CN110452351A - A kind of aqueous polyurethane emulsion, preparation method and dipped gloves - Google Patents
A kind of aqueous polyurethane emulsion, preparation method and dipped gloves Download PDFInfo
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- CN110452351A CN110452351A CN201910780843.0A CN201910780843A CN110452351A CN 110452351 A CN110452351 A CN 110452351A CN 201910780843 A CN201910780843 A CN 201910780843A CN 110452351 A CN110452351 A CN 110452351A
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- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D19/00—Gloves
- A41D19/0055—Plastic or rubber gloves
- A41D19/0058—Three-dimensional gloves
- A41D19/0062—Three-dimensional gloves made of one layer of material
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
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- Textile Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Gloves (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of aqueous polyurethane emulsions, when preparing the aqueous polyurethane emulsion, the modification silicon nano that its raw material contains organosilicon polyalcohol and can react with hydrophilic radical in polyurethane molecular chain makes aqueous polyurethane strand be introduced into response type organosilicon and modified silicon nano.Preparation method are as follows: the use of isocyanates and polyalcohol is raw material, reaction obtains base polyurethane prepolymer for use as under catalyst, chain extender existence condition when preparing base polyurethane prepolymer for use as；Contain at least one organosilicon polyalcohol in the polyalcohol；When preparing aqueous polyurethane emulsion, the base polyurethane prepolymer for use as and the aqueous solution containing modified silicon nano are subjected to mixing and emulsifying, obtain aqueous polyurethane emulsion.Compared to existing in such a way that physical mixed addition filler is modified to waterborne polyurethane resin, the present invention can improve water-fast/solvent resistance, low-temperature flexibility, the wearability of waterborne polyurethane resin, and the holding timeliness of excellent properties is longer.
Description
Technical field
The invention belongs to macromolecule polyurethane lotion preparation technical field, more particularly to having both high abrasion, matter after solidification
Soft, hydrolysis aqueous polyurethane emulsion and preparation method thereof, and the dipped gloves prepared using the polyaminoester emulsion.
Background technique
Polyurethane dipped gloves are to be covered on resolidification outside knitting or cotton gloves embryo with Polyurethane resin slurry to obtain,
The main component of Polyurethane resin slurry is polyurethane resin.The Polyurethane resin slurry for being currently used for production dipped gloves is main
There are two types of system, respectively DMF (n,N-Dimethylformamide) solvent type polyurethane resin slurry and lotion type polyurethane resins
Slurry.Solvent type polyurethane resin slurry is unavoidably used in production and use process and can largely be generated to human liver
The organic solvent DMF seriously damaged, and a large amount of using for DMF has final gloves finished product still largely
DMF residual all generates very big harm to user and ecological environment, gloves (such as drug is raw using also restrained
It produces).Further, since a large amount of DMF residual, gloves need to be washed by multistage, very big to water resource waste.Therefore, using water as
The aqueous polyurethane dipped gloves of decentralized medium gradually replace the oiliness polyurethane dipped gloves using organic solvent as decentralized medium,
Aqueous polyurethane because itself matter is hard, poor water resistance, it is not wear-resisting the problems such as, hinder preparation and the hair of aqueous polyurethane dipped gloves
Exhibition.
In the prior art, for solve aqueous polyurethane dipped gloves matter hard, poor water resistance, it is not wear-resisting the problems such as, usually exist
In aqueous polyurethane coating dipped gloves preparation process, when modulating coating paste in aqueous polyurethane introducing crosslinked structure or
Person's addition carbonaceous inorganic elements (graphene, carbon nanotube, carbon black etc.), inorganic clay or ore (kaolin, montmorillonite etc.) etc.
Waterborne polyurethane resin is modified, or NBR latex is added and is blended with aqueous polyurethane, frequently with leaching slurry, soaking paste in technique
Mode coats repeatedly, as CN 108977027 A, CN 102113717 A and 105885664 A of CN Chinese invention patent Shen
Coupling agent or NBR latex are please added in aqueous polyurethane emulsion.Though these aqueous polyurethane dipped gloves technologies of preparing
It can be improved the wearability of aqueous polyurethane, but also glove coating caused to become while improving aqueous polyurethane wearability
Firmly, wear comfort is not good enough, and the nanoparticle stability of simple physical blending addition is poor, timeliness is short, is easy to be precipitated, seriously
Affect aqueous polyurethane coating gloves product quality and service life.
In addition, introducing hydrophilic radical in waterborne polyurethane resin preparation process, in strand (usually by hydrophily cream
Agent introduces, and such as dihydroxymethyl alkyl acid, specifically includes dimethylolpropionic acid, dihydromethyl propionic acid etc.), these hydrophilic radicals make
Aqueous polyurethane glue-line is easy to happen hydrolysis (ester linkage hydrolyzing), lead to the water resistances of aqueous polyurethane dipped gloves, resistance to wearing
Property be deteriorated.
In summary problem it is to be understood that existing aqueous polyurethane dipped gloves there are wearability, water resistance, matter is soft is difficult
It combines (physical mixed nano inoganic particle causes matter hard, does not mix and causes to wear no resistance), and its water resistance and resistance to
The property worn is all poor, seriously hinders the innovation and development and popularization and application of aqueous polyurethane dipped gloves.Therefore, a kind of environmental protection is developed
And it can get excellent abrasive resistance, the lotion of soft, hydrolysis the polyurethane resin product of matter and preparation method and be of great significance.
Summary of the invention
(1) technical problems to be solved
In order to solve the above problem of the prior art, the present invention provides a kind of aqueous polyurethane emulsion and preparation method thereof,
And the dipped gloves prepared using the aqueous polyurethane emulsion.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
On the one hand, the application provides a kind of aqueous polyurethane emulsion, when preparing the aqueous polyurethane emulsion, raw material
The modification silicon nano that contains organosilicon polyalcohol and can react with hydrophilic radical in polyurethane molecular chain makes aqueous poly-
Urethane strand is introduced into response type organosilicon and modified silicon nano.
The application provides a kind of preparation method of aqueous polyurethane emulsion, it includes:
It the use of isocyanates and polyalcohol is raw material, in catalyst, chain extender, there are items when preparing base polyurethane prepolymer for use as
Reaction obtains base polyurethane prepolymer for use as under part；Contain at least one organosilicon polyalcohol in the polyalcohol；
When preparing aqueous polyurethane emulsion, by the base polyurethane prepolymer for use as and the aqueous solution containing modified silicon nano
Mixing and emulsifying is carried out, aqueous polyurethane emulsion is obtained；Wherein, the modified silicon nano be can in polyurethane molecular chain
Hydrophilic radical chemically reacts and bonded modification silicon nano.
It is thereby achieved that introduce response type organosilicon and modified silicon nano simultaneously on aqueous polyurethane strand, one
Aspect, while can also be to polyurethane point to the wearability and flexibility that glue-line after aqueous polyurethane sizing material baking and curing can be improved
The hydrophilic radical that hydrolysis may be caused in subchain carries out reducing hydrophilic processing.
Organosilicon polyalcohol refers to the organic matter containing multiple hydroxyls and siloxanes functional structure；Wherein, the organosilicon
Polyalcohol is selected from hydroxyl endblocked polydimethylsiloxane, alkane hydroxyl endblocked polydimethylsiloxane and polyether hydroxyl and blocks poly- diformazan
One or more of radical siloxane.
As a preferred embodiment of the present invention, wherein the polyalcohol is by not siliceous polyalcohol and organosilicon polyalcohol
Composition；Wherein the silicon polyalcohol that is free of includes one or more of following polyalcohol of molecular weight 300~3000: poly- tetrahydro
Furans ethoxylated polyhydric alcohol, polyethylene glycol, polyethylene glycol adipate polyalcohol, polypropylene glycol adipate polyalcohol, polyadipate
Butanediol ester polyalcohol, polyneopentyl glycol adipate polyalcohol, polycaprolactone polyol, sulfonate type polyester polyol, sulphur
The pure and mild carboxylate polyether polyol of hydrochlorate type polyether polyol, carboxylate polyester polyols.
As a preferred embodiment of the present invention, wherein in the polyalcohol, the ratio of the not siliceous polyalcohol is 1
~90wt%, surplus are organosilicon polyalcohol.
As a preferred embodiment of the present invention, wherein the modified silicon nano is that silica solution, amino modified silicon are molten
Glue, epoxy-modified silica solution, fumed silica, amino modified fumed silica, epoxy-modified fumed silica,
Silica lotion, amino modified silica lotion, epoxy-modified silica lotion, aqueous emulsion of dimethyl polysiloxane fluid,
One or more of amino-terminated aqueous emulsion of dimethyl polysiloxane fluid and epoxy radicals end-blocking aqueous emulsion of dimethyl polysiloxane fluid.
When the above-mentioned modified silicon nano selected is lotion, solid content is the solid content of general commercial product, generally
Between about 30-45wt%.
As a preferred embodiment of the present invention, the method preparation method includes the following steps:
S1: base polyurethane prepolymer for use as is prepared: by 6-70 mass parts without water-polyol, 5-15 mass parts isocyanates and 0.1-
5 mass parts of catalyst are added in container, are stirred evenly, and 1-3h is reacted at a temperature of 40-80 DEG C, add 0.5-10 mass
In 40-80 DEG C of the reaction was continued 1-3h 5-30 mass parts acetone viscosity reduction is then added, and be added in 0.2-2 mass parts in part chain extender
It is neutralized with agent, in the content constant of 40-80 DEG C of the reaction was continued 1-3h to isocyanate group-NCO, it is pre- that cooling obtains polyurethane
Aggressiveness；
S2: it prepares ester-polyurethane resin emulsion: the obtained base polyurethane prepolymer for use as of step S1 is added to containing 0.5-10 mass
It is emulsified in the aqueous solution of part chain extender and the modification silicon nano of 0.1-10 mass parts, obtains aqueous polyurethane emulsion.
By aqueous polyurethane emulsion obtained by the above method, the solid content of waterborne polyurethane resin therein is 20-70%,
Average diameter is 50-500nm, and zeta current potential is -30mV~-65mV.Atypically, the mass parts without water-polyol in step S1
Number is 6 parts~15 parts, 15-20 parts, 20-25 parts, 25-50 parts, 30-35 parts, 35-40 parts, 40-45 parts, 45-50 parts, 50-55
Part, 55-60 parts, 60-65 parts or 65-70 parts.Atypically, in step S1, the mass fraction of isocyanates is 5~8 parts, 8-10
Part, 10-12 parts, 12-15 parts.Wherein, the mass fraction of catalyst is 0.1~1 part, 1~2 part, 2~3 parts, 3-4 parts or 4-5
Part.Atypically, in step S1, reaction temperature is 40-45 DEG C, 45-50 DEG C, 50-55 DEG C, 55-60 DEG C, 60-65 DEG C, 65-70
DEG C, 70-75 DEG C or 75-80 DEG C.Atypically, the mass fraction of chain extender be 0.5~2 part, 2-4 parts, 4-6 parts, 6-8 parts or
8-10 parts；The mass fraction of neutralizer is 0.2~0.5 part, 0.5-1 parts, 1-1.5 parts or 1.5-2 parts.
In above-mentioned preparation method, acetone primarily serves dilution herein reduces the effect of viscosity, and dosage can be according to isocyanide
The amount of acid esters reaction product determines, preferably 5-10 parts, 10-20 parts, 20-30 parts, 3-40 parts or 40-50 parts.
As a preferred embodiment of the present invention, wherein in step S1, the isocyanates be toluene di-isocyanate(TDI),
Methyl diphenylene diisocyanate, carbodiimide modified methyl diphenylene diisocyanate, polyether-modified diphenyl methane two are different
Oneself is two different by cyanate, liquefaction methyl diphenylene diisocyanate, isophorone diisocyanate, 1,5 naphthalene diisocyanates, 1,6-
One or more of cyanate, dicyclohexyl methyl hydride diisocyanate and Methylcyclohexyl diisocyanate.
As a preferred embodiment of the present invention, in step S1, the catalyst is triethylenediamine, bis- (dimethyl
Amino-ethyl) in ether, N-ethylmorpholine, stannous octoate, dibutyl tin dilaurate, dibutyltin diacetate and organo-bismuth one
Kind is several.
As a preferred embodiment of the present invention, in step S1, the neutralizer be triethylamine, ethanol amine, sodium hydroxide,
One or more of potassium hydroxide and ammonium hydroxide.Neutralizer is used to neutralize carboxylic acid group in isocyanates, control isocyanates with
The degree that polyalcohol polyaddition reaction carries out.
As a preferred embodiment of the present invention, in step S1-S2, the chain extender is ethylenediamine, ethylene glycol, Isosorbide-5-Nitrae-fourth
Glycol, 1,6-HD, 1,4- cyclohexanediol, hexamethylene diamine, ethylenediamine base ethanesulfonic acid sodium, ethylenediamine base ethanesulfonic acid, trihydroxy methyl
One in propane, melamine, triethanolamine, dihydromethyl propionic acid, dimethylolpropionic acid, ethylene glycol amine and dimethylolpropionic acid
Kind is several.
The application also provides a kind of aqueous polyurethane emulsion, is prepared using any one of the above method.
The another further aspect of the application provides a kind of polyurethane dipped gloves, includes gloves embryo, the gloves embryo surface leaching
Sizing material and baking and curing made of stain or the coating aqueous polyurethane emulsion described in any of the above-described embodiment.
Specifically, the preparation step of the polyurethane dipped gloves includes:
Step 1: impregnation, 100 mass parts aqueous polyurethane emulsions prepared by any of the above-described embodiment, while stirring plus
Enter 0.5~5 mass parts antitack agent, 0.5~5 mass parts titanium dioxide stirs evenly addition dyestuff, and thickener is added, is adjusted to viscosity
The sizing material of 1000~4000mPaS；
Step 2: gloves embryo is put into baking oven and is dried to 40 DEG C -50 DEG C, impregnates coagulator for the first time, taking-up is dried in the air by dip forming
To 30 seconds, impregnate the aqueous polyurethane sizing material modulated, second soaks coagulator, and taking-up is dried in the air to 30-90min, drying to get
To aqueous polyurethane dipped gloves.
In above-mentioned preparation step, coagulator can be molten for the calcium chloride of low concentration, the aqueous solution of magnesium chloride or zinc chloride or alcohol
Liquid, such as the calcium chloride ethanol solution of mass fraction 2-8wt%.
In above-mentioned preparation step, the thickener includes PVA aqueous solution, polystyrene solution, silicone rubber solution, emulsification silicon
The one or more of oil, stearic acid solution, paraffin solution and mineral oil etc..
In above-mentioned preparation step, the thickener include starch, pectin, agar, gelatin, seaweed rouge, carrageenan, dextrin,
The cellulose derivatives such as tragacanth gum, polysaccharide element derivative, methylcellulose, carboxymethyl cellulose, starch derivatives, casein,
Sodium Polyacrylate, polyethylene glycol oxide, polyvinylpyrrolidone, polyvinyl alcohol, low-molecular polyethylene wax and polyacrylamide etc.
It is one or more of；
In above-mentioned preparation step, the coagulator includes the aqueous solution of ammonium acetate and acetic acid, the alcoholic solution of calcium nitrate, fluorine silicon
The one or more of aqueous solution, acetic acid and the formic acid of sour sodium etc..
The principle of the present invention program:
During the preparation process, having used response type organosilicon, (organosilicon is polynary for aqueous polyurethane emulsion provided by the invention
Alcohol) it is reacted with isocyanates, organosilicon is combined on the strand of the base polyurethane prepolymer for use as made.Whereby, using organic
The excellent water resistance of silicon, be easy to material surface migrate, matter is soft, flexibility is good, wearability is good, good permeability the advantages that, can
Improve water resistance, low-temperature flexibility and feel, the wearability of waterborne polyurethane resin, and then modified aqueous polyurethane coating/leaching
The texture of the hydrolysis of Rubber gloves, wearability and softness.
At the same time, when preparing aqueous polyurethane resin emulsion, being also added into can be with the parent in aqueous polyurethane molecule
The modification silicon nano of aqueous group reaction, makes bonding on aqueous polyurethane strand be connected to modified silicon nano.It borrows
This, will be easier to cause the hydrophilic radical of hydrolysis (such as by hydrophilic surfactant active or expansion in aqueous polyurethane strand
The carboxylic acid group that chain agent provides) reaction passivation is carried out, the inducement for causing ester linkage hydrolyzing is eliminated, prepared aqueous polyurethane impregnation is made
Gloves have good hydrolysis, the resistance to property worn.Moreover, the hydrophilic group in modified silicon nano and aqueous polyurethane emulsion
Organosilicon is also formed after (especially carboxyl etc.) reaction, is shown and " excellent water resistance, matter as response type organic silicon
It is soft, flexibility is good, wearability is good, good permeability " the advantages that.
Compared to the prior art, in such a way that physical mixed adds inorganic nano-particle, have used in the present invention
Machine silicon polyalcohol and modified silicon nano are with aqueous polyurethane molecule with chemical bonding, therefore aqueous polyurethane emulsion is deposited
Storage stability is good, and excellent properties timeliness is longer, is not concerned about the problem of silicon nano is precipitated.
(3) beneficial effect
The beneficial effects of the present invention are:
Compared with prior art, technical solution of the present invention has the advantage that
1) aqueous polyurethane used in and related compounding agent are environmentally protective reagent, and environmental pollution is small.
2) response type organosilicon and the modification silicon nano that can be reacted with hydrophilic radical are introduced into aqueous polyurethane simultaneously
In strand, organosilicon on one side aqueous polyurethane strand is easy to migrate to material surface, improves aqueous polyurethane
Water resistance, wearability, and organosilicon potential energy is lower, low-temperature flexibility is good, improves aqueous polyurethane texture, enhances aqueous poly-
The flexibility of urethane, the modified Nano particle that another party reacts with hydrophilic radical also substantially increase Water-resistance of Waterborne Polyurethane solution
Property.
3) organosilicon of response type is introduced into the surface tension that aqueous polyurethane system advantageously reduces lotion, so that aqueous
The surface tension homogenization for the surface tension gradient and wet film surface layer that wet film generates in polyurethane compositions film forming procedure, promotes gloves
Glue-line forms a smooth, smooth, uniform film during the drying and film forming process, had both improved the quality of glove coating, and had also subtracted
Processing cost is greatly saved in the use for having lacked other auxiliary agents, simplifies the technique for preparing dipped gloves, easily operated.
4) by the adjustment to aqueous polyurethane emulsion preparation formula, regulation is modified to aqueous polyurethane, it is prepared
Aqueous polyurethane dipped gloves out have the characteristics that high abrasion, matter be soft, hydrolysis, greener compared to oiliness polyurethane glove
Colour circle guarantor, safety and sanitation.And verified according to actual test, dipped gloves made from modified aqueous polyurethane of the invention, have really
Take into account the good characteristics such as the soft, hydrolysis of high abrasion, matter.
Specific embodiment
In order to preferably explain the present invention, in order to understand, With reference to embodiment, present invention work is retouched in detail
It states.
Below in each embodiment, every 1 mass parts are 100g.
Embodiment 1
The present embodiment prepares a kind of modified aqueous polyurethane dipped gloves, comprising the steps of:
S1: by hydroxyl endblocked polydimethylsiloxane dihydric alcohol and 40 mass parts polyadipate second two after the dehydration of 10 mass parts
Alcohol ester, 10 mass parts toluene di-isocyanate(TDI)s and 0.5 mass parts stannous octoate are added in container, are stirred evenly and are reacted in 60 DEG C
2h adds 2 mass parts chain extender ethylenediamine base ethanesulfonic acid sodium, in 50 DEG C of the reaction was continued 2h, then adds 30 mass parts third
Ketone viscosity reduction, and 0.5 mass parts triethylamine is added and is neutralized, it is permanent in the content of 60 DEG C of the reaction was continued 1h to isocyanate group-NCO
Fixed, cooling obtains base polyurethane prepolymer for use as.
S2: base polyurethane prepolymer for use as addition 120mL is then contained into 2 mass parts ethylenediamine base ethanesulfonic acid sodium and 1 mass parts ring
It is emulsified in oxygroup modified silicasol, obtains aqueous polyurethane emulsion.
S3: being added 3 mass parts antitack agents (paraffin powder) for aqueous polyurethane emulsion made from step S2,3 mass parts white
It starches (titanium white), is stirring evenly and then adding into dyestuff, thickener PVA is added while stirring, obtains viscosity and is adjusted to 1000~4000mPa
The gloves embryo being baked first is soaked coagulator and dried in the air to the sizing material modulated is immersed again after 30 seconds, finally soaks primary solidification again by the sizing material of S
Agent, after taking-up is dried in the air 30 minutes, aqueous polyurethane dipped gloves are can be obtained in drying.
Embodiment 2
Response type organosilicon is mainly chosen to be " the hydroxy-end capped poly- diformazan of alkane on the basis of embodiment 1 by the present embodiment
The type and each raw material dosage number of micro-adjustment of radical siloxane ", change isocyanates, catalyst, modified silicon nano.
The present embodiment prepares a kind of modified aqueous polyurethane dipped gloves, comprising the steps of:
S1: by alkane hydroxyl endblocked polydimethylsiloxane and 40 mass parts polypropylene glycol adipates after the dehydration of 8 mass parts
Polyalcohol, 7 mass parts methyl diphenylene diisocyanates and 0.5 mass parts N-ethylmorpholine are added in container, are stirred evenly
In 70 DEG C of reaction 2h, 2 mass parts chain extender Isosorbide-5-Nitraes-cyclohexanediol is added, in 70 DEG C of the reaction was continued 2h, then adds 30 matter
Part acetone viscosity reduction is measured, and 0.5 mass parts ethanol amine is added and is neutralized, in 70 DEG C of the reaction was continued 1h to isocyanate group-NCO's
Content constant, cooling obtain base polyurethane prepolymer for use as.
S2: base polyurethane prepolymer for use as addition 150mL is then contained into 2 mass parts 1,4- cyclohexanediols and 1 mass parts amino changes
It is emulsified in property silica solution, obtains aqueous polyurethane emulsion.
S3: 2 mass parts antitack agents (paraffin powder) is added in aqueous polyurethane emulsion made from step S2,0.5 mass parts are white
Mill base (titanium white), is stirring evenly and then adding into dyestuff, and thickener casein is added while stirring, obtain viscosity be adjusted to 1000~
The gloves embryo being baked first is soaked coagulator and dried in the air to the sizing material modulated is immersed again after 30 seconds, finally again by the sizing material of 4000mPaS
A coagulator is soaked, taking-up is dried in the air after sixty minutes, and aqueous polyurethane dipped gloves can be obtained in drying.
Embodiment 3
Response type organosilicon is mainly chosen to be " polyether hydroxyl's sealing end poly- two on the basis of embodiment 1 by the present embodiment
The type and each raw material dosage number of micro-adjustment of methylsiloxane ", change isocyanates, catalyst, modified silicon nano.
The present embodiment prepares a kind of modified aqueous polyurethane dipped gloves, comprising the steps of:
S1: polyether hydroxyl after the dehydration of 9 mass parts is blocked into dimethyl silicone polymer and 35 mass parts polyadipate propylene glycol
Ester polyol, 12 mass parts 1, hexamethylene-diisocyanate and 0.5 mass parts dibutyl tin dilaurate are added in container, stirring
Uniformly in 50 DEG C of reaction 2h, 2 mass parts 1,4-butanediol are added, in 50 DEG C of the reaction was continued 2h, then add 25 mass parts
Acetone viscosity reduction, and 0.5 mass parts triethylamine is added and is neutralized, the reaction was continued that 1h is constant to isocyanate group content in 60 DEG C,
Cooling obtains base polyurethane prepolymer for use as.
S2: base polyurethane prepolymer for use as addition 150mL is then contained into 2 mass parts 1,4- butanediols and 1 mass parts are amino modified
It is emulsified in fumed silica, obtains aqueous polyurethane emulsion.
S3: being added 2 mass parts antitack agents (paraffin powder) for aqueous polyurethane emulsion made from step S2,1 mass parts white
It starches (titanium white), is stirring evenly and then adding into dyestuff, thickener CMC is added while stirring, obtains viscosity and is adjusted to 1000~4000mPa
The gloves embryo being baked first is soaked coagulator and dried in the air to the sizing material modulated is immersed again after 30 seconds, finally soaks primary solidification again by the sizing material of S
Agent, taking-up are dried in the air after sixty minutes, and aqueous polyurethane dipped gloves can be obtained in drying.
Embodiment 4
The present embodiment mainly changes polyalcohol, isocyanates, catalyst, modified silicon nanometer on the basis of embodiment 1
The type of particle and each raw material dosage number of micro-adjustment.
The present embodiment prepares a kind of modified aqueous polyurethane dipped gloves, comprising the steps of:
S1: by hydroxyl endblocked polydimethylsiloxane dihydric alcohol and 30 mass parts polyadipates new penta after the dehydration of 5 mass parts
Terephthalate polyols, 8 mass parts, 1,5 naphthalene diisocyanate and 1 mass parts dibutyltin diacetate are added in container, and stirring is equal
Even to add 2 mass parts chain extenders 1 in 80 DEG C of reaction 2h, 6- hexylene glycol then adds 40 matter in 80 DEG C of the reaction was continued 2h
Part acetone viscosity reduction is measured, and 1 mass parts triethylamine is added and is neutralized, in 80 DEG C of the reaction was continued 1h to isocyanate group content perseverance
Fixed, cooling obtains base polyurethane prepolymer for use as.
S2: base polyurethane prepolymer for use as addition 150mL is then contained into 2 mass parts 1,6-HDs and 1 mass parts epoxy group changes
It is emulsified in property fumed silica, obtains aqueous polyurethane emulsion.
S3: being added 2 mass parts antitack agents (paraffin powder) for aqueous polyurethane emulsion made from step S2,1 mass parts white
It starches (titanium white), is stirring evenly and then adding into dyestuff, thickener CMC is added while stirring, obtains viscosity and is adjusted to 1000~4000mPa
The gloves embryo being baked first is soaked coagulator and dried in the air to the sizing material modulated is immersed again after 30 seconds, finally soaks primary solidification again by the sizing material of S
Agent, taking-up are dried in the air after sixty minutes, and aqueous polyurethane dipped gloves can be obtained in drying.
Embodiment 5
Response type organosilicon is mainly selected as " the hydroxy-end capped poly- diformazan of alkane on the basis of embodiment 1 by the present embodiment
The type and each raw material dosage number of micro-adjustment of radical siloxane ", change polyalcohol, catalyst, modified silicon nano.
The present embodiment prepares a kind of modified aqueous polyurethane dipped gloves, and it includes following steps:
S1: by alkane hydroxyl endblocked polydimethylsiloxane and 38 mass parts sulfonate type polyether polyols after the dehydration of 15 mass parts
Alcohol, 15 mass parts toluene di-isocyanate(TDI)s and 2 mass parts dibutyl tin dilaurates are added in container, are stirred evenly in 60 DEG C
3h is reacted, 5 mass parts chain extender trimethylolpropanes are added, in 60 DEG C of the reaction was continued 3h, then adds 40 mass parts third
Ketone viscosity reduction, and 1.5 mass parts triethylamines are added and are neutralized, the reaction was continued that 3h is constant to isocyanate group content in 70 DEG C, drop
Temperature obtains base polyurethane prepolymer for use as.
S2: base polyurethane prepolymer for use as addition 150mL is then contained into 2 mass parts trimethylolpropanes and 2 mass parts amino change
It is emulsified in property silica solution, obtains aqueous polyurethane emulsion.
2 mass parts antitack agents (paraffin powder) is added in aqueous polyurethane emulsion made from step S2,1 mass parts stock white
(titanium white) is stirring evenly and then adding into dyestuff, and thickener CMC is added while stirring, obtains viscosity and is adjusted to 1000~4000mPaS
Sizing material, the gloves embryo being baked first is soaked into coagulator and is dried in the air to the sizing material modulated is immersed again after 30 seconds, finally soaks primary solidification again
Agent, taking-up are dried in the air after sixty minutes, and aqueous polyurethane dipped gloves can be obtained in drying.
Comparative example 1
This comparative example is on the basis of embodiment 1, hydroxyl endblocked polydimethylsiloxane binary to be added without in step S1
Alcohol is added without epoxy-modified silica solution in step S2, remaining each step is same as Example 1.
Comparative example 2
This comparative example is on the basis of embodiment 1, hydroxyl endblocked polydimethylsiloxane binary to be added without in step S1
Alcohol, but step S2 reservation is same as Example 1, and remaining each step is same as Example 1.
Comparative example 3
This comparative example is that on the basis of embodiment 1, step S1 reservation is same as Example 1, but is added without in step S2
Epoxy-modified silica solution, remaining each step are same as Example 1.
According to Europe superscript EN388 standard test protocol, dipped gloves progressive prepared by embodiment 1-5 and comparative example 1-3
It can test, statistical result such as table 1.
Wear-resisting property is to be fixed on friction testing end, then spin friction by intercepting gloves glue-line sample, records glue
The revolution of layer crack damage.Revolution is bigger, and expression wear-resisting property is better.
Anti-hydrolytic performance is that gloves are soaked in water and washed by rubbing with the hands by wearer, stranding when record dipped gloves crack
Wash number.Number more multilist shows that anti-hydrolytic performance is better.
Table 1
In conclusion the dipped gloves of embodiment 1-5 preparation, (flexible in wearability, stretch modulus, elongation at break
Property), water resistance etc. has excellent performance.And the dipped gloves various aspects of performance of comparative example 1 is then worst.Comparative example 2,3 is slightly excellent
In comparative example 1.It can be seen that response type organosilicon and modified Nano silicon particle all modified water-solubles are poly- when preparing aqueous polyurethane emulsion
The performance of urethane has apparent optimization, and " modified Nano silicon particle " is mainly manifested in the hydrolysis for improving aqueous polyurethane glue-line
Property aspect, take second place for wearability, and response type organosilicon then to the hydrolytic resistance and wearability for improving aqueous polyurethane glue-line all
It is obviously improved.
Claims (10)
1. a kind of aqueous polyurethane emulsion, which is characterized in that when preparing the aqueous polyurethane emulsion, raw material has been contained
Machine silicon polyalcohol and the modification silicon nano that can be reacted with hydrophilic radical in polyurethane molecular chain, make aqueous polyurethane molecule
Chain is introduced into response type organosilicon and modified silicon nano.
2. a kind of preparation method of aqueous polyurethane emulsion, which is characterized in that it includes:
It the use of isocyanates and polyalcohol is raw material, under catalyst, chain extender existence condition when preparing base polyurethane prepolymer for use as
Reaction obtains base polyurethane prepolymer for use as；Contain at least one organosilicon polyalcohol in the polyalcohol；
When preparing aqueous polyurethane emulsion, the base polyurethane prepolymer for use as and the aqueous solution containing modified silicon nano are carried out
Mixing and emulsifying obtains aqueous polyurethane emulsion；Wherein, the modified silicon nano be can with it is hydrophilic in polyurethane molecular chain
Group chemical reacts and bonded modification silicon nano.
3. preparation method according to claim 2, which is characterized in that the organosilicon polyalcohol is selected from hydroxy-end capped poly- two
Methylsiloxane, alkane hydroxyl endblocked polydimethylsiloxane and polyether hydroxyl block one of dimethyl silicone polymer or several
Kind.
4. preparation method according to claim 3, which is characterized in that the polyalcohol is by not siliceous polyalcohol and organosilicon
Polyalcohol composition；Wherein the silicon polyalcohol that is free of includes one or more of following polyalcohol of molecular weight 300~3000:
Polytetrahydrofuran ethoxylated polyhydric alcohol, polyethylene glycol adipate polyalcohol, polypropylene glycol adipate polyalcohol, gathers polyethylene glycol
Tetramethylene adipate polyalcohol, polyneopentyl glycol adipate polyalcohol, polycaprolactone polyol, sulfonate type polyester polyols
The pure and mild carboxylate polyether polyol of alcohol, sulfonate type polyether polyol, carboxylate polyester polyols.
5. the preparation method according to claim 4, which is characterized in that in the polyalcohol, the not siliceous polyalcohol
Ratio is 1~90wt%, and surplus is organosilicon polyalcohol.
6. preparation method according to claim 3, which is characterized in that the modified silicon nano is silica solution, amino
Modified silicasol, epoxy-modified silica solution, fumed silica, amino modified fumed silica, epoxy-modified gas phase
Silica, silica lotion, amino modified silica lotion, epoxy-modified silica lotion, poly dimethyl silicon
One of oxygen alkane lotion, amino-terminated aqueous emulsion of dimethyl polysiloxane fluid and epoxy radicals end-blocking aqueous emulsion of dimethyl polysiloxane fluid are several
Kind.
7. according to preparation method described in claim 4 or 5 or 6, which is characterized in that the method preparation method includes following step
It is rapid:
S1: base polyurethane prepolymer for use as is prepared: by 6-70 mass parts without water-polyol, 5-15 mass parts isocyanates and 0.1-5 matter
Amount part catalyst is added in container, stirs evenly, 1-3h is reacted at a temperature of 40-80 DEG C, add 0.5-10 mass parts
5-30 mass parts acetone viscosity reduction is then added in 40-80 DEG C of the reaction was continued 1-3h in chain extender, and the neutralization of 0.2-2 mass parts is added
Agent is neutralized, and in the content constant of 40-80 DEG C of the reaction was continued 1-3h to isocyanate group-NCO, cooling obtains polyurethane prepolymer
Body；
S2: it prepares ester-polyurethane resin emulsion: the obtained base polyurethane prepolymer for use as of step S1 being added to and is expanded containing 0.5-10 mass parts
It is emulsified in the aqueous solution of the modification silicon nano of chain agent and 0.1-10 mass parts, obtains aqueous polyurethane emulsion.
8. preparation method according to claim 7, which is characterized in that
In step S1, the isocyanates is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, carbodiimide modified two
Methylenebis phenyl isocyanate, polyether-modified methyl diphenylene diisocyanate, liquefaction methyl diphenylene diisocyanate, different Buddhist
That ketone diisocyanate, 1,5 naphthalene diisocyanates, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate and methyl
One or more of cyclohexyl diisocyanate；
In step S1, the catalyst is triethylenediamine, bis- (dimethyl aminoethyl) ethers, N-ethylmorpholine, octanoic acid Asia
One or more of tin, dibutyl tin dilaurate, dibutyltin diacetate and organo-bismuth；The neutralizer be triethylamine,
One or more of ethanol amine, sodium hydroxide, potassium hydroxide and ammonium hydroxide；
In step S1-S2, the chain extender be ethylenediamine, ethylene glycol, 1,4-butanediol, 1,6- hexylene glycol, Isosorbide-5-Nitrae-cyclohexanediol,
Hexamethylene diamine, ethylenediamine base ethanesulfonic acid sodium, ethylenediamine base ethanesulfonic acid, trimethylolpropane, melamine, triethanolamine, dihydroxy first
One or more of base propionic acid, dimethylolpropionic acid, ethylene glycol amine and dimethylolpropionic acid.
9. a kind of aqueous polyurethane emulsion is made using the described in any item preparation methods of claim 2-8.
10. a kind of polyurethane dipped gloves comprising gloves embryo, which is characterized in that the gloves embryo surface be impregnated or coated by
Sizing material made of aqueous polyurethane emulsion described in claim 1 or 9 and baking and curing.
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Application publication date: 20191115 |