NCO groups have been removed;
2b preparation of monohydroxydiol acetoacetate
Adding ethyl acetoacetate and a dihydric alcohol chain extender into a reactor according to the molar ratio of 1:1.05-1.1, then adding 5-10 mass percent of sodium methoxide into the ethyl acetoacetate, heating to react and distilling out ethanol to obtain the mono-hydroxy glycol acetoacetate, wherein the structural formula is shown as follows:
Figure FDA0003195634150000013
wherein R is2Is a part of the glycol chain extender without OH groups;
2c preparation of carbamates
Adding the isocyanate prepolymer prepared by the step 2a and the acetoacetic acid monohydroxy diol ester prepared by the step 2B into a reactor according to the molar ratio of 1:2.01-2.05, heating for reaction, and performing infrared detection until NCO groups disappear to obtain carbamate, namely a component B, wherein the structural formula is as follows:
Figure FDA0003195634150000014
and step 3: preparation of solvent-free polyurethane resin
Mixing the component A prepared in the step 1 and the component B prepared in the step 2 according to the molar ratio of 1:1.01-1.05, adding DBU organic acid salt accounting for 0.1-0.2% of the total mass of the mixture of the component A and the component B, heating to 110-130 ℃, reacting for 5-10min, and fully drying to obtain the solvent-free polyurethane resin.
2. The method of claim 1, wherein:
in the step 1, the polycarbonate diol is dehydrated for 2 to 3 hours under the conditions of 100-110 ℃ and-0.09 to-0.095 MPa in advance, then is cooled to the room temperature, acryloyl chloride is added, a reflux condenser tube is installed, nitrogen is filled for protection, and a balloon is used for sealing; and slowly dropwise adding triethylamine with the molar quantity equal to that of the polycarbonate diol while fully stirring, after dropwise adding, heating to 40-50 ℃, reacting for 3-5h, and reacting until infrared detection hydroxyl groups disappear to obtain the acrylic polycarbonate diol ester.
3. The method of claim 2, wherein:
in the step 1, the molar ratio of the polycarbonate diol to the acryloyl chloride is 1: 2.02-2.1.
4. The method of claim 1, wherein:
in the step 2a, the temperature of a reaction bottle is raised to 55-65 ℃ in advance, then the weighed isocyanate component is added into the reaction container, then the dehydrated polycarbonate diol is added into the reaction bottle, the temperature is raised for reaction for 2-4h, and infrared detection is carried out until hydroxyl groups disappear, so as to prepare the polycarbonate diol modified isocyanate prepolymer.
5. The method of claim 4, wherein:
in step 2a, the feeding molar ratio of the polycarbonate diol to the isocyanate is 1: 2.02-2.1.
6. The method of claim 1, wherein:
in the step 2b, adding ethyl acetoacetate and a dihydric alcohol chain extender into a reactor, then adding a sodium methoxide catalyst, heating to 100-; the dihydric alcohol chain extender is one of ethylene glycol, 1, 4-butanediol, 1, 2-propanediol and 1, 3-propanediol, and the hydroxyl value of the prepared corresponding acetoacetic acid monohydroxy diol ester is 310-400mg KOH/g.
7. The method of claim 1, wherein:
in step 2c, the isocyanate prepolymer prepared in step 2a and the acetoacetic acid monohydroxy diol ester prepared in step 2B are respectively added into a reactor, the temperature is gradually increased to 80-90 ℃ under the condition of full stirring, the reaction lasts for 2-4h, and the carbamate-B component is prepared after infrared detection until NCO groups disappear.
8. The method of claim 1, wherein:
in step 3, the DBU organic acid salt is one of DBU phenate, DBU formate and DBU isooctanoate.
9. Use of the solvent-free polyurethane resin obtained by the production method according to any one of claims 1 to 8, wherein:
the solvent-free polyurethane resin is applied to the field of synthetic leather, is used as a surface resin coating or a middle resin coating, and is used for bonding synthetic leather base materials.
10. Use according to claim 9, characterized in that:
mixing the acrylic polycarbonate diol ester prepared in the step 1 and the carbamate prepared in the step 2, adding DBU organic acid salt, fully and uniformly stirring, coating on a surface resin coating on release paper or directly coating on the release paper, baking for 2-3min at the temperature of 60-80 ℃, attaching a synthetic leather base material, and baking for 5-8min at the temperature of 110-130 ℃ to obtain the solvent-free polyurethane synthetic leather product.
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