CN104356342B - Organic silicon modified aqueous polyurethane leather finishing agent and preparation method - Google Patents
Organic silicon modified aqueous polyurethane leather finishing agent and preparation method Download PDFInfo
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- CN104356342B CN104356342B CN201410611121.XA CN201410611121A CN104356342B CN 104356342 B CN104356342 B CN 104356342B CN 201410611121 A CN201410611121 A CN 201410611121A CN 104356342 B CN104356342 B CN 104356342B
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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- 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
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- C08G18/348—Hydroxycarboxylic acids
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- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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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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- Organic Chemistry (AREA)
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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of organic silicon modified aqueous polyurethane leather finishing agent, its primary raw material formula in parts by weight is as follows：PPG 30 ~ 50, isocyanates 10 ~ 30, castor oil 1 ~ 8, hydroxyl alkyl-terminated dimethyl silicone polymer 0.1 ~ 11, catalyst 0.01 ~ 1, hydrophilic chain extender 1 ~ 10, organic solvent 5 ~ 25, salt forming agent 1 ~ 5, small molecule chain extender 1 ~ 3, deionized water 120 ~ 250.Accordingly, the present invention also provides a kind of method for preparing above-mentioned organic silicon modified aqueous polyurethane leather finishing agent.Using the present invention, the aqueous polyurethane emulsion of synthesis is significantly improved in water resistance, cold resistance, solvent resistance, surface characteristic etc., and technique is simple and convenient to operate, emulsion stable homogeneous is made, produced during moisture dissipates and stores without precipitation, glued membrane is transparent, bright, is had a extensive future in terms of leather finish.
Description
Technical field
The present invention relates to leather finishing agent technical field, more particularly to a kind of organic silicon modified aqueous polyurethane leather finish
Agent and preparation method thereof.
Background technology
Covering with paint is an important procedure in leather making processes, and it is attractive in appearance that covering with paint can increase leather, protect leather, extend
Usage time, improve leather class.In all kinds of finishing agents, Aqueous Polyurethane Leather Finishing Agent has non-toxic and safe, environment friend
The advantages that good, good leveling property during covering with paint, filming performance is good, and covering power is strong.Leather surface is smooth after covering with paint, bright, and feel is relaxed
It is suitable, the grade of resultant Leather can be greatly improved, is used widely.Monocomponent waterborne polyurethane emulsion is due to hydrophilic on strand
The characteristics of on property group and this body structure, there is water resistance, solvent resistance, heat resistance are poor, the poor grade of stability of emulsion lacks
Point, seriously limit its application in leather finishing agent.
Using acrylate, epoxy resin, the organic-silicon-modified combination property that can significantly improve aqueous polyurethane.It is domestic
Research of the outer scholar to organic silicon modified polyurethane is relatively more.
Such as the B of patent CN 102633983 disclose a kind of organic block polyurethane pre-polymerization system of siloxane blocking
Preparation Method.Silicone segments are incorporated into this method using end hydroxyl silicone oil in polyurethane molecular as chain extender, but hydroxyl
The reactivity of base silicone oil is low, and with polyurethane poor compatibility, the emulsion of preparation is unstable, and the Si-O-C keys for reacting generation are water-fast
Property is poor.
The A of patent CN 103435772 disclose a kind of preparation method of silane-modified aqueous polyurethane, are contained by preparing
Active hydrogen silane coupler, chain extension-crosslinking modification is carried out to aqueous polyurethane, but because silane coupler molecular weight is small, divided
The siloxanes segment introduced in son is shorter, and modified Property of Waterborne Polyurethane is not obviously improved, and siloxane group exists
Molecule chain end, it is easily broken off hydrolyzing, stability of emulsion is bad.
The A's of patent CN 1884335 discloses a kind of manufacturer of polysiloxane-polyether copolymer modified aqueous polyurethane
Method, it is bridging agent using polyisocyanates, excessive Hydrophilicrto polyether, liquid polydimethylsiloxane tri-block is copolymerized, obtained
To copolymer, reacted with polyisocyanates, polyurethane and organosilicon are introduced on main chain.Using progressively polymerization technique, reacted
Journey is complicated, and energy consumption is big.
The A of patent CN 101225150 disclose the synthetic method that a kind of moisture dissipates Silicon Oligomer-polyuretyane Block Copolymer.
Using polyisocyanates and castor oil, polyol reaction generation performed polymer, chain extension is then carried out using ammonia alkyl polysiloxanes, in
It is made with scattered.Although the addition of siloxanes is up to more than 70% in such a method, modified good emulsion stability, silica
Alkane segment is soft, and the mechanical property of material does not have significant change, it is difficult to meets the needs of leather finish is wear-resisting durable.
The content of the invention
The technical problems to be solved by the invention are, there is provided a kind of water resistance is strong, solvent resistance is good, mechanical property is excellent
The organic silicon modified aqueous polyurethane leather finishing agent that different, technique is simple and course of reaction is easily controlled.
The technical problems to be solved by the invention also reside in, there is provided one kind prepares above-mentioned organic silicon modified aqueous polyurethane skin
The method for removing from office finishing agent, the preparation method is simple, is adapted to industrial applications.
To reach above-mentioned technique effect, the invention provides a kind of organic silicon modified aqueous polyurethane leather finishing agent, its
Primary raw material formula in parts by weight is as follows：
PPG 30 ~ 50
Isocyanates 10 ~ 30
Castor oil 1 ~ 8
Hydroxyl alkyl-terminated dimethyl silicone polymer 0.1 ~ 11
Catalyst 0.01 ~ 1
Hydrophilic chain extender 1 ~ 10
Organic solvent 5 ~ 25
Salt forming agent 1 ~ 5
Small molecule chain extender 1 ~ 3
Deionized water 120 ~ 250.
As the improvement of such scheme, the PPG is in polyethylene glycol, polytetrahydrofuran diol, polypropylene glycol
One kind or combination；
The isocyanates be toluene di-isocyanate(TDI), IPDI, methyl diphenylene diisocyanate,
One kind or combination in hexamethylene diisocyanate；
The catalyst is stannous octoate, one kind in dibutyl tin laurate or combination；
The hydrophilic chain extender is dihydromethyl propionic acid, one kind in dimethylolpropionic acid or combination；
The organic solvent is 1-METHYLPYRROLIDONE, one kind or group in DMF, acetone, butanone
Close；
The salt forming agent is triethanolamine, one kind in triethylamine or combination；
The small molecule chain extender is hexamethylene diamine, ethylenediamine, propane diols or one kind in 1,4- butanediols or combination.
As the improvement of such scheme, the hydroxyl value of the castor oil is 79 ~ 185mgKOH/g；
The PPG is polypropylene glycol, and molecular weight is 1000 ~ 2000；
The hydrophilic chain extender is dihydromethyl propionic acid；
The isocyanates is IPDI；
NCO and hydroxyl in polypropylene glycol, dihydromethyl propionic acid, castor oil in the IPDI
The mol ratio of base is 1.3 ~ 1.7:1.
As the improvement of such scheme, the molecular structural formula of the hydroxyl alkyl-terminated dimethyl silicone polymer is：
Wherein n=1 ~ 5.
As the improvement of such scheme, the solid content of the leather finishing agent is 25 ~ 35%.
Accordingly, the present invention also provides a kind of method for preparing above-mentioned organic silicon modified aqueous polyurethane leather finishing agent,
Including：
（1）The isocyanic acid after dehydration is sequentially added into the four-hole boiling flask equipped with agitator and reflux condensing tube by proportioning
Ester, PPG, castor oil, hydroxyl alkyl-terminated dimethyl silicone polymer and catalyst, react 2 ~ 3h at 70 ~ 80 DEG C and obtain pre-polymerization
Body；
（2）Hydrophilic chain extender and organic solvent are added into performed polymer, continues to react 3 ~ 4h at 70 ~ 80 DEG C, is had
There is the performed polymer of hydrophilic terminal isocyanate group；
（3）Add salt forming agent to neutralize, neutral temperature is 40 ~ 50 DEG C, stirs 20 ~ 40min；
（4）The performed polymer high speed shear that will be obtained after neutralization, the deionized water dissolved with small molecule chain extender is slowly added to, breast
Change scattered 20 ~ 40min；
（5）Organic silicon modified aqueous polyurethane leather finishing agent is made after removing organic solvent；
Wherein, the PPG, isocyanates, castor oil, hydroxyl alkyl-terminated dimethyl silicone polymer, catalyst, parent
The formula of water-based chain extender, organic solvent, salt forming agent, small molecule chain extender and deionized water in parts by weight is as follows：
PPG 30 ~ 50
Isocyanates 10 ~ 30
Castor oil 1 ~ 8
Hydroxyl alkyl-terminated dimethyl silicone polymer 0.1 ~ 11
Catalyst 0.01 ~ 1
Hydrophilic chain extender 1 ~ 10
Organic solvent 5 ~ 25
Salt forming agent 1 ~ 5
Small molecule chain extender 1 ~ 3
Deionized water 120 ~ 250.
As the improvement of such scheme, the PPG is in polyethylene glycol, polytetrahydrofuran diol, polypropylene glycol
One kind or combination；
The isocyanates be toluene di-isocyanate(TDI), IPDI, methyl diphenylene diisocyanate,
One kind or combination in hexamethylene diisocyanate；
The catalyst is stannous octoate, one kind in dibutyl tin laurate or combination；
The hydrophilic chain extender is dihydromethyl propionic acid, one kind in dimethylolpropionic acid or combination；
The organic solvent is 1-METHYLPYRROLIDONE, one kind or group in DMF, acetone, butanone
Close；
The salt forming agent is triethanolamine, one kind in triethylamine or combination；
The small molecule chain extender is hexamethylene diamine, ethylenediamine, propane diols or one kind in 1,4- butanediols or combination.
As the improvement of such scheme, the hydroxyl value of the castor oil is 79 ~ 185mgKOH/g；
The PPG is polypropylene glycol, and molecular weight is 1000 ~ 2000；
The hydrophilic chain extender is dihydromethyl propionic acid；
The isocyanates is IPDI；
NCO and hydroxyl in polypropylene glycol, dihydromethyl propionic acid, castor oil in the IPDI
The mol ratio of base is 1.3 ~ 1.7:1.
As the improvement of such scheme, the molecular structural formula of the hydroxyl alkyl-terminated dimethyl silicone polymer is：
Wherein n=1 ~ 5.
As the improvement of such scheme, the solid content of the leather finishing agent is 25 ~ 35%.
Implement the present invention to have the advantages that：
（1）The present invention replaces petroleum derivative oligomer polyol using the vegetable oil castor oil part of abundance, pacifies
Loopful is protected.Certain cross-linked structure can be introduced in the molecular structure by polyfunctionality castor oil, so as to make up polydimethylsiloxanes
Alkane is poor in terms of mechanical property the defects of；And contain longer hydrophobic fatty acid chain in its molecule so that film it is water-fast
Property improve.
（2）The present invention is reacted using-OH in hydroxyl alkyl-terminated dimethyl silicone polymer and NCO so that poly- silicon
Oxygen alkane can be bonded by Si-C with polyurethane and be closed.The aqueous polyurethane emulsion of synthesis water resistance, cold resistance, solvent resistance,
Surface characteristic etc. is significantly improved.
（3）Present invention process is simple and convenient to operate, and emulsion stable homogeneous is made, the equal nothing during moisture dissipates and stores
Precipitation produces, and glued membrane is transparent, bright, is had a extensive future in terms of leather finish.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, the present invention will be made below further detailed
Description.
The invention provides a kind of organic silicon modified aqueous polyurethane leather finishing agent, its primary raw material in parts by weight
Formula is as follows：
PPG 30 ~ 50
Isocyanates 10 ~ 30
Castor oil 1 ~ 8
Hydroxyl alkyl-terminated dimethyl silicone polymer 0.1 ~ 11
Catalyst 0.01 ~ 1
Hydrophilic chain extender 1 ~ 10
Organic solvent 5 ~ 25
Salt forming agent 1 ~ 5
Small molecule chain extender 1 ~ 3
Deionized water 120 ~ 250.
Preferably, the primary raw material formula of the leather finishing agent in parts by weight is as follows：
PPG 35 ~ 45
Isocyanates 15 ~ 25
Castor oil 4 ~ 8
Hydroxyl alkyl-terminated dimethyl silicone polymer 1 ~ 10
Catalyst 0.01 ~ 1
Hydrophilic chain extender 1 ~ 8
Organic solvent 5 ~ 20
Salt forming agent 2 ~ 4
Small molecule chain extender 1 ~ 2
Deionized water 150 ~ 200.
Specifically, the PPG is polyethylene glycol, polytetrahydrofuran diol, one kind or group in polypropylene glycol
Close.Preferably, the PPG is one kind in polyethylene glycol, polytetrahydrofuran diol, polypropylene glycol.More preferably, institute
It is polypropylene glycol to state PPG, and molecular weight is 1000 ~ 2000, there is longer strand, in the aqueous polyurethane point of synthesis
It is sub, middle to be used as soft segment so that the aqueous polyurethane of preparation has certain pliability.
The isocyanates be toluene di-isocyanate(TDI), IPDI, methyl diphenylene diisocyanate,
One kind or combination in hexamethylene diisocyanate.Preferably, the isocyanates is toluene di-isocyanate(TDI), isophorone
One kind in diisocyanate, methyl diphenylene diisocyanate, hexamethylene diisocyanate.More preferably, the isocyanic acid
Ester is IPDI.
The hydroxyl value of the castor oil is preferably 79 ~ 185mgKOH/g, to ensure that castor oil plays a part of crosslinking agent.
The molecular structural formula of the hydroxyl alkyl-terminated dimethyl silicone polymer is：
Wherein n=1 ~ 5.Preferably, n=3, the hydroxyl alkyl-terminated dimethyl silicone polymer is hydroxypropyl silicone oil, and hydroxyl contains
Measure as 0.8% ~ 1.7%, molecular weight is 2000 ~ 4000, can pass through hydroxyl and be reacted with-NCO, there is provided longer polysiloxanes segment.
The catalyst is stannous octoate, one kind in dibutyl tin laurate or combination.Preferably, the catalyst
For one kind in stannous octoate, dibutyl tin laurate.
The hydrophilic chain extender is dihydromethyl propionic acid, one kind in dimethylolpropionic acid or combination.Preferably, it is described
Hydrophilic chain extender is one kind in dihydromethyl propionic acid, dimethylolpropionic acid.More preferably, the hydrophilic chain extender is dihydroxy
Methylpropanoic acid.
The organic solvent is 1-METHYLPYRROLIDONE, one kind or group in DMF, acetone, butanone
Close.Preferably, the organic solvent is 1-METHYLPYRROLIDONE, one kind in DMF, acetone, butanone.More
Good, the organic solvent is acetone.
The salt forming agent is triethanolamine, one kind in triethylamine or combination.Preferably, the salt forming agent is three ethanol
One kind in amine, triethylamine.
The small molecule chain extender is hexamethylene diamine, ethylenediamine, propane diols or one kind in 1,4- butanediols or combination.It is preferred that
, the small molecule chain extender is one kind in hexamethylene diamine, ethylenediamine, propane diols or BDO.
Further, NCO and polypropylene glycol, dihydromethyl propionic acid, castor-oil plant in the IPDI
The mol ratio of hydroxyl is 1.3 ~ 1.7 in oil:1, less than 1.3:When 1, because performed polymer relative molecular mass is big, viscosity is larger,
Emulsification is difficult;When higher than 1.7:When 1, more urea bond cross-linked structure is generated because-NCO and the water of residual react,
Condensation product is also easy to produce, stability is also bad.Further, the mol ratio is preferably 1.3:1.
The solid content of the leather finishing agent is 25 ~ 35%, preferably 30%.
Aqueous polyurethane is made using the castor oil part substitution oligomer polyol containing longer hydrophobic segment in the present invention
There is appropriately crosslinked structure and hydrophobic segment, water resistance improves in molecule；Using the higher hydroxyl alkyl-terminated poly dimethyl of-OH activity
Siloxanes segment in silane is incorporated into aqueous polyurethane molecule, when aqueous polyurethane film forming by siloxanes as chain extender
When, because the surface energy of siloxanes is low, it is intended to surface enrichment so that the surface property of material changes.Silicone segments,
The introducing of cross-linked structure can effectively prevent moisture from penetrating into glued membrane and in glued membrane diffusion inside, and the water absorption rate of glued membrane substantially reduces, resistance to
Water-based raising.In addition the presence of cross-linked structure causes the mechanical property of polyurethane to improve.
Accordingly, the present invention also provides a kind of method for preparing above-mentioned organic silicon modified aqueous polyurethane leather finishing agent,
Including：
（1）It is prepared by the ricinolein based polyurethanes performed polymer containing silicon oxygen bond：By proportioning to equipped with agitator and returned cold
Isocyanates, PPG, castor oil, hydroxyl alkyl-terminated poly dimethyl silicon after dehydration are sequentially added in the four-hole boiling flask of solidifying pipe
Oxygen alkane and catalyst, react 2 ~ 3h at 70 ~ 80 DEG C and obtain performed polymer, wherein, reaction temperature is preferably 75 ~ 80 DEG C.
（2）Hydrophilic chain extender and organic solvent are added into performed polymer, continues to react 3 ~ 4h at 70 ~ 80 DEG C, is had
There is the performed polymer of hydrophilic terminal isocyanate group, wherein, reaction temperature is preferably 75 ~ 80 DEG C.
（3）Salt forming agent is added to neutralize, neutral temperature is 40 ~ 50 DEG C, stirs 20 ~ 40min, wherein, reaction temperature is preferably
45 DEG C, stir 30min.
（4）The performed polymer high speed shear that will be obtained after neutralization, the deionized water dissolved with small molecule chain extender is slowly added to, breast
Change scattered 20 ~ 40min, wherein, the emulsion dispersion time is preferably 30min.
（5）Organic silicon modified aqueous polyurethane leather finishing agent is made after removing organic solvent.
Wherein, it is the PPG that is related in leather finishing agent preparation method, isocyanates, castor oil, hydroxyl alkyl-terminated poly-
Dimethyl siloxane, catalyst, hydrophilic chain extender, organic solvent, salt forming agent, the dosage of small molecule chain extender and deionized water
Selected with material, it is consistent with foregoing leather finishing agent, it will not be repeated here.
The present invention is expanded on further with specific embodiment below
Embodiment 1
By the 16.05g IPDI after dehydration, 40.00g PPG2000,4.61g castor oil, 2.12g hydroxypropyls silicone oil is successively
Add and be equipped with the four-hole boiling flask of electric mixer, reflux condensing tube, 3 ~ 5 drop dibutyl tin laurates are added dropwise, it is anti-in 80 DEG C
2 ~ 3h is answered, obtains silicone-modified performed polymer.3.87g DMPA and 15g acetone is added into performed polymer, continues to react 3 at 80 DEG C
~ 4h, obtain the performed polymer with hydrophilic terminal isocyanate group.Then 50 DEG C are cooled to, 2.92gTEA is added and neutralizes into salt,
Stir 30min.Take 1.00g ethylenediamines to be dissolved in 164.66g deionized waters, be slowly added into the performed polymer of high speed shear
In, emulsion dispersion 30min, finally acetone is evaporated under reduced pressure away, organic silicon modified aqueous polyurethane emulsion is made.
Obtained emulsion appearance is creamy white, micro- blueing light.By desk centrifuge with 3000r/min centrifugations
15min, no precipitation, illustrate that emulsion can stablize storage more than 6 months.Glued membrane is in light yellow clear shape, relatively soft, micro- viscous, is inhaled
Water rate is 13.7%, and it is 41.3% to soak 24h swelling ratios in ethanol.
It should be noted that PPG2000 refers to that the polypropylene glycol that molecular weight is 2000, IPDI refer to the isocyanide of isophorone two
Acid esters, DMPA refer to that dihydromethyl propionic acid, TEA refer to triethylamine.
Embodiment 2
By the 16.05g IPDI after dehydration, 40.00g PPG2000,4.61g castor oil, 3.60g hydroxypropyls silicone oil is successively
Add and be equipped with the four-hole boiling flask of electric mixer, reflux condensing tube, 3 ~ 5 drop dibutyl tin laurates are added dropwise, it is anti-in 80 DEG C
2 ~ 3h is answered, obtains silicone-modified performed polymer.3.87g DMPA and 15g acetone is added into performed polymer, continues to react 3 at 80 DEG C
~ 4h, obtain the performed polymer with hydrophilic terminal isocyanate group.Then 50 DEG C are cooled to, 2.92gTEA is added and neutralizes into salt,
Stir 30min.Take 1.00g ethylenediamines to be dissolved in 168.13g deionized waters, be slowly added into the performed polymer of high speed shear
In, emulsion dispersion 30min, finally acetone is evaporated under reduced pressure away, organic silicon modified aqueous polyurethane emulsion is made.
Obtained emulsion appearance is creamy white, micro- blueing light.By desk centrifuge with 3000r/min centrifugations
15min, no precipitation, illustrate that emulsion can stablize storage more than 6 months.Glued membrane is in light yellow clear shape, relatively soft, tack-free,
Water absorption rate 11.5%.It is 36.0% to soak 24h swelling ratios in ethanol.
Embodiment 3
By the 16.05g IPDI after dehydration, 40.00g PPG2000,4.61g castor oil, 5.15g hydroxypropyls silicone oil is successively
Add and be equipped with the four-hole boiling flask of electric mixer, reflux condensing tube, 3 ~ 5 drop dibutyl tin laurates are added dropwise, it is anti-in 80 DEG C
2 ~ 3h is answered, obtains silicone-modified performed polymer.3.87g DMPA and 15g acetone is added into performed polymer, continues to react 3 at 80 DEG C
~ 4h, obtain the performed polymer with hydrophilic terminal isocyanate group.Then 50 DEG C are cooled to, 2.92gTEA is added and neutralizes into salt,
Stir 30min.Take 1.00g ethylenediamines to be dissolved in 171.75g deionized waters, be slowly added into the performed polymer of high speed shear
In, emulsion dispersion 30min, finally acetone is evaporated under reduced pressure away, organic silicon modified aqueous polyurethane emulsion is made.
Obtained emulsion appearance is creamy white, blueing light.By desk centrifuge with 3000r/min centrifugation 15min,
Without precipitation, illustrate that emulsion can stablize storage more than 6 months.Glued membrane is in light yellow clear shape, relatively soft, tack-free, water absorption rate
9.6%, it is 30.7% to soak 24h swelling ratios in ethanol.
Embodiment 4
By the 16.05g IPDI after dehydration, 40.00g PPG2000,4.61g castor oil, 6.77g hydroxypropyls silicone oil is successively
Add and be equipped with the four-hole boiling flask of electric mixer, reflux condensing tube, 3 ~ 5 drop dibutyl tin laurates are added dropwise, it is anti-in 80 DEG C
2 ~ 3h is answered, obtains silicone-modified performed polymer.3.87g DMPA and 15g acetone is added into performed polymer, continues to react 3 at 80 DEG C
~ 4h, obtain the performed polymer with hydrophilic terminal isocyanate group.Then 50 DEG C are cooled to, 2.92gTEA is added and neutralizes into salt,
Stir 30min.Take 1.00g ethylenediamines to be dissolved in 175.52g deionized waters, be slowly added into the performed polymer of high speed shear
In, emulsion dispersion 30min, finally acetone is evaporated under reduced pressure away, organic silicon modified aqueous polyurethane emulsion is made.
Obtained emulsion appearance is creamy white, blueing light.By desk centrifuge with 3000r/min centrifugation 15min,
Without precipitation, illustrate that emulsion can stablize storage more than 6 months.Glued membrane is in light yellow clear shape, relatively soft, tack-free, water absorption rate
7.9%, it is 25.3% to soak 24h swelling ratios in ethanol.
Embodiment 5
By the 16.05g IPDI after dehydration, 40.00g PPG2000,4.61g castor oil, 8.46g hydroxypropyls silicone oil is successively
Add and be equipped with the four-hole boiling flask of electric mixer, reflux condensing tube, 3 ~ 5 drop dibutyl tin laurates are added dropwise, it is anti-in 80 DEG C
2 ~ 3h is answered, obtains silicone-modified performed polymer.3.87g DMPA and 15g acetone is added into performed polymer, continues to react 3 at 80 DEG C
~ 4h, obtain the performed polymer with hydrophilic terminal isocyanate group.Then 50 DEG C are cooled to, 2.92gTEA is added and neutralizes into salt,
Stir 30min.Take 1.00g ethylenediamines to be dissolved in 179.47g deionized waters, be slowly added into the performed polymer of high speed shear
In, emulsion dispersion 30min, finally acetone is evaporated under reduced pressure away, organic silicon modified aqueous polyurethane emulsion is made.
Obtained emulsion appearance is creamy white, blueing light.By desk centrifuge with 3000r/min centrifugation 15min,
Without precipitation, illustrate that emulsion can stablize storage more than 6 months.Glued membrane is in light yellow clear shape, relatively soft, tack-free, water absorption rate
5.3%, it is 21.9% to soak 24h swelling ratios in ethanol.
Embodiment 6
By the 10.00g toluene di-isocyanate(TDI)s after dehydration, 30.00g PPG1500,1.00g castor oil, 1.00g hydroxyl first
Base silicone oil sequentially add equipped with electric mixer, reflux condensing tube four-hole boiling flask in, be added dropwise 3 ~ 5 drop stannous octoates, in 75 DEG C
2 ~ 3h is reacted, obtains silicone-modified performed polymer.1.00 dihydroxymethyl acetic acid and 5g butanone are added into performed polymer, is continued 75
DEG C reaction 3 ~ 4h, obtain the performed polymer with hydrophilic terminal isocyanate group.Then 40 DEG C are cooled to, adds the second of 1.00g tri-
Amine is neutralized into salt, stirs 30min.Take 1.50g hexamethylene diamines to be dissolved in 120.00g deionized waters, be slowly added into cutting at a high speed
In the performed polymer cut, emulsion dispersion 30min, finally acetone is evaporated under reduced pressure away, organic silicon modified aqueous polyurethane breast is made
Liquid.
Obtained emulsion appearance is creamy white, blueing light.By desk centrifuge with 3000r/min centrifugation 15min,
Without precipitation, illustrate that emulsion can stablize storage more than 6 months.Glued membrane is in light yellow clear shape, relatively soft, glues hand, water absorption rate
15.7%, it is 45.9% to soak 24h swelling ratios in ethanol.
It should be noted that PPG1500 refers to the polypropylene glycol that molecular weight is 1500.
Embodiment 7
By the 20.66g methyl diphenylene diisocyanates after dehydration, 45.00g polyethylene glycol, 6.12 g castor oil,
8.75g ends hydroxyl butyl dimethyl silicone polymer sequentially add equipped with electric mixer, reflux condensing tube four-hole boiling flask in, be added dropwise
3 ~ 5 drop dibutyl tin laurates, react 2 ~ 3h in 78 DEG C, obtain silicone-modified performed polymer.5.27 are added into performed polymer
G dimethylolpropionic acids and 12gN- methyl pyrrolidones, continue to react 3 ~ 4h at 78 DEG C, obtain that there is hydrophilic end isocyanic acid
The performed polymer of ester group.Then 45 DEG C are cooled to, 2.58gTEA is added and neutralizes into salt, stir 20min.Take 2.00g1,4- butanediols
It is dissolved in 200.00g deionized waters, is slowly added into the performed polymer of high speed shear, emulsion dispersion 30min, finally by third
Ketone is evaporated under reduced pressure away, and organic silicon modified aqueous polyurethane emulsion is made.
Obtained emulsion appearance is creamy white, blueing light.By desk centrifuge with 3000r/min centrifugation 15min,
Without precipitation, illustrate that emulsion can stablize storage more than 6 months.Glued membrane is in light yellow clear shape, relatively soft, tack-free, water absorption rate
8.7%, it is 27.2% to soak 24h swelling ratios in ethanol.
Embodiment 8
By the 30.00g hexamethylene diisocyanates after dehydration, 50.00g polytetrahydrofuran diols, 8.00g castor oil,
11.00g ends hydroxyl amyl group dimethyl silicone polymer sequentially add equipped with electric mixer, reflux condensing tube four-hole boiling flask in, drop
Add 3 ~ 5 drop stannous octoates, react 2 ~ 3h in 79 DEG C, obtain silicone-modified performed polymer.10.00 DMPA are added into performed polymer
And 25.00g acetone, continue to react 3 ~ 4h at 79 DEG C, obtain the performed polymer with hydrophilic terminal isocyanate group.Then cool
To 48 DEG C, add 5.00gTEA and neutralize into salt, stir 40min.3.00g ethylenediamines are taken to be dissolved in 250.00g deionized waters, slowly
It is added into the performed polymer of high speed shear, emulsion dispersion 30min, is finally evaporated under reduced pressure away acetone, organosilicon is made
Modified aqueous polyurethane emulsion.
Obtained emulsion appearance is creamy white, blueing light.By desk centrifuge with 3000r/min centrifugation 15min,
Without precipitation, illustrate that emulsion can stablize storage more than 6 months.Glued membrane is in light yellow clear shape, relatively soft, tack-free, water absorption rate
9.3%, it is 28.5% to soak 24h swelling ratios in ethanol.
To sum up, the present invention selects hydroxyl alkyl-terminated dimethyl silicone polymer as chain extender, and using the natural of polyfunctionality
Vegetable oil castor oil part introduces certain cross-linked structure in the molecular structure instead of polyalcohol, overcomes single group to a certain extent
Divide existing for aqueous polyurethane the shortcomings of water-fast, chemically-resistant, weatherability difference.Preparation technology of the present invention is simple, and the water-based of synthesis is gathered
Urethane finishing agent has preferable stability, water resistance, solvent resistance, cold resistance, surface characteristic and mechanical property.
Described above is the preferred embodiment of the present invention, it is noted that although the present invention only gives above example,
But many possible variants for needing not move through creative work and drawing also are provided, though it is still impossible to exhaust, in the art
Those of ordinary skill, with reference to common knowledge, should be able to associate more embodiments, such tool after this specification is readed over
The spirit of the not unconventional the claims in the present invention of body embodiment, any type of equivalent substitution or some improvements and modifications all should
It is considered as the embodiment being included by the present invention, belongs to protection scope of the present invention.
Claims (6)
1. a kind of organic silicon modified aqueous polyurethane leather finishing agent, it is characterised in that its primary raw material in parts by weight is matched somebody with somebody
Side is as follows：
The hydroxyl value of the castor oil is 79~185mgKOH/g；
The solid content of the leather finishing agent is 25~35%；
The molecular structural formula of the hydroxyl alkyl-terminated dimethyl silicone polymer is：
Wherein n=3, molecular weight are 2000~4000.
2. leather finishing agent as claimed in claim 1, it is characterised in that the PPG is polyethylene glycol, poly- tetrahydrochysene
One kind or combination in furans glycol, polypropylene glycol；
The isocyanates is toluene di-isocyanate(TDI), IPDI, methyl diphenylene diisocyanate, six Asias
One kind or combination in methyl diisocyanate；
The catalyst is stannous octoate, one kind in dibutyl tin laurate or combination；
The hydrophilic chain extender is dihydromethyl propionic acid, one kind in dimethylolpropionic acid or combination；
The organic solvent is 1-METHYLPYRROLIDONE, one kind or combination in DMF, acetone, butanone；
The salt forming agent is triethanolamine, one kind in triethylamine or combination；
The small molecule chain extender is hexamethylene diamine, ethylenediamine, propane diols or one kind in 1,4- butanediols or combination.
3. leather finishing agent as claimed in claim 2, it is characterised in that the PPG is polypropylene glycol, molecular weight
For 1000~2000；
The hydrophilic chain extender is dihydromethyl propionic acid；
The isocyanates is IPDI；
NCO and hydroxyl in polypropylene glycol, dihydromethyl propionic acid, castor oil in the IPDI
Mol ratio is 1.3~1.7:1.
A kind of 4. method for preparing the leather finishing agent as described in any one of claims 1 to 3, it is characterised in that including：
(1) isocyanates after dehydration sequentially added into the four-hole boiling flask equipped with agitator and reflux condensing tube by proportioning, gathered
Ethoxylated polyhydric alcohol, castor oil, hydroxyl alkyl-terminated dimethyl silicone polymer and catalyst, react 2~3h at 70~80 DEG C and obtain performed polymer；
(2) hydrophilic chain extender and organic solvent are added into performed polymer, continues to react 3~4h at 70~80 DEG C, is had
The performed polymer of hydrophilic terminal isocyanate group；
(3) add salt forming agent to neutralize, neutral temperature is 40~50 DEG C, stirs 20~40min；
(4) the performed polymer high speed shear that will be obtained after neutralization, the deionized water dissolved with small molecule chain extender, emulsification point are slowly added to
Dissipate 20~40min；
(5) organic silicon modified aqueous polyurethane leather finishing agent is made after removing organic solvent；
Wherein, the PPG, isocyanates, castor oil, hydroxyl alkyl-terminated dimethyl silicone polymer, catalyst, hydrophily
The formula of chain extender, organic solvent, salt forming agent, small molecule chain extender and deionized water in parts by weight is as follows：
The hydroxyl value of the castor oil is 79~185mgKOH/g；
The solid content of the leather finishing agent is 25~35%；
The molecular structural formula of the hydroxyl alkyl-terminated dimethyl silicone polymer is：
Wherein n=3,2000~4000.
5. preparation method as claimed in claim 4, it is characterised in that the PPG is polyethylene glycol, poly- tetrahydrochysene furan
One kind or the combination muttered in glycol, polypropylene glycol；
The isocyanates is toluene di-isocyanate(TDI), IPDI, methyl diphenylene diisocyanate, six Asias
One kind or combination in methyl diisocyanate；
The catalyst is stannous octoate, one kind in dibutyl tin laurate or combination；
The hydrophilic chain extender is dihydromethyl propionic acid, one kind in dimethylolpropionic acid or combination；
The organic solvent is 1-METHYLPYRROLIDONE, one kind or combination in DMF, acetone, butanone；
The salt forming agent is triethanolamine, one kind in triethylamine or combination；
The small molecule chain extender is hexamethylene diamine, ethylenediamine, propane diols or one kind in 1,4- butanediols or combination.
6. preparation method as claimed in claim 5, it is characterised in that
The PPG is polypropylene glycol, and molecular weight is 1000~2000；
The hydrophilic chain extender is dihydromethyl propionic acid；
The isocyanates is IPDI；
NCO and hydroxyl in polypropylene glycol, dihydromethyl propionic acid, castor oil in the IPDI
Mol ratio is 1.3~1.7:1.
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