CN103073692A - Producing method of water-base polyurethane - Google Patents
Producing method of water-base polyurethane Download PDFInfo
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- CN103073692A CN103073692A CN2013100358642A CN201310035864A CN103073692A CN 103073692 A CN103073692 A CN 103073692A CN 2013100358642 A CN2013100358642 A CN 2013100358642A CN 201310035864 A CN201310035864 A CN 201310035864A CN 103073692 A CN103073692 A CN 103073692A
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Abstract
The invention discloses a producing method of water-base polyurethane, which comprises the steps of preparing a polyurethane prepolymer, preparing polyurethane prepolymer salt and finally obtaining water-base polyurethane. Water-base polyurethane prepared by the method has the characteristics of good strength, moderate crosslinking degree, uniform particle size, good water resistance, high binding power and the like, can be applied to spinning adhesive, and can serve as the spinning adhesive.
Description
Technical field
The present invention relates to a kind of production method of aqueous polyurethane, the aqueous polyurethane that adopts the method to produce is mainly used in weaving sizing agent such as stamp sizing agent, flocking sizing agent etc.
Background technology
At present, traditional weaving tackiness agent on the market is as main take the ACRYLIC EMULSION sizing agent.In recent years, along with more and more higher to environmental requirement of people, the conventional acrylic emulsion sizing agent overwhelming majority contains formaldehyde, can work the mischief to the healthy of people, simultaneously along with socioeconomic development, people are more and more higher to the requirement of weaving face fabric feel, and the self-characteristic of ACRYLIC EMULSION sizing agent hot sticky cold crisp has caused its bad feel, can not the satisfying the market requirement.The polyurethanes sizing agent more and more is subject to the welcome in market, but the conventional urethane class sizing agent overwhelming majority is solvent-borne type, contain a large amount of toluene, ethyl acetate equal solvent, produce and use procedure in inflammable, explosive, a large amount of contaminate environment, and also can work the mischief to the healthy of operating personnel.
As everyone knows: aqueous polyurethane (WPU) refers to that urethane is dissolved in water or is scattered in the water and a kind of urethane resin that forms.With respect to solvent borne polyurethane, aqueous polyurethane is take water as medium, have do not fire, smell is little, do not pollute, energy-conservation, the advantage such as operation is easy to process, more and more be subject to people's attention.The Schlack P of former West Germany in 1943 is emulsifiable in the water vulcabond under vigorous stirring and adds diamines in the presence of emulsifying agent and protective colloid, has successfully developed first WPU.There is the research of a small amount of WPU in the 50's of 20th century, will hold the isocyanato base polyurethane prepolymer for use as to be scattered in the water such as the researchist of DuPont company in 1953, have then synthesized WPU with the quadrol chain extension.Aqueous polyurethane came across American market first in 1967, and some aqueous polyurethane products such as the 70-80 age U.S., Japan, Germany develop into application from advanced development, have polytype aqueous polyurethane product to emerge.The research work of China's aqueous polyurethane starts from the 70's of 20th century, is at first begun development by the Shenyang leather, and after this appearance of the synthetic coating material for leather in the leather research institute on the ground such as Beijing, Tianjin is arranged in succession.After the 80's, the development of WPU is more active, and many units have carried out development work in succession, and main application is wood lacquer, hide finishes, adhesive for shoes, fabric coating etc.
Disclosed aqueous polyurethane in the prior art, the weak point of the sizing agent that is applied to weave be, its solid content is low, degree of crosslinking is low, intensity difference, poor water resistance, and requires very high to apparatus and process.Therefore to the research of the aspects such as control of the molecular chain phase separation structure of aqueous polyurethane and crosslinking degree, become aqueous polyurethane be applied to the to weave new problem in sizing agent field.
Summary of the invention
The objective of the invention is to want to overcome above-mentioned the deficiencies in the prior art, a kind of production method of new aqueous polyurethane is provided, the aqueous polyurethane that adopts the method the to produce sizing agent field that can be applicable to weave, use as the weaving sizing agent, it is as the weaving sizing agent, intensity is good, degree of crosslinking is moderate, particle diameter is even, water-tolerant, and cohesive force is strong.
For realizing that the technical scheme that above-mentioned purpose of the present invention adopts is: a kind of production method of aqueous polyurethane is characterized in that following these steps to carry out:
The first step: the preparation of base polyurethane prepolymer for use as:
1. take by weighing polyvalent alcohol: take by weighing by weight at least a in polyester polyol or the polyether glycol, behind 100～120 ℃ of lower vacuum-drying 1～3h, be cooled to 40～100 ℃;
2. add vulcabond, the add-on of vulcabond is: the mol ratio of vulcabond and polyvalent alcohol is 0.5～2:1, maintains the temperature at 40～100 ℃ of polyreaction 2～5h;
3. add polyvalent alcohol chainextender and wetting ability chainextender, the add-on of polyvalent alcohol chainextender is: polyvalent alcohol chainextender hydroxyl value molar equivalent is 0.4～2.4:1 with the ratio of above-mentioned polyvalent alcohol hydroxyl value molar equivalent, the hydrophilic chain extender quality is 3%～7% of performed polymer total mass, maintains the temperature at 40～100 ℃ of polyreaction 2～10h;
Second step: neutralization reaction, preparation base polyurethane prepolymer for use as salt:
Keep temperature of reaction at 30～50 ℃, triethylamine is added drop-wise in the base polyurethane prepolymer for use as, and neutralization reaction 0.5～1h, degree of neutralization are 80%～120%, with in the base polyurethane prepolymer for use as and salify, the add-on of triethylamine is the triethylamine amount with the ratio of hydrophilic chain extender amount is 0.8～1.2:1
The 3rd step: make aqueous polyurethane:
Under the high speed shear effect of high speed dispersor, during deionized water joined and in the base polyurethane prepolymer for use as of salify, emulsification 15～30min makes aqueous polyurethane.
The present invention be preferably in carry out step 2. before, add first acetone or the butanone of 0～2 times of polyvalent alcohol quality, and add the catalyzer of polyvalent alcohol quality 0～0.1%, and then carry out step 2.; When adding acetone or butanone in the preparation process of the present invention, make in the aqueous polyurethane step in the 3rd step, after emulsification finishes, slough acetone or butanone in the aqueous polyurethane with the vacuum decompression method again.Slough acetone or butanone in the aqueous polyurethane with the vacuum decompression method, pressure is generally-0.098Mpa about, temperature is generally 40～70 ℃.
Described acetone (or butanone) can add simultaneously with catalyzer, also can only add wherein a kind of.
The present invention made in the aqueous polyurethane step in the 3rd step, during deionized water is joined and after in the base polyurethane prepolymer for use as of salify, preferably used first the icy salt solution circulating cooling, maintained the temperature at 5～20 ℃, carried out emulsification again, made aqueous polyurethane.Described icy salt solution is the ice calcium chloride water, during cooling, and control icy salt solution temperature range-18 ℃～0 ℃.
The present invention preferably in the prepared aqueous polyurethane low rate mixing drip the polyamine compound, further expand and connect, polyamine compound amount is 0.33～0.73:1 with the ratio of polyester polyol or polyether glycol amount, stirs 0.5～1.5h.
The quality optimization of the deionized water of adding of the present invention is 1.5～2.5 times of base polyurethane prepolymer for use as salt.
The molecular weight of polyester polyol of the present invention or polyether glycol is preferably 500～3000.
The present invention both can mix adding simultaneously at the step of the first step polyvalent alcohol chainextender and the wetting ability chainextender described in 3., also can add respectively.
Polyester polyol of the present invention adopts at least a in the following material: polyethylene glycol adipate glycol, polypropylene adipate (PPA) glycol, polybutylene glyool adipate, polyhexamethylene adipate glycol, polyneopentyl glycol adipate glycol, poly-hexanodioic acid cyclohexanedimethanoester ester glycol, polycaprolactone glycol, polycarbonate diol.
Polyether glycol of the present invention adopts at least a in the following material: polyoxypropyleneglycol, Polyoxyethylene glycol, polytetrahydrofuran diol.
Polyvalent alcohol chainextender of the present invention adopts at least a in the following material: ethylene glycol, propylene glycol, Diethylene Glycol, 1,4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, cyclohexanedimethanol, glycol ether, sorbyl alcohol, glycerol, TriMethylolPropane(TMP).
Wetting ability chainextender of the present invention adopts at least a in the following material: dimethylol propionic acid, dimethylolpropionic acid, thionamic acid sodium.First the wetting ability chainextender is dissolved under 60～75 ℃ in N-methyl-2 pyrrolidone (NMP) and makes solution, and then join in the reactant, the mass ratio of wetting ability chainextender and NMP is 1:2～3.
Vulcabond of the present invention adopts at least a in the following material: hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, 4,4-diphenylmethanediisocyanate, tolylene diisocyanate.
Catalyzer of the present invention adopts at least a in the following catalyzer: stannous octoate, dibutyl tin dilaurate, dibutyl two stannous octoates, triethylene diamine.
Polyamine of the present invention adopts at least a in the following material: quadrol, hexanediamine, diethylenetriamine, triethylene tetramine.
The consumption of triethylamine of the present invention can calculate with reference to following equation:
m
0 =m
1 + m
2 + m
3 + m
4 + m
5
m
5 / M
5 : m
3 / M
3 = 0.8～1.2
m
3 / m
0 ×100%= 3% ～7%
m
0-performed polymer total mass m
1-polyvalent alcohol quality m
2-polyvalent alcohol chainextender quality
m
3-hydrophilic chain extender quality m
4-polyamine quality m
5-triethylamine quality
M
3-hydrophilic chain extender molecular weight M
5-triethylamine molecular weight
The present invention compared with prior art has the following advantages:
1, preparation method provided by the invention has introduced the polyfunctionality monomer, in the situation that does not affect emulsion dispersion, has given the degree of crosslinking of polyurethane molecular chain appropriateness, finally obtains the aqueous polyurethane of the high performance sizing agent that can be applicable to weave.
2, preparation technology provided by the invention can well control the polyurethane molecular chain structure, has namely well controlled the distribution of soft or hard section in the molecular chain structure, makes to be separated in the scope of appropriateness, makes aqueous polyurethane have good mechanical property and cohesive strength.
3, preparation technology provided by the invention has well controlled the distribution of hydrophilic radical on the polyurethane molecular chain, the dispersion and emulsion process of base polyurethane prepolymer for use as is carried out smoothly, obtain the aqueous polyurethane of high stability, add again behind the polyamine behind the chainextender, make made aqueous polyurethane have very high bonding strength, water tolerance, dry cleaning resistance and high thermal resistance.
4, preparation technology provided by the invention has reduced the difficulty in prepolymer reaction and the dispersion process, and equipment requirements is obviously reduced, and makes production technique simple, and the production process less wastage obviously reduces production costs.
5, the aqueous polyurethane of producing according to production formula provided by the invention and preparation method has really been accomplished formaldehydeless, pollution-free.
Embodiment
Example below in conjunction with implementation is done further detailed description to the present invention, yet described embodiment should not explain in the mode of restriction.
Embodiment 1:
Take by weighing by weight following material, the preparation aqueous polyurethane:
100 parts of polyethylene glycol adipate glycol (molecular weight 500)
200 parts of isophorone diisocyanates
28 parts of ethylene glycol
1 part of TriMethylolPropane(TMP)
10.6 parts of dimethylol propionic acids
8.8 parts of triethylamines
4 parts of quadrols
0.1 part of dibutyl tin dilaurate
100 parts in acetone
560.55 parts of deionized waters
21.2 parts of NMP
The first step: the preparation of base polyurethane prepolymer for use as:
1. add molecular weight and be 100 parts of 500 polyethylene glycol adipate glycol in the four-hole boiling flask that reflux condensing tube, thermometer, agitator and vacuum orifice are housed, then vacuum-drying dehydration 3h under 100 ℃ temperature, removes vacuum cool-down to 40 ℃;
2. add 100 parts in acetone, add simultaneously 0.1 part of dibutyl tin dilaurate;
3. add 200 parts of isophorone diisocyanates, maintain the temperature at 40 ℃ of polyreaction 5h;
4. add 1 part of 28 parts of ethylene glycol and TriMethylolPropane(TMP), maintain the temperature at 40 ℃ of polyreaction 5h, 5. add the solution that has dissolved 10.6 parts of dimethylol propionic acids with 21.2 parts of NMP, maintain the temperature at 40 ℃ of polyreaction 5h;
Second step: neutralization reaction: keep temperature of reaction at 30 ℃, 8.8 parts of triethylamines are added drop-wise in the base polyurethane prepolymer for use as, neutralization reaction 1h obtains the base polyurethane prepolymer for use as of salify, and its degree of neutralization is 120%.
The 3rd step: make aqueous polyurethane:
1. the base polyurethane prepolymer for use as with salify in inciting somebody to action joins in the high speed dispersion, and under the high speed shear effect of high speed dispersor, ice calcium chloride water circulating cooling maintains the temperature at 5 ℃, adds 560.55 parts of deionized waters, and emulsification 30min obtains aqueous polyurethane;
2. with above-mentioned aqueous polyurethane under low rate mixing, drip 4 parts of quadrols, continue to stir 1.5h, expand and connect;
3. slough acetone in the aqueous polyurethane with the vacuum decompression method, make 934.25 parts of the aqueous polyurethanes of 40% content, pressure for about-0.098Mpa, temperature is 40 ℃;
4. prepared aqueous polyurethane is carried out packing.
Embodiment 2:
Take by weighing by weight following material, the preparation aqueous polyurethane:
150 parts of polyhexamethylene adipate glycols (molecular weight 1000)
150 parts of isophorone diisocyanates
20 parts of butyleneglycols
1 part of TriMethylolPropane(TMP)
18 parts of dimethylol propionic acids
13.6 parts of triethylamines
8.6 parts of diethylenetriamines
0.05 part of dibutyl tin dilaurate
100 parts in acetone
595.88 parts of deionized waters
36 parts of NMP
The first step: the preparation of base polyurethane prepolymer for use as:
1. in the four-hole boiling flask that reflux condensing tube, thermometer, agitator and vacuum orifice are housed, add molecular weight and be 150 parts of 1000 polyhexamethylene adipate glycols, at 110 ℃ of vacuum-dryings dehydration 2h, remove vacuum cool-down to 60 ℃;
2. add 100 parts in acetone, add simultaneously 0.05 part of dibutyl tin dilaurate;
3. add 150 parts of isophorone diisocyanates, maintain the temperature at 60 ℃, polyreaction 3h;
4. add 1 part of 20 parts of butyleneglycols and TriMethylolPropane(TMP), maintain the temperature at 60 ℃, polyreaction 3h,
5. add the solution that has dissolved 18 parts of dimethylol propionic acids with 36 parts of NMP, maintain the temperature at 60 ℃, polyreaction 3h.
Second step: neutralization reaction:
Keep temperature of reaction at 40 ℃, 13.6 parts of triethylamines are added drop-wise in the base polyurethane prepolymer for use as, neutralization reaction 40min obtains the base polyurethane prepolymer for use as of salify, and its degree of neutralization is 100%,
The 3rd step: make aqueous polyurethane:
1. will in and the base polyurethane prepolymer for use as of salify add in the high speed dispersion, under the high speed shear effect of high speed dispersor, ice calcium chloride water circulating cooling maintains the temperature at 10 ℃, adds 595.88 parts of deionized waters, emulsification 20min obtains aqueous polyurethane;
2. with above-mentioned aqueous polyurethane under low rate mixing, drip 8.6 parts of diethylenetriamines, continue to stir 1.5h, expand and connect;
3. slough acetone in the aqueous polyurethane with the vacuum decompression method, make 993.13 parts of the aqueous polyurethanes of 40% content, pressure for about-0.098Mpa, temperature is 50 ℃;
4. prepared aqueous polyurethane is carried out packing.
Embodiment 3:
Take by weighing by weight following material, the preparation aqueous polyurethane:
200 parts of polyoxypropyleneglycols (molecular weight 2000)
100 parts of isophorone diisocyanates
3.5 parts of neopentyl glycol
1 part of TriMethylolPropane(TMP)
24 parts of dimethylol propionic acids
14.5 parts of triethylamines
9.5 parts of tetraethylene pentamine
100 parts of butanone
603.63 parts of deionized waters
48 parts of NMP
The first step: the preparation of base polyurethane prepolymer for use as:
1. in the four-hole boiling flask that reflux condensing tube, thermometer, agitator and vacuum orifice are housed, add molecular weight and be 200 parts of 2000 polyoxypropyleneglycols, at 120 ℃ of vacuum-dryings dehydration 1h, remove vacuum cool-down to 60 ℃;
2. add 100 parts of butanone;
3. add 100 parts of isophorone diisocyanates, maintain the temperature at 80 ℃, polyreaction 2h;
4. add 1 part of 3.5 parts of neopentyl glycol and TriMethylolPropane(TMP), maintain the temperature at 80 ℃, polyreaction 2h,
5. add the solution that has dissolved 24 parts of dimethylol propionic acids with 48 parts of NMP, maintain the temperature at 80 ℃, polyreaction 2h.
Second step: neutralization reaction:
Keep temperature of reaction at 50 ℃, 14.5 parts of triethylamines are added drop-wise in the base polyurethane prepolymer for use as, neutralization reaction 30min obtains the base polyurethane prepolymer for use as of salify, and its degree of neutralization is 80%,
The 3rd step: make aqueous polyurethane:
1. will in and the base polyurethane prepolymer for use as of salify add in the high speed dispersion, under the high speed shear effect of high speed dispersor, ice calcium chloride water circulating cooling maintains the temperature at 10 ℃, adds 603.63 parts of deionized waters, emulsification 15min obtains aqueous polyurethane;
2. above-mentioned aqueous polyurethane drips 9.5 parts of tetraethylene pentamine under low rate mixing, continues to stir 1.5h, expands to connect;
3. slough butanone in the aqueous polyurethane with the vacuum decompression method, make 1004.13 parts of the aqueous polyurethanes of 40% content, pressure is-0.098Mpa about, temperature 70 C.
4. prepared aqueous polyurethane is carried out packing.
Embodiment 4:
Take by weighing by weight following material, the preparation aqueous polyurethane:
200 parts of polyoxypropyleneglycols (molecular weight 3000)
100 parts of isophorone diisocyanates
8 parts of ethylene glycol
1 part of TriMethylolPropane(TMP)
18 parts of dimethylol propionic acids
13.6 parts of triethylamines
5 parts of diethylenetriamines
0.02 part of stannous octoate
100 parts of butanone
890.44 parts of deionized waters
36 parts of NMP
The first step: the preparation of base polyurethane prepolymer for use as:
1. in the four-hole boiling flask that reflux condensing tube, thermometer, agitator and vacuum orifice are housed, add molecular weight and be 200 parts of 3000 polyoxypropyleneglycols, at 120 ℃ of vacuum-dryings dehydration 1h, remove vacuum cool-down to 60 ℃;
2. add 100 parts of butanone, add simultaneously 0.02 part of stannous octoate;
3. add 100 parts of isophorone diisocyanates, maintain the temperature at 80 ℃, polyreaction 2h;
4. add 1 part of 8 parts of ethylene glycol and TriMethylolPropane(TMP), maintain the temperature at 80 ℃, polyreaction 2h,
5. add the solution that has dissolved 18 parts of dimethylol propionic acids with 36 parts of NMP, maintain the temperature at 80 ℃, polyreaction 2h.
Second step: neutralization reaction:
Keep temperature of reaction at 50 ℃, 13.6 parts of triethylamines are added drop-wise in the base polyurethane prepolymer for use as, neutralization reaction 30min obtains the base polyurethane prepolymer for use as of salify, and its degree of neutralization is 100%,
The 3rd step: make aqueous polyurethane:
1. in inciting somebody to action and in the base polyurethane prepolymer for use as adding high speed dispersion of salify, under the high speed shear effect of high speed dispersor, the icy salt solution circulating cooling maintains the temperature at 20 ℃, adds 890.44 parts of deionized waters, and emulsification 15min obtains aqueous polyurethane;
2. with above-mentioned aqueous polyurethane under low rate mixing, drip 5 parts of diethylenetriamines, continue to stir 1.5h, expand and connect;
3. slough butanone in the aqueous polyurethane with the vacuum decompression method, make 1272.06 parts of the aqueous polyurethanes of 30% content, pressure for about-0.098Mpa, temperature is 60 ℃.
4. prepared aqueous polyurethane is carried out packing.
Embodiment 5:
Take by weighing by weight following material, the preparation aqueous polyurethane:
200 parts of polybutylene glyool adipates (molecular weight 2000)
100 parts of isophorone diisocyanates
4 parts of butyleneglycols
24 parts of dimethylol propionic acids
14.5 parts of triethylamines
5.2 parts of diethylenetriamines
603.63 parts of deionized waters
48 parts of NMP
The first step: the preparation of base polyurethane prepolymer for use as:
1. in the four-hole boiling flask that reflux condensing tube, thermometer, agitator and vacuum orifice are housed, add molecular weight and be 200 parts of 2000 polyoxypropyleneglycols, at 120 ℃ of vacuum-dryings dehydration 1h, remove vacuum cool-down to 100 ℃;
2. add 100 parts of isophorone diisocyanates, maintain the temperature at 100 ℃, polyreaction 2h;
3. add 4 parts of butyleneglycols, maintain the temperature at 100 ℃, polyreaction 2h,
4. add the solution that has dissolved 24 parts of dimethylol propionic acids with 50 parts of NMP, maintain the temperature at 100 ℃, polyreaction 2h.
Second step: neutralization reaction:
Keep temperature of reaction at 50 ℃, 14.5 parts of triethylamines are added drop-wise in the base polyurethane prepolymer for use as, neutralization reaction 30min obtains the base polyurethane prepolymer for use as of salify, and its degree of neutralization is 80%,
The 3rd step: make aqueous polyurethane:
1. will in and the base polyurethane prepolymer for use as of salify add in the high speed dispersion, under the high speed shear effect of high speed dispersor, ice calcium chloride water circulating cooling maintains the temperature at 15 ℃, adds 603.63 parts of deionized waters, emulsification 15min obtains aqueous polyurethane;
2. above-mentioned aqueous polyurethane drips 5.2 parts of diethylenetriamines under low rate mixing, continues to stir 1.5h, expands to connect;
3. make 999.43 parts of the aqueous polyurethanes of 40% content;
4. prepared aqueous polyurethane is carried out packing.
Embodiment 6:
Take by weighing by weight following material, the preparation aqueous polyurethane:
200 parts of polyoxypropyleneglycols (molecular weight 2000)
100 parts of isophorone diisocyanates
6 parts of ethylene glycol
1 part of TriMethylolPropane(TMP)
15 parts of dimethylol propionic acids
11.3 parts of triethylamines
3 parts of quadrols
0.02 part of stannous octoate
680.3 parts of deionized waters
30 parts of NMP
The first step: the preparation of base polyurethane prepolymer for use as:
1. in the four-hole boiling flask that reflux condensing tube, thermometer, agitator and vacuum orifice are housed, add molecular weight and be 200 parts of 2000 polyoxypropyleneglycols, at 120 ℃ of vacuum-dryings dehydration 1h, remove vacuum cool-down to 60 ℃;
2. stannous octoate is 0.02 part;
3. add 100 parts of isophorone diisocyanates, maintain the temperature at 80 ℃, polyreaction 2h;
4. add 1 part of 6 parts of ethylene glycol and TriMethylolPropane(TMP), maintain the temperature at 80 ℃, polyreaction 2h,
5. add the solution that has dissolved 15 parts of dimethylol propionic acids with 30 parts of NMP, maintain the temperature at 80 ℃, polyreaction 2h.
Second step: neutralization reaction:
Keep temperature of reaction at 50 ℃, 11.3 parts of triethylamines are added drop-wise in the base polyurethane prepolymer for use as, neutralization reaction 30min obtains the base polyurethane prepolymer for use as of salify, and its degree of neutralization is 100%,
The 3rd step: make aqueous polyurethane:
1. will in and the base polyurethane prepolymer for use as of salify add in the high speed dispersion, under the high speed shear effect of high speed dispersor, ice calcium chloride water circulating cooling maintains the temperature at 10 ℃, adds 680.3 parts of deionized waters, emulsification 15min obtains aqueous polyurethane;
2. above-mentioned aqueous polyurethane is under low rate mixing, drips 3 parts of quadrols, continues to stir 1.5h, expands to connect 1046.62 parts of aqueous polyurethanes that make 35% content;
3. prepared aqueous polyurethane is carried out packing.
Embodiment 7:
Take by weighing by weight following material, the preparation aqueous polyurethane:
150 parts of polyhexamethylene adipate glycols (molecular weight 1000)
150 parts of isophorone diisocyanates
22.4 parts of butyleneglycols
16 parts of dimethylol propionic acids
11.45 parts of triethylamines
0.05 part of dibutyl tin dilaurate
100 parts in acetone
572.85 parts of deionized waters
32 parts of NMP
The first step: the preparation of base polyurethane prepolymer for use as:
1. in the four-hole boiling flask that reflux condensing tube, thermometer, agitator and vacuum orifice are housed, add molecular weight and be 150 parts of 1000 polyhexamethylene adipate glycols, at 110 ℃ of vacuum-dryings dehydration 2h, remove vacuum cool-down to 60 ℃;
2. add 100 parts in acetone, add simultaneously 0.05 part of dibutyl tin dilaurate;
3. add 150 parts of isophorone diisocyanates, maintain the temperature at 60 ℃, polyreaction 3h;
4. add 22.4 parts of butyleneglycols, maintain the temperature at 60 ℃, polyreaction 3h,
5. add the solution that has dissolved 16 parts of dimethylol propionic acids with 32 parts of NMP, maintain the temperature at 60 ℃, polyreaction 3h.
Second step: neutralization reaction:
Keep temperature of reaction at 45 ℃, 11.45 parts of triethylamines are added drop-wise in the base polyurethane prepolymer for use as, neutralization reaction 35min obtains the base polyurethane prepolymer for use as of salify, and its degree of neutralization is 95%,
The 3rd step: make aqueous polyurethane:
1. will in and the base polyurethane prepolymer for use as of salify add in the high speed dispersion, under the high speed shear effect of high speed dispersor, ice calcium chloride water circulating cooling maintains the temperature at 10 ℃, adds 572.85 parts of deionized waters, emulsification 20min obtains aqueous polyurethane;
2. slough acetone in the aqueous polyurethane with the vacuum decompression method, make 954.75 parts of the aqueous polyurethanes of 40% content, pressure for about-0.098Mpa, temperature is 60 ℃.
3. prepared aqueous polyurethane is carried out packing.
Claims (9)
1. the production method of an aqueous polyurethane is characterized in that following these steps to carry out:
The first step: the preparation of base polyurethane prepolymer for use as:
1. take by weighing polyvalent alcohol: take by weighing by weight at least a in polyester polyol or the polyether glycol, after the drying, be cooled to 40～100 ℃ under the vacuum;
2. add vulcabond, the add-on of vulcabond is: the mol ratio of vulcabond and polyvalent alcohol is 0.5～2:1, maintains the temperature at 40～100 ℃ and carries out polyreaction;
3. add polyvalent alcohol chainextender and wetting ability chainextender, the add-on of polyvalent alcohol chainextender is: polyvalent alcohol chainextender hydroxyl value molar equivalent is 0.4～2.4:1 with the ratio of the hydroxyl value molar equivalent of above-mentioned polyvalent alcohol, the quality of the hydrophilic chain extender that adds is 3%～7% of performed polymer total mass, maintain the temperature at 40～100 ℃ and carry out polyreaction, make base polyurethane prepolymer for use as;
Second step: neutralization reaction, preparation base polyurethane prepolymer for use as salt:
Triethylamine is added drop-wise to carries out neutralization reaction in the base polyurethane prepolymer for use as, degree of neutralization is 80%～120%, and with in the base polyurethane prepolymer for use as and salify, the add-on of triethylamine is: the triethylamine amount is 0.8～1.2:1 with the ratio of hydrophilic chain extender amount;
The 3rd step: make aqueous polyurethane:
Under the effect of high speed dispersor, during deionized water joined and in the base polyurethane prepolymer for use as of salify, after the emulsification, make aqueous polyurethane.
2. according to the production method of aqueous polyurethane claimed in claim 1, it is characterized in that carry out step 2. before, add first the catalyzer of the acetone of 0～2 times of polyvalent alcohol quality or butanone, adding polyvalent alcohol quality 0～0.1%, and then carry out step 2.; When adding acetone or butanone in the preparation process, make in the aqueous polyurethane step in the 3rd step, after emulsification finishes, slough acetone or butanone in the aqueous polyurethane with the vacuum decompression method again.
3. according to the production method of claim 1 or 2 described aqueous polyurethanes, it is characterized in that making in the aqueous polyurethane step in the 3rd step, during deionized water joined and after in the base polyurethane prepolymer for use as of salify, use first the icy salt solution circulating cooling, maintain the temperature at 5～20 ℃, carry out again emulsification, make aqueous polyurethane.
4. according to the production method of aqueous polyurethane claimed in claim 3, it is characterized in that low rate mixing drips the polyamine compound in the prepared aqueous polyurethane, polyamine compound amount is 0.33～0.73:1 with the ratio of polyvalent alcohol amount.
5. according to the production method of aqueous polyurethane claimed in claim 1, the quality that it is characterized in that the deionized water of described adding is 1.5～2.5 times of base polyurethane prepolymer for use as salt.
6. according to the production method of aqueous polyurethane claimed in claim 1, it is characterized in that first the wetting ability chainextender being dissolved under 60～75 ℃ make solution in N-methyl-2 pyrrolidone after, join in the reactant, the mass ratio of wetting ability chainextender and N-methyl-2 pyrrolidone is 1:2～3 again.
7. according to the production method of aqueous polyurethane claimed in claim 1, the molecular weight that it is characterized in that described polyester polyol or polyether glycol is 500～3000.
8. according to the production method of claim 1 or 2 described aqueous polyurethanes, it is characterized in that described polyester polyol adopts at least a in the following material: polyethylene glycol adipate glycol, polypropylene adipate (PPA) glycol, polybutylene glyool adipate, polyhexamethylene adipate glycol, polyneopentyl glycol adipate glycol, poly-hexanodioic acid cyclohexanedimethanoester ester glycol, polycaprolactone glycol, polycarbonate diol; Described polyether glycol adopts at least a in the following material: polyoxypropyleneglycol, Polyoxyethylene glycol, polytetrahydrofuran diol; Described polyvalent alcohol chainextender adopts at least a in the following material: ethylene glycol, propylene glycol, Diethylene Glycol, BDO, neopentyl glycol, 1,6-hexylene glycol, cyclohexanedimethanol, glycol ether, sorbyl alcohol, glycerol, TriMethylolPropane(TMP); Described wetting ability chainextender adopts at least a in the following material: dimethylol propionic acid, dimethylolpropionic acid, thionamic acid sodium; Described vulcabond adopts at least a in the following material: hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, 4,4-diphenylmethanediisocyanate, tolylene diisocyanate; Described catalyzer adopts at least a in the following catalyzer: stannous octoate, dibutyl tin dilaurate, dibutyl two stannous octoates, triethylene diamine.
9. according to the production method of aqueous polyurethane claimed in claim 4, it is characterized in that described polyamine adopts at least a in the following material: quadrol, hexanediamine, diethylenetriamine, triethylene tetramine.
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