CN117567717A - Self-homogenizing wet polyurethane resin and preparation method and application thereof - Google Patents

Self-homogenizing wet polyurethane resin and preparation method and application thereof Download PDF

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Publication number
CN117567717A
CN117567717A CN202311530940.7A CN202311530940A CN117567717A CN 117567717 A CN117567717 A CN 117567717A CN 202311530940 A CN202311530940 A CN 202311530940A CN 117567717 A CN117567717 A CN 117567717A
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polyurethane resin
self
diol
homogenizing
polyol
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夏佳弟
王志根
张大华
吕华波
江平
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XUCHUAN CHEMICAL (SUZHOU) CO Ltd
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XUCHUAN CHEMICAL (SUZHOU) 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
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    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
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    • 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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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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    • 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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a self-homogenizing wet polyurethane resin, a preparation method and application thereof, wherein the resin is prepared from the following raw materials in parts by weight: 10-20% of dihydric alcohol, 0.1-5% of chain extender, 5-20% of diisocyanate, 60-80% of solvent, 0-200 ppm of reaction activity regulator and 0-1% of reaction terminator; the polyol is a mixture of polytetrahydrofuran ether glycol and polyether modified polydimethylsiloxane glycol; or a mixture of at least one of a polyester polyol, a polycarbonate diol, and a polycaprolactone diol with a polytetrahydrofuran ether diol and a polyether-modified polydimethylsiloxane diol; the mass fraction of polytetrahydrofuran ether glycol in the polyol should not be less than 40%. The microfiber base cloth prepared by the polyurethane resin has uniform foaming of the resin layer, and can improve the fine and smooth and solid hand feeling and moisture permeability and air permeability of microfiber products.

Description

Self-homogenizing wet polyurethane resin and preparation method and application thereof
Technical Field
The invention belongs to the technical field of polyurethane synthetic leather, and particularly relates to self-homogenizing wet polyurethane resin and a preparation method and application thereof.
Background
Polyurethane is used as a novel polymer material with rubber and plastic characteristics, and is widely applied to the fields of clothing, shoe materials, sofas, bags, automobile interiors and the like in folk life and various fields of military industry, aerospace and the like due to the excellent elasticity and high strength, so that the polyurethane becomes a fifth polymer synthetic material, and the sales volume of the fifth polymer synthetic material is gradually increased year by year at a higher speed.
Polyurethane synthetic leather is one of the most important varieties of artificial synthetic leather nowadays, and polyurethane superfine fiber synthetic leather is the highest-end product in polyurethane synthetic leather.
However, although the polyurethane superfine fiber synthetic leather is the synthetic leather product closest to natural leather, certain differences still exist between the polyurethane superfine fiber synthetic leather and high-end leather in the folding effect, softness and meat feel. If the gap between the microfiber and the dermis can be eliminated, the sales and the added value of the product can be greatly improved.
Polyurethane resins for synthetic leather are classified into wet polyurethane resins, dry polyurethane resins, and adhesive layer resins. The wet process of preparing impregnated synthetic leather with polyurethane resin includes compounding wet process polyurethane resin and DMF solvent into impregnating liquid, adding the impregnating liquid into impregnating tank, vacuum defoaming, impregnating non-woven fabric in the impregnating tank, replacing DMF solvent in water, setting polyurethane resin to form microporous polyurethane 'muscle', rolling, stoving to set and cooling. The synthesis of the wet polyurethane resin on the market at present is mainly obtained by polymerizing polyalcohol (one or more of polyester polyol, polyether polyol and polycarbonate polyol), micromolecular alcohol (one or more of ethylene glycol, 1, 4-butanediol and neopentyl glycol) and diphenylmethane diisocyanate in a solvent DMF system.
The cell structure of the wet polyurethane resin determines the myogenic property, the softness, the mechanical property and the hand feeling of the microfiber synthetic leather base cloth. If the pores are large and uneven, the myogenic property of the base fabric is poor, the hand feeling is empty, and the folds are bigger and not fine; if the cells are too small, the hardness of the base cloth is higher, and the dead hand feeling can cause coarse folds. How to obtain fine and uniform cells, so that the microfiber leather has finer wrinkles and plump meat feel is pursued by synthetic leather enterprises.
The research of using the organosilicon for polyurethane modification is increasingly rising, and the organosilicon or the modified organosilicon is generally used as a leveling agent or a handfeel agent of a dry method or a foam regulator of a wet polyurethane resin.
There are also literature on directly modifying polyurethane directly with hydroxyalkyl-terminated polydimethylsiloxanes at the stage of synthesis, but there are few applications in synthetic leather. Patent document CN115894851a discloses a preparation method of organosilicon modified waterborne polyurethane for leather finishing, which comprises the steps of mixing 5-10 parts by mass of dihydroxyl polyether modified siloxane and 20-30 parts by mass of polyester diol, adding isophorone diisocyanate, dropwise adding stannous octoate, and reacting for 1.5-2.5 hours at 65-75 ℃; then adding 2-4 parts by mass of dimethylolpropionic acid, and continuously reacting for 1-3 hours at 65-75 ℃ to obtain a prepolymer; cooling to 40-50 ℃, adding 2-4 parts by mass of triethylamine, adding 35-45 parts by mass of water and 1-3 parts by mass of ethylenediamine under stirring, and reacting for 1-2 hours to obtain the organosilicon modified waterborne polyurethane emulsion. However, the polyurethane emulsion of this document is used for leather surface finishing and cannot be used for wet impregnation.
However, the silicone cell regulator of the existing wet polyurethane resin is of a post-addition type, and most of the silicone cell regulator can be extruded to be separated from the resin along with the wet solidification process, so that not only is the cell regulating function of the polyurethane resin reduced, but also the silicone enters circulating water to finally form solid waste, thereby increasing the processing cost and being disadvantageous to the environment. The invention aims to embed the polydimethylsiloxane playing the role of regulating the cells into a molecular main chain directly through reaction, so that the polydimethylsiloxane can not be extruded out in a molecular structure in the wet solidification process, thereby enabling wet resin to form fine and uniform cells, improving the fine and smooth wrinkles and full meat feel of microfiber leather, and preventing the siloxane from entering a circulating water system to form solid wastes.
Disclosure of Invention
The invention aims to provide a self-homogenizing wet polyurethane resin, a preparation method and application thereof, and the resin is used for wet impregnation of superfine fiber synthetic leather, can form fine and uniform cells, and enables the produced superfine fiber leather to have fine wrinkles and full meat feel and stronger leather feel.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the invention relates to a self-homogenizing wet polyurethane resin which is characterized by being prepared from the following raw materials in parts by weight: 10-20% of dihydric alcohol, 0.1-5% of chain extender, 5-20% of diisocyanate, 60-80% of solvent, 0-200 ppm of reaction activity regulator and 0-1% of reaction terminator;
the polyol is a mixture of polytetrahydrofuran ether glycol (PTMG) and polyether modified polydimethylsiloxane glycol (PSI); or a mixture of at least one of a polyester Polyol (PE), a polycarbonate diol (PCD), a polycaprolactone diol (PCL) with a polytetrahydrofuran ether diol (PTMG) and a polyether modified polydimethylsiloxane diol (PSI);
the polytetrahydrofuran ether glycol (PTMG) is a commercial general product, and the number average molecular weight (the same below) is 1000-3000, especially 1500-2500 optimally; the mass fraction of PTMG in the polyol is not less than 40%, and if the content of PTMG is less than 40%, the hydrolysis resistance of PTMG cannot meet the application requirement;
the molecular weight of the polyether modified polydimethylsiloxane dihydric alcohol (PSI) is 500-3000, preferably 1500-2200, wherein the mass content of the siloxane is more than or equal to 70%, preferably more than or equal to 75%, for example, the product with the brand number of X-22-176F, X-22-176DX manufactured by Japanese Xinyue company; the mass fraction of PSI in the polyol is 5% -10%, if the mass fraction of PSI is lower than 5%, the effect of small cells cannot be achieved, and if the mass fraction of PSI is higher than 10%, the solidification speed of resin in the processing process is too slow, and the production efficiency is affected;
the polycarbonate diol (PCD) and the polycaprolactone diol (PCL) are commercial general products, and the molecular weight is 500-3000, preferably 1000-2000;
the polyester polyol is formed by high-temperature dehydration condensation of at least one C3-C8 dibasic acid and at least one C2-C6 aliphatic dibasic alcohol, and has a number average molecular weight of 1500-5000, preferably 2000-4000; the dibasic acid comprises at least one of aliphatic dibasic acid, alicyclic dibasic acid or aromatic dibasic acid, preferably 1, 6-adipic acid or/and 1, 4-succinic acid; the aliphatic dihydric alcohol is at least one of 1, 6-hexanediol, 1, 4-butanediol, ethylene glycol, neopentyl glycol and 1, 3-propanediol;
the chain extender is one or more of saturated aliphatic glycol with 2-6 carbon atoms, hydroquinone-bis (beta-hydroxyethyl) ether (HQEE) or resorcinol-bis (2-Hydroxyethyl) Ether (HER); as an example, the saturated aliphatic diol is one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, pentanediol, hexanediol, diethylene glycol, dipropylene glycol;
the diisocyanate is at least one of 4, 4-xylyl Methane (MDI), 4' -diisocyanato dicyclohexylmethane (hydrogenated MDI) and Hexamethylene Diisocyanate (HDI);
the reaction activity regulator is small molecular organic monoacid or inorganic acid, preferably phosphoric acid or/and acetic acid, and the addition amount is based on the pH value of the measurement system of 5.5-6.5;
the reaction terminator is at least one of methanol, ethanol and n-butanol;
the solvent is N, N-dimethylformamide DMF and/or dimethylacetamide DMAC, preferably DMF.
The self-homogenizing wet polyurethane resin also comprises 10-100 ppm of antioxidant by mass, and any antioxidant suitable for the wet polyurethane resin can be selected, preferably BHT.
The invention relates to a preparation method of self-homogenizing wet polyurethane resin, which is characterized by comprising the following steps:
s1, putting the polyol, the antioxidant, the reactivity regulator and part of chain extender into a reaction kettle with a stirring device, keeping the temperature at 45-50 ℃, and uniformly stirring;
s2, adding MDI, wherein the mole ratio of the MDI to the polyol is (1.2-2.5): 1, after the natural heat release is finished, heating to 65-75 ℃, stirring and preserving heat for reaction for 60-180 min;
s3, cooling to below 50 ℃, adding part of solvent and the rest of chain extender, heating to 75-80 ℃ after natural heat release is finished, stirring and preserving heat for reaction for 60-180 min;
s4, sampling and detecting NCO value and system viscosity, and if the viscosity does not reach the standard and the NCO value is not detected, supplementing a proper amount of MDI; and after the viscosity of the system is increased to a qualified range, adding the residual solvent and the reaction terminator, sampling, detecting the NCO value, and discharging.
Preferably, in order to make the molecular weight of the polyurethane resin more uniform, the temperature rising rate in the step S2 and the step S3 is 0.5 to 1 ℃/min.
The self-foaming wet polyurethane resin is used for preparing superfine fiber synthetic leather or imitation superfine fiber synthetic leather, and is generally prepared by a conventional production method of [ Qu Jianbo, synthetic leather technology [ M ], chemical industry press, 2010 ] in a wet impregnation process or a wet foaming process, wherein the conventional production method comprises the following steps of: the non-woven fabric with a certain density and uniform thickness is sent into an impregnation tank, and after the non-woven fabric is repeatedly soaked in polyurethane resin (the resin is usually diluted to a viscosity below 20000cps/25 ℃ by DMF and proper auxiliary agents are added), the polyurethane superfine fiber synthetic leather is prepared through the procedures of solidification, water washing (DMF removal), decrement (dissolution of low-density polyethylene in fibers), drying, chemical softening, shaping, drying, skin kneading, skin grinding, dry surface making and the like.
Compared with the prior art, the invention has the advantages that:
the invention adopts polyether modified polydimethylsiloxane dihydric alcohol (PSI), polytetrahydrofuran ether dihydric alcohol (PTMG) and other polyols for matching, reasonable formula setting and an isocyanate radical excessive prepolymerization method, and part of chain extender is added in the prepolymerization process, so that the molecular structure of the product has proper microphase mixing degree, and the product has fine and uniform cells and reasonable solidification speed in the application process. In addition, the reaction speed regulator is added in the prepolymerization process, so that the phenomenon that isocyanate groups undergo self-crosslinking reaction to cause gel phenomenon in a high-viscosity system can be prevented, and the molecular weight distribution of polyurethane is more uniform.
Drawings
Fig. 1 to 5 are cross-sectional microscopic enlarged views of ultrafine fiber synthetic leather base cloths produced by wet polyurethane resin impregnation of examples 1 to 3 and comparative examples 1 to 2, respectively.
Detailed Description
It will be appreciated by persons skilled in the art that the present embodiment is provided for illustration only and not for limitation of the invention, and that modifications and variations may be made to the embodiment within the scope of the invention as defined in the appended claims.
Example 1
A self-homogenizing wet polyurethane resin comprises the following steps:
s1, charging 100g of PTMG (molecular weight 2000), 70g of polybutylene adipate (PBA, molecular weight 3000), 10g of PSI (Japanese Xinyue X-22-176F, molecular weight 2000), 0.1g of antioxidant BHT, a proper amount of phosphoric acid (pH is adjusted to 5.5-6.5) and 5g of Ethylene Glycol (EG) into a reaction flask with a stirring device and a nitrogen protection device, and uniformly stirring at 45-50 ℃;
s2, adding 100.19g of MDI, slowly heating to 70 ℃ at a speed of 0.5 ℃/min after the natural heat release is finished, and stirring for 120min;
s3, cooling to below 50 ℃, adding 600g of solvent DMF, 3.82g of chain extender EG and 5g of HQEE, slowly heating to 80 ℃ at a speed of 0.8 ℃/min after the natural heat release is finished, and stirring and preserving heat for reaction for 120min;
s4, sampling and detecting an NCO value and system viscosity, wherein the NCO value adopts a colorimetric method after dropwise adding hydrogen peroxide, and if the viscosity does not reach the standard and the NCO value cannot be detected, a proper amount of MDI is added; after the viscosity of the system is increased to a qualified range, adding the residual 100g of solvent DMF and 0.5g of reaction terminator methanol, sampling, detecting the NCO value, and discharging.
Example 2
A self-homogenizing wet polyurethane resin comprises the following steps:
s1, putting 100g of PTMG (molecular weight 2000), 27g of polycarbonate diol (PCD, molecular weight 2000), 18g of PSI (X-22-176F), 45g of polycaprolactone diol (PCL, molecular weight 2000), 0.1g of antioxidant BHT, a proper amount of phosphoric acid (pH is adjusted to 5.5-6.5) and 13.28g of HQEE into a reaction flask with a stirring device and a nitrogen protection device, and keeping the temperature at 45-50 ℃ and stirring uniformly;
s2, adding 100.19g of MDI, slowly heating to 70 ℃ at a speed of 0.7 ℃/min after the natural heat release is finished, and stirring for 120min;
s3, cooling to below 50 ℃, adding 600g of solvent DMF, 4.26g of chain extender HER and 29.45g of HQEE, slowly heating to 75 ℃ at a speed of 0.5 ℃/min after the natural heat release is finished, and stirring and preserving heat for reaction for 120min;
s4, sampling and detecting an NCO value and system viscosity, wherein the NCO value adopts a colorimetric method after dropwise adding hydrogen peroxide, and if the viscosity does not reach the standard and the NCO value cannot be detected, a proper amount of MDI is added; after the viscosity of the system is increased to a qualified range, adding the residual 100g of solvent DMF and 0.5g of reaction terminator methanol, sampling, detecting the NCO value, and discharging.
Example 3
A self-homogenizing wet polyurethane resin comprises the following steps:
s1, putting 90g of PTMG (molecular weight 2000), 30g of polycarbonate diol (PCD, molecular weight 2000), 19.8g of PSI (6001 of Japanese Xinyue, molecular weight 1000), 71.8g of polycaprolactone diol (PCL, molecular weight 2000), 0.1g of antioxidant BHT, a proper amount of phosphoric acid (pH is adjusted to 5.5-6.5) and 8.9g of HQEE into a reaction flask with a stirring device and a nitrogen protection device, and keeping the temperature at 45-50 ℃ and stirring uniformly;
s2, adding 100.19g of MDI, slowly heating to 70 ℃ at a speed of 0.7 ℃/min after the natural heat release is finished, and stirring for 120min;
s3, cooling to below 50 ℃, adding 600g of solvent DMF, 4.26g of chain extender HER and 29.45g of HQEE, slowly heating to 75 ℃ at a speed of 0.5 ℃/min after the natural heat release is finished, and stirring and preserving heat for reaction for 120min;
s4, sampling and detecting an NCO value and system viscosity, wherein the NCO value adopts a colorimetric method after dropwise adding hydrogen peroxide, and if the viscosity does not reach the standard and the NCO value cannot be detected, a proper amount of MDI is added; after the viscosity of the system is increased to a qualified range, adding the residual 100g of solvent DMF and 0.5g of reaction terminator methanol, sampling, detecting the NCO value, and discharging.
Example 4
A self-homogenizing wet polyurethane resin comprises the following steps:
s1, charging 108g of PTMG (molecular weight 2000), 21.6g of polyethylene glycol butanediol adipate (PEBA, molecular weight 2000), 14.4g of PSI (Japanese Kogyo 6003, molecular weight 3000), 18g of PCD (molecular weight 2000), 18g of PCL (molecular weight 2000), 0.1g of antioxidant BHT, an appropriate amount of phosphoric acid (pH is adjusted to 5.5-6.5) and 7.5g of EG into a reaction flask with a stirring device and a nitrogen protection device, and keeping the temperature at 45-50 ℃ and stirring uniformly;
s2, adding 100.13g of MDI, slowly heating to 75 ℃ at a speed of 1 ℃/min after the natural heat release is finished, and stirring for 120min;
s3, cooling to below 50 ℃, adding 600g of solvent DMF, 9.23g of chain extender EG and 1.99g of 1,4-BG, slowly heating to 80 ℃ at a speed of 0.5 ℃/min after the natural heat release is finished, stirring and preserving the heat for 120min;
s4, sampling and detecting an NCO value and system viscosity, wherein the NCO value adopts a colorimetric method after dropwise adding hydrogen peroxide, and if the viscosity does not reach the standard and the NCO value cannot be detected, a proper amount of MDI is added; after the viscosity of the system is increased to a qualified range, adding the residual 100g of solvent DMF and 0.5g of reaction terminator methanol, sampling, detecting the NCO value, and discharging.
Example 5
A self-homogenizing wet polyurethane resin comprises the following steps:
s1, charging 108g of PTMG (molecular weight 2000), 21.6g of polyethylene glycol butanediol adipate (PEBA, molecular weight 2000), 14.4g of PSI (X-22-176F), 18g of PCD (molecular weight 2000), 18g of PCL (molecular weight 2000), 0.1g of antioxidant BHT, a proper amount of phosphoric acid (pH is regulated to 5.5-6.5) and 7.5g of EG into a reaction flask with a stirring device and a nitrogen protection device, and uniformly stirring at 45-50 ℃;
s2, adding 115.12g of MDI, slowly heating to 75 ℃ at a speed of 1 ℃/min after the natural heat release is finished, and stirring for 120min;
s3, cooling to below 50 ℃, adding 600g of solvent DMF, 10.38g of chain extender EG and 1.99g of 1,4-BG, slowly heating to 80 ℃ at a speed of 0.5 ℃/min after the natural heat release is finished, stirring and preserving the heat for 120min;
s4, sampling and detecting an NCO value and system viscosity, wherein the NCO value adopts a colorimetric method after dropwise adding hydrogen peroxide, and if the viscosity does not reach the standard and the NCO value cannot be detected, a proper amount of MDI is added; after the viscosity of the system is increased to a qualified range, adding the residual 100g of solvent DMF and 0.5g of reaction terminator methanol, sampling, detecting the NCO value, and discharging.
Comparative example 1
This comparative example 1 is a comparative example of example 1, with the PSI being replaced entirely by PEBA, and the remainder being the same as example 1, the preparation process comprising the steps of:
s1, putting 100g of PTMG (molecular weight 2000), 70g of PBA (molecular weight 3000), 10g of PEBA (molecular weight 2000), 0.1g of antioxidant BHT, a proper amount of phosphoric acid (with pH adjusted to 5.5-6.5) and 5g of Ethylene Glycol (EG) into a reaction flask with a stirring device and a nitrogen protection device, keeping the temperature at 45-50 ℃ and stirring uniformly;
s2, adding 100.19g of MDI, slowly heating to 70 ℃ at a speed of 0.5 ℃/min after the natural heat release is finished, and stirring for 120min;
s3, cooling to below 50 ℃, adding 600g of solvent DMF, 3.82g of chain extender EG and 5g of HQEE, slowly heating to 80 ℃ at a speed of 0.8 ℃/min after the natural heat release is finished, and stirring and preserving heat for reaction for 120min;
s4, sampling and detecting an NCO value and system viscosity, wherein the NCO value adopts a colorimetric method after dropwise adding hydrogen peroxide, and if the viscosity does not reach the standard and the NCO value cannot be detected, a proper amount of MDI is added; after the viscosity of the system is increased to a qualified range, adding the residual 100g of solvent DMF and 0.5g of reaction terminator methanol, sampling, detecting the NCO value, and discharging.
Comparative example 2
This comparative example 2 is a comparative example of example 1, a part of PTMG was changed to PEBA, the addition amount of PTMG was less than 40%, and the preparation process was the same as in example 1, comprising the steps of:
s1, putting 70g of PTMG (molecular weight 2000), 30g of PEBA (molecular weight 2000), 70g of PBA (molecular weight 3000), 10g of PSI (Japanese Xinyue X-22-176F, molecular weight 2000), 0.1g of antioxidant BHT, a proper amount of phosphoric acid (pH is adjusted to 5.5-6.5) and 5g of Ethylene Glycol (EG) into a reaction flask with a stirring device and a nitrogen protection device, and keeping the temperature at 45-50 ℃ and stirring uniformly;
s2, adding 100.19g of MDI, slowly heating to 70 ℃ at a speed of 0.5 ℃/min after the natural heat release is finished, and stirring for 120min;
s3, cooling to below 50 ℃, adding 600g of solvent DMF, 3.82g of chain extender EG and 5g of HQEE, slowly heating to 80 ℃ at a speed of 0.8 ℃/min after the natural heat release is finished, and stirring and preserving heat for reaction for 120min;
s4, sampling and detecting an NCO value and system viscosity, wherein the NCO value adopts a colorimetric method after dropwise adding hydrogen peroxide, and if the viscosity does not reach the standard and the NCO value cannot be detected, a proper amount of MDI is added; after the viscosity of the system is increased to a qualified range, adding the residual 100g of solvent DMF and 0.5g of reaction terminator methanol, sampling, detecting the NCO value, and discharging.
The wet process polyurethane resins of examples 1 to 5 and comparative examples 1 to 2 were used for impregnation to produce a superfine fiber synthetic leather base cloth, and fig. 1 to 5 are cross-sectional microscopic enlarged views of the superfine fiber synthetic leather base cloth produced by the wet process polyurethane resins of examples 1 to 3 and comparative examples 1 to 2, respectively; and detecting the obtained base cloth, detecting the moisture permeability and the air permeability according to ISO 20344 and ISO 20345, and detecting the hydrolysis resistance according to QB/T4671-2014. The test results are shown in Table 1.
Table 1 test results of examples 1 to 5 and comparative examples 1 to 2
The microfiber base cloth prepared by adopting the polyurethane resin synthesized in the examples 1-5 has uniform foaming of the resin layer, can greatly improve the fine and smooth and solid hand feeling and the moisture permeability and air permeability of the microfiber product, and improves the added value of the microfiber product. As can be seen from the electron micrographs, the resins of examples 1 to 3 have an extremely fine and uniform cell structure; the resin of comparative example 1 has no cells, resulting in a microfiber base fabric with empty hand feel and reduced moisture permeability; the addition of too little PTMG in comparative example 2 resulted in a significant decrease in peel strength after 24 hours of hydrolysis.

Claims (10)

1. The self-homogenizing wet polyurethane resin is characterized by being prepared from the following raw materials in parts by weight: 10-20% of dihydric alcohol, 0.1-5% of chain extender, 5-20% of diisocyanate, 60-80% of solvent, 0-200 ppm of reaction activity regulator and 0-1% of reaction terminator;
the polyol is a mixture of polytetrahydrofuran ether glycol and polyether modified polydimethylsiloxane glycol; or a mixture of at least one of a polyester polyol, a polycarbonate diol, and a polycaprolactone diol with a polytetrahydrofuran ether diol and a polyether-modified polydimethylsiloxane diol; the mass fraction of polytetrahydrofuran ether glycol in the polyol should not be less than 40%.
2. The self-homogenizing wet polyurethane resin according to claim 1, wherein the molecular weight of the polytetrahydrofuran ether glycol is between 1000 and 3000; the molecular weight of the polycarbonate diol and the polycaprolactone diol is 500-3000; the diisocyanate is at least one of 4, 4-xylylmethane, 4' -diisocyanato dicyclohexylmethane and hexamethylene diisocyanate.
3. The self-homogenizing wet polyurethane resin according to claim 1, wherein the molecular weight of the polyether-modified polydimethylsiloxane dihydric alcohol is 500-3000, wherein the mass content of siloxane is more than or equal to 70%; the polyester polyol is formed by high-temperature dehydration condensation of at least one C3-C8 dibasic acid and at least one C2-C6 aliphatic dibasic alcohol, and the molecular weight is 1500-5000.
4. The self-homogenizing wet polyurethane resin of claim 3 wherein the diacid comprises at least one of an aliphatic diacid, a cycloaliphatic diacid, or an aromatic diacid; the aliphatic dihydric alcohol is at least one of 1, 6-hexanediol, 1, 4-butanediol, ethylene glycol, neopentyl glycol and 1, 3-propanediol.
5. The self-foaming wet polyurethane resin according to claim 1, wherein the chain extender is at least one of saturated aliphatic diol with 2-6 carbon atoms, hydroquinone-bis (beta-hydroxyethyl) ether or resorcinol-bis (2-hydroxyethyl) ether.
6. The self-homogenizing wet polyurethane resin according to claim 1, wherein the reactivity regulator is small molecular organic monoacid or inorganic acid, and the addition amount is based on the pH value of the measurement system of 5.5-6.5; the reaction terminator is at least one of methanol, ethanol and n-butanol; the solvent is N, N-dimethylformamide DMF and/or dimethylacetamide DMAC.
7. The self-foaming wet polyurethane resin according to claim 1, further comprising an antioxidant in an amount of 10 to 100ppm by mass.
8. The method for preparing a self-foaming wet polyurethane resin according to any one of claims 1 to 7, characterized by comprising the steps of:
s1, putting the polyol, the antioxidant, the reactivity regulator and part of chain extender into a reaction kettle with a stirring device, keeping the temperature at 45-50 ℃, and uniformly stirring;
s2, adding MDI, wherein the mole ratio of the MDI to the polyol is (1.2-2.5): 1, after the natural heat release is finished, heating to 65-75 ℃, stirring and preserving heat for reaction for 60-180 min;
s3, cooling to below 50 ℃, adding part of solvent and the rest of chain extender, heating to 75-80 ℃ after natural heat release is finished, stirring and preserving heat for reaction for 60-180 min;
s4, sampling and detecting NCO value and system viscosity, and if the viscosity does not reach the standard and the NCO value is not detected, supplementing a proper amount of MDI; and after the viscosity of the system is increased to a qualified range, adding the residual solvent and the reaction terminator, sampling, detecting the NCO value, and discharging.
9. The method for producing a self-foaming wet polyurethane resin according to claim 8, wherein the heating rate in the step S2 and the step S3 is 0.5 to 1 ℃/min.
10. The self-foaming wet process polyurethane resin according to any one of claims 1 to 7, which is used for preparing superfine fiber synthetic leather or imitation superfine fiber synthetic leather.
CN202311530940.7A 2023-11-16 2023-11-16 Self-homogenizing wet polyurethane resin and preparation method and application thereof Pending CN117567717A (en)

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