CN106146785B - Leather finishing agent organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane and its method - Google Patents
Leather finishing agent organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane and its method Download PDFInfo
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- CN106146785B CN106146785B CN201610616172.0A CN201610616172A CN106146785B CN 106146785 B CN106146785 B CN 106146785B CN 201610616172 A CN201610616172 A CN 201610616172A CN 106146785 B CN106146785 B CN 106146785B
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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 field of coating agent, disclose a kind of leather finishing agent organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane and its method.The aqueous polyurethane is prepared by component, neutralizer and the water based on molfraction: the component based on molfraction are as follows: 10~30 parts of oligomer polyol, 6~20 parts of end hydroxy polyether modified silicon oil, 0.01~0.06 part of catalyst, 30~60 parts of polyisocyanates, 3~6 parts of carboxyl chain extender, 2~8 parts of sulfonate chain extender, 1~10 part of small molecule diamine；The neutralizer dosage is 0.11~1.1 times of carboxyl chain extender and sulfonate chain extender moles total number.Prepared aqueous polyurethane stability is good, and storage time is long, the water-tolerant of film.In short, aqueous polyurethane environmental protection of the invention, have excellent performance, effect it is good.
Description
Technical field
The invention belongs to field of coating agent, in particular to the organic-silicon-modified carboxylic acid/sulfonic acid type water of a kind of leather finishing agent
Property polyurethane and preparation method thereof.
Background technique
Leather finish can improve leather surface appearance, correct leather surface defect, expand the use scope of leather, improve the usability of leather
Energy and economic value.Leather after covering with paint, lacquer, colour wash, etc., surface formed one layer of uniform protective film, make leather have certain solvent resistant,
Flex endurant, wearability and waterproofness.Currently used leather finishing agent has 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 small, not flex endurant, and it is poor containing hydrophilic radicals, water-resistance property of coating such as amino, carboxyl, hydroxyls in casein.Nitrocotton class applies
It adorns that agent appearance of film is bright, water-fast, oil resistant, avoids leather surface tacky, improve the fastness of coating, but nitrocotton type coating is intolerant to old
Change, poor air permeability after film forming limits its use scope.Acrylic compounds finishing agent filming performance is good, cohesive force is strong, production technology
Simply, it is rapidly developed in leather industry, but acrylic acid has the disadvantages of " hot sticky cold crisp ", not solvent resistant, it is often necessary to it
It is modified.Polyurethane is one of the main direction of development of current leather finishing agent, since it is with bright, plentiful, wear-resisting, resistance to
Deflect, be low temperature resistant, high resilience the features such as, the grade of resultant Leather can be greatly improved.
Polyurethane (PU) is the block copolymer as made of hard section and soft segment alternating, and isocyanates and chain extender constitute poly- ammonia
Ester hard section assigns polymer with intensity and rigidity, and macromolecular polyol constitutes soft segment, assigns polymer with flexible, toughness, adjustment
The composition and ratio of soft and hard segments are adapted to different substrates.When traditional solvent borne polyurethane finishing agent is constructed, organic solvent
Volatilization, had both been unfavorable for the health of worker, had also damaged to environment.Aqueous polyurethane (WPU) using water as decentralized medium, gram
It has taken solvent borne polyurethane and has largely used harm caused by solvent.Hydrophilic group is introduced by chain extender in polyurethane molecular chain
Group, makes strand partially or completely have hydrophily, is the key that prepare aqueous polyurethane, the preparation of anionic hydrophilic chain extender
Aqueous polyurethane is always the hot spot direction of the area research, mainly there is carboxylic acid type and sulfonic acid type two major classes.Publication No.
The Chinese invention patent application of CN104356330A discloses a kind of method for preparing WPU using carboxylic acid type chain extender, but makes
Carboxyl need to be neutralized at salt to enhance its hydrophilic ability with carboxylic acid type chain extender preparation WPU, since carboxylic acid belongs to weak acid, hydrophily compared with
Difference, carboxylic acid type WPU emulsion viscosity is big, and solid content is not easy to improve.Sulfonic acid is based polar strong, and hydrophily is better than carboxylic acid group, is easier to make
Standby high solids content WPU lotion.The Chinese invention patent of Publication No. CN103305175A and CN103421462A disclose one kind
The preparation method of WPU, but sulfonic group is only introduced in preparation process, carboxyl is not introduced, is not easy that solid content height is made, is broken and stretches
The big WPU product of long rate.
Organosilicon has many advantages, such as low surface energy, resistance to oxidation, water-fast, fire retardant, insulation and hydrophobic, air-permeability, is widely used in
The every field such as industry, agricultural, military and daily life.But there are easy to migrate, adhesive force and bad mechanical property to lack for organosilicon
Point needs to be used in compounding with other resins.Aqueous polyurethane is modified by being blended or being copolymerized introducing organosilicon, it can
To significantly improve the water-fast of polyurethane, oil resistivity and high-low temperature resistant ability.Method of modifying has physical blending and chemical synthesis modified,
Physical modification would generally use and arrive emulsifier, bring a negative impact to the performance of film；Chemical synthesis modification generally uses
Terminal hydroxy group or amino silicane coupling agent are reacted with polyurethane molecular chain end-NCO, but introduce organosilicon by silane coupling agent
Segment is often in the end of polyurethane chain, it is difficult to solve the migration problem of organosilicon.Chinese patent CN102604026 is by hydroxyl
Silicone oil is by significantly improving the compatibility of organosilicon and polyurethane, but the polyurethane tree prepared in chemical bonding access polyurethane
Rouge is still solvent borne polyurethane, leads to that production efficiency is low, energy consumption is high, process is complicated, does not meet environmental requirement.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of leather finishing agent use
Organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane.Present invention introduces double hydroxy polyethers-polysiloxane copolymers, by organosilicon
Segment is linked into polyurethane backbone and controls its molecular weight, effectively reduces organosilicon and migrates, obtains multimodel particle size distribution
Large arch dam WPU lotion certain hydrophily can be provided, reduced and due to containing polyether component in silicone segments
Hydrophilic chain extender dosage, to improve the water resistance of film, therefore, aqueous polyurethane environmental protection of the invention is had excellent performance, effect
It is good.
Another object of the present invention is to provide the above-mentioned leather finishing agent aqueous poly- ammonia of organic-silicon-modified carboxylic acid/sulfonic acid type
The preparation method of ester.
The purpose of the present invention is achieved through the following technical solutions:
A kind of organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane of leather finishing agent, by based on molfraction component,
Neutralizer is prepared with water:
The component based on molfraction are as follows: 10~30 parts of oligomer polyol, end hydroxy polyether modified silicon oil 6~20
Part, 0.01~0.06 part of catalyst, 30~60 parts of polyisocyanates, 3~6 parts of carboxyl chain extender, 2~8 parts of sulfonate chain extender,
1~10 part of small molecule diamine；
The neutralizer dosage is 0.11~1.1 times of carboxyl chain extender and sulfonate chain extender moles total number.
The oligomer polyol is in polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol or polycaprolactone glycol
One or more, molecular weight is 1000~4000.
The end hydroxy polyether modified silicon oil be both-end hydroxyl polyether-polysiloxane copolymers, molecular weight be 500~
3000；Preferably Dow Corning Corporation, SF 8427.
The polyisocyanates be isophorone diisocyanate, hexa-methylene isocyanates, toluene di-isocyanate(TDI) or
One or more of methyl diphenylene diisocyanate；
The catalyst is one of dibutyl tin dilaurate, stannous octoate or Bismuth Octoate；
The carboxyl chain extender is one or more of dihydromethyl propionic acid, dimethylolpropionic acid；
The sulfonate chain extender is ethylenediamine base ethanesulfonic acid sodium, 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium or N/N- (2- hydroxyl second
One or more of base) -2-aminoethanesulfonic acid sodium；
The neutralizer is one of triethylamine, triethanolamine, N, N- dimethylethanolamine；Degree of neutralization be 95~
110%.
The small molecule diamine is one or more of ethylenediamine, isophorone diamine.
The preparation method of the organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane of the leather finishing agent, including walk as follows
It is rapid:
(1) oligomer polyol and end hydroxy polyether modified silicon oil are subjected to heating in vacuum dehydration, obtain dewatered production
Object；
(2) nitrogen protection and stirring under conditions of, by dewatered product temperature adjustment to 65~75 DEG C, be added catalyst and
Polyisocyanates, after temperature is stablized, temperature adjustment to 76~86 DEG C, 1.1~2.1h of insulation reaction obtains 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, it is warming up to 82~
90 DEG C, the reaction was continued 2~4h, obtain chain extension product；The carboxyl expanding chain pharmaceutical solution be carboxyl chain extender is dissolved in it is organic molten
It is obtained in agent；
(4) low boiling point organic solvent is added in the chain extension product of step (3), reduces system viscosity；Mixing speed is improved,
55~65 DEG C are warming up to, sulfonate chain extender, 25~45min of insulation reaction is added；Be cooled to 35~50 DEG C, be added neutralizer into
Row neutralization reaction, obtains neutralized reaction product；
(5) be added deionized water into the neutralized reaction product of step (4), high speed shear dispersion, be added small molecule diamine into
Row chain extending reaction, revolving removing solvent, obtains organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane.
The temperature of thermal dehydration described in step (1) is 100~120 DEG C, and the time of the thermal dehydration is 1~2.5h.
The revolving speed of stirring described in step (2) is 80~150r/min.
The dosage of organic solvent is 1~3 times of carboxyl chain extender quality in carboxyl expanding chain pharmaceutical solution described in step (3)；
Organic solvent described in step (3) is n-methyl-2-pyrrolidone；Time for adding described in step (3) be 10~
30min；
Low boiling point organic solvent described in step (4) is acetone；System viscosity described in step (4) is down to 200~
500mPa, mixing speed described in step (4) are 500~1500r/min；, the time of neutralization reaction described in step (4) is
20~40min；
High speed shear described in step (5) dispersion condition 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 rotated described in step (5)
The temperature of solvent is 30~50 DEG C.
Deionized water dosage described in step (5) is 0.8~1.5 times of total mass of raw material added by step (1)~(4).
A kind of leather finishing agent is prepared with organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane by the above method.
Organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane the stability is good, can store 6 months or more；Partial size 150~
210nm, film forming post-tensioning intensity are 10~30Mpa, and elongation at break is 300~600%.
The present invention compared with the existing technology, has the advantage that
(1) the organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane of leather finishing agent prepared by the present invention, polyethers-is poly-
Siloxanes is linked into polyurethane backbone in the form of segment, is increased the hydrophily and water resistance of polyurethane, is made to store and make
It is greatly increased with stability in the process；
(2) present invention accesses organosilicon in polyurethane molecular chain, can overcome organosilicon adhesive force, wearability, mechanicalness
Can be poor the disadvantages of, makes polyurethane have better heat-resisting quantity, flexibility, breathe freely while holding polyurethane original advantage
The excellent performances such as property and biocompatibility；
(3) organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane prepared by the present invention, using carboxylic acid type and two kinds of sulfonic acid type
Chain extender, emulsion particle diameter are in polynary distribution, can prepare the polyaminoester emulsion of large arch dam, low viscosity, improve production efficiency, reduce fortune
Defeated cost；
(4) organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane prepared by the present invention, product are free of organic solvent, use
Safely, meet the requirement of environmental protection；
(5) preparation condition of the invention is mild, and energy consumption is lower.
Specific embodiment
For a better understanding of the present invention, below with reference to embodiment, the present invention is described in further detail, but the present invention
Embodiment it is without being limited thereto.
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 (revolving speed 100r/min), by dewatered product temperature adjustment to 65 DEG C,
After temperature is stablized, the isophorone diisocyanate of 30 molar parts and the dibutyl tin dilaurate of 0.04 molar part is added,
After temperature is stablized, temperature adjustment reacts 1.5h, obtains polyurethane product to 80 DEG C；
(3) by 3 molar parts 2,2- dihydromethyl propionic acid n-methyl-2-pyrrolidone dissolves (the two mass ratio is 1:1),
Obtain dihydromethyl propionic acid solution；Dihydromethyl propionic acid solution is added drop-wise to the polyurethane product of step (2) with peristaltic pump constant speed
In, control time for adding is 20min, after being added dropwise to complete, is warming up to 82 DEG C, reacts 4h, obtain chain extension product；
(4) acetone is added in the chain extension product of rapid (3), reduces system viscosity to 200mPa；Improve mixing speed extremely
1000r/min is warming up to 55 DEG C, and 5 molar part ethylenediamine base ethanesulfonic acid sodium are added, and reacts 30min；Then temperature is reduced to 38
DEG C, the triethylamine neutralization reaction 20min of 3.2 molar parts is added, obtains neutralized reaction product；
(5) after discharging, deionized water is slowly added into the neutralized reaction product of step (4), and (quality is neutralized reaction product quality
0.8 times), disperse 20min in 3000r/min high speed shear, the ethylenediamine room temperature chain extending reaction of 2 molar parts is added after the completion of dispersion
10min, 30 DEG C of revolvings remove acetone solvent, obtain leather finishing agent with organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane.
Organic-silicon-modified carboxylic acid/the sulfonic acid type water-based polyurethane of prepared leather finishing agent: emulsion solid content 52%,
Viscosity 1000mPas, average grain diameter 310nm, storage-stable 6 months, film water absorption rate 3%, tensile strength 17Mpa broke
It splits elongation and reaches 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 (revolving speed 100r/min), by dewatered product temperature adjustment to 75 DEG C,
After temperature is stablized, the isophorone diisocyanate of 50 molar parts is added, adds the dibutyl tin osmanthus of 0.03 molar part
Sour tin, after temperature is stablized, temperature adjustment reacts 1.1h, obtains polyurethane product to 76 DEG C；
(3) by 5 molar parts 2,2- dihydromethyl propionic acid n-methyl-2-pyrrolidone dissolves (the two mass ratio is 1:2),
Obtain dihydromethyl propionic acid solution；Dihydromethyl propionic acid solution is added drop-wise to the polyurethane product of step (2) with peristaltic pump constant speed
In, control time for adding is 30min, after being added dropwise to complete, is warming up to 90 DEG C, reacts 2h, obtain chain extension product；
(4) acetone is added in the chain extension product of rapid (3), reduces system viscosity to 300mPa, improves blender revolving speed
To 1500r/min, 65 DEG C are warming up to, 2 molar part ethylenediamine base ethanesulfonic acid sodium are added, reacts 25min, then reduces temperature to 35
DEG C, the triethylamine neutralization reaction 40min of 5 molar parts is added, obtains neutralized reaction product；
(5) after discharging, deionized water is slowly added into the neutralized reaction product of step (4), and (quality is neutralized reaction product quality
1.5 times), disperse 10min in 5000r/min high speed shear, the ethylenediamine chain extending reaction of 5 molar parts is added after the completion of dispersion
20min；40 DEG C of revolvings remove acetone solvent, obtain leather finishing agent with organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane.
Organic-silicon-modified carboxylic acid/the sulfonic acid type water-based polyurethane of prepared leather finishing agent: emulsion solid content 49%,
Viscosity 650mPas, average grain diameter 305nm, storage-stable 6 months, film water absorption rate 3.1%, tensile strength
16.8Mpa, elongation at break reach 850%.
Embodiment 3
(1) by 30 molar part polycaprolactone glycols (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 and produce
Object；
(2) under conditions of nitrogen protection and stirring (revolving speed 100r/min), by dewatered product temperature adjustment to 70 DEG C,
After temperature is stablized, the isophorone diisocyanate of 40 molar parts is added, adds the dibutyl tin osmanthus of 0.06 molar part
Sour tin, after temperature is stablized, temperature adjustment reacts 2.1h, obtains polyurethane product to 86 DEG C；
(3) it by the dissolution of 4 molar part dihydromethyl propionic acid n-methyl-2-pyrrolidone (the two mass ratio is 1:3), obtains
Dihydromethyl propionic acid solution；Dihydromethyl propionic acid solution is added drop-wise in the polyurethane product of step (2) with peristaltic pump constant speed, is controlled
Time for adding processed is 10min, after being added dropwise to complete, is warming up to 86 DEG C, reacts 3.5h, obtain chain extension product；
(4) acetone is added in the chain extension product of rapid (3), reduces system viscosity to 500mPa, improves blender revolving speed
To 500r/min, 60 DEG C are warming up to, 4 molar part ethylenediamine base ethanesulfonic acid sodium are added, reacts 30min, then reduces temperature to 50
DEG C, the triethylamine neutralization reaction 30min of 3.5 molar parts is added, obtains neutralized reaction product；
(5) after discharging, deionized water is slowly added into the neutralized reaction product of step (4), and (quality is neutralized reaction product quality
1.2 times), disperse 15min in 4000r/min high speed shear, the ethylenediamine chain extending reaction of 6 molar parts is added after the completion of dispersion
25min, 45 DEG C of revolvings remove acetone solvent, obtain leather finishing agent with organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane.
Organic-silicon-modified carboxylic acid/the sulfonic acid type water-based polyurethane of prepared leather finishing agent: emulsion solid content 50%,
Viscosity 720mPas, average grain diameter 296nm, storage-stable 6 months or more, film water absorption rate 2.9%, tensile strength
17.2Mpa, elongation at break reach 870%.
Embodiment 4
(1) by 20 molar part polypropylene glycols (molecular weight 3000), 13 molar part end hydroxy polyether modified polyorganosiloxane (molecules
Measure 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 (revolving speed 100r/min), by dewatered product temperature adjustment to 75 DEG C,
After temperature is stablized, the isophorone diisocyanate of 60 molar parts is added, adds the dibutyl tin osmanthus of 0.02 molar part
Sour tin, after temperature is stablized, temperature adjustment reacts 1.8h, obtains polyurethane product to 85 DEG C；
(3) by 3 molar part 2,2- dihydromethyl propionic acid n-methyl-2-pyrrolidone dissolution (the two mass ratio be 1:
2.5) dihydromethyl propionic acid solution, is obtained；Dihydromethyl propionic acid solution is added drop-wise to the polyurethane of step (2) with peristaltic pump constant speed
In product, control time for adding is 15min, after being added dropwise to complete, is warming up to 84 DEG C, reacts 3h, obtain chain extension product；
(4) acetone is added in the chain extension product of rapid (3), reduces system viscosity to 400mPa, improves blender revolving speed
To 1200r/min, 64 DEG C are warming up to, 8 molar part ethylenediamine base ethanesulfonic acid sodium are added, reacts 45min, then reduces temperature to 45
DEG C, the triethylamine neutralization reaction 20min of 2.5 molar parts is added, obtains neutralized reaction product；
(5) after discharging, deionized water is slowly added into the neutralized reaction product of step (4), and (quality is neutralized reaction product quality
1.1 times), disperse 18min in 4500r/min high speed shear, the ethylenediamine chain extending reaction of 10 molar parts is added after the completion of dispersion
30min；50 DEG C of rotary evaporations remove solvent acetone, obtain the leather finishing agent aqueous poly- ammonia of organic-silicon-modified carboxylic acid/sulfonic acid type
Ester.
Organic-silicon-modified carboxylic acid/the sulfonic acid type water-based polyurethane of prepared leather finishing agent: emulsion solid content 51%,
Viscosity 760mPas, average grain diameter is in 286nm, and storage-stable 6 months, film water absorption rate 3.2%, tensile strength
16.4Mpa, elongation at break reach 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 (revolving speed 100r/min), by dewatered product temperature adjustment to 73 DEG C,
After temperature is stablized, the isophorone diisocyanate of 45 molar parts is added, adds the dibutyl tin osmanthus of 0.01 molar part
Sour tin, after temperature is stablized, temperature adjustment reacts 2h, obtains polyurethane product to 82 DEG C；
(3) by 4 molar part 2,2- dihydromethyl propionic acid n-methyl-2-pyrrolidone dissolution (the two mass ratio be 1:
1.3) dihydromethyl propionic acid solution, is obtained；Dihydromethyl propionic acid solution is added drop-wise to the polyurethane of step (2) with peristaltic pump constant speed
In product, control time for adding is 18min, after being added dropwise to complete, is warming up to 84 DEG C, reacts 3h, obtain chain extension product；
(4) acetone is added in the chain extension product of rapid (3), reduces system viscosity to 300mPa, improves blender revolving speed
To 1000r/min, 62 DEG C are warming up to, 8 molar part ethylenediamine base ethanesulfonic acid sodium are added, reacts 45min, then reduces temperature to 45
DEG C, the triethylamine neutralization reaction 20min of 2.5 molar parts is added, obtains neutralized reaction product；
(5) after discharging, deionized water is slowly added into the neutralized reaction product of step (4), and (quality is neutralized reaction product quality
0.9 times), the ethylenediamine chain extension 15min of 3 molar parts is added after the completion of 4500r/min high speed dispersion 18min, dispersion；45 DEG C of rotations
Turn evaporation removing solvent acetone, obtains leather finishing agent with organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane.
Organic-silicon-modified carboxylic acid/the sulfonic acid type water-based polyurethane of prepared leather finishing agent: emulsion solid content 51%,
Viscosity 920mPas, average grain diameter is in 278nm, and storage-stable 6 months, film water absorption rate 2.7%, tensile strength
17.3Mpa, elongation at break reach 830%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the limit of above-described embodiment
System, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (6)
1. a kind of organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane of leather finishing agent, it is characterised in that: by pressing molfraction
Component, neutralizer and the water of meter are prepared:
The component based on molfraction are as follows: 10 ~ 30 parts of oligomer polyol, 6 ~ 20 parts of end hydroxy polyether modified silicon oil, urge
0.01 ~ 0.06 part of agent, 30 ~ 60 parts of polyisocyanates, 3 ~ 6 parts of carboxyl chain extender, 2 ~ 8 parts of sulfonate chain extender, small molecule two
1 ~ 10 part of first amine；
The neutralizer dosage is 0.11 ~ 1.1 times of carboxyl chain extender and sulfonate chain extender moles total number；
The oligomer polyol is one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol or polycaprolactone glycol
More than, molecular weight is 1000 ~ 4000；
The molecular weight of the end hydroxy polyether modified silicon oil is 500 ~ 3000；The end hydroxy polyether modified silicon oil is linear pair
The polyether-polysiloxane copolymers of terminal hydroxy group；
The polyisocyanates is isophorone diisocyanate, hexa-methylene isocyanates, toluene di-isocyanate(TDI) or hexichol
One or more of dicyclohexylmethane diisocyanate；
The carboxyl chain extender is one or more of 2,2- dihydromethyl propionic acid, 2,2- dimethylolpropionic acid；
The sulfonate chain extender is ethylenediamine base ethanesulfonic acid sodium, 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium or (the 2- hydroxyl second of N, N- bis-
One or more of base) -2-aminoethanesulfonic acid sodium；
The small molecule diamine is one or more of ethylenediamine, isophorone diamine；
The leather finishing agent preparation method of organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, includes the following steps:
(1) oligomer polyol and end hydroxy polyether modified silicon oil are subjected to heating in vacuum dehydration, obtain dewatered product；
(2) under conditions of nitrogen protection and stirring, by dewatered product temperature adjustment to 65 ~ 75 DEG C, catalyst and polyisocyanate is added
Cyanate, after temperature is stablized, temperature adjustment to 76 ~ 86 DEG C, 1.1 ~ 2.1h of insulation reaction obtains 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,
The reaction was continued 2 ~ 4h, obtains chain extension product；The carboxyl expanding chain pharmaceutical solution is to be dissolved in carboxyl chain extender in organic solvent to obtain
It arrives；
(4) low boiling point organic solvent is added in the chain extension product of rapid (3), reduces system viscosity；Mixing speed is improved, is warming up to
55 ~ 65 DEG C, sulfonate chain extender, 25 ~ 45min of insulation reaction is added；35 ~ 50 DEG C are cooled to, neutralizer is added and neutralize instead
It answers, obtains neutralized reaction product；
(5) discharge, be added deionized water into the neutralized reaction product of step (4), high speed shear dispersion, be added small molecule diamine into
Row chain extending reaction, revolving removing solvent, obtains organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane.
2. leather finishing agent is existed with organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, feature according to claim 1
In: the neutralizer is one of triethylamine, triethanolamine, N, N- dimethylethanolamine；The catalyst is dibutyl two
One of tin laurate, stannous octoate or Bismuth Octoate.
3. leather finishing agent is existed with organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, feature according to claim 1
In: the temperature of thermal dehydration described in step (1) is 100 ~ 120 DEG C, and the time of the thermal dehydration is 1 ~ 2.5h；
Organic solvent described in step (3) is n-methyl-2-pyrrolidone；Time for adding described in step (3) is 10 ~ 30min；
Low boiling point organic solvent described in step (4) is acetone；System viscosity described in step (4) is down to 200 ~ 500m Pa.s.
4. leather finishing agent is existed with organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, feature according to claim 1
In: the condition of the dispersion of high speed shear described in step (5) is to disperse 10 ~ 20min in 3000 ~ 5000r/min high speed shear；Step
(5) time of chain extending reaction described in is 10 ~ 30min；The time of neutralization reaction described in step (4) is 20 ~ 40min.
5. leather finishing agent is existed with organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, feature according to claim 1
In: the dosage of organic solvent is 1 ~ 3 times of carboxylic acid chain extender quality in carboxyl expanding chain pharmaceutical solution described in step (3)；
Deionized water dosage described in step (5) is 0.8 ~ 1.5 times of total mass of raw material added by step (1) ~ (4).
6. leather finishing agent is existed with organic-silicon-modified carboxylic acid/sulfonic acid type water-based polyurethane, feature according to claim 1
In: mixing speed described in step (4) is 500 ~ 1500r/min；The revolving speed of stirring described in step (2) is 80 ~ 150r/min；
The temperature of the solvent of revolving removing described in step (5) is 30 ~ 50 DEG C.
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| CN108276896B (en) * | 2018-02-28 | 2020-04-28 | 华南理工大学 | Moisture-cured leather finishing agent and preparation method thereof |
| CN113614134A (en) * | 2019-03-15 | 2021-11-05 | 陶氏环球技术有限责任公司 | Aqueous polyurethane dispersion and process for producing the same |
| CN110669196A (en) * | 2019-08-14 | 2020-01-10 | 合肥科天水性科技有限责任公司 | Waterborne polyurethane and method for preparing transfer agent by using same and application of waterborne polyurethane |
| CN110951039A (en) * | 2019-11-24 | 2020-04-03 | 华南理工大学 | Environment-friendly self-extinction waterborne polyurethane and preparation method and application thereof |
| CN111978476B (en) * | 2020-08-25 | 2022-09-27 | 青岛大学 | Sulfonic acid/carboxylic acid type silicon-containing polyurethane acrylate water repellent agent and preparation and application thereof |
| CN113087868B (en) * | 2021-05-19 | 2022-09-30 | 上海矽璃材料科技有限公司 | Solvent-free carboxyl organic silicon polyurethane resin copolymer and preparation method thereof |
| CN115772714A (en) * | 2022-12-07 | 2023-03-10 | 华峰化学股份有限公司 | High-strength high-heat-resistance spandex and preparation method thereof |
| CN115894851B (en) * | 2022-12-19 | 2023-11-24 | 江苏钟山新材料有限公司 | Preparation method of organosilicon modified waterborne polyurethane for leather finishing |
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