CN106146785A - Leather finishing agent organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane and method thereof - Google Patents
Leather finishing agent organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane and method thereof Download PDFInfo
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- CN106146785A CN106146785A CN201610616172.0A CN201610616172A CN106146785A CN 106146785 A CN106146785 A CN 106146785A CN 201610616172 A CN201610616172 A CN 201610616172A CN 106146785 A CN106146785 A CN 106146785A
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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
- C08G18/48—Polyethers
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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
- C08G18/08—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
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
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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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
- C08G18/632—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
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- 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
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to finishing agent field, disclose a kind of leather finishing agent organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane and method thereof.Described aqueous polyurethane is prepared from water by the component based on molfraction, nertralizer: described component based on molfraction is: oligomer polyol 10～30 parts, end hydroxy polyether modified silicon oil 6～20 parts, catalyst 0.01～0.06 part, polyisocyanates 30～60 parts, carboxyl chain extender 3～6 parts, sulfonate chain extender 2～8 parts, little molecule diamine 1～10 parts；Described nertralizer consumption is carboxyl chain extender and 0.11～1.1 times of sulfonate chain extender mole total amount.Prepared aqueous polyurethane good stability, stores the time long, the water-tolerant of film.In a word, the aqueous polyurethane environmental protection of the present invention, excellent performance, effective.
Description
Technical field
The invention belongs to finishing agent field, particularly to a kind of leather finishing agent by organic-silicon-modified carboxylic acid/sulfonic acid type water
Property polyurethane and preparation method thereof.
Background technology
Leather finish can improve leather surface outward appearance, revises leather surface defect, expands the range of leather, improves the usability of leather
Energy and economic worth.Leather after covering with paint, lacquer, colour wash, etc., surface forms one layer of uniform protecting film, make leather have certain solvent resistant,
Flex endurant, wearability and water proofing property.At present conventional leather finishing agent have casein class finishing agent, nitrocotton class finishing agent, third
Olefin(e) acid class finishing agent, polyurethanes finishing agent.Casein class finishing agent bonding force is strong, good hand touch, but casein film is brittle, extends
Property little, containing the hydrophilic group such as amino, carboxyl, hydroxyl in not flex endurant, and casein, water-resistance property of coating is poor.Nitrocotton class is coated with
Decorations agent appearance of film is bright, water-fast, oil resistant, it is to avoid leather surface is tacky, improves the fastness of coating, but nitrocotton type coating is weak to always
Change, poor air permeability after film forming, limit its range.Acrylic compounds finishing agent filming performance is good, cohesive force strong, production technology
Simply, develop rapidly in leather industry, but acrylic acid exists the shortcomings such as " hot sticky cold crisp ", not solvent resistant, it is often necessary to it
It is modified.Polyurethane is one of main development direction of current leather finishing agent, owing to it has light, plentiful, wear-resisting, resistance to
Deflect, the feature such as low temperature resistant, high resilience, the grade of resultant Leather can be greatly improved.
Polyurethane (PU) is to be constituted poly-ammonia by hard section and soft section of block copolymer alternately, isocyanates and chain extender
Ester hard section, imparting polymer is with intensity and rigidity, and macromolecular polyol constitutes soft section, gives polymer with flexible, toughness, adjustment
The composition of soft or hard section and ratio are adapted to different base materials.When traditional solvent borne polyurethane finishing agent is constructed, organic solvent
Volatilization, had both been unfavorable for that workman's was healthy, had also damaged environment.Aqueous polyurethane (WPU) with water as disperse medium, gram
Take the harm that solvent borne polyurethane uses solvent to cause in a large number.Hydrophilic group is introduced by chain extender in polyurethane molecular chain
Group, makes strand partially or completely have hydrophilic, is the key preparing aqueous polyurethane, prepared by anionic hydrophilic chain extender
Aqueous polyurethane is always the focus direction of this area research, mainly has carboxylic acid type and the big class of sulfonic acid type two.Publication No.
The Chinese invention patent application of CN104356330A, discloses a kind of method using carboxylic acid type chain extender to prepare WPU, but makes
Preparing WPU with carboxylic acid type chain extender to neutralize carboxyl and become salt to strengthen its hydrophilic ability, owing to carboxylic acid belongs to weak acid, hydrophilic is relatively
Difference, carboxylic acid type WPU emulsion viscosity is big, and solid content is difficult to improve.Sulfonic group polarity is strong, and hydrophilic is better than carboxylic acid group, is easier to system
Standby high solids content WPU emulsion.The Chinese invention patent of Publication No. CN103305175A and CN103421462A discloses one
The preparation method of WPU, but preparation process only introduces sulfonic group, do not introduce carboxyl, be difficult to prepare solid content height, rupture and stretch
The WPU product that long rate is big.
Organosilicon have surface can the advantage such as low, resistance to oxidation, combustion water-fast, difficult, insulation and hydrophobic, air-permeability, be widely used in
The every field such as industry, agricultural, military affairs and daily life.But there is lacking of easy migration, adhesive force and bad mechanical property in organosilicon
Point, needs to carry out compounding use with other resins.Introduce organosilicon by blended or copolymerization aqueous polyurethane is modified, can
To significantly improve water-fast, oil resistivity and the high-low temperature resistant ability of polyurethane.Method of modifying has physical blending and chemosynthesis modified,
Physical modification would generally use emulsifying agent, is negatively affected to the performance of film；Chemosynthesis modification generally uses
Terminal hydroxy group or amino silicane coupling agent react with polyurethane molecular chain end-NCO, but introduce organosilicon by silane coupler
Segment is often at the end of polyurethane chain, it is difficult to solve the migration problem of organosilicon.Chinese patent CN102604026 is by hydroxyl
Silicone oil is accessed in polyurethane by chemical bonding, significantly improves the compatibility of organosilicon and polyurethane, but the polyurethane tree prepared
Fat remains solvent borne polyurethane, causes that production efficiency is low, energy consumption is high, process is complicated, does not meets environmental requirement.
Summary of the invention
In order to overcome the shortcoming and defect of prior art, the primary and foremost purpose of the present invention is to provide a kind of leather finishing agent to use
Organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane.Present invention introduces double hydroxy polyethers-polysiloxane copolymer, by organosilicon
Segment is linked in polyurethane backbone and controls its molecular weight, effectively reduces organosilicon and migrates, obtains multimodel particle size distribution
Large arch dam WPU emulsion, and due in silicone segments containing polyether component, it is provided that certain hydrophilic, decrease
Hydrophilic chain extender consumption, thus improve the resistance to water of film, therefore, the aqueous polyurethane environmental protection of the present invention, excellent performance, effect
Good.
Another object of the present invention is to provide the organic-silicon-modified carboxylic acid of above-mentioned leather finishing agent/poly-ammonia of sulfonic acid type aqueous
The preparation method of ester.
The purpose of the present invention is achieved through the following technical solutions:
A kind of leather finishing agent by organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, by the component based on molfraction,
Nertralizer is prepared from water:
Described component based on molfraction is: oligomer polyol 10～30 parts, end hydroxy polyether modified silicon oil 6～20
Part, catalyst 0.01～0.06 part, polyisocyanates 30～60 parts, carboxyl chain extender 3～6 parts, sulfonate chain extender 2～8 parts,
Little molecule diamine 1～10 parts；
Described nertralizer consumption is carboxyl chain extender and 0.11～1.1 times of sulfonate chain extender mole total amount.
Described oligomer polyol is in Polyethylene Glycol, polypropylene glycol, polytetrahydrofuran diol or polycaprolactone glycol
One or more, molecular weight is 1000～4000.
Described end hydroxy polyether modified silicon oil is the polyether-polysiloxane copolymers of both-end hydroxyl, molecular weight be 500～
3000；It is preferably Dow Corning Corporation, SF 8427.
Described polyisocyanates be isophorone diisocyanate, hexa-methylene isocyanates, toluene di-isocyanate(TDI) or
More than one in methyl diphenylene diisocyanate；
Described catalyst is the one in dibutyl tin dilaurate, stannous octoate or Bismuth Octoate；
Described carboxyl chain extender is more than one in dihydromethyl propionic acid, dimethylolpropionic acid；
Described sulfonate chain extender is ethylenediamine base ethyl sulfonic acid sodium, 1,2-dihydroxy-3-N-morpholinopropanesulfonic acid sodium or N/N-(2-hydroxyl second
Base) more than one in-2-aminoethyl sulfonic acid sodium；
Described nertralizer is the one in triethylamine, triethanolamine, N, N-dimethylethanolamine；Degree of neutralization be 95～
110%.
Described little molecule diamine is more than one in ethylenediamine, isophorone diamine.
The described leather finishing agent preparation method of organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, including walking as follows
Rapid:
(1) oligomer polyol and end hydroxy polyether modified silicon oil are carried out heating in vacuum dehydration, the product after being dehydrated
Thing；
(2) nitrogen protection and stirring under conditions of, will dehydration after product homoiothermic to 65～75 DEG C, add catalyst and
Polyisocyanates, after temperature stabilization, homoiothermic to 76～86 DEG C, insulation reaction 1.1～2.1h, obtain polyurethane product；
(3) carboxyl expanding chain pharmaceutical solution is added drop-wise in the polyurethane product of step (2), after being added dropwise to complete, be warming up to 82～
90 DEG C, continue reaction 2～4h, obtain chain extension product；Described carboxyl expanding chain pharmaceutical solution be carboxyl chain extender is dissolved in organic molten
Agent obtains；
(4) low boiling point organic solvent is added in the chain extension product of step (3), reduce system viscosity；Improve mixing speed,
It is warming up to 55～65 DEG C, adds sulfonate chain extender, insulation reaction 25～45min；It is cooled to 35～50 DEG C, adds nertralizer and enter
Row neutralizes reaction, obtains neutralized reaction product；
(5) adding deionized water in the neutralized reaction product of step (4), high speed shear is disperseed, is added little molecule diamine and enter
Row chain extending reaction, rotation is steamed desolvation, is obtained organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane.
Described in step (1), the temperature of thermal dehydration is 100～120 DEG C, and the time of described thermal dehydration is 1～2.5h.
Described in step (2), the rotating speed of stirring is 80～150r/min.
Described in step (3), in carboxyl expanding chain pharmaceutical solution, the consumption of organic solvent is 1～3 times of carboxyl chain extender quality；
Described in step (3), organic solvent is METHYLPYRROLIDONE；Time for adding described in step (3) be 10～
30min；
Described in step (4), low boiling point organic solvent is acetone；System viscosity described in step (4) be down to 200～
500m Pa, described in step (4), mixing speed is 500～1500r/min；, the time neutralizing reaction described in step (4) is
20～40min；
The scattered condition of high speed shear described in step (5) be in 3000～5000r/min high speed shear disperse 10～
20min；The time of chain extending reaction described in step (5) is 10～30min, and temperature is room temperature；Removing is steamed in rotation described in step (5)
The temperature of solvent is 30～50 DEG C.
Deionized water consumption described in step (5) is added by step (1)～(4) 0.8～1.5 times of raw material gross mass.
A kind of leather finishing agent is prepared by said method by organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane.
Described organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane good stability, can store more than 6 months；Particle diameter 150～
210nm, film forming after-drawing intensity is 10～30Mpa, and elongation at break is 300～600%.
The present invention, relative to prior art, has the advantage that
(1) leather finishing agent prepared by the present invention is by organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, by polyethers-poly-
Siloxanes is linked in polyurethane backbone with the form of segment, increases hydrophilic and the resistance to water of polyurethane, makes storage and make
During with, stability is greatly increased；
(2) organosilicon is accessed in polyurethane molecular chain by the present invention, can overcome organosilicon adhesive force, wearability, mechanicalness
The shortcomings such as energy difference, while keeping the original advantage of polyurethane, make polyurethane have more preferable heat-resisting quantity, pliability, breathe freely
The premium properties such as property and biocompatibility；
(3) organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane prepared by the present invention, uses carboxylic acid type and sulfonic acid type two kinds
Chain extender, emulsion particle diameter is polynary distribution, can prepare large arch dam, low viscous polyaminoester emulsion, improves production efficiency, reduces fortune
Defeated cost；
(4) organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane prepared by the present invention, product does not contains organic solvent, uses
Safely, the requirement of environmental conservation is met；
(5) preparation condition of the present invention is gentle, and energy consumption is relatively low.
Detailed description of the invention
For a better understanding of the present invention, below in conjunction with embodiment, the present invention is described in further detail, but the present invention
Embodiment be not limited to this.
Embodiment 1
(1) by 10 molar part Polyethylene Glycol (molecular weight 1000) and 7 molar part end hydroxy polyether modified polyorganosiloxane (molecules
Amount 1000, Dow Corning Corporation SF 8427) in dried and clean container, 100 DEG C of vacuum dehydration 1.5h, obtain dehydration product；
(2) under conditions of nitrogen protection and stirring (rotating speed is 100r/min), by the product homoiothermic after dehydration to 65 DEG C,
After temperature stabilization, add isophorone diisocyanate and the dibutyl tin dilaurate of 0.04 molar part of 30 molar part,
After temperature stabilization, homoiothermic to 80 DEG C, react 1.5h, obtain polyurethane product；
(3) by 3 molar part 2,2-dihydromethyl propionic acid METHYLPYRROLIDONE dissolves (the two mass ratio is 1:1),
Obtain dihydromethyl propionic acid solution；Dihydromethyl propionic acid solution peristaltic pump constant speed is added drop-wise to the polyurethane product of step (2)
In, control time for adding is 20min, after being added dropwise to complete, is warming up to 82 DEG C, reacts 4h, obtains chain extension product；
(4) acetone is added in the chain extension product of rapid (3), reduction system viscosity to 200m Pa；Improve mixing speed extremely
1000r/min, is warming up to 55 DEG C, adds 5 molar part ethylenediamine base ethyl sulfonic acid sodium, reacts 30min；Then temperature is reduced to 38
DEG C, add in the triethylamine of 3.2 molar part and reaction 20min, obtain neutralized reaction product；
(5), after discharging, (quality is neutralized reaction product quality to be slowly added to deionized water in the neutralized reaction product of step (4)
0.8 times), disperse 20min in 3000r/min high speed shear, after having disperseed, add the ethylenediamine room temperature chain extending reaction of 2 molar part
10min, 30 DEG C of rotations are steamed removing acetone solvent, are obtained the organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane of leather finishing agent.
Prepared leather finishing agent is by organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane: emulsion solid content is 52%,
Viscosity 1000mPa s, mean diameter is 310nm, storage-stable 6 months, film water absorption rate 3%, hot strength 17Mpa, disconnected
Split percentage elongation and reach 800%.
Embodiment 2
(1) by 25 molar part polypropylene glycols (molecular weight 4000), 6 molar part end hydroxy polyether modified polyorganosiloxane (molecules
Amount 500, Dow Corning Corporation SF 8427) in dried and clean container, 110 DEG C of vacuum dehydration 1h, obtain dehydration product；
(2) under conditions of nitrogen protection and stirring (rotating speed is 100r/min), by the product homoiothermic after dehydration to 75 DEG C,
After temperature stabilization, add the isophorone diisocyanate of 50 molar part, add the dibutyl tin osmanthus of 0.03 molar part
Acid stannum, after temperature stabilization, homoiothermic to 76 DEG C, react 1.1h, obtain polyurethane product；
(3) by 5 molar part 2,2-dihydromethyl propionic acid METHYLPYRROLIDONE dissolves (the two mass ratio is 1:2),
Obtain dihydromethyl propionic acid solution；Dihydromethyl propionic acid solution peristaltic pump constant speed is added drop-wise to the polyurethane product of step (2)
In, control time for adding is 30min, after being added dropwise to complete, is warming up to 90 DEG C, reacts 2h, obtains chain extension product；
(4) acetone is added in the chain extension product of rapid (3), reduce system viscosity to 300m Pa, raising blender rotating speed
To 1500r/min, it is warming up to 65 DEG C, adds 2 molar part ethylenediamine base ethyl sulfonic acid sodium, react 25min, then reduce temperature to 35
DEG C, add in the triethylamine of 5 molar part and reaction 40min, obtain neutralized reaction product；
(5), after discharging, (quality is neutralized reaction product quality to be slowly added to deionized water in the neutralized reaction product of step (4)
1.5 times), disperse 10min in 5000r/min high speed shear, after having disperseed, add the ethylenediamine chain extending reaction of 5 molar part
20min；Removing acetone solvent is steamed in 40 DEG C of rotations, obtains the organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane of leather finishing agent.
Prepared leather finishing agent is by organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane: emulsion solid content is 49%,
Viscosity 650mPa s, mean diameter is 305nm, storage-stable 6 months, film water absorption rate 3.1%, hot strength
16.8Mpa, elongation at break reaches 850%.
Embodiment 3
(1) by 30 molar part polycaprolactone glycol (molecular weight 2000), 20 molar part end hydroxy polyether modified polyorganosiloxanes
(molecular weight 3000, Dow Corning Corporation SF 8427) in dried and clean container, 110 DEG C of vacuum dehydration 1.2h, obtain dehydration produce
Thing；
(2) under conditions of nitrogen protection and stirring (rotating speed is 100r/min), by the product homoiothermic after dehydration to 70 DEG C,
After temperature stabilization, add the isophorone diisocyanate of 40 molar part, add the dibutyl tin osmanthus of 0.06 molar part
Acid stannum, after temperature stabilization, homoiothermic to 86 DEG C, react 2.1h, obtain polyurethane product；
(3) 4 molar part dihydromethyl propionic acid METHYLPYRROLIDONEs are dissolved (the two mass ratio is 1:3), obtain
Dihydromethyl propionic acid solution；Dihydromethyl propionic acid solution peristaltic pump constant speed is added drop-wise in the polyurethane product of step (2), control
Time for adding processed is 10min, after being added dropwise to complete, is warming up to 86 DEG C, reacts 3.5h, obtains chain extension product；
(4) acetone is added in the chain extension product of rapid (3), reduce system viscosity to 500m Pa, raising blender rotating speed
To 500r/min, it is warming up to 60 DEG C, adds 4 molar part ethylenediamine base ethyl sulfonic acid sodium, react 30min, then reduce temperature to 50
DEG C, add in the triethylamine of 3.5 molar part and reaction 30min, obtain neutralized reaction product；
(5), after discharging, (quality is neutralized reaction product quality to be slowly added to deionized water in the neutralized reaction product of step (4)
1.2 times), disperse 15min in 4000r/min high speed shear, after having disperseed, add the ethylenediamine chain extending reaction of 6 molar part
25min, 45 DEG C of rotations are steamed removing acetone solvent, are obtained the organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane of leather finishing agent.
Prepared leather finishing agent is by organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane: emulsion solid content is 50%,
Viscosity 720mPa s, mean diameter is 296nm, storage-stable more than 6 months, film water absorption rate 2.9%, hot strength
17.2Mpa, elongation at break reaches 870%.
Embodiment 4
(1) by 20 molar part polypropylene glycols (molecular weight 3000), 13 molar part end hydroxy polyether modified polyorganosiloxane (molecules
Amount 2000), Dow Corning Corporation SF 8427) in dried and clean container, 120 DEG C of vacuum dehydration 1.5h, obtain dehydration product；
(2) under conditions of nitrogen protection and stirring (rotating speed is 100r/min), by the product homoiothermic after dehydration to 75 DEG C,
After temperature stabilization, add the isophorone diisocyanate of 60 molar part, add the dibutyl tin osmanthus of 0.02 molar part
Acid stannum, after temperature stabilization, homoiothermic to 85 DEG C, react 1.8h, obtain polyurethane product；
(3) 3 molar part 2,2-dihydromethyl propionic acid METHYLPYRROLIDONEs are dissolved (the two mass ratio is 1:
2.5) dihydromethyl propionic acid solution, is obtained；Dihydromethyl propionic acid solution peristaltic pump constant speed is added drop-wise to the polyurethane of step (2)
In product, control time for adding is 15min, after being added dropwise to complete, is warming up to 84 DEG C, reacts 3h, obtains chain extension product；
(4) acetone is added in the chain extension product of rapid (3), reduce system viscosity to 400m Pa, raising blender rotating speed
To 1200r/min, it is warming up to 64 DEG C, adds 8 molar part ethylenediamine base ethyl sulfonic acid sodium, react 45min, then reduce temperature to 45
DEG C, add in the triethylamine of 2.5 molar part and reaction 20min, obtain neutralized reaction product；
(5), after discharging, (quality is neutralized reaction product quality to be slowly added to deionized water in the neutralized reaction product of step (4)
1.1 times), disperse 18min in 4500r/min high speed shear, after having disperseed, add the ethylenediamine chain extending reaction of 10 molar part
30min；50 DEG C of rotary evaporation desolvation acetone, obtain the organic-silicon-modified carboxylic acid of leather finishing agent/poly-ammonia of sulfonic acid type aqueous
Ester.
Prepared leather finishing agent is by organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane: emulsion solid content is 51%,
Viscosity 760mPa s, mean diameter at 286nm, storage-stable 6 months, film water absorption rate 3.2%, hot strength
16.4Mpa, elongation at break reaches 840%.
Embodiment 5
(1) by 25 molar part polypropylene glycols (molecular weight 2000), 15 molar part end hydroxy polyether modified polyorganosiloxane (molecules
Amount 2000, Dow Corning Corporation SF 8427) in dried and clean container, 100 DEG C of vacuum dehydration 1.5h, obtain dehydration product；
(2) under conditions of nitrogen protection and stirring (rotating speed is 100r/min), by the product homoiothermic after dehydration to 73 DEG C,
After temperature stabilization, add the isophorone diisocyanate of 45 molar part, add the dibutyl tin osmanthus of 0.01 molar part
Acid stannum, after temperature stabilization, homoiothermic to 82 DEG C, react 2h, obtain polyurethane product；
(3) 4 molar part 2,2-dihydromethyl propionic acid METHYLPYRROLIDONEs are dissolved (the two mass ratio is 1:
1.3) dihydromethyl propionic acid solution, is obtained；Dihydromethyl propionic acid solution peristaltic pump constant speed is added drop-wise to the polyurethane of step (2)
In product, control time for adding is 18min, after being added dropwise to complete, is warming up to 84 DEG C, reacts 3h, obtains chain extension product；
(4) acetone is added in the chain extension product of rapid (3), reduce system viscosity to 300m Pa, raising blender rotating speed
To 1000r/min, it is warming up to 62 DEG C, adds 8 molar part ethylenediamine base ethyl sulfonic acid sodium, react 45min, then reduce temperature to 45
DEG C, add in the triethylamine of 2.5 molar part and reaction 20min, obtain neutralized reaction product；
(5), after discharging, (quality is neutralized reaction product quality to be slowly added to deionized water in the neutralized reaction product of step (4)
0.9 times), in 4500r/min high speed dispersion 18min, after having disperseed, add the ethylenediamine chain extension 15min of 3 molar part；45 DEG C of rotations
Turn evaporation desolvation acetone, obtain the organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane of leather finishing agent.
Prepared leather finishing agent is by organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane: emulsion solid content is 51%,
Viscosity 920mPa s, mean diameter at 278nm, storage-stable 6 months, film water absorption rate 2.7%, hot strength
17.3Mpa, elongation at break reaches 830%.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not limited by above-described embodiment
System, the change made, modifies, substitutes, combines, simplifies, all under other any spirit without departing from the present invention and principle
Should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. a leather finishing agent is by organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, it is characterised in that: by by molfraction
The component of meter, nertralizer are prepared from water:
Described component based on molfraction is: oligomer polyol 10～30 parts, end hydroxy polyether modified silicon oil 6～20 parts,
Catalyst 0.01～0.06 part, polyisocyanates 30～60 parts, carboxyl chain extender 3～6 parts, sulfonate chain extender 2～8 parts are little
Molecule diamine 1～10 parts；
Described nertralizer consumption is carboxyl chain extender and 0.11～1.1 times of sulfonate chain extender mole total amount.
The most according to claim 1, leather finishing agent organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, its feature exists
In: described oligomer polyol be one in Polyethylene Glycol, polypropylene glycol, polytetrahydrofuran diol or polycaprolactone glycol with
On, molecular weight is 1000～4000；
The molecular weight of described end hydroxy polyether modified silicon oil is 500～3000.
The most according to claim 2, leather finishing agent organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, its feature exists
In: described end hydroxy polyether modified silicon oil is the polyether-polysiloxane copolymers of linear both-end hydroxyl.
The most according to claim 1, leather finishing agent organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, its feature exists
In: described polyisocyanates is isophorone diisocyanate, hexa-methylene isocyanates, toluene di-isocyanate(TDI) or diphenyl
More than one in methane diisocyanate；
Described carboxyl chain extender is more than one in 2,2-dihydromethyl propionic acid, 2,2-dimethylolpropionic acid；
Described sulfonate chain extender be ethylenediamine base ethyl sulfonic acid sodium, 1,2-dihydroxy-3-N-morpholinopropanesulfonic acid sodium or N/N-(2-ethoxy)-
More than one in 2-aminoethyl sulfonic acid sodium；
Described little molecule diamine is more than one in ethylenediamine, isophorone diamine.
The most according to claim 1, leather finishing agent organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, its feature exists
In: described nertralizer is the one in triethylamine, triethanolamine, N, N-dimethylethanolamine；Described catalyst is dibutyl two
One in tin laurate, stannous octoate or Bismuth Octoate.
6. according to leather finishing agent described in any one of Claims 1 to 5 by organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane
Preparation method, it is characterised in that: comprise the steps:
(1) oligomer polyol and end hydroxy polyether modified silicon oil are carried out heating in vacuum dehydration, the product after being dehydrated；
(2) under conditions of nitrogen protection and stirring, by the product homoiothermic after dehydration to 65～75 DEG C, catalyst and polyisocyanate are added
Cyanate, after temperature stabilization, homoiothermic to 76～86 DEG C, insulation reaction 1.1～2.1h, obtain polyurethane product；
(3) carboxyl expanding chain pharmaceutical solution is added drop-wise in the polyurethane product of step (2), after being added dropwise to complete, is warming up to 82～90 DEG C,
Continue reaction 2～4h, obtain chain extension product；Described carboxyl expanding chain pharmaceutical solution is to be dissolved in organic solvent by carboxyl chain extender
Arrive；
(4) low boiling point organic solvent is added in the chain extension product of rapid (3), reduce system viscosity；Improve mixing speed, be warming up to
55～65 DEG C, add sulfonate chain extender, insulation reaction 25～45min；It is cooled to 35～50 DEG C, adds nertralizer and be neutralized
Reaction, obtains neutralized reaction product；
(5) discharging, adds deionized water in the neutralized reaction product of step (4), and high speed shear is disperseed, added little molecule diamine and enter
Row chain extending reaction, rotation is steamed desolvation, is obtained organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane.
The leather finishing agent preparation method of organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane the most according to claim 6,
It is characterized in that: described in step (1), the temperature of thermal dehydration is 100～120 DEG C, the time of described thermal dehydration be 1～
2.5h；
Described in step (3), organic solvent is METHYLPYRROLIDONE；Time for adding described in step (3) be 10～
30min；
Described in step (4), low boiling point organic solvent is acetone；Described in step (4), system viscosity is down to 200～500m Pa.
The leather finishing agent preparation method of organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane the most according to claim 6,
It is characterized in that: the scattered condition of high speed shear described in step (5) in 3000～5000r/min high speed shear disperse 10～
20min；The time of chain extending reaction described in step (5) is 10～30min；The time neutralizing reaction described in step (4) is 20
～40min.
The leather finishing agent preparation method of organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane the most according to claim 6,
It is characterized in that: described in step (3), in carboxyl expanding chain pharmaceutical solution, the consumption of organic solvent is the 1～3 of carboxylic acid chain extender quality
Times；
Deionized water consumption described in step (5) is added by step (1)～(4) 0.8～1.5 times of raw material gross mass.
The leather finishing agent preparation side of organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane the most according to claim 6
Method, it is characterised in that: described in step (4), mixing speed is 500～1500r/min；Described in step (2), the rotating speed of stirring is
80～150r/min；It is 30～50 DEG C that the temperature of desolvation is steamed in rotation described in step (5).
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