CN105646816B - A kind of preparation method for holding viscous aqueous dispersions of polyurethanes - Google Patents
A kind of preparation method for holding viscous aqueous dispersions of polyurethanes Download PDFInfo
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- CN105646816B CN105646816B CN201610070903.6A CN201610070903A CN105646816B CN 105646816 B CN105646816 B CN 105646816B CN 201610070903 A CN201610070903 A CN 201610070903A CN 105646816 B CN105646816 B CN 105646816B
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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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
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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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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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
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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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Dispersion Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention discloses a kind of preparation method for holding viscous aqueous dispersions of polyurethanes, and described method includes following steps：(1) crust layer performed polymer synthesizes：By hyperbranched living polymer, it is obtained by the reaction with isocyanates, hydrophilic chain extender；(2) sticky core performed polymer synthesis：It is reacted and is made with the catalyst of isocyanates, hydrophilic chain extender by macromolecular polyol；(3) core, the grafting of shell performed polymer：By performed polymer hybrid reaction made from performed polymer made from (1) and (2)；(4) viscosity dispersion preparation is held：After deionized water is added in the performed polymer of graft poly-ether network made from (3), high speed dispersion emulsification, then according to needing that the further chain extending reaction of appropriate small molecule amine is added, finally product of the present invention.The product that the method is prepared in addition to outstanding tack, hold viscosity and peel strength and water-fast, resistance to alcohol performance other than, and cohesive force is strong, with after matrix stripping without residue glue.
Description
Technical field
The present invention relates to one kind holding viscous aqueous dispersions of polyurethanes and preparation method thereof, more particularly to a kind of suitable for paper
, the soft matrix such as cloth, plastics hold viscous aqueous dispersions of polyurethanes and preparation method thereof.
Background technology
Aqueous polyurethane is as a kind of emerging organic synthesis material, and comprehensive performance is superior, molecular structure designability is strong,
It has been more than other aqueous high scores in film forming, ageing-resistant, rub resistance, intensity etc. with the continuous promotion of technology of preparing
Sub- material is even more the advantage for having other aqueous high molecular materials incomparable in gas permeability, flexibility, feel etc., because
Application field is constantly expanded in recent years for this, is all gradually being taken in industries such as printing, automobile, electronics, weaving, leather, furniture, building materials
For solvent borne polyurethane material.
Water-borne polyurethane bond is compared with water soluble acrylic acid glue, and good with all kinds of pigment compatibilities, stripping performance is superior, in glued membrane
Poly- power is strong, is remained after being not easily stripped；But exist simultaneously that tack is insufficient, viscosity remains short, the shortcomings that poor water resistance.In order to improve
These are insufficient, and relevant research has appeared in the newspapers.Such as use Nano-meter SiO_22、TiO2Particle improves water resistance (CN103031103A)；Make
Peel strength and heat resistance (CN103820071A) are improved with compounding crosslinking agent；At the beginning of using the improvement such as fibrin, plant polyose
Viscosity holds viscosity, but peel strength is relatively low (CN104491922A).
Special soft/hard section the nucleocapsid of aqueous polyurethane makes its properties of product is abundant to change, but current technology tack,
Holding viscosity and peel strength cannot preferably coordinate, and soft segment fraction is excessive easily causes emulsifying stage microphase-separated tired
Difficulty, emulsion system is unstable or even is demulsified.It is an object of the invention to provide a kind of cohesive force strong and tack, to hold viscosity excellent
Aqueous polyurethane dispersion preparation method.
Invention content
The purpose of the present invention is to provide a kind of preparation method for holding viscous aqueous dispersions of polyurethanes, prepared by the method
Obtain hold after viscous aqueous dispersions of polyurethanes film forming in addition to should have outstanding tack, hold viscosity and peel strength with
Except water-fast, resistance to alcohol performance, and cohesive force is strong, with after matrix stripping without residue glue.
The present invention is achieved through the following technical solutions：
A kind of preparation method for holding viscous aqueous dispersions of polyurethanes, includes the following steps：
(1) crust layer performed polymer synthesizes：By hyperbranched living polymer, reacted with isocyanates, hydrophilic chain extender
It arrives；
(2) sticky core performed polymer synthesis：Catalyst by macromolecular polyol and isocyanates, hydrophilic chain extender is anti-
It should be made；
(3) core, the grafting of shell performed polymer：By performed polymer hybrid reaction made from performed polymer made from (1) and (2), two kinds pre-
Aggressiveness is grafted to obtain the performed polymer of graft poly-ether network；
(4) viscosity dispersion preparation is held：After deionized water is added in the performed polymer of graft poly-ether network made from (3), high speed
Dispersion and emulsion, rotating speed are more than 1500rpm, and then foundation needs that the further chain extending reaction of appropriate small molecule amine is added, and must finally hold
Viscous aqueous dispersions of polyurethanes.
In the preparation process (1) of the present invention for holding viscous aqueous elastic polyurethane dispersion, hyperbranched activity poly
Object (the Shanghai bio tech ltd Xi Bao) is closed, hyperbranched poly ester polyol is selected from, sees formula (I)~formula (III)；Disulphide
Dendritic (the Shanghai bio tech ltd Xi Bao), is shown in formula (IV)；Diammine dendritic [self-control, system
Preparation Method is shown in Chemical Journal of Chinese Universities, 33 (1)：176-181,2012], see formula (V), preferably disulphide dendritic
With diammine dendritic；Isocyanates is selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, to benzene two
Isocyanates, dimethyl diphenyl diisocyanate, preferably toluene di-isocyanate(TDI)；Hydrophilic chain extender is selected from dihydromethyl propionic acid
(DMPA), dimethylolpropionic acid, second diamino ethanesulfonic acid sodium (AAS salt), 1,4-butanediol -2- sodium sulfonates, polyethylene glycol
Arbitrary a kind or at least two kinds of of combination in monomethyl ether, preferably dihydromethyl propionic acid, dimethylolpropionic acid or second diamino second sulphur
Arbitrary a kind or at least two kinds of of the combination of sour sodium.
Preferably, the hyperbranched living polymer and isocyanates, hydrophilic chain extender reaction temperature are 20~40 DEG C,
Such as 20 DEG C, 26 DEG C, 31 DEG C, 37 DEG C, 40 DEG C etc., preferably 31-36 DEG C.
Preferably, the hyperbranched living polymer and isocyanates, hydrophilic chain extender reaction time are 1-2h, such as
1h, 1.2h, 1.5h, 1.7h, 1.9h, 2h etc., preferably 1.4-1.7h.
Preferably, described to hold in the preparation process (1) of viscous aqueous elastic polyurethane dispersion, hyperbranched living polymerization
Object reacts 20-30min in advance with isocyanates, then adds hydrophilic chain extender and is reacted.
Preferably, described to hold in the preparation process (1) of viscous aqueous elastic polyurethane dispersion, isocyanates accounts for over-expense
Change living polymerization amount of substance 100wt%~600wt%, such as 100wt%, 130wt%, 190wt%, 240wt%,
280wt%, 360wt%, 410wt%, 570wt%, 600wt% etc., preferably 300wt%~500wt%, further preferred 350
~450wt%.
Preferably, described to hold in the preparation process (1) of viscous aqueous elastic polyurethane dispersion, hydrophilic chain extender accounts for
The 5-18wt% of hyperbranched living polymerization amount of substance, for example, 5wt%, 5.3wt%, 5.8wt%, 6.7wt%, 7.3wt%,
8.5wt%, 10.6wt%, 12.4wt%, 13.5wt%, 14.3wt%, 15wt%, 16.8wt%, 18wt% etc., preferably 10-
16wt%, further preferred 13~15wt%.
In the preparation process (2) of the present invention for holding viscous aqueous elastic polyurethane dispersion, macromolecular polyol
Selected from polyether polyol, polyester polyol, polytetrahydrofuran ether, polycaprolactone, preferred, polyethers dihydric alcohol and polytetrahydrofuran ether
In arbitrary a kind or at least two kinds of of combination；Its weight average molecular weight be 2000~5000, such as 2000,2600,3500,4000,
4700,5000 etc., preferably 3000~4000.
In the preparation process (2) of the present invention for holding viscous aqueous elastic polyurethane dispersion, isocyanates is selected from
1,6- hexamethylene diisocyanate, isophorone diisocyanate, preferably isophorone diisocyanate；Hydrophilic chain extender
Selected from dihydromethyl propionic acid (DMPA), dimethylolpropionic acid, second diamino ethanesulfonic acid sodium (AAS salt), 1,4-butanediol -2- sulfonic acid
Arbitrary a kind or at least two kinds of of combination in sodium, polyethylene glycol monomethyl ether, preferably dihydromethyl propionic acid, dimethylolpropionic acid
Or arbitrary a kind or at least two kinds of of the combination of second diamino ethanesulfonic acid sodium；Catalyst is selected from stannous octoate or di lauric dibutyl
Tin.
Preferably, described big in the preparation process (2) of the present invention for holding viscous aqueous elastic polyurethane dispersion
Molecular polylol and isocyanates, hydrophilic chain extender reaction temperature are 60~110 DEG C, for example, 60 DEG C, 64 DEG C, 72 DEG C, 83 DEG C,
92 DEG C, 106 DEG C, 110 DEG C etc., preferably 65~75 DEG C.
Preferably, the macromolecular polyol and isocyanates, hydrophilic chain extender reaction time are 0.5-3h, such as
0.5h, 1.0h, 1.5h, 2.1h, 2.4h, 3h etc., preferably 0.7~1.2h.
Preferably, in the preparation process (2) of the present invention for holding viscous aqueous elastic polyurethane dispersion, macromolecular
Polyalcohol is with after isocyanates elder generation hybrid reaction 5-10min, and dropwise addition hydrophilic chain extender is in reaction system dropwise, rate of addition
It is the 0.3%~0.8% of macromolecular polyol per minute and isocyanates gross mass, preferably 0.5%~0.7%.
Preferably, in the preparation process (2) of the present invention for holding viscous aqueous elastic polyurethane dispersion, macromolecular
For polyalcohol with after isocyanates elder generation hybrid reaction 5-10min, addition catalyst, dosage is the 0.02% of macromolecular polyol quality
~0.03%, it is preferred that catalyst is added in hydrophilic chain extender after mixing and is added dropwise together.
Preferably, described to hold in the preparation process (2) of viscous aqueous elastic polyurethane dispersion, isocyanates accounts for big point
The 10-30wt% of sub- polyol quality, for example, 10wt%, 13wt%, 18wt%, 21wt%, 24wt%, 26wt%, 28wt%,
30wt% etc., preferably 16-22wt%.
Preferably, described to hold in the preparation process (2) of viscous aqueous elastic polyurethane dispersion, hydrophilic chain extender accounts for
The 1-6wt% of macromolecular polyol quality, for example, 1wt%, 1.3wt%, 2.2wt%, 2.7wt%, 3.3wt%, 3.9wt%,
4.6wt%, 4.9wt%, 5.3wt%, 5.6wt%, 6wt% etc., preferably 2~3wt%.
It, will be pre- made from (1) in the preparation process (3) of the present invention for holding viscous aqueous elastic polyurethane dispersion
Aggressiveness is stirred to react after being mixed with performed polymer made from (2), and reaction temperature is controlled at 70~90 DEG C, preferably 75~85 DEG C, reaction
1~3.5h of time, preferably 2~3h；Preferably, crust layer performed polymer dosage accounts for 5wt~20wt% of macromolecular polyol, more excellent
Select 8wt~12wt%.
In the preparation process (4) of the present invention for holding viscous aqueous elastic polyurethane dispersion, it is made by step (3)
Graft poly-ether network performed polymer be cooled to 0~10 DEG C after, disposably rapidly join deionized water and high speed shear dispersion and emulsion, turn
Speed is more than 1500rpm, and after emulsifying 0.5~1h, foundation needs that the further 0.5~1h of chain extending reaction of appropriate small molecule amine is added, most
It is made afterwards and holds viscous aqueous dispersions of polyurethanes.Small molecule amine is in ammonium hydroxide, ethylenediamine, hydrazine hydrate, isophorone diamine etc.
One or more combination.Small molecule amine use is slowly added dropwise mode and is added, until system NCO% contents are zero.Preferably, described
The additive amount of deionized water in order to control aqueous polyurethane emulsion emulsion solid content be 28wt%~32wt%, such as 28wt%,
29wt%, 30wt%, 31wt%, 32wt% etc..
Compared with prior art, the present invention has the advantages that：
(1) provided by the invention to hold viscous aqueous dispersions of polyurethanes as special sticky core/rigidity shell structure, similar spherical shape
The hyperbranched living polymer of structure contains a large amount of hydrophilic radicals, partially grafted with flexible macromolecular polyol and when being hydrated,
Shell is shifted and is distributed in due to microphase-separated, it, cannot be complete since rigid shell is less compared to flexible core part mass
Portion coats flexible core, and during water is removed in solidification, rigid crust can be squeezed and " rupture ", and the flexible chain of core part can migrate
Out and then form continuous phase.Since rigidity and flexible portion contain a large amount of polar groups, cohesive force is strong, peel strength
It is high.The hyperbranched living polymer part of rigidity plays the role of adjusting micmstructure of polymer, so that product obtained is had outstanding
Tack, hold viscosity and with water-fast, resistance to alcohol performance, and with after matrix stripping without residue glue.
(2) it is provided by the invention hold viscous aqueous dispersions of polyurethanes can not have to additional tackifier, only by component
Adjustment makes product have highly adherent, and adhesiveness is strong after film forming, is suitable for paper, fabric, plastics and other base；
(3) preparation process provided by the invention for holding sticky dispersions of polyurethanes is simple, easy to operate.
Specific implementation mode
A kind of preparation method that holding viscous aqueous dispersions of polyurethanes includes the following steps：
(1) hyperbranched living polymer and isocyanates and hydrophilic chain extender are added in three-necked flask, heating is stirred to react
Obtain crust layer performed polymer；
(2) macromolecular polyol and isocyanates, hydrophilic chain extender, catalyst are added in three-necked flask, in certain temperature
Under be stirred to react, viscosity core performed polymer is made；
(3) performed polymer hybrid reaction, two kinds of performed polymers made from performed polymer made from (1) and (2) are connect in three-necked flask
Branch obtains the performed polymer of graft poly-ether network；
(4) after the performed polymer of graft poly-ether network made from (3) being cooled to certain temperature in three-necked flask, rapidly join from
Sub- water carries out high speed shear dispersion and emulsion, and rotating speed is more than 1500rpm, then further according to needing appropriate small molecule amine is added
Chain extending reaction must finally hold viscous aqueous dispersions of polyurethanes.
For the present invention is better described, it is easy to understand technical scheme of the present invention, of the invention is typical but non-limiting
Embodiment is as follows：
Embodiment 1
A kind of preparation method that holding viscous aqueous elastic polyurethane dispersion includes the following steps：
(1) hyperbranched poly ester polyol is added in three-necked flask【Formula (I)】(the Shanghai bio tech ltd Xi Bao)
10g, after polyalcohol temperature is down to 10 DEG C in flask, being added with stirring methyl diphenylene diisocyanate, (Shanghai Hensel steps poly-
Urethane Co., Ltd) 10g and second diamino ethanesulfonic acid sodium ((goldschmidt chemical corporation)) 0.5g, by temperature of charge control at 20 DEG C
It is stirred to react 1h and obtains crust layer performed polymer；
(2) polyether Glycols (weight average molecular weight 2000, the big chemical industry in Shandong blue star east) 410g and 1 is added in three-necked flask,
6- hexamethylene diisocyanates (Shanghai Chun Xiao Bioisystech Co., Ltd) 41g, after 60 DEG C of reaction 5min are warming up under stirring
Stannous octoate (the sharp chemical company of Beijing benefit, C.P.) 0.082g is added, after stirring evenly, 5.47g dimethyl sulfoxide (DMSO)s will be dissolved in
The polyethylene glycol monomethyl ether (Beijing lark waffle technology company, C.P.) of (the sharp chemical company of Beijing benefit, C.P.)
4.1g is added dropwise in reaction system dropwise, and rate of addition is 1.353g (polyethylene glycol monomethyl ether)/min, after being added dropwise
The reaction was continued 0.5h, obtains sticky core performed polymer；
(3) it is stirred in 70 DEG C after mixing performed polymer made from step (1) with performed polymer made from step (2) in three-necked flask
Reaction 1h is mixed, the performed polymer of graft poly-ether network is obtained；
(4) after the performed polymer of the obtained graft poly-ether network of step (3) being cooled to 0~10 DEG C, deionization is disposably rapidly joined
Water (self-control) 1223g and high speed shear dispersion and emulsion, rotating speed 2000rpm, after emulsifying 0.5~1h, foundation needs that appropriate second is added dropwise
Diamines (the sharp chemical company of Beijing benefit, C.P.) is zero to system NCO% contents, and further 0.5~1h of chain extending reaction finally makes
Viscous aqueous dispersions of polyurethanes, emulsion solid content 28% must be held.
Embodiment 2
A kind of preparation method of Waterborne polyurethane elastic dispersion includes the following steps：
(1) hyperbranched poly ester polyol is added in three-necked flask【Formula (II)】(the Shanghai bio tech ltd Xi Bao)
10g is added with stirring paraphenylene diisocyanate (the limited public affairs of upper seamount Jilin Chemical work after polyalcohol temperature is down to 10 DEG C in flask
Department) 24g, be warming up to 26 DEG C reaction 25min after, then be added dimethylolpropionic acid (Shanghai Yan Yu bioengineering Co., Ltd)
1.8g the reaction was continued 47min, crust layer performed polymers；
(2) polyester diol (weight average molecular weight 3000, Qingdao New Yutian Chemical Co., Ltd.) is added in three-necked flask
238.6g and isophorone diisocyanate (Paasche support company) 71.6g is added after being warming up to 110 DEG C of reaction 10min under stirring
Dibutyl tin laurate (the sharp chemical company of Beijing benefit, C.P.) 0.0716g, after stirring evenly, will be dissolved in 4.7g dimethyl
Sulfoxide (the sharp chemical company of Beijing benefit, C.P.) polyethylene glycol monomethyl ether (Beijing lark waffle technology company,
C.P.) 14.3g is added dropwise in reaction system dropwise, and rate of addition is 1.551g (polyethylene glycol monomethyl ether)/min, is added dropwise
After the reaction was continued 1.0h, obtain sticky core performed polymer；
(3) it is stirred in 75 DEG C after mixing performed polymer made from step (1) with performed polymer made from step (2) in three-necked flask
Reaction 1.5h is mixed, the performed polymer of graft poly-ether network is obtained；
(4) after the performed polymer of the obtained graft poly-ether network of step (3) being cooled to 0~10 DEG C, deionization is disposably rapidly joined
Water (self-control) 882.2g and high speed shear dispersion and emulsion, rotating speed 2500rpm, after emulsifying 0.5~1h, foundation needs that suitable quantity of water is added dropwise
It is zero that hydrazine (the sharp chemical company of Beijing benefit, C.P.), which is closed, to system NCO% contents, and further 0.5~1h of chain extending reaction finally makes
Viscous aqueous dispersions of polyurethanes, emulsion solid content 29% must be held.
Embodiment 3
A kind of preparation method of Waterborne polyurethane elastic dispersion includes the following steps：
(1) hyperbranched poly ester polyol is added in three-necked flask【Formula (III)】(the Shanghai bio tech ltd Xi Bao)
10g is added with stirring dimethyl diphenyl diisocyanate (upper seamount Jilin Chemical work after polyalcohol temperature is down to 10 DEG C in flask
Co., Ltd) 36g, after being warming up to 36 DEG C of reaction 30min, dihydromethyl propionic acid (Paasche support company) 0.67g is then added and continues
React 1.0h, crust layer performed polymer；
(2) polycaprolactone diols (weight average molecular weight 4000, upper seamount Jilin Chemical work Co., Ltd) is added in three-necked flask
233.4g and 1,6- hexamethylene diisocyanate (Shanghai Chun Xiao Bioisystech Co., Ltd) 60.7g, 83 are warming up under stirring
After DEG C reaction 8min, by dibutyl tin laurate (the sharp chemical company of Beijing benefit, C.P.) 0.0467g, second diamino second sulphur
Sour sodium (goldschmidt chemical corporation) 11.6g be added dropwise dropwise after being dissolved in 4g dimethyl sulfoxide (DMSO)s (the sharp chemical company of Beijing benefit, C.P.) in
In reaction system, rate of addition is 2.353g (second diamino ethanesulfonic acid sodium)/min, and the reaction was continued 3.0h after being added dropwise is obtained viscous
Property core performed polymer；
(3) it is stirred in 80 DEG C after mixing performed polymer made from step (1) with performed polymer made from step (2) in three-necked flask
Reaction 2.0h is mixed, the performed polymer of graft poly-ether network is obtained；
(4) after the performed polymer of the obtained graft poly-ether network of step (3) being cooled to 0~10 DEG C, deionization is disposably rapidly joined
Water (self-control) 822.2g and high speed shear dispersion and emulsion, rotating speed 3000rpm are appropriate different according to needing to be added dropwise after emulsifying 0.5~1h
Isophoronediamine (the sharp chemical company of Beijing benefit, C.P.) to system NCO% contents are zero, further 0.5~1h of chain extending reaction,
It is finally made and holds viscous aqueous dispersions of polyurethanes, emulsion solid content 30%.
Embodiment 4
A kind of preparation method of Waterborne polyurethane elastic dispersion, includes the following steps：
(1) hyperbranched poly ester polyol is added in three-necked flask【Formula (III)】(the Shanghai bio tech ltd Xi Bao)
10g is added with stirring toluene di-isocyanate(TDI) (the limited public affairs of upper seamount Jilin Chemical work after polyalcohol temperature is down to 10 DEG C in flask
Department) 41g, be warming up to 33 DEG C reaction 23min after, then be added dimethylolpropionic acid (Shanghai Yan Yu bioengineering Co., Ltd)
0.24g, polyethylene glycol monomethyl ether (Beijing lark waffle technology company, C.P.) 1.0g the reaction was continued 79min, crust layer
Performed polymer；
(2) polytetrahydrofuran ether (weight average molecular weight 5000, upper seamount Jilin Chemical work Co., Ltd) is added in three-necked flask
653g and 1,6- hexamethylene diisocyanate (Shanghai Chun Xiao Bioisystech Co., Ltd) 130.6g, is warming up to 65 DEG C under stirring
After reacting 6min, by stannous octoate (the sharp chemical company of Beijing benefit, C.P.) 0.1306g, polyethylene glycol monomethyl ether (Beijing
Lark waffle technology company, C.P.) to be dissolved in 10g dimethyl sub- by 16.1g, second diamino ethanesulfonic acid sodium (goldschmidt chemical corporation) 10g
It is added dropwise in reaction system dropwise after in sulfone (the sharp chemical company of Beijing benefit, C.P.), is added dropwise in reaction system, is added dropwise dropwise
Speed is 5.485g (polyethylene glycol monomethyl ether+second diamino ethanesulfonic acid sodium)/min, the reaction was continued 1.5h after being added dropwise,
Obtain sticky core performed polymer；
(3) it is stirred in 90 DEG C after mixing performed polymer made from step (1) with performed polymer made from step (2) in three-necked flask
Reaction 3.0h is mixed, the performed polymer of graft poly-ether network is obtained；
(4) after the performed polymer of the obtained graft poly-ether network of step (3) being cooled to 0~10 DEG C, deionization is disposably rapidly joined
Water (self-control) 1918.6g and high speed shear dispersion and emulsion, rotating speed 4500rpm are appropriate according to needing to be added dropwise after emulsifying 0.5~1h
Ethylenediamine (the sharp chemical company of Beijing benefit, C.P.) to system NCO% contents are zero, further 0.5~1h of chain extending reaction, finally
It is made and holds viscous aqueous dispersions of polyurethanes, emulsion solid content 31%.
Embodiment 5
A kind of preparation method of Waterborne polyurethane elastic dispersion, includes the following steps：
(1) disulphide dendritic is added in three-necked flask【Formula (IV】(the limited public affairs of the precious biotechnology in Shanghai west
Department) 10g is added with stirring methyl diphenylene diisocyanate (upper seamount Jilin Chemical after polyalcohol temperature is down to 10 DEG C in flask
Work Co., Ltd) 50g, be warming up to 37 DEG C reaction 28min after, then be added second diamino ethanesulfonic acid sodium (goldschmidt chemical corporation) 1.3g
The reaction was continued 86min, crust layer performed polymer；
(2) polyether Glycols (weight average molecular weight 4000, upper seamount Jilin Chemical work Co., Ltd) 518g is added in three-necked flask
With isophorone diisocyanate (Paasche support company) 93.2g, be warming up under stirring 72 DEG C reaction 10min after, by tin dilaurate
Dibutyl tin (the sharp chemical company of Beijing benefit, C.P.) 0.1554g, dimethylolpropionic acid (grind the limited public affairs of domain bioengineering in Shanghai
Department) 2.0g, second diamino ethanesulfonic acid sodium (goldschmidt chemical corporation) 13.5g be dissolved in 6g dimethyl sulfoxide (DMSO)s (the sharp chemical company of Beijing benefit,
C.P. it is added dropwise in reaction system dropwise after in), rate of addition is 4.278g (dimethylolpropionic acids+second diamino ethanesulfonic acid
Sodium)/min, the reaction was continued 2.1h after being added dropwise obtains sticky core performed polymer；
(3) it is stirred in 85 DEG C after mixing performed polymer made from step (1) with performed polymer made from step (2) in three-necked flask
Reaction 2.8h is mixed, the performed polymer of graft poly-ether network is obtained；
(4) after the performed polymer of the obtained graft poly-ether network of step (3) being cooled to 0~10 DEG C, deionization is disposably rapidly joined
Water (self-control) 1462g and high speed shear dispersion and emulsion, rotating speed 6000rpm, after emulsifying 0.5~1h, foundation needs that suitable quantity of water is added dropwise
It is zero that hydrazine (the sharp chemical company of Beijing benefit), which is closed, to system NCO% contents, and further 0.5~1h of chain extending reaction is finally made and holds
Viscous aqueous dispersions of polyurethanes, emulsion solid content 32%.
Embodiment 6
A kind of preparation method of Waterborne polyurethane elastic dispersion includes the following steps：
(1) diammine dendritic is added in three-necked flask【See formula (V)】[self-control, preparation method are shown in high
School chemistry journal, 33 (1)：176-181,2012] 10g is added with stirring toluene after polyalcohol temperature is down to 10 DEG C in flask
Then dihydroxymethyl third is added after being warming up to 40 DEG C of reaction 30min in diisocyanate (upper seamount Jilin Chemical work Co., Ltd) 60g
Acid (Paasche support company) 1.5g the reaction was continued 1.5h, crust layer performed polymers；
(2) polytetrahydrofuran ether (weight average molecular weight 3000, upper seamount Jilin Chemical work Co., Ltd) is added in three-necked flask
715g and isophorone diisocyanate (Paasche support company) 150.1g, after 75 DEG C of reaction 6min are warming up under stirring, by February
Dilaurylate (the sharp chemical company of Beijing benefit, C.P.) 0.143g, 1,4-butanediol -2- sodium sulfonates 14.3g is dissolved in 4g bis-
It is added dropwise in reaction system, is added dropwise dropwise in reaction system dropwise after in methyl sulfoxide (the sharp chemical company of Beijing benefit, C.P.)
In, rate of addition is 4.326g (1,4-butanediol -2- sodium sulfonates)/min, and the reaction was continued 1.2h after being added dropwise obtains sticky core
Performed polymer；
(3) it is stirred in 80 DEG C after mixing performed polymer made from step (1) with performed polymer made from step (2) in three-necked flask
Reaction 2.6h is mixed, the performed polymer of graft poly-ether network is obtained；
(4) after the performed polymer of the obtained graft poly-ether network of step (3) being cooled to 0~10 DEG C, deionization is disposably rapidly joined
Water (self-control) 2218.8g and high speed shear dispersion and emulsion, rotating speed 5000rpm are appropriate according to needing to be added dropwise after emulsifying 0.5~1h
Ammonium hydroxide (the sharp chemical company of Beijing benefit) is zero to system NCO% contents, and further 0.5~1h of chain extending reaction is finally made and holds
Viscous aqueous dispersions of polyurethanes, emulsion solid content 30%.
Comparative example
A kind of Waterborne polyurethane elastic dispersion, raw material composition are as shown in table 1：
Table 1, elastic polyurethane dispersion formula
The preparation method of the Waterborne polyurethane elastic dispersion is the known technology of fields, fields technology people
Member can select as needed, will not be had an impact to the Waterborne polyurethane elastic dispersion performance of preparation, details are not described herein.
Performance test：Embodiment 1-6 and the comparative example Waterborne polyurethane elastic dispersion provided are spread evenly across through electricity
On the polyethylene film of dizzy processing, coating weight 8g/m2, after 80 DEG C are dried 3min, carry out following performance test：
Tack：It is tested using inclined-plane rolling ball method according to GB/4852-84 standards；
Hold viscosity：According to GB/T4851-1988 standard testings；
180 ° of peel strengths：It is tested according to GB/T2792-1998；
Water resistance, resistance to ethyl alcohol (95%) property：It tests and uses infusion method, observation sample turned white, hair for 25 DEG C~28 DEG C in room temperature
It glues and records the time；
Residue glue degree after stripping：Polyethylene film after gluing is uniformly coated on 100mm*150mm stainless steel plates, above
80 DEG C of baking ovens are put into after placing the 1Kg weights that volume is 100mm*100mm*100mm, weight is removed in recession for 24 hours, is removed from steel plate
Polyethylene film simultaneously observes residue glue situation；
Stability：The test aqueous polyurethane emulsion number of days that boiling is agglomerated to layering at 70 DEG C obtained.
The performance test results are as shown in table 2：
The performance test results of 2 embodiment 1-6 of table
As can be seen from Table 2, it is provided by the invention it is aqueous hold that sticky dispersions of polyurethanes is highly stable, have it is outstanding just
Viscosity, hold sticky and water-fast, resistance to alcohol performance, with after steel sheet peeling off without residue glue.
(2) it is provided by the invention hold viscous aqueous dispersions of polyurethanes can not have to additional tackifier, only by component
Adjustment makes product have highly adherent, and adhesiveness is strong after film forming, is suitable for paper, fabric, plastics and other base；
It should be noted that and understanding, the feelings of the spirit and scope of the present invention required by not departing from appended claims
Under condition, various modifications and improvements can be made to the present invention of foregoing detailed description.It is therefore desirable to the model of the technical solution of protection
It encloses and is not limited by given any specific exemplary teachings.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (10)
1. a kind of preparation method for holding viscous aqueous dispersions of polyurethanes, which is characterized in that described method includes following steps：
（1）Crust layer performed polymer synthesizes：By hyperbranched living polymer, it is obtained by the reaction with isocyanates, hydrophilic chain extender, this step
Hyperbranched living polymer described in rapid is selected from formula（I）~ formula（III）Hyperbranched poly ester polyol, formula（IV）Disulphide
Dendritic and formula（V）Diammine dendritic, isocyanates described in this step be selected from toluene diisocyanate
Acid esters, methyl diphenylene diisocyanate, paraphenylene diisocyanate and dimethyl diphenyl diisocyanate, it is close described in this step
Water chain extender is in dihydromethyl propionic acid, dimethylolpropionic acid, second diamino ethanesulfonic acid sodium, 1,4- butanediol -2- sodium sulfonates
Arbitrary a kind or at least two kinds of of combination；
Formula（I）
Formula（II）
Formula（III）
Formula（IV）
Formula（V）；
（2）Sticky core performed polymer synthesis：It is made by macromolecular polyol and isocyanates, hydrophilic chain extender, catalyst reaction,
Middle macromolecular polyol is selected from polyether polyol, polyester polyol, and weight average molecular weight is 2000 ~ 5000, described in this step
Isocyanates is selected from 1,6- hexamethylene diisocyanates and isophorone diisocyanate, hydrophilic chain extender described in this step
Arbitrary a kind in dihydromethyl propionic acid, dimethylolpropionic acid, second diamino ethanesulfonic acid sodium, 1,4- butanediol -2- sodium sulfonates
Or at least two kinds of combinations, the catalyst are selected from stannous octoate or dibutyl tin laurate；
（3）Core, the grafting of shell performed polymer：It will（1）Performed polymer obtained with（2）Performed polymer hybrid reaction obtained, two kinds of performed polymers
Grafting obtains the performed polymer of graft poly-ether network, and wherein crust layer performed polymer dosage accounts for 5wt ~ 20wt% of macromolecular polyol；
（4）Hold viscosity dispersion preparation：（3）After deionized water is added in the performed polymer of graft poly-ether network obtained, high speed dispersion
Emulsification, rotating speed are more than 1500rpm, and then foundation needs that the further chain extending reaction of appropriate small molecule amine is added, and must finally hold viscosity
Aqueous polyurethane dispersion, wherein small molecule amine are selected from one or more of ethylenediamine, hydrazine hydrate, isophorone diamine group
It closes.
2. the preparation method of claim 1, which is characterized in that in preparation process（1）In, the hyperbranched living polymer with it is different
Cyanate, hydrophilic chain extender reaction temperature are 20 ~ 40 DEG C, reaction time 1-2h；The isocyanates accounts for hyperbranched activity poly
100wt% ~ 600wt% of amount of substance is closed, hydrophilic chain extender accounts for the 5-18wt% of hyperbranched living polymerization amount of substance.
3. the preparation method of claim 1, which is characterized in that in preparation process（1）In, hyperbranched living polymer and isocyanic acid
Ester reacts 20-30 min in advance, then adds hydrophilic chain extender and is reacted.
4. the preparation method of claim 1, which is characterized in that in preparation process（2）In, the macromolecular polyol and isocyanic acid
Ester, hydrophilic chain extender reaction temperature are 60 ~ 110 DEG C, and the reaction time is 0.5-3 h.
5. the preparation method of claim 1, which is characterized in that in preparation process（2）In, macromolecular polyol is first with isocyanates
After hybrid reaction 5-10 min, hydrophilic chain extender is added dropwise dropwise in reaction system, rate of addition is that macromolecular per minute is polynary
Alcohol and the 0.3% ~ 0.8% of isocyanates gross mass.
6. the preparation method of claim 1, which is characterized in that in preparation process（2）In, macromolecular polyol and isocyanates
After first hybrid reaction 5-10 min, catalyst is added, dosage is the 0.02% ~ 0.03% of macromolecular polyol quality.
7. the preparation method of claim 1, which is characterized in that in preparation process（2）In, isocyanates accounts for macromolecular polyol matter
The 10-30wt% of amount, hydrophilic chain extender account for the 1-6wt% of macromolecular polyol quality.
8. the preparation method of claim 1, which is characterized in that in preparation process（3）In, it will（1）Performed polymer obtained with（2）
It is stirred to react after performed polymer obtained mixing, reaction temperature control is at 70 ~ 90 DEG C, 1 ~ 3.5 h of reaction time.
9. the preparation method of claim 1, which is characterized in that in preparation process（4）In, by step（3）Graft poly-ether network obtained
Performed polymer be cooled to 0 ~ 10 DEG C after, disposably rapidly join deionized water and high speed shear dispersion and emulsion, rotating speed is more than
1500rpm, after emulsifying 0.5 ~ 1 h, foundation needs that further 0.5 ~ 1 h of chain extending reaction of appropriate small molecule amine is added, and is finally made
Hold viscous aqueous dispersions of polyurethanes.
10. the preparation method of claim 1, which is characterized in that in preparation process（4）In, small molecule amine uses the side of being slowly added dropwise
Formula is added, until system NCO% contents are zero；The lotion of the additive amount of deionized water aqueous polyurethane emulsion in order to control contains admittedly
Amount is 28wt% ~ 32wt%.
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