CN110343230A - A kind of water-based polyurethane ink resin and preparation method thereof - Google Patents
A kind of water-based polyurethane ink resin and preparation method thereof Download PDFInfo
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- CN110343230A CN110343230A CN201910697042.8A CN201910697042A CN110343230A CN 110343230 A CN110343230 A CN 110343230A CN 201910697042 A CN201910697042 A CN 201910697042A CN 110343230 A CN110343230 A CN 110343230A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
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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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 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
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of water-based polyurethane ink resins and preparation method thereof; by weight; under the conditions of inert gas shielding, take cyclic annular isocyanates 100-140 parts, molecular weight be 2000 95-160 parts of polyoxypropyleneglycol, self-control molecular weight be 200-400 40-70 parts of polyester polyol, 20-35 parts of hydrophilic radical be placed in container；To the solution stirring in container, slow heating, when temperature reaches 80 DEG C, insulation reaction 5 hours, sample detection nco value started to cool down when nco value is in prescribed limit, obtained the performed polymer of NCO sealing end；Ethylenediamine 10-20 parts is added in performed polymer, 600-650 parts of deionized water, when temperature is 30 DEG C, high-speed stirred two hours, sample detection nco value continued high-speed stirred two hours when nco value is zero, stands, obtains waterborne polyurethane resin.Aqueous polyurethane of the present invention is prepared using anion self-emulsifying technology, and the toughness and rigidity of the aqueous polyurethane of anionic preferably, have good dispersibility, water resistance and stability, so that aqueous polyurethane is convenient for film forming.
Description
Technical field
The present invention relates to the technical fields of polyurethane, more particularly, to a kind of water-based polyurethane ink resin and its preparation side
Method.
Background technique
Ink is the important materials for printing, it is expressed the pattern and text on stock by printing.Ink is general
It is made of pigment, link stuff, solvent and auxiliary agent etc., these ingredients equably mix and form a kind of stickiness glue through repeat-rolling
Fluid.Ink is widely used in the various printings such as books and periodicals, packing and decorating, building decoration；As social demand increases, ink variety and
Yield also respective extension and growth.The link stuff of ink is usually aqueous polyurethane, and aqueous polyurethane is with its high-low temperature resistant, resistance to crisp
Change, rub resistance, adhesive force is strong, flexibility is good, elasticity is good and the excellent performances such as tensile strength height, is widely used.
In printing ink, using aqueous polyurethane as the printing ink of link stuff, volatile organic solvent is free of, is had
Therefore safe and nontoxic feature is widely used in food, drug, the flexible packaging printing in toy for children.Currently, being used for flexible package
The water-based polyurethane ink of film is due to the defect with material formula, preparation process etc., and there are problems, such as: stability compared with
Compared with slow, filming performance is general, especially adhesive force is not high, needs to be advanced optimized for difference, drying.
Most of aqueous polyurethanes be all by anion and it is cationic self-emulsified be prepared, aqueous polyurethane is according to poly- ammonia
Whether contain ionic group on ester molecule side chain or main chain, i.e., whether belongs to iolon (ionomer), aqueous polyurethane can
It is divided into anionic, cationic, non-ionic.Non-ion aqueous polyurethane, i.e., it is aqueous without ionic group in molecule
Polyurethane carries out high shear force forced emulsification in the presence of emulsifier, this is also earliest aqueous polyurethane technology, but is obtained
Aqueous polyurethane stability it is very poor.Cation-type water-thinned polyurethane generally refers to (general containing ammonium ion on main chain or side chain
For quaternary ammonium ion) or sulfonium cation aqueous polyurethane, most situations are quaternary ammonium cations.And main chain is containing the aqueous of ammonium ion
The preparation of polyurethane is generally based on use chain extender containing tertiary amine group, the work of tertiary amine and secondary amine through acid or alkylating reagent
With forming hydrophilic ammonium ion.Also it can react to form ammonium ion with epoxychloropropane and acid by amino-containing polyurethane.Sun
Though ionic aqueous polyurethane is improved than non-ion aqueous polyurethane technology, either from cost of material or resistance to
Aqueous and stability is not the first choice of industrial application.Anion-type water-thinned polyurethane can be subdivided into sulfonic acid type, carboxylic acid type again,
With side chain containing the in the majority of ionic group.Most of aqueous polyurethanes are induced one carboxyl with chain extender containing carboxyl or chain extender containing sulfonate
Ion and azochlorosulfonate acid ion, two kinds of anion compare glue, and the dispersed and stability of azochlorosulfonate acid ion in water is more preferable.In technique,
Prepolymer method can be selected and acetone method prepares aqueous polyurethane, prepolymer method does not need plus acetone and other organic solvent, and acetone method exists
Viscosity is larger when prepared by performed polymer, needs to be added organic solvent to dilute, reduces viscosity, the solvent generally used is acetone, N-
The hydrophilic organic solvents such as methyl pyrrolidone, but acetone method can evaporate when finally obtaining aqueous polyurethane product and dispel acetone
Equal organic solvents.
What the Chinese patent literature that existing notification number is CN103450440B and CN105622886A proposed prepares aqueous
The method of polyurethane all uses the synthesis of acetone method and prepolymer method, i.e., during preparation, acetone or other esters are added
Class solvent dilutes performed polymer, then through chain extending reaction, is finally dispersed in water, and obtains waterborne polyurethane resin, but aqueous polyurethane
Resin finally dispels organic solvent without evaporation, cannot can be regarded as the aqueous polyurethane of real meaning.The present invention proposes a kind of aqueous
The preparation process of polyurethane ink resin and preparation method thereof, water-based polyurethane ink resin does not use organic solvent, to make
The aqueous polyurethane of standby real meaning, aqueous polyurethane have good dispersibility and stability in water.
Summary of the invention
The object of the present invention is to provide a kind of water-based polyurethane ink resin and preparation method thereof, what is be prepared is aqueous poly-
Urethane has good dispersibility and stability in water.In technique, using prepolymer method, system is participated in without using organic solvent
Standby aqueous polyurethane, dispels organic solvent it is therefore not necessary to evaporate, realizes real Water-borne modification.On formula, using soft and hard segments knot
Structure collocation, soft segment structure are liner polyesterdiols or polyether polyol, and hard segment structure is cyclic annular isocyanates, are improved aqueous
The filming performance of polyurethane.
Foregoing invention purpose of the invention has the technical scheme that
A kind of preparation method of water-based polyurethane ink resin includes the following steps: by weight
Step 1: under the conditions of inert gas shielding, cyclic annular isocyanates 100-140 parts are taken, the polyoxygenated that molecular weight is 2000
95-160 parts of propylene glycol, self-control molecular weight be 200-400 40-70 parts of polyester polyol, 20-35 parts of hydrophilic radical be placed in appearance
In device；
Step 2: stirring the solution in step 1 container, and slow heating when temperature reaches 80 DEG C, insulation reaction 5 hours, takes
Sample detects nco value, when nco value is in prescribed limit, starts to cool down, and obtains the performed polymer of NCO sealing end；
Step 3: ethylenediamine 10-20 parts of addition in the performed polymer made from step 2,600-650 parts of deionized water, when temperature is
At 30 DEG C, high-speed stirred two hours, sample detection nco value continued high-speed stirred two hours when nco value is zero, stands, obtains
To waterborne polyurethane resin.
By using above-mentioned technical proposal, the molecular structure of cyclic annular isocyanates is hard segment structure, and cricoid molecule guarantees
Aqueous polyurethane product has good rigid nature；The molecular structure of polyester polyol is soft segment structure, polyester polyol
On the one hand toughness is provided for aqueous polyurethane product, on the other hand, increases the solubility of aqueous polyurethane product in water,
To enhance the water resistance and stability of aqueous polyurethane product；The collective effect of polyester polyol and cyclic annular isocyanates,
On molecular structure, the cyclic annular isocyanates of the pure and mild hard segment structure of the polyester polyols of soft segment structure provides for aqueous polyurethane product
Good film forming physical property；The addition of hydrophilic radical, disperses in water convenient for aqueous polyurethane product.The present invention is aqueous poly-
Urethane is prepared using anion self-emulsifying technology, and the toughness and rigidity of the aqueous polyurethane of anionic preferably, and have good
Dispersibility, water resistance and stability so that aqueous polyurethane convenient for film forming；In technique, using prepolymer method, without using having
Solvent participation prepares aqueous polyurethane, dispels organic solvent it is therefore not necessary to evaporate, and realizes that aqueous polyurethane is really aqueous
Change.It on formula, is arranged in pairs or groups using Soft hard segment structure, soft segment structure is liner polyesterdiols or polyether polyol, hard segment structure
For cyclic annular isocyanates, the filming performance of aqueous polyurethane is improved.
The present invention is further arranged to: the cyclic annular isocyanates of the step 1 includes isophorone diisocyanate and 4,
One of 4'- dicyclohexyl methyl hydride diisocyanate.
The present invention is further arranged to: the dihydric alcohol in the polyester polyol selects small molecule dihydric alcohol, polyester polyols
The dihydric alcohol of alcohol can by one of ethylene glycol, propylene glycol, butanediol, neopentyl glycol and hexylene glycol or it is a variety of be made.
By using above-mentioned technical proposal, the present invention synthesizes aqueous polyurethane using prepolymer method, therefore to polyester polyols
The molecular weight of alcohol has strict requirements, synthesizes polyester polyol using the lesser dihydric alcohol of molecular weight as a result,.
The present invention is further arranged to: the binary acid in the polyester polyol selects small molecule binary acid, polyester polyols
Binary acid in alcohol by one of ethanedioic acid, malonic acid, glutaric acid and adipic acid or a variety of can be made.
By using above-mentioned technical proposal, the present invention synthesizes aqueous polyurethane using prepolymer method, therefore to polyester polyols
The molecular weight of alcohol has strict requirements, synthesizes polyester polyol using the lesser binary acid of molecular weight as a result,.
The present invention is further arranged to: the hydrophilic radical of the step 1 includes 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium and 2-
One of sodium sulfonate -1,4- butanediol.
The present invention is further arranged to: the inert gas of the step 1 includes one of nitrogen, helium, neon or more
Kind.
The present invention is further arranged to: by weight, being included the following steps:
Step 1: under the conditions of nitrogen protection, 100-120 parts of isophorone diisocyanate is taken, the polyoxy that molecular weight is 2000
Change 95-120 parts of propylene glycol, self-control molecular weight is 50-70 parts of the polyester polyol of 200-400,1,2- dihydroxy -3-N-morpholinopropanesulfonic acid
20-25 parts of sodium are placed in container；
Step 2: stirring the solution in step 1 container, and slow heating when temperature reaches 80 DEG C, insulation reaction 5 hours, takes
Sample detects nco value, when nco value is in prescribed limit, starts to cool down, and obtains the performed polymer of NCO sealing end；
Step 3: ethylenediamine 10-20 parts of addition in the performed polymer made from step 2,600-650 parts of deionized water, when temperature is
At 30 DEG C, high-speed stirred two hours, sample detection nco value continued high-speed stirred two hours when nco value is zero, stands, obtains
To waterborne polyurethane resin.
By using above-mentioned technical proposal, the solid content using waterborne polyurethane resin made from the above method is about
33.9%。
The present invention is further arranged to: by weight, being included the following steps:
Step 1: under the conditions of nitrogen protection, 120-140 parts of 4, the 4'- dicyclohexyl methyl hydride diisocyanate, molecular weight is taken to be
2000 110-160 parts of polyoxypropyleneglycol, self-control molecular weight are 40-55 parts of the polyester polyol of 200-400,2- sulfonic acid
25-35 parts of sodium -1,4- butanediol is placed in container；
Step 2: stirring the solution in step 1 container, and slow heating when temperature reaches 80 DEG C, insulation reaction 5 hours, takes
Sample detects nco value, when nco value is in prescribed limit, starts to cool down, and obtains the performed polymer of NCO sealing end；
Step 3: ethylenediamine 10-20 parts of addition in the performed polymer made from step 2,600-650 parts of deionized water, when temperature is
At 30 DEG C, high-speed stirred two hours, sample detection nco value continued high-speed stirred two hours when nco value is zero, stands, obtains
To waterborne polyurethane resin.
By using above-mentioned technical proposal, the solid content using waterborne polyurethane resin made from the above method is about
38.6%。
The present invention is further arranged to: the water-based polyurethane ink tree of the preparation method preparation of water-based polyurethane ink resin
Rouge.
In conclusion advantageous effects of the invention are as follows:
Aqueous polyurethane of the present invention is prepared using anion self-emulsifying technology, the toughness and rigidity of the aqueous polyurethane of anionic
Preferably, and there is good dispersibility, water resistance and stability, so that aqueous polyurethane is convenient for film forming；In technique, using pre-
Aggressiveness method, prepares aqueous polyurethane without using organic solvent participation, dispels organic solvent it is therefore not necessary to evaporate, and realizes aqueous poly-
The real Water-borne modification of urethane.It on formula, is arranged in pairs or groups using Soft hard segment structure, soft segment structure is that liner polyesterdiols or polyethers are more
First alcohol, hard segment structure are cyclic annular isocyanates, improve the filming performance of aqueous polyurethane.
Specific embodiment
Preparation method 1
Embodiment 1
The preparation of polyester polyol
Since the present invention is synthetically prepared aqueous polyurethane using prepolymer method, for the molecule of linear polyester polyol
Amount has strict requirements, and the molecular weight of polyester polyol is limited between 100-500, and the molecular weight of polyester polyol is in 200-
Between 400 preferably.Polyester polyol needs to synthesize, in order to control the molecular weight of polyester polyol, therefore, in polyester polyol
Dihydric alcohol selects the dihydric alcohol of small molecule, and the binary acid in polyester polyol selects small molecule binary acid；In polyester polyol
Dihydric alcohol can be by one of ethylene glycol, propylene glycol, butanediol, neopentyl glycol and hexylene glycol or a variety of obtained, polyester polyols
Binary acid in alcohol by one of ethanedioic acid, malonic acid, glutaric acid and adipic acid or a variety of can be made；In the preparation, it uses
Batch process preparation, dicarboxylic acids and dihydric alcohol is added in reaction vessel, nitrogen is passed through, and heat to container, 150 DEG C in container
Left and right reaction production water and low molecular weight polyester polyalcohol；Since temperature is 150 DEG C in container, the water in container can gradually steam
Out；With steaming for dampening, the temperature in container is gradually risen, when the temperature in container is between 170-230 DEG C, in container
Vacuum degree gradually reduces, until 500Pa, consequently facilitating by excessive dihydric alcohol or binary acid, a small amount of side reaction product and anti-
The water that should be produced steams together, so that the polyester polyol that molecular weight is 200-400 is obtained, it is spare.
The preparation of aqueous polyurethane
By weight, protective gas is usually using inert gas, and common inert gas includes nitrogen, helium, in neon
It is one or more, usually using nitrogen as protective gas, under conditions of nitrogen protection, different Fo Er is sequentially added into container
The polyester polyols that 100 parts of polyoxypropyleneglycol that 110 parts of ketone diisocyanate, molecular weight are 2000, molecular weight are 200-400
50 parts of alcohol, 1,2- dihydroxy -20 parts of 3-N-morpholinopropanesulfonic acid sodium stir the solution in container using agitating device, and are slowly heated,
When temperature reaches 80 DEG C, keeping the temperature in container is 80 DEG C, so that behind solution reaction five hours in container, in extracting container
Sample liquid detect nco value, when NCO is in 4-4.3%, stop keeping the temperature in container so that the temperature in container reduces, from
And the precast body of NCO sealing end is obtained, it is spare.
10 parts and 600 parts of deionized water of ethylenediamine are added in the precast body made from the previous step, the temperature for controlling container is
30 DEG C, the mixing speed of agitating device is turned up, starts the dispersion of high speed chain extension, after two hours, sampling and testing nco value works as NCO
When value is zero, chain extension dispersion is completed, and is continued high-speed stirred chain extension and dispersed two hours, is stopped stirring, is obtained aqueous polyurethane, quiet
It sets eight hours, packs, obtain the waterborne polyurethane resin product of finished product.
Embodiment 2
Embodiment 2 difference from example 1 is that:
The preparation of aqueous polyurethane
By weight, under conditions of nitrogen protection, isophorone diisocyanate 100 part, point are sequentially added into container
Son measures 110 parts of the polyoxypropyleneglycol for 2000,60 parts of the polyester polyol that molecular weight is 200-400,1,2- dihydroxy -3-
23 parts of propanesulfonate, the solution in container is stirred using agitating device, and is slowly heated, when temperature reaches 80 DEG C, is protected
Holding the temperature in container is 80 DEG C, so that the sample liquid in extracting container detects nco value behind solution reaction five hours in container, when
NCO stops keeping the temperature in container in 4-4.3%, so that the temperature in container reduces, to obtain the prefabricated of NCO sealing end
Body, it is spare.
15 parts and 630 parts of deionized water of ethylenediamine are added in the precast body made from the previous step, the temperature for controlling container is
30 DEG C, the mixing speed of agitating device is turned up, starts the dispersion of high speed chain extension, after two hours, sampling and testing nco value works as NCO
When value is zero, chain extension dispersion is completed, and is continued high-speed stirred chain extension and dispersed two hours, is stopped stirring, is obtained aqueous polyurethane, quiet
It sets eight hours, packs, obtain the waterborne polyurethane resin product of finished product.
Embodiment 3
Embodiment 3 and embodiment 1 the difference is that:
The preparation of aqueous polyurethane
By weight, under conditions of nitrogen protection, isophorone diisocyanate 120 part, point are sequentially added into container
Son measures 118 parts of the polyoxypropyleneglycol for 2000,70 parts of the polyester polyol that molecular weight is 200-400,1,2- dihydroxy -3-
24 parts of propanesulfonate, the solution in container is stirred using agitating device, and is slowly heated, when temperature reaches 80 DEG C, is protected
Holding the temperature in container is 80 DEG C, so that the sample liquid in extracting container detects nco value behind solution reaction five hours in container, when
NCO stops keeping the temperature in container in 4-4.3%, so that the temperature in container reduces, to obtain the prefabricated of NCO sealing end
Body, it is spare.
19 parts and 650 parts of deionized water of ethylenediamine are added in the precast body made from the previous step, the temperature for controlling container is
30 DEG C, the mixing speed of agitating device is turned up, starts the dispersion of high speed chain extension, after two hours, sampling and testing nco value works as NCO
When value is zero, chain extension dispersion is completed, and is continued high-speed stirred chain extension and dispersed two hours, is stopped stirring, is obtained aqueous polyurethane, quiet
It sets eight hours, packs, obtain the waterborne polyurethane resin product of finished product.
Embodiment 4
Embodiment 4 difference from example 1 is that:
The preparation of aqueous polyurethane
By weight, under conditions of nitrogen protection, isophorone diisocyanate 110 part, point are sequentially added into container
Son measures 100 parts of the polyoxypropyleneglycol for 2000,68 parts of the polyester polyol that molecular weight is 200-400,1,2- dihydroxy -3-
23 parts of propanesulfonate, the solution in container is stirred using agitating device, and is slowly heated, when temperature reaches 80 DEG C, is protected
Holding the temperature in container is 80 DEG C, so that the sample liquid in extracting container detects nco value behind solution reaction five hours in container, when
NCO stops keeping the temperature in container in 4-4.3%, so that the temperature in container reduces, to obtain the prefabricated of NCO sealing end
Body, it is spare.
15 parts and 600 parts of deionized water of ethylenediamine are added in the precast body made from the previous step, the temperature for controlling container is
30 DEG C, the mixing speed of agitating device is turned up, starts the dispersion of high speed chain extension, after two hours, sampling and testing nco value works as NCO
When value is zero, chain extension dispersion is completed, and is continued high-speed stirred chain extension and dispersed two hours, is stopped stirring, is obtained aqueous polyurethane, quiet
It sets eight hours, packs, obtain the waterborne polyurethane resin product of finished product.
Preparation method 2
Embodiment 5
The preparation method of polyester polyol is identical as the preparation method of polyester polyol in the embodiment 1 of preparation method 1.
The preparation of aqueous polyurethane
By weight, under the protective condition of inert nitrogen gas, 4,4'- dicyclohexyl methyl hydride two is sequentially added into container
The polyester polyol 41 that 111 parts of polyoxypropyleneglycol that 120 parts of isocyanates, molecular weight are 2000, molecular weight are 200-400
Part, 25 parts of butanediol of 2- sodium sulfonate -1,4-；The solution in container is stirred using agitating device, and is slowly heated；Work as temperature
When reaching 80 DEG C, keeping the temperature in container is 80 DEG C；So that behind solution reaction five hours in container, the sample liquid in extracting container
Nco value is detected, when nco value is in 3-3.2%, stopping keeps the temperature in container, so that the temperature in container reduces, thus
The precast body blocked to NCO, it is spare.
12 parts and 600 parts of deionized water of ethylenediamine are added in the precast body made from the previous step, controls the temperature in container
It is 30 DEG C, the mixing speed of agitating device is turned up, starts the dispersion of high speed chain extension, after two hours, sampling and testing nco value, when
When nco value is zero, chain extension dispersion is completed, and is continued high-speed stirred chain extension and dispersed two hours, is stopped stirring, is obtained aqueous poly- ammonia
Ester stands eight hours, and packaging obtains the waterborne polyurethane resin product of finished product.
Embodiment 6
Embodiment 6 and embodiment 5 the difference is that:
The preparation of aqueous polyurethane
By weight, under the protective condition of inert nitrogen gas, 4,4'- dicyclohexyl methyl hydride two is sequentially added into container
The polyester polyol 47 that 140 parts of polyoxypropyleneglycol that 130 parts of isocyanates, molecular weight are 2000, molecular weight are 200-400
Part, 29 parts of butanediol of 2- sodium sulfonate -1,4-；The solution in container is stirred using agitating device, and is slowly heated；Work as temperature
When reaching 80 DEG C, keeping the temperature in container is 80 DEG C；So that behind solution reaction five hours in container, the sample liquid in extracting container
Nco value is detected, when nco value is in 3-3.2%, stopping keeps the temperature in container, so that the temperature in container reduces, thus
The precast body blocked to NCO, it is spare.
16 parts and 630 parts of deionized water of ethylenediamine are added in the precast body made from the previous step, controls the temperature in container
It is 30 DEG C, the mixing speed of agitating device is turned up, starts the dispersion of high speed chain extension, after two hours, sampling and testing nco value, when
When nco value is zero, chain extension dispersion is completed, and is continued high-speed stirred chain extension and dispersed two hours, is stopped stirring, is obtained aqueous poly- ammonia
Ester stands eight hours, and packaging obtains the waterborne polyurethane resin product of finished product.
Embodiment 7
Embodiment 7 and embodiment 5 the difference is that:
The preparation of aqueous polyurethane
By weight, under the protective condition of inert nitrogen gas, 4,4'- dicyclohexyl methyl hydride two is sequentially added into container
The polyester polyol 53 that 158 parts of polyoxypropyleneglycol that 140 parts of isocyanates, molecular weight are 2000, molecular weight are 200-400
Part, 35 parts of butanediol of 2- sodium sulfonate -1,4-；The solution in container is stirred using agitating device, and is slowly heated；Work as temperature
When reaching 80 DEG C, keeping the temperature in container is 80 DEG C；So that behind solution reaction five hours in container, the sample liquid in extracting container
Nco value is detected, when nco value is in 3-3.2%, stopping keeps the temperature in container, so that the temperature in container reduces, thus
The precast body blocked to NCO, it is spare.
19 parts and 648 parts of deionized water of ethylenediamine are added in the precast body made from the previous step, controls the temperature in container
It is 30 DEG C, the mixing speed of agitating device is turned up, starts the dispersion of high speed chain extension, after two hours, sampling and testing nco value, when
When nco value is zero, chain extension dispersion is completed, and is continued high-speed stirred chain extension and dispersed two hours, is stopped stirring, is obtained aqueous poly- ammonia
Ester stands eight hours, and packaging obtains the waterborne polyurethane resin product of finished product.
Embodiment 8
Embodiment 8 and embodiment 5 the difference is that:
The preparation of aqueous polyurethane
By weight, under the protective condition of inert nitrogen gas, 4,4'- dicyclohexyl methyl hydride two is sequentially added into container
The polyester polyol 50 that 150 parts of polyoxypropyleneglycol that 136 parts of isocyanates, molecular weight are 2000, molecular weight are 200-400
Part, 33 parts of butanediol of 2- sodium sulfonate -1,4-；The solution in container is stirred using agitating device, and is slowly heated；Work as temperature
When reaching 80 DEG C, keeping the temperature in container is 80 DEG C；So that behind solution reaction five hours in container, the sample liquid in extracting container
Nco value is detected, when nco value is in 3-3.2%, stopping keeps the temperature in container, so that the temperature in container reduces, thus
The precast body blocked to NCO, it is spare.
18 parts and 600 parts of deionized water of ethylenediamine are added in the precast body made from the previous step, controls the temperature in container
It is 30 DEG C, the mixing speed of agitating device is turned up, starts the dispersion of high speed chain extension, after two hours, sampling and testing nco value, when
When nco value is zero, chain extension dispersion is completed, and is continued high-speed stirred chain extension and dispersed two hours, is stopped stirring, is obtained aqueous poly- ammonia
Ester stands eight hours, and packaging obtains the waterborne polyurethane resin product of finished product.
The embodiment of present embodiment is presently preferred embodiments of the present invention, not limits protection of the invention according to this
Range, therefore: the equivalence changes that all structures under this invention, shape, principle are done, should all be covered by protection scope of the present invention it
It is interior.
Claims (9)
1. a kind of preparation method of water-based polyurethane ink resin, it is characterised in that: by weight, include the following steps:
Step 1: under the conditions of inert gas shielding, cyclic annular isocyanates 100-140 parts are taken, the polyoxygenated that molecular weight is 2000
95-160 parts of propylene glycol, self-control molecular weight be 200-400 40-70 parts of polyester polyol, 20-35 parts of hydrophilic radical be placed in appearance
In device；
Step 2: stirring the solution in step 1 container, and slow heating when temperature reaches 80 DEG C, insulation reaction 5 hours, takes
Sample detects nco value, when nco value is in prescribed limit, starts to cool down, and obtains the performed polymer of NCO sealing end；
Step 3: ethylenediamine 10-20 parts of addition in the performed polymer made from step 2,600-650 parts of deionized water, when temperature is
At 30 DEG C, high-speed stirred two hours, sample detection nco value continued high-speed stirred two hours when nco value is zero, stands, obtains
To waterborne polyurethane resin.
2. a kind of preparation method of water-based polyurethane ink resin according to claim 1, it is characterised in that: the step
One cyclic annular isocyanates includes one of isophorone diisocyanate and 4,4'- dicyclohexyl methyl hydride diisocyanate.
3. a kind of preparation method of water-based polyurethane ink resin according to claim 1, it is characterised in that: the polyester
Dihydric alcohol in polyalcohol selects small molecule dihydric alcohol, the dihydric alcohol of polyester polyol can by ethylene glycol, propylene glycol, butanediol,
One of neopentyl glycol and hexylene glycol are a variety of obtained.
4. a kind of preparation method of water-based polyurethane ink resin according to claim 3, it is characterised in that: the polyester
Binary acid in polyalcohol selects small molecule binary acid, and the binary acid in polyester polyol can be by ethanedioic acid, malonic acid, glutaric acid
With one of adipic acid or a variety of be made.
5. a kind of preparation method of water-based polyurethane ink resin according to claim 2, it is characterised in that: the step
One hydrophilic radical includes one of 1,2- dihydroxy -3-N-morpholinopropanesulfonic acid sodium and 2- sodium sulfonate -1,4- butanediol.
6. a kind of preparation method of water-based polyurethane ink resin according to claim 5, it is characterised in that: the step
One inert gas includes one of nitrogen, helium, neon or a variety of.
7. a kind of preparation method of water-based polyurethane ink resin according to claim 6, it is characterised in that: by weight
Meter, includes the following steps:
Step 1: under the conditions of nitrogen protection, 100-120 parts of isophorone diisocyanate is taken, the polyoxy that molecular weight is 2000
Change 95-120 parts of propylene glycol, self-control molecular weight is 50-70 parts of the polyester polyol of 200-400,1,2- dihydroxy -3-N-morpholinopropanesulfonic acid
20-25 parts of sodium are placed in container；
Step 2: stirring the solution in step 1 container, and slow heating when temperature reaches 80 DEG C, insulation reaction 5 hours, takes
Sample detects nco value, when nco value is in prescribed limit, starts to cool down, and obtains the performed polymer of NCO sealing end；
Step 3: ethylenediamine 10-20 parts of addition in the performed polymer made from step 2,600-650 parts of deionized water, when temperature is
At 30 DEG C, high-speed stirred two hours, sample detection nco value continued high-speed stirred two hours when nco value is zero, stands, obtains
To waterborne polyurethane resin.
8. a kind of preparation method of water-based polyurethane ink resin according to claim 6, it is characterised in that: by weight
Meter, includes the following steps:
Step 1: under the conditions of nitrogen protection, 120-140 parts of 4, the 4'- dicyclohexyl methyl hydride diisocyanate, molecular weight is taken to be
2000 110-160 parts of polyoxypropyleneglycol, self-control molecular weight are 40-55 parts of the polyester polyol of 200-400,2- sulfonic acid
25-35 parts of sodium -1,4- butanediol is placed in container；
Step 2: stirring the solution in step 1 container, and slow heating when temperature reaches 80 DEG C, insulation reaction 5 hours, takes
Sample detects nco value, when nco value is in prescribed limit, starts to cool down, and obtains the performed polymer of NCO sealing end；
Step 3: ethylenediamine 10-20 parts of addition in the performed polymer made from step 2,600-650 parts of deionized water, when temperature is
At 30 DEG C, high-speed stirred two hours, sample detection nco value continued high-speed stirred two hours when nco value is zero, stands, obtains
To waterborne polyurethane resin.
9. a kind of water-based polyurethane ink resin described in any one of -7 according to claim 1, it is characterised in that: using aqueous poly-
The water-based polyurethane ink resin of the preparation method preparation of urethane ink resin.
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Cited By (1)
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