CN108794717A - A kind of modified aqueous polyurethane emulsion and its preparation method and application - Google Patents
A kind of modified aqueous polyurethane emulsion and its preparation method and application Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C08G18/04—Polymeric products of isocyanates or isothiocyanates with vinyl compounds
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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
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—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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- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- 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
- C08J2375/06—Polyurethanes from polyesters
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
The invention belongs to chemical field more particularly to a kind of modified aqueous polyurethane emulsion and its preparation method and application, which is mixed by aqueous polyurethane emulsion and propene carbonate；Aqueous polyurethane emulsion is made of the raw material including following parts by weight of component：60 parts of poly (propylene carbonate) polyalcohol；18~63 parts of diisocyanate；2~10 parts of hydrophilic chain extender；0.6~3 part of non-hydrophilic chain extender；0.06~0.36 part of catalyst；2~10 parts of neutralizer；100~300 parts of water.The present invention uses poly (propylene carbonate) polyalcohol and diisocyanate for main Material synthesis aqueous polyurethane emulsion, and the aqueous polyurethane emulsion of synthesis is modified using propene carbonate, to be obviously improved the performance of aqueous polyurethane emulsion, it is embodied in：The modified aqueous polyurethane emulsion has higher tensile strength and hardness after forming glued membrane, and lower water absorption rate, water resistance is more preferable.
Description
Technical field
The invention belongs to chemical fields more particularly to a kind of modified aqueous polyurethane emulsion and its preparation method and application.
Background technology
Polyurethane is the high molecular material obtained by polymer polyatomic alcohol and isocyanates alternating polymerization, due to that can pass through
Its soft or hard monomer ratio is adjusted to reach different performances, is widely used general.There are mainly two types of the raw materials of polyurethane-and it is different
Cyanate and polymer polyatomic alcohol, wherein most commonly seen polyalcohol is polyester polyol and polyether polyol.Polyester-type is aqueous
Polyurethane mechanical strength is high, but its ester bond facile hydrolysis, and water resistance is very poor, therefore aqueous polyurethane on the market is with polyethers substantially
Based on type polyalcohol.Polyether type aqueous polyurethane low-temperature flexibility is good, hydrolysis, but polyether type aqueous polyurethane itself is strong
Degree, hardness are low, not scratch-resistant, therefore properties of product are poor.
It is primary raw material and two isocyanides that CN103755911A, which discloses one kind based on poly (propylene carbonate) dihydric alcohol (PPC),
Acid esters and small molecule hydrophilic chain extender react and the water-base polyurethane material to obtain that a kind of intensity is high, hydrolytic resistance is good are made.So
And simple aqueous polyurethane due to introducing hydrophilic radical still there is higher water absorption rate, glued membrane to impregnate water suction and bleach, mechanical property
It can decline.CN107141438A reports one kind using PPC, TDI, DMPA as Material synthesis performed polymer, and silicon is added in neutralization stage
Alkane coupling agent KH560 is modified to obtain a kind of aqueous polyurethane emulsion of enhanced water resistance.It introduces hydrophobic grouping in side chain, makes silane
Coupling agent is enriched in film surface, reduces surface tension, and film surface hydrophobicity greatly enhances, to have good water resistance,
Glued membrane impregnates 5 days still water white transparencies through water.Studies have found that glued membrane tensile strength, hardness can be caused by introducing silane coupling agent
It declines to a great extent, and epoxy group open loop during storage causes stability of emulsion to be deteriorated.
Therefore, how to prepare a kind of aqueous polyurethane having both high intensity, high rigidity, enhanced water resistance and low water absorption becomes
Those skilled in the art's urgent problem to be solved.
Invention content
In view of this, the purpose of the present invention is to provide a kind of modified aqueous polyurethane emulsion and preparation method thereof and answering
With modified aqueous polyurethane emulsion provided by the invention has good tensile strength and hardness, lower water suction after film forming
Rate and excellent water resistance energy.
The present invention provides a kind of modified aqueous polyurethane emulsions, by aqueous polyurethane emulsion and propene carbonate mixing system
At；The aqueous polyurethane emulsion is made of the raw material including following parts by weight of component：
Preferably, the propene carbonate account for the aqueous polyurethane emulsion and propene carbonate gross mass 0.2~
5wt%.
Preferably, the number-average molecular weight of the poly (propylene carbonate) polyalcohol is 1000~3000；The polymerized thylene carbonate third
The hydroxy functionality of ester polyol is 2~3；The mole fraction of the intramolecular carbonate group of the poly (propylene carbonate) polyalcohol
It is 0.3~0.4.
Preferably, the diisocyanate includes isofoer diisocyanate, hexamethylene diisocyanate and hydrogenation
It is one or more in methyl diphenylene diisocyanate.
Preferably, the hydrophilic chain extender includes ethylenediamine base ethanesulfonic acid sodium, dihydromethyl propionic acid and dimethylolpropionic acid
In it is one or more；
The non-hydrophilic chain extender includes one kind or more in ethylenediamine, triethylene diamine and ethylenediamine base ethanesulfonic acid sodium
Kind.
Preferably, the catalyst includes one kind or more in stannous octoate, di-n-butyltin dilaurate and tin acetate
Kind.
The present invention provides a kind of preparation method of modified aqueous polyurethane emulsion described in above-mentioned technical proposal, including it is following
Step：
A) by poly (propylene carbonate) polyalcohol, diisocyanate, hydrophilic chain extender and catalyst hybrid reaction, pre-polymerization is obtained
Body；
B) performed polymer, with neutralizer and water hybrid reaction, is obtained into emulsion with after organic solvent mixing viscosity reduction；
C) by the emulsion and non-hydrophilic chain extender hybrid reaction, the organic solvent is removed later, is obtained aqueous poly-
Urethane lotion；
D) aqueous polyurethane emulsion and propene carbonate are mixed, obtains modified aqueous polyurethane emulsion.
Preferably, further include：Heating reaction is carried out to the modified aqueous polyurethane emulsion that step d) is mixed to get.
Preferably, the temperature of the heating reaction is 70~90 DEG C；The time of the heating reaction is 0.5~2h.
The present invention provides described in above-mentioned technical proposal modified aqueous polyurethane emulsion or above-mentioned technical proposal described in side
The glued membrane formed after modified aqueous polyurethane emulsion film forming prepared by method.
Compared with prior art, the present invention provides a kind of modified aqueous polyurethane emulsions and its preparation method and application.
Modified aqueous polyurethane emulsion provided by the invention is mixed by aqueous polyurethane emulsion and propene carbonate；It is described aqueous poly-
Urethane lotion is made of the raw material including following parts by weight of component：60 parts of poly (propylene carbonate) polyalcohol；Diisocyanate 18~
63 parts；2~10 parts of hydrophilic chain extender；0.6~3 part of non-hydrophilic chain extender；0.06~0.36 part of catalyst；2~10 parts of neutralizer；
100~300 parts of water.The present invention uses poly (propylene carbonate) polyalcohol and diisocyanate for main Material synthesis aqueous polyurethane
Lotion, and the aqueous polyurethane emulsion of synthesis is modified using propene carbonate, to be obviously improved aqueous polyurethane
The performance of lotion, is embodied in：The modified aqueous polyurethane emulsion has higher stretch by force after forming glued membrane
Degree and hardness, lower water absorption rate, water resistance are more preferable.The experimental results showed that：Modified aqueous polyurethane emulsion provided by the invention
Tensile strength > 32MPa, elongation at break > 920%, pendulum-rocker hardness > 45s, water absorption rate < after forming glued membrane
8.5%, appearance is substantially unchanged after glued membrane impregnates for 24 hours.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
The every other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.
The present invention provides a kind of modified aqueous polyurethane emulsions, by aqueous polyurethane emulsion and propene carbonate mixing system
At；The aqueous polyurethane emulsion is made of the raw material including following parts by weight of component：
Modified aqueous polyurethane emulsion provided by the invention is mixed by aqueous polyurethane emulsion and propene carbonate.Its
In, the aqueous polyurethane emulsion is by including poly (propylene carbonate) polyalcohol, diisocyanate, hydrophilic chain extender, non-hydrophilic expansion
Chain agent, catalyst, neutralizer and water raw material be made.
In the present invention, the number-average molecular weight of the poly (propylene carbonate) polyalcohol is preferably 1000~3000, specifically may be used
It is 1000,1500,2000,2500 or 3000；The hydroxy functionality of the poly (propylene carbonate) polyalcohol is preferably 2~3；It is described
The mole fraction of the intramolecular carbonate group of poly (propylene carbonate) polyalcohol is preferably 0.3~0.4, concretely 0.3,
0.31,0.32,0.33,0.34,0.35,0.36,037,0.38,0.39 or 0.4.
In the present invention, the diisocyanate includes but not limited to that isofoer diisocyanate, hexa-methylene two are different
It is one or more in cyanate and hydrogenated diphenyl methane diisocyanate, preferably isophorone diisocyanate.At this
In invention, by the content of the poly (propylene carbonate) polyalcohol in the feed in terms of 60 parts by weight, the diisocyanate is in original
Content in material is 18~63 parts by weight, concretely 18 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 weight
Part, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight or 63 parts by weight.
In the present invention, the hydrophilic chain extender include but not limited to ethylenediamine base ethanesulfonic acid sodium, dihydromethyl propionic acid and
It is one or more in dimethylolpropionic acid, preferably dihydromethyl propionic acid.In the present invention, more with the poly (propylene carbonate)
The content of first alcohol in the feed is 60 parts by weight meters, and the content of the hydrophilic chain extender in the feed is 2~10 parts by weight, specifically
Can be 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 4.7 parts by weight, 5 parts by weight,
5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 weights
Measure part or 10 parts by weight.
In the present invention, the non-hydrophilic chain extender includes but not limited to ethylenediamine, triethylene diamine and ethylenediamine base second
It is one or more in sodium sulfonate, preferably ethylenediamine.In the present invention, in the feed with the poly (propylene carbonate) polyalcohol
Content be 60 parts by weight meters, the content of the non-hydrophilic chain extender in the feed is 0.6~3 parts by weight, concretely 0.6 weight
Measure part, 0.8 parts by weight, 1 parts by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 weights
Measure part, 2.4 parts by weight, 2.6 parts by weight, 2.8 parts by weight or 3 parts by weight.
In the present invention, the catalyst includes but not limited to stannous octoate, di-n-butyltin dilaurate and tin acetate
In one or more, preferably stannous octoate.In the present invention, containing in the feed with the poly (propylene carbonate) polyalcohol
Amount be 60 parts by weight meters, the content of the catalyst in the feed be 0.06~0.36 parts by weight, concretely 0.06 parts by weight,
0.09 parts by weight, 0.12 parts by weight, 0.15 parts by weight, 0.18 parts by weight, 0.21 parts by weight, 0.24 parts by weight, 0.27 parts by weight,
0.3 parts by weight, 0.33 parts by weight or 0.36 parts by weight.
In the present invention, the neutralizer includes one kind in triethylamine, tripropyl amine (TPA), tri-n-butylamine, sodium hydroxide and ammonium hydroxide
Or a variety of, preferably triethylamine.In the present invention, with poly (propylene carbonate) polyalcohol content in the feed for 60 weight
Part meter, the content of the neutralizer in the feed be 2~10 parts by weight, concretely 2 parts by weight, 2.5 parts by weight, 3 parts by weight,
3.5 parts by weight, 3.54 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7
Parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight or 10 parts by weight.
In the present invention, the water is preferably deionized water, with the poly (propylene carbonate) polyalcohol containing in the feed
Amount is 60 parts by weight meters, and the content of the water in the feed is 100~300 parts by weight, concretely 100 parts by weight, 150 weight
Part, 200 parts by weight, 250 parts by weight or 300 parts by weight.
The present invention also provides a kind of preparation methods of modified aqueous polyurethane emulsion described in above-mentioned technical proposal, including with
Lower step：
A) by poly (propylene carbonate) polyalcohol, diisocyanate, hydrophilic chain extender and catalyst hybrid reaction, pre-polymerization is obtained
Body；
B) performed polymer, with neutralizer and water hybrid reaction, is obtained into emulsion with after organic solvent mixing viscosity reduction；
C) by the emulsion and non-hydrophilic chain extender hybrid reaction, the organic solvent is removed later, is obtained aqueous poly-
Urethane lotion；
D) aqueous polyurethane emulsion and propene carbonate are mixed, obtains modified aqueous polyurethane emulsion.
In preparation method provided by the invention, first by poly (propylene carbonate) polyalcohol, diisocyanate, hydrophilic chain extension
Agent and catalyst hybrid reaction.Wherein, the temperature of the hybrid reaction is preferably 70~90 DEG C, concretely 70 DEG C, 75 DEG C, 80
DEG C, 85 DEG C or 90 DEG C；The time of the hybrid reaction is preferably 2~6h, concretely 2h, 2.5h, 3h, 3.5h, 4h, 4.5h,
5h, 5.5h or 6h.After reaction, performed polymer is obtained.
After obtaining the performed polymer, by the performed polymer and organic solvent mixing viscosity reduction.Wherein, the organic solvent is preferred
For acetone；The mass ratio of the organic solvent and the poly (propylene carbonate) polyalcohol is preferably (5~20)：60, concretely
5:60,10:60,15:60 or 20:60.
After viscosity reduction, with neutralizer and water hybrid reaction.In the present invention, the performed polymer after viscosity reduction is preferred first mixed with neutralizer
Close reaction, later again with water hybrid reaction.Wherein, it is preferably -10~40 DEG C with the temperature of neutralizer hybrid reaction, specifically may be used
Be -10 DEG C, 0 DEG C, 10 DEG C, 20 DEG C, 30 DEG C or 40 DEG C, the time is preferably 5~60min, concretely 5min, 10min, 20min,
30min, 40min, 50min or 60min；It is preferably -10~25 DEG C with the temperature of water hybrid reaction, concretely -10 DEG C, -5
DEG C, 0 DEG C, 5 DEG C, 10 DEG C, 15 DEG C, 20 DEG C or 25 DEG C, the time is preferably 10~60min, concretely 10min, 15min,
20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, stir speed (S.S.) is preferably 1200~
2500r/min, concretely 1200r/min, 1500r/min, 2000r/min or 2500r/min.After reaction, breast is obtained
Shape liquid.
After obtaining the emulsion, by the emulsion and non-hydrophilic chain extender hybrid reaction.Wherein, the hybrid reaction
Temperature be preferably 15~35 DEG C, concretely 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C or 35 DEG C；The time of the hybrid reaction is preferred
For 10~60min, concretely 10min, 20min, 30min, 40min, 50min or 60min.After reaction, viscosity reduction is removed
The mode of the organic solvent of Shi Tianjia, the removing preferably depressurizes.After organic solvent removes, aqueous polyurethane breast is obtained
Liquid.
After obtaining the aqueous polyurethane emulsion, the aqueous polyurethane emulsion and propene carbonate are mixed.Wherein, institute
The temperature for stating mixing is preferably 10~35 DEG C, concretely 10,15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C or 35 DEG C；The mixing is stirred
It is preferably 200~800r/min to mix rate, concretely 200r/min, 300r/min, 400r/min, 500r/min, 600r/
Min, 700r/min or 800r/min；The time of the mixing is preferably 10~30min, concretely 10min, 15min,
20min, 25min or 30min.After mixing, modified aqueous polyurethane emulsion is obtained.
In the present invention, in order to further enhance the performance for the modified aqueous polyurethane emulsion being prepared, preferably
Heating reaction is carried out to the modified aqueous polyurethane emulsion being mixed to get.Wherein, the temperature of the heating reaction is preferably
70~90 DEG C, concretely 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C；The time of the heating reaction is preferably 0.5~2h, tool
Body can be 0.5h, 1h, 1.5h or 2h.
The present invention uses poly (propylene carbonate) polyalcohol and diisocyanate for main Material synthesis aqueous polyurethane emulsion,
And the aqueous polyurethane emulsion of synthesis is modified using propene carbonate, to be obviously improved aqueous polyurethane emulsion
Performance.Specifically, modified aqueous polyurethane emulsion provided by the invention and preparation method thereof has at least the following advantages：
1) present invention utilizes propene carbonate modified aqueous polyurethane emulsion, is reacted with isocyanates by propene carbonate
Formed cross-linked network structure, improve glued membrane tensile strength, reduce glued membrane water absorption rate, product have high intensity, water-tolerant etc.
Advantage.
2) propene carbonate that this hair uses belongs to the synthesising by-product of poly (propylene carbonate), almost cost free, and can solve
Certainly problem is recycled in the processing of poly (propylene carbonate) by-product, and modified technique is simple, there is industrial application value.
3) present invention does not need to introduce high boiling solvent during the aqueous polyurethane emulsion of synthesis, is applying
VOC free discharges in journey, belongs to solvent-free environment-protection aqueous polyurethane emulsion.
4) present invention using poly (propylene carbonate) polyalcohol is made as raw material using carbon dioxide and propylene oxide, has carbon
The structure of perester radical and ether, intensity is high, and hydrolysis is at low cost, and mass produces and can't cause damages to environment, right
Environmental protection, energy-saving and emission-reduction have a very big significance.
The experimental results showed that：Tensile strength > of the modified aqueous polyurethane emulsion provided by the invention after forming glued membrane
32MPa, elongation at break > 920%, pendulum-rocker hardness > 45s, water absorption rate < 8.5%, appearance is substantially without change after glued membrane impregnates for 24 hours
Change.
The present invention also provides the modified aqueous polyurethane emulsions or above-mentioned technical proposal described in a kind of above-mentioned technical proposal
The glued membrane formed after modified aqueous polyurethane emulsion film forming prepared by the method.Glued membrane provided by the invention is by the modified water
Property polyaminoester emulsion film forming after formed, there is good tensile strength and hardness, lower water absorption rate and excellent water resistance energy.It is real
Test the result shows that：Tensile strength > 32MPa, elongation at break > 920%, the pendulum-rocker hardness > 45s of glued membrane provided by the invention,
Water absorption rate < 8.5%, appearance is substantially unchanged after glued membrane impregnates for 24 hours.
For the sake of becoming apparent from, it is described in detail below by following embodiment.
Embodiment 1
It is 3000 to take 60 parts by weight molecular weight, the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2, after dehydration, is added
25 parts by weight isophorone diisocyanate, 4.7 parts by weight dihydromethyl propionic acids and 0.12 parts by weight of octanoic acid stannous catalyst,
It is reacted 4 hours at 85 DEG C, 10 pbw acetones, which are added, reduces viscosity, is reduced to 40 DEG C, is added in 3.54 parts by weight triethylamines and 5
Minute, 200 parts by weight of deionized water high speed (1200r/min) at 25 DEG C is added and emulsifies 15 minutes, 1.2 parts by weight second two are added
Amine chain extension 30 minutes at 25 DEG C, removed under reduced pressure acetone obtain aqueous polyurethane emulsion.Take 99.5 parts by weight aqueous polyurethane breasts
0.5 parts by weight propene carbonate is added dropwise under 25 DEG C, low speed (500r/min) dispersion in liquid, disperses 30 minutes, then stirring heating
It is reacted 1 hour to 80 DEG C, obtains the ester modified aqueous polyurethane emulsion of propylene carbonate.
Embodiment 2
It is 3000 to take 60 parts by weight molecular weight, the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2, after dehydration, is added
25 parts by weight isophorone diisocyanate, 4.7 parts by weight dihydromethyl propionic acids and 0.12 parts by weight of octanoic acid stannous catalyst,
It is reacted 4 hours at 85 DEG C, 10 pbw acetones, which are added, reduces viscosity, is reduced to 40 DEG C, is added in 3.54 parts by weight triethylamines and 5
Minute, 200 parts by weight of deionized water high speed (1200r/min) at 25 DEG C is added and emulsifies 15 minutes, 1.2 parts by weight second two are added
Amine chain extension 30 minutes at 25 DEG C, removed under reduced pressure acetone obtain aqueous polyurethane emulsion.Take 99 parts by weight aqueous polyurethane breasts
1 parts by weight propene carbonate is added dropwise under 25 DEG C, low speed (500r/min) dispersion in liquid, disperses 30 minutes, then stirring is warming up to
80 DEG C are reacted 1 hour, and the ester modified aqueous polyurethane emulsion of propylene carbonate is obtained.
Embodiment 3
It is 3000 to take 60 parts by weight molecular weight, the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2, after dehydration, is added
25 parts by weight isophorone diisocyanate, 4.7 parts by weight dihydromethyl propionic acids and 0.12 parts by weight of octanoic acid stannous catalyst,
It is reacted 4 hours at 85 DEG C, 10 pbw acetones, which are added, reduces viscosity, is reduced to 40 DEG C, is added in 3.54 parts by weight triethylamines and 5
Minute, 200 parts by weight of deionized water high speed (1200r/min) at 25 DEG C is added and emulsifies 15 minutes, 1.2 parts by weight second two are added
Amine chain extension 30 minutes at 25 DEG C, removed under reduced pressure acetone obtain aqueous polyurethane emulsion.Take 98 parts by weight aqueous polyurethane breasts
2 parts by weight propene carbonates are added dropwise under 25 DEG C, low speed (500r/min) dispersion in liquid, disperse 30 minutes, then stirring is warming up to
80 DEG C are reacted 1 hour, and the ester modified aqueous polyurethane emulsion of propylene carbonate is obtained.
Embodiment 4
It is 3000 to take 60 parts by weight molecular weight, the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2, after dehydration, is added
25 parts by weight isophorone diisocyanate, 4.7 parts by weight dihydromethyl propionic acids and 0.12 parts by weight of octanoic acid stannous catalyst,
It is reacted 4 hours at 85 DEG C, 10 pbw acetones, which are added, reduces viscosity, is reduced to 40 DEG C, is added in 3.54 parts by weight triethylamines and 5
Minute, 200 parts by weight of deionized water high speed (1200r/min) at 25 DEG C is added and emulsifies 15 minutes, 1.2 parts by weight second two are added
Amine chain extension 30 minutes at 25 DEG C, removed under reduced pressure acetone obtain aqueous polyurethane emulsion.Take 97 parts by weight aqueous polyurethane breasts
3 parts by weight propene carbonates are added dropwise under 25 DEG C, low speed (500r/min) dispersion in liquid, disperse 30 minutes, then stirring is warming up to
80 DEG C are reacted 1 hour, and the ester modified aqueous polyurethane emulsion of propylene carbonate is obtained.
Embodiment 5
It is 3000 to take 60 parts by weight molecular weight, the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2, after dehydration, is added
25 parts by weight isophorone diisocyanate, 4.7 parts by weight dihydromethyl propionic acids and 0.12 parts by weight of octanoic acid stannous catalyst,
It is reacted 4 hours at 85 DEG C, 10 pbw acetones, which are added, reduces viscosity, is reduced to 40 DEG C, is added in 3.54 parts by weight triethylamines and 5
Minute, 200 parts by weight of deionized water high speed (1200r/min) at 25 DEG C is added and emulsifies 15 minutes, 1.2 parts by weight second two are added
Amine chain extension 30 minutes at 25 DEG C, removed under reduced pressure acetone obtain aqueous polyurethane emulsion.Take 96 parts by weight aqueous polyurethane breasts
4 parts by weight propene carbonates are added dropwise under 25 DEG C, low speed (500r/min) dispersion in liquid, disperse 30 minutes, then stirring is warming up to
80 DEG C are reacted 1 hour, and the ester modified aqueous polyurethane emulsion of propylene carbonate is obtained.
Embodiment 6
It is 3000 to take 60 parts by weight molecular weight, the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2, after dehydration, is added
25 parts by weight isophorone diisocyanate, 4.7 parts by weight dihydromethyl propionic acids and 0.12 parts by weight of octanoic acid stannous catalyst,
It is reacted 4 hours at 85 DEG C, 10 pbw acetones, which are added, reduces viscosity, is reduced to 40 DEG C, is added in 3.54 parts by weight triethylamines and 5
Minute, 200 parts by weight of deionized water high speed (1200r/min) at 25 DEG C is added and emulsifies 15 minutes, 1.2 parts by weight second two are added
Amine chain extension 30 minutes at 25 DEG C, removed under reduced pressure acetone obtain aqueous polyurethane emulsion.Take 97 parts by weight aqueous polyurethane breasts
Liquid is added dropwise 3 parts by weight propene carbonates under 25 DEG C, low speed (500r/min) dispersion, disperses 30 minutes, obtain propene carbonate
Modified aqueous polyurethane emulsion.
Comparative example 1
It is 3000 to take 60 parts by weight molecular weight, the poly (propylene carbonate) dihydric alcohol that hydroxy functionality is 2, after dehydration, is added
25 parts by weight isophorone diisocyanate, 4.7 parts by weight dihydromethyl propionic acids and 0.12 parts by weight of octanoic acid stannous catalyst,
It is reacted 4 hours at 85 DEG C, 10 pbw acetones, which are added, reduces viscosity, is reduced to 40 DEG C, is added in 3.54 parts by weight triethylamines and 5
Minute, 200 parts by weight of deionized water high speed (1200r/min) at 25 DEG C is added and emulsifies 15 minutes, 1.2 parts by weight second two are added
Amine chain extension 30 minutes at 25 DEG C, removed under reduced pressure acetone are warming up to 80 DEG C of curings and obtain aqueous polyurethane emulsion in 1 hour.
Performance test
Lotion made from Example 1~6 and comparative example 1 prepares 100um wet films, in 80 DEG C of baking ovens with four sides spreader
Middle drying 24 hours measures examination film pendulum-rocker hardness with BGD pendulum-rocker hardness, and experimental result is as shown in table 1.
Lotion made from Example 1~6 and comparative example 1, is placed in Teflon mould, air drying 24 hours,
It is 24 hours dry in baking oven at 80 DEG C again, aqueous polyurethane glued membrane is made, cutting out sample with dumbbell shape cut-off knife carries out extension test, real
Test that the results are shown in Table 1.
Lotion made from Example 1~6 and comparative example 1, is placed in Teflon mould, air drying 24 hours,
It is 24 hours dry in baking oven at 80 DEG C again, aqueous polyurethane glued membrane is made, cuts 2cm*2cm glue films, is soaked in normal-temperature water
Bubble 24 hours surveys water absorption rate, observes glued membrane cosmetic variation, and experimental result is as shown in table 1.
Table 1：Glue film performance test result
To sum up, table 1 the result shows that, it is relatively single using the aqueous polyurethane (Examples 1 to 6) of the ester modified preparation of propylene carbonate
The aqueous polyurethane (comparative example 1) of pure PPC types, with higher tensile strength, hardness, lower water absorption rate, water resistance is more preferable.
Pass through embodiment 4 and embodiment 6, it can be seen that after propene carbonate is added, then cure 1 hour at 80 DEG C, modified effect is more preferable.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of modified aqueous polyurethane emulsion, is mixed by aqueous polyurethane emulsion and propene carbonate；It is described aqueous poly-
Urethane lotion is made of the raw material including following parts by weight of component：
2. modified aqueous polyurethane emulsion according to claim 1, which is characterized in that the propene carbonate accounts for the water
0.2~5wt% of property polyaminoester emulsion and propene carbonate gross mass.
3. modified aqueous polyurethane emulsion according to claim 1, which is characterized in that the poly (propylene carbonate) polyalcohol
Number-average molecular weight be 1000~3000；The hydroxy functionality of the poly (propylene carbonate) polyalcohol is 2~3；The poly- carbonic acid
The mole fraction of the intramolecular carbonate group of sub- propyl ester polyalcohol is 0.3~0.4.
4. modified aqueous polyurethane emulsion according to claim 1, which is characterized in that the diisocyanate include it is different not
It is one or more in your ketone diisocyanate, hexamethylene diisocyanate and hydrogenated diphenyl methane diisocyanate.
5. modified aqueous polyurethane emulsion according to claim 1, which is characterized in that the hydrophilic chain extender includes second two
It is one or more in amido ethanesulfonic acid sodium, dihydromethyl propionic acid and dimethylolpropionic acid；
The non-hydrophilic chain extender includes one or more in ethylenediamine, triethylene diamine and ethylenediamine base ethanesulfonic acid sodium.
6. modified aqueous polyurethane emulsion according to claim 1, which is characterized in that the catalyst includes that octanoic acid is sub-
It is one or more in tin, di-n-butyltin dilaurate and tin acetate.
7. the preparation method of modified aqueous polyurethane emulsion, includes the following steps described in a kind of claim 1：
A) by poly (propylene carbonate) polyalcohol, diisocyanate, hydrophilic chain extender and catalyst hybrid reaction, performed polymer is obtained；
B) performed polymer, with neutralizer and water hybrid reaction, is obtained into emulsion with after organic solvent mixing viscosity reduction；
C) by the emulsion and non-hydrophilic chain extender hybrid reaction, the organic solvent is removed later, obtains aqueous polyurethane
Lotion；
D) aqueous polyurethane emulsion and propene carbonate are mixed, obtains modified aqueous polyurethane emulsion.
8. preparation method according to claim 7, which is characterized in that further include：Described change to what step d) was mixed to get
Property aqueous polyurethane emulsion carries out heating reaction.
9. preparation method according to claim 8, which is characterized in that the temperature of the heating reaction is 70~90 DEG C；Institute
The time for stating heating reaction is 0.5~2h.
10. described in a kind of claim 1~6 any one of them modified aqueous polyurethane emulsion or any one of claim 7~9
The glued membrane formed after modified aqueous polyurethane emulsion film forming prepared by method.
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| CN112266475A (en) * | 2020-11-05 | 2021-01-26 | 中国科学院长春应用化学研究所 | Carbon dioxide polyester polyol, full-biodegradable carbon dioxide-based polyurethane and preparation method thereof |
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| CN112266475A (en) * | 2020-11-05 | 2021-01-26 | 中国科学院长春应用化学研究所 | Carbon dioxide polyester polyol, full-biodegradable carbon dioxide-based polyurethane and preparation method thereof |
| CN112266475B (en) * | 2020-11-05 | 2022-02-22 | 中国科学院长春应用化学研究所 | Carbon dioxide polyester polyol, full-biodegradable carbon dioxide-based polyurethane and preparation method thereof |
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