CN109111837A - A kind of preparation method of low temperature resistant leather finishing agent - Google Patents
A kind of preparation method of low temperature resistant leather finishing agent Download PDFInfo
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- CN109111837A CN109111837A CN201810772717.6A CN201810772717A CN109111837A CN 109111837 A CN109111837 A CN 109111837A CN 201810772717 A CN201810772717 A CN 201810772717A CN 109111837 A CN109111837 A CN 109111837A
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- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
- C14C11/006—Surface finishing of leather using macromolecular compounds using polymeric products of isocyanates (or isothiocyanates) with compounds having active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The present invention relates to leather agent preparation fields, particularly with regard to a kind of preparation method of low temperature resistant leather finishing agent；A kind of preparation method of low temperature resistant leather finishing agent disclosed in the method for the present invention, a kind of low temperature resistant leather finishing agent of this method preparation has preferable solvent resistance and lower temperature resistance, it is easy to use and operate, it brushes or sprays, the secured folding of the coating of preparation, heat resistance are good, Bearable dry and wet wipe, do not account for plate, not astigmatism does not split slurry, there is preferable commercial application value.
Description
Technical field
The present invention relates to leather agent preparation fields, particularly with regard to a kind of preparation method of low temperature resistant leather finishing agent.
Background technique
Acrylic resin coating finiss is exactly the important EFFECTS OF LEATHER FINISHING material that China's leather industry generallys use always.It has one
The advantage of series, the after study improvement of recent two decades various aspects, product quality and performances are continuously improved.
CN105586804A discloses a kind of modified acrylic resin finish used for decorative paper and preparation method thereof.The painting
Adorn agent includes following components according to parts by weight: 50-55 parts of water, 5-8 parts of ethyl alcohol, and 10-15 parts of acrylic resin, casein 21-
25 parts, 3-5 parts of thickener, 1-3 parts of fumed silica, 0.5-1 parts of dispersing agent.Body paper is after covering with paint, lacquer, colour wash, etc., surface smoothness, printability
Property improve, advantageous guarantee is provided for the printing technology in body paper later period, to improve the quality of facing paper.
CN102786644A discloses a kind of acrylic resin modified painting of multi-walled carbon nanotube of nano silica cladding
Adorn the preparation method of agent.Emulsion acrylic resin has excellent film forming, mechanical stability and adhesiveness, but polyacrylate point
The characteristics of sub- linear structure, results in film and there is the problems such as " hot sticky cold crisp ", not solvent resistant, coating is adhered loosely.The invention is adopted
It is prepared for MWCNTs/SiO2 nano-complex particle with ethyl orthosilicate sol-gel process, and it is carried out with silane coupling agent
It is modified, by in-situ emulsion polymerization, silane coupler modified MWCNTs/SiO2 nano-complex particle is bonded to polyacrylic acid
In ester molecule chain.The invention is conducive to environmental protection, continuous operation easy to accomplish by medium of water；By the excellent of MWCNTs and nanosized SiO_2
Good characteristic introduces acrylic resin, overcome the defect of acrylic resin " hot sticky cold crisp ", the intensity for further improving coating,
Water resistance, heat resistance, gas permeability, color inhibition, anti-flammability.
CN101560353A discloses a kind of water-fast, solvent resistance leather acrylic resin coating finiss preparation method.
Water and emulsifier are added in three-necked flask, after mixing evenly, ethyl orthosilicate and organo silane coupling agent is added in heating water bath
React 10min；Esters of acrylic acid mix monomer is added, is warming up to 75 DEG C, keeps the temperature 30min；Acrylate is then added simultaneously
Class mix monomer and initiator solution, addition finish, and are warming up to 80~85 DEG C, keep the temperature 2h；Again by the adipic acid of 10wt% two
Hydrazides aqueous solution is added reaction system and stirs evenly, and adjusting pH with ammonium hydroxide is 6.0~7.0, discharging.This acrylic resin applies
Decorations agent raw material is easy to get, and introduces inorganic nano SiO2 particle during the preparation process and uses ambient self-crosslinking monomer simultaneously, significantly mentions
The high water resistance of coating, solvent resistance and transparency；It develops and is suitable for special leather such as military shoes, sofa artificial leather etc.
Acrylic resin coating finiss.
There is " hot sticky ", " cold short " to ask mostly for the acrylic compounds finishing agent of the above patent and prior art preparation
Topic, especially northern China cold district, it is anxious wait improve its cold short performance, it is badly in need of developing a kind of new low temperature resistant finishing agent.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of preparation methods of low temperature resistant leather finishing agent.
A kind of preparation method of low temperature resistant leather finishing agent, technology of preparing scheme are as follows:
According to mass fraction, 80-120 parts of organic silicon modified aqueous polyurethane lotion is added in reaction kettle, then will
5.6-12.8 parts of propylene glycol n-butyl ether, 0.001-0.05 parts of dimethylamino dithiocarbonic acid nickel, 0.1-0.8 parts of N, N '-
Two salicylidene ethylenediamine iron, 0.5-1.6 parts of active silane coupling agents are added in reaction kettle, and 30-50 DEG C of temperature control, stirring
10-30min；Then by 50-70 parts, (thio Glycolic acid is different by bis- containing 5-20 parts of bisphenol A epoxide resin and 0.05-0.5 part
Zinc rouge) dioctyltin is added in reaction kettle, is added and finishes in 60-150min, 70-90 DEG C is then increased the temperature to, reaction
150-300min；It completes that system temperature is dropped to room temperature after reacting, a kind of low temperature resistant leather finishing agent can be obtained.
The bisphenol A epoxide resin is epoxy resin E-51 or epoxy resin E-44 or epoxy resin E-20 or asphalt mixtures modified by epoxy resin
Rouge E-06.
The active silane coupling agents are ethylenediamine ethyl triethoxy silicane alkane or (ethylenediamine base) methyltriethoxy silane
Alkane or diethylenetriamine base propyl trimethoxy silicane.
The organic silicon modified aqueous polyurethane lotion is prepared according to following scheme:
According to mass fraction, by 70-90 parts of polycarbonate glycol, 10-15 parts of isophorone diisocyanate and 80-
100 parts of 4,4'- dicyclohexyl methyl hydride diisocyanate is added in reaction kettle, is then protected using high pure nitrogen, controls in kettle
Temperature is 60-80 DEG C, and the polyaminopropyl biguanide stearate that 0.1-0.5 parts are added under agitation is stirred into reaction kettle
React 60-120min；Then temperature is controlled at 30-50 DEG C, 5-10 parts of organosilicon chain extender is added, is stirred to react 40-
Then system temperature is controlled to 75-85 DEG C, 3.8-8.6 parts of trimethylolpropane is added, is stirred to react 30- by 60min
150min controls temperature at 30-50 DEG C, and 1.5-6.5 parts of triethylamine is added and is added in reaction kettle, 20-40 DEG C of temperature control, stirs
Mix reaction 50-100min；After completing reaction, 380-560 parts of purified water is added in reaction kettle under high velocity agitation, high speed
Disperse 60-180min, a kind of organic silicon modified aqueous polyurethane lotion can be obtained.
The organosilicon chain extender is dialkyl polydimethylsiloxane or dihydroxymethyl dimethoxysilane or hexichol
Base silicon diol.
One kind of a kind of preparation method of low temperature resistant leather finishing agent disclosed in the method for the present invention, this method preparation is low temperature resistant
Leather finishing agent has preferable solvent resistance and lower temperature resistance, easy to use and operate, brushes or sprays, the coating of preparation
Secured folding, heat resistance it is good, Bearable dry and wet wipe does not account for plate, not astigmatism, does not split slurry, there is preferable commercial application value.
Specific embodiment
The invention is described further below by specific embodiment:
Embodiment 1
A kind of preparation method of low temperature resistant leather finishing agent, technology of preparing scheme are as follows:
According to mass fraction, 110 parts of organic silicon modified aqueous polyurethane lotion is added in reaction kettle, then by 8.8 parts
Propylene glycol n-butyl ether, 0.0028 part of dimethylamino dithiocarbonic acid nickel, 0.4 part of N ,-two salicylidene ethylenediamine iron of N ',
0.8 part of active silane coupling agents are added in reaction kettle, 40 DEG C of temperature control, stir 20min；Then double containing 12 parts by 60 parts
Phenol A epoxy resin and 0.25 part of bis- (the thio different zinc rouge of Glycolic acid) dioctyltins are added in reaction kettle, are added in 90min
It finishes, then increases the temperature to 80 DEG C, react 200min；It completes that system temperature is dropped to room temperature after reacting, one kind can be obtained
Low temperature resistant leather finishing agent.
The bisphenol A epoxide resin is epoxy resin E-51.
The active silane coupling agents are ethylenediamine ethyl triethoxy silicane alkane.
The organic silicon modified aqueous polyurethane lotion is prepared according to following scheme:
According to mass fraction, by 80 parts of polycarbonate glycol, 13 parts of isophorone diisocyanate and the 4,4'- of 90 parts
Dicyclohexyl methyl hydride diisocyanate is added in reaction kettle, is then protected using high pure nitrogen, and control temperature in the kettle is 70 DEG C,
The polyaminopropyl biguanide stearate that 0.4 part is added under stirring condition is stirred to react 80min into reaction kettle；Then by temperature
Control is added 8 parts of organosilicon chain extender, is stirred to react 50min at 40 DEG C, then controls system temperature to 80 DEG C, is added
5.6 parts of trimethylolpropane, is stirred to react 80min, and temperature is controlled at 40 DEG C, and 3.5 parts of triethylamine is added and is added to instead
It answers in kettle, 30 DEG C of temperature control, is stirred to react 80min；After completing reaction, 460 parts of purified water is added to instead under high velocity agitation
It answers in kettle, high speed dispersion 120min, a kind of organic silicon modified aqueous polyurethane lotion can be obtained.
The organosilicon chain extender is dialkyl polydimethylsiloxane.
It is -37 DEG C that the low temperature of the film of the low temperature resistant finishing agent of this experiment preparation, which does not split temperature, tensile strength 24.73MPa.
Embodiment 2
A kind of preparation method of low temperature resistant leather finishing agent, technology of preparing scheme are as follows:
According to mass fraction, 80 parts of organic silicon modified aqueous polyurethane lotion is added in reaction kettle, then by 5.6 parts
Propylene glycol n-butyl ether, 0.001 part of dimethylamino dithiocarbonic acid nickel, 0.1 part of N ,-two salicylidene ethylenediamine iron of N ', 0.5
The active silane coupling agents of part are added in reaction kettle, 30 DEG C of temperature control, stir 10min；Then by 5 parts of bisphenol A epoxide resin
Bis- (the thio different zinc rouge of Glycolic acid) dioctyltins with 0.05 part are added in reaction kettle, are added and are finished in 60min, then rise
High-temperature reacts 150min to 70 DEG C；It completes that system temperature is dropped to room temperature after reacting, a kind of low temperature resistant leather painting can be obtained
Adorn agent.
The bisphenol A epoxide resin is epoxy resin E-44.
The active silane coupling agents are (ethylenediamine base) methyltriethoxysilane.
The organic silicon modified aqueous polyurethane lotion is prepared according to following scheme:
According to mass fraction, by 70 parts of polycarbonate glycol, 10 parts of isophorone diisocyanate and the 4,4'- of 80 parts
Dicyclohexyl methyl hydride diisocyanate is added in reaction kettle, is then protected using high pure nitrogen, and control temperature in the kettle is 60- DEG C,
The polyaminopropyl biguanide stearate that 0.1 part is added under agitation is stirred to react 60min into reaction kettle；It then will be warm
Degree control is added 5 parts of organosilicon chain extender, is stirred to react 40min at 30 DEG C, then controls system temperature to 75 DEG C, adds
The trimethylolpropane for entering 3.8 parts, is stirred to react 30min, and temperature is controlled at 30 DEG C, and 1.5 parts of triethylamine is added and is added to
In reaction kettle, 20 DEG C of temperature control, it is stirred to react 50min；After completing reaction, 380 parts of purified water is added under high velocity agitation
In reaction kettle, a kind of organic silicon modified aqueous polyurethane lotion is can be obtained in high speed dispersion 60min.
The organosilicon chain extender is dihydroxymethyl dimethoxysilane.
It is -35 DEG C that the low temperature of the film of the low temperature resistant finishing agent of this experiment preparation, which does not split temperature, tensile strength 23.89MPa.
Embodiment 3
A kind of preparation method of low temperature resistant leather finishing agent, technology of preparing scheme are as follows:
According to mass fraction, 120 parts of organic silicon modified aqueous polyurethane lotion is added in reaction kettle, then by 12.8 parts
Propylene glycol n-butyl ether, 0.05 part of dimethylamino dithiocarbonic acid nickel, 0.8 part of N ,-two salicylidene ethylenediamine iron of N ',
1.6 parts of active silane coupling agents are added in reaction kettle, 50 DEG C of temperature control, stir 30min；Then by 20 parts of bisphenol-A epoxy
Resin and 0.5 part of bis- (the thio different zinc rouge of Glycolic acid) dioctyltins are added in reaction kettle, are added and are finished in 150min,
Then 90 DEG C are increased the temperature to, 300min is reacted；It completes that system temperature is dropped to room temperature after reacting, can be obtained a kind of low temperature resistant
Leather finishing agent.
The bisphenol A epoxide resin is epoxy resin E-20.
The active silane coupling agents are diethylenetriamine base propyl trimethoxy silicane.
The organic silicon modified aqueous polyurethane lotion is prepared according to following scheme:
According to mass fraction, by 90 parts of polycarbonate glycol, 15 parts of isophorone diisocyanate and the 4 of 100 parts,
4'- dicyclohexyl methyl hydride diisocyanate is added in reaction kettle, is then protected using high pure nitrogen, and control temperature in the kettle is 80
DEG C, the polyaminopropyl biguanide stearate that 0.5 part is added under agitation is stirred to react 120min into reaction kettle；Then
Temperature is controlled at 50 DEG C, 10 parts of organosilicon chain extender is added, is stirred to react 60min, then controls system temperature to 85
DEG C, 3.6 parts of trimethylolpropane is added, is stirred to react 150min, temperature is controlled at 50 DEG C, 6.5 parts of triethylamine is added
It is added in reaction kettle, 40 DEG C of temperature control, is stirred to react 100min；After completing reaction, under high velocity agitation by 560 parts of purified water
It is added in reaction kettle, high speed dispersion 180min, a kind of organic silicon modified aqueous polyurethane lotion can be obtained.
The organosilicon chain extender is diphenyl silanediol.
It is -40 DEG C that the low temperature of the film of the low temperature resistant finishing agent of this experiment preparation, which does not split temperature, tensile strength 25.67MPa.
Embodiment 4
A kind of preparation method of low temperature resistant leather finishing agent, technology of preparing scheme are as follows:
According to mass fraction, 80 parts of organic silicon modified aqueous polyurethane lotion is added in reaction kettle, then by 5.6 parts
Propylene glycol n-butyl ether, 0.005 part of dimethylamino dithiocarbonic acid nickel, 0.1 part of N ,-two salicylidene ethylenediamine iron of N ', 0.5
The active silane coupling agents of part are added in reaction kettle, 30 DEG C of temperature control, stir 10min；Then it will contain 5 parts of bisphenol-A epoxy
Resin and 0.05 part of bis- (the thio different zinc rouge of Glycolic acid) dioctyltins are added in reaction kettle, are added and are finished in 60min, so
After increase the temperature to 70 DEG C, react 150min；It completes that system temperature is dropped to room temperature after reacting, a kind of low temperature resistant skin can be obtained
Remove from office finishing agent.
The bisphenol A epoxide resin is epoxy resin E-51.
The active silane coupling agents are diethylenetriamine base propyl trimethoxy silicane.
The organic silicon modified aqueous polyurethane lotion is prepared according to following scheme:
According to mass fraction, by 90 parts of polycarbonate glycol, 15 parts of isophorone diisocyanate and the 4 of 100 parts,
4'- dicyclohexyl methyl hydride diisocyanate is added in reaction kettle, is then protected using high pure nitrogen, and control temperature in the kettle is 80
DEG C, the polyaminopropyl biguanide stearate that 0.5 part is added under agitation is stirred to react 120min into reaction kettle；Then
Temperature is controlled at 50 DEG C, 10 parts of organosilicon chain extender is added, is stirred to react 60min, then controls system temperature to 85
DEG C, 3.6 parts of trimethylolpropane is added, is stirred to react 150min, temperature is controlled at 50 DEG C, 6.5 parts of triethylamine is added
It is added in reaction kettle, 40 DEG C of temperature control, is stirred to react 100min；After completing reaction, under high velocity agitation by 560 parts of purified water
It is added in reaction kettle, high speed dispersion 180min, a kind of organic silicon modified aqueous polyurethane lotion can be obtained.
The organosilicon chain extender is dialkyl polydimethylsiloxane.
It is -35 DEG C that the low temperature of the film of the low temperature resistant finishing agent of this experiment preparation, which does not split temperature, tensile strength 24.21MPa.
Embodiment 5
A kind of preparation method of low temperature resistant leather finishing agent, technology of preparing scheme are as follows:
According to mass fraction, 120 parts of organic silicon modified aqueous polyurethane lotion is added in reaction kettle, then by 12.8 parts
Propylene glycol n-butyl ether, 0.009 part of dimethylamino dithiocarbonic acid nickel, 0.8 part of N ,-two salicylidene ethylenediamine iron of N ',
1.6 parts of active silane coupling agents are added in reaction kettle, 50 DEG C of temperature control, stir 30min；Then by 20 parts of bisphenol-A epoxy
Resin and 0.5 part of bis- (the thio different zinc rouge of Glycolic acid) dioctyltins are added in reaction kettle, are added and are finished in 150min,
Then 90 DEG C are increased the temperature to, 300min is reacted；It completes that system temperature is dropped to room temperature after reacting, can be obtained a kind of low temperature resistant
Leather finishing agent.
The bisphenol A epoxide resin is epoxy resin E-06.
The active silane coupling agents are (ethylenediamine base) methyltriethoxysilane.
The organic silicon modified aqueous polyurethane lotion is prepared according to following scheme:
According to mass fraction, by 70 parts of polycarbonate glycol, 10 parts of isophorone diisocyanate and the 4,4'- of 80 parts
Dicyclohexyl methyl hydride diisocyanate is added in reaction kettle, is then protected using high pure nitrogen, and control temperature in the kettle is 60- DEG C,
The polyaminopropyl biguanide stearate that 0.1 part is added under agitation is stirred to react 60min into reaction kettle；It then will be warm
Degree control is added 5 parts of organosilicon chain extender, is stirred to react 40min at 30 DEG C, then controls system temperature to 75 DEG C, adds
The trimethylolpropane for entering 3.8 parts, is stirred to react 30min, and temperature is controlled at 30 DEG C, and 1.5 parts of triethylamine is added and is added to
In reaction kettle, 20 DEG C of temperature control, it is stirred to react 50min；After completing reaction, 380 parts of purified water is added under high velocity agitation
In reaction kettle, a kind of organic silicon modified aqueous polyurethane lotion is can be obtained in high speed dispersion 60min.
The organosilicon chain extender is diphenyl silanediol.
It is -38 DEG C that the low temperature of the film of the low temperature resistant finishing agent of this experiment preparation, which does not split temperature, tensile strength 24.81MPa.
Comparative example 1
Isophorone diisocyanate, the other the same as in Example 1 is not added.
It is -30 DEG C that the low temperature of the film of the low temperature resistant finishing agent of this experiment preparation, which does not split temperature, tensile strength 21.60MPa.
Comparative example 2
N ,-two salicylidene ethylenediamine iron of N ', the other the same as in Example 1 is not added.
It is -33 DEG C that the low temperature of the film of the low temperature resistant finishing agent of this experiment preparation, which does not split temperature, tensile strength 21.24MPa.
Comparative example 3
Polyaminopropyl biguanide stearate, the other the same as in Example 1 is not added.
It is -34 DEG C that the low temperature of the film of the low temperature resistant finishing agent of this experiment preparation, which does not split temperature, tensile strength 20.62MPa.
Comparative example 4
Dimethylamino dithiocarbonic acid nickel, the other the same as in Example 1 is not added.
It is -30 DEG C that the low temperature of the film of the low temperature resistant finishing agent of this experiment preparation, which does not split temperature, tensile strength 22.05MPa.
Comparative example 5
Bis- (the thio different zinc rouge of Glycolic acid) dioctyltins, the other the same as in Example 1 is not added.
It is -31 DEG C that the low temperature of the film of the low temperature resistant finishing agent of this experiment preparation, which does not split temperature, tensile strength 23.17MPa.
Claims (5)
1. a kind of preparation method of low temperature resistant leather finishing agent, technology of preparing scheme are as follows:
According to mass fraction, 80-120 parts of organic silicon modified aqueous polyurethane lotion is added in reaction kettle, then will
5.6-12.8 parts of propylene glycol n-butyl ether, 0.001-0.05 parts of dimethylamino dithiocarbonic acid nickel, 0.1-0.8 parts of N, N '-
Two salicylidene ethylenediamine iron, 0.5-1.6 parts of active silane coupling agents are added in reaction kettle, and 30-50 DEG C of temperature control, stirring
10-30min；Then by 50-70 parts, (thio Glycolic acid is different by bis- containing 5-20 parts of bisphenol A epoxide resin and 0.05-0.5 part
Zinc rouge) dioctyltin is added in reaction kettle, is added and finishes in 60-150min, 70-90 DEG C is then increased the temperature to, reaction
150-300min；It completes that system temperature is dropped to room temperature after reacting, a kind of low temperature resistant leather finishing agent can be obtained.
2. a kind of preparation method of low temperature resistant leather finishing agent according to claim 1, it is characterised in that: the bis-phenol
A epoxy resin is epoxy resin E-51 or epoxy resin E-44 or epoxy resin E-20 or epoxy resin E-06.
3. a kind of preparation method of low temperature resistant leather finishing agent according to claim 1, it is characterised in that: the activity
Silane coupling agent is ethylenediamine ethyl triethoxy silicane alkane or (ethylenediamine base) methyltriethoxysilane or diethylenetriamine base third
Base trimethoxy silane.
4. a kind of preparation method of low temperature resistant leather finishing agent according to claim 1, it is characterised in that: described is organic
Silicone modified waterborne polyurethane lotion is prepared according to following scheme:
According to mass fraction, by 70-90 parts of polycarbonate glycol, 10-15 parts of isophorone diisocyanate and 80-
100 parts of 4,4'- dicyclohexyl methyl hydride diisocyanate is added in reaction kettle, is then protected using high pure nitrogen, controls in kettle
Temperature is 60-80 DEG C, and the polyaminopropyl biguanide stearate that 0.1-0.5 parts are added under agitation is stirred into reaction kettle
React 60-120min；Then temperature is controlled at 30-50 DEG C, 5-10 parts of organosilicon chain extender is added, is stirred to react 40-
Then system temperature is controlled to 75-85 DEG C, 3.8-8.6 parts of trimethylolpropane is added, is stirred to react 30- by 60min
150min controls temperature at 30-50 DEG C, and 1.5-6.5 parts of triethylamine is added and is added in reaction kettle, 20-40 DEG C of temperature control, stirs
Mix reaction 50-100min；After completing reaction, 380-560 parts of purified water is added in reaction kettle under high velocity agitation, high speed
Disperse 60-180min, a kind of organic silicon modified aqueous polyurethane lotion can be obtained.
5. a kind of preparation method of low temperature resistant leather finishing agent according to claim 4, it is characterised in that: described is organic
Silicon chain extender is dialkyl polydimethylsiloxane or dihydroxymethyl dimethoxysilane or diphenyl silanediol.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810772717.6A CN109111837A (en) | 2018-07-14 | 2018-07-14 | A kind of preparation method of low temperature resistant leather finishing agent |
| CN201910341369.1A CN109880503B (en) | 2018-07-14 | 2019-04-26 | Preparation method of low-temperature-resistant leather finishing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810772717.6A CN109111837A (en) | 2018-07-14 | 2018-07-14 | A kind of preparation method of low temperature resistant leather finishing agent |
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| CN201810772717.6A Withdrawn CN109111837A (en) | 2018-07-14 | 2018-07-14 | A kind of preparation method of low temperature resistant leather finishing agent |
| CN201910341369.1A Active CN109880503B (en) | 2018-07-14 | 2019-04-26 | Preparation method of low-temperature-resistant leather finishing agent |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201910341369.1A Active CN109880503B (en) | 2018-07-14 | 2019-04-26 | Preparation method of low-temperature-resistant leather finishing agent |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5167706A (en) * | 1990-12-04 | 1992-12-01 | American Standard Inc. | Silane primer composition |
| JP2000119556A (en) * | 1998-10-20 | 2000-04-25 | Nippon Paint Co Ltd | Aqueous coating material composition, and coating using the same |
| JP5460640B2 (en) * | 2003-02-28 | 2014-04-02 | エスケー化研株式会社 | Curing agent for polyurethane resin paint |
| CN103382245A (en) * | 2012-05-03 | 2013-11-06 | 高明志 | Preparation method for organosilicon-modified crosslinking polyurethane emulsion |
| CN104846635A (en) * | 2015-05-28 | 2015-08-19 | 青岛国航祥玉技术服务有限公司 | Leather finishing agent |
| CN107353824A (en) * | 2016-11-28 | 2017-11-17 | 德阳力久云智知识产权运营有限公司 | A kind of wax Emulsion for Leather containing oxidized paraffin wax and preparation method thereof |
-
2018
- 2018-07-14 CN CN201810772717.6A patent/CN109111837A/en not_active Withdrawn
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2019
- 2019-04-26 CN CN201910341369.1A patent/CN109880503B/en active Active
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| CN109880503B (en) | 2021-04-13 |
| CN109880503A (en) | 2019-06-14 |
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