CN108034039A - A kind of aqueous polyurethane emulsion of color inhibition and preparation method thereof - Google Patents
A kind of aqueous polyurethane emulsion of color inhibition and preparation method thereof Download PDFInfo
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- CN108034039A CN108034039A CN201711464252.XA CN201711464252A CN108034039A CN 108034039 A CN108034039 A CN 108034039A CN 201711464252 A CN201711464252 A CN 201711464252A CN 108034039 A CN108034039 A CN 108034039A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines acyclic
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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
- C08G18/44—Polycarbonates
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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
- C08G18/70—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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- Chemical Kinetics & Catalysis (AREA)
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of aqueous polyurethane emulsion of color inhibition and preparation method thereof, the aqueous polyurethane emulsion of the color inhibition includes the component of following quality proportioning：Side chain contains 0.6~1.2 part of 5~20 parts of 12 parts of 0.06~0.36 part of 18~63 parts of 115~125 parts of poly (propylene carbonate) polyalcohol, aliphatic diisocyanate, catalyst, neutralizer, acetone, 332~460 parts of deionized water and the chain extender of carboxyl.The aqueous polyurethane emulsion of the color inhibition by side chain contain carboxyl poly (propylene carbonate) polyalcohol and aliphatic diisocyanate under the action of catalyst, add chain extender reaction generate to obtain.The present invention provides a kind of aqueous polyurethane emulsion of color inhibition and preparation method thereof, the aqueous polyurethane emulsion block for the color inhibition being prepared is uniform, soft and hard segments are evenly distributed and stable quality, xanthochromia will not occur for long-term storage, improved preparation method generating process safety and environmental protection, used raw material is environmentally friendly and cost is low, and preparation process is simple, has actual application value.
Description
Technical field
The present invention relates to high-molecular organic material technical field, especially a kind of aqueous polyurethane emulsion of color inhibition and its
Preparation method.
Background technology
Aqueous polyurethane is a kind of new material, is widely used in coating, adhesive, fabric coating and finishing agent, leather
The fields such as finishing agent, sheet surface treating agent and fiber surface treatment agent.Conventional solvent type polyurethane needs in the synthesis process
Using substantial amounts of organic solvent, such as toluene, benzene, alkyl chloride, produce and application process in produce substantial amounts of volatility organic
Thing, not only inflammable and explosive, high volatility, pollutes environment, but also is largely detrimental to health.With
The constantly improve of laws and regulations and environmental protection, safety, low-carbon consciousness are rooted in the hearts of the people, and aqueous polyurethane is organic molten due to being replaced using water
Agent, volatile organic content is low, and smell is small, its develop and its application have received widespread attention and aqueous polyurethane by
Step substitution solvent borne polyurethane is applied into market.
The raw material of polyurethane mainly has two kinds, is isocyanates and polyalcohol, and traditional isocyanates is aromatic series isocyanic acid
Ester, it is high as aqueous polyurethane intensity prepared by raw material using it, but there are the shortcomings that easy xanthochromia, aliphatic isocyanates are in recent years
Aqueous polyurethane emulsion prepared by raw material is taken seriously due to color inhibition.Traditional waterborne polyurethane is usually frequently with polyester polyols
Alcohol or polyether polyol are main Material synthesis.But since polyester polyol facile hydrolysis, aqueous polyurethane are basic
It is based on polyether polyol, polyether type aqueous polyurethane low-temperature flexibility is good, hydrolysis, but polyether type aqueous polyurethane
Intensity itself, hardness are low, not scratch-resistant, bonding force difference, therefore be very restricted in actually using.Using poly- tetrahydrochysene furan
Mutter, polyethylencarbonate glycol can obtain intensity height, scratch-resistant and the good aqueous polyurethane product of cohesive force, but product
Cost is too high, is unfavorable for industrialized large-scale production.
A kind of aqueous polyurethane emulsion of color inhibition and preparation method thereof（Publication No.：CN105504215）Disclose one kind
Use prepared by traditional handicraft based on poly (propylene carbonate) dihydric alcohol for primary raw material, and aliphatic isocyanates, small molecule are close
Water chain extender and chain extension-crosslinking agent react and the high water-base polyurethane material of a kind of high intensity, high rigidity, cohesive force are made.But
When being traditional handicraft synthesis aqueous polyurethane, it is by introducing hydrophilic chain extender in hard section, but can so causes finally to close
Into polyurethane products block lack of homogeneity, soft and hard segments skewness and emulsion appearance is bad the shortcomings of.And usual water
Property polyurethane can add some high boiling solvents in preparation process makes small molecule hydrophilic chain extender and whole reaction system anti-
Should be uniform, therefore can equally cause a small amount of Volatile organic emissions.
However, it has been investigated that, it can not only improve poly- ammonia by introducing hydrophilic radical synthesis aqueous polyurethane in soft segment
Block uniformity, the soft and hard segments of ester product are evenly distributed and relatively good emulsion appearance, and are not introduced in preparation process
The use of the low boiling point solvents such as high boiling solvent, acetone is also largely reduced.
For above-mentioned technical problem, there is provided a kind of block uniformity is good, and soft and hard segments are evenly distributed and relatively good lotion
Appearance, and high boiling solvent is not introduced in preparation process, reduce the aqueous polyurethane for the color inhibition that low boiling point solvent uses
Emulsion preparation method is technical problem in the urgent need to address at present.
The content of the invention
The technical problem to be solved is that the water-based poly- ammonia for the color inhibition being prepared for the prior art for the invention
The shortcomings of ester product emulsion block lack of homogeneity, soft and hard segments skewness and bad emulsion appearance, propose a kind of color inhibition
The preparation method of aqueous polyurethane emulsion, gained aqueous polyurethane emulsion product block uniformity is good, soft and hard segments be evenly distributed and
Emulsion appearance is good.
To reach above-mentioned purpose, the present invention adopts the following technical scheme that：A kind of aqueous polyurethane emulsion of color inhibition, including
The component of following quality proportioning：Side chain contains 115~125 parts of poly (propylene carbonate) polyalcohol, the aliphatic isocyanates of carboxyl
18~63 parts, 0.06~0.36 part of catalyst, 12 parts of neutralizer, 5~20 parts of acetone, 332~460 parts of deionized water and chain extender
0.6~1.2 part.Reacted based on the poly (propylene carbonate) polyalcohol that soft segment contains carboxyl for raw material with aliphatic isocyanates
The aqueous polyurethane emulsion that soft and hard segments are evenly distributed is can obtain, since aliphatic isocyanates will not be converted into during storage
Quinoid structure, makes the aqueous polyurethane emulsion of generation have color inhibition, and without introducing high boiling solvent, acetone in preparation process
Deng low boiling point solvent use also largely reduce avoid produce and application process in produce substantial amounts of volatile organic matter, environmental protection
Safety.
Further, the component of following quality proportioning is included：Side chain contain the poly (propylene carbonate) polyalcohol 115 of carboxyl~
125 parts, 30~50 parts of aliphatic isocyanates, 0.06~0.36 part of catalyst, 12 parts of neutralizer, 10~18 parts of acetone, go from
0.6~1.2 part of 332~460 parts of sub- water and chain extender.Based on soft segment contain the poly (propylene carbonate) polyalcohol of carboxyl for raw material with
Aliphatic isocyanates carry out reaction and can obtain the aqueous polyurethane emulsion that soft and hard segments are evenly distributed, and do not draw in preparation process
Enter the uses of the low boiling point solvents such as high boiling solvent, acetone also largely reduce avoid produce and application process in produce it is substantial amounts of
Volatile organic matter, Environmental Safety.
Yet further, the poly (propylene carbonate) polyalcohol that the side chain contains carboxyl is with poly (propylene carbonate) polyalcohol
It is raw material with the glycol of small molecule containing carboxyl, under the action of catalyst, ester exchange reaction occurs and is made, the side chain contains carboxyl
Poly (propylene carbonate) polyalcohol molecular weight be 1000~3000, hydroxy functionality be 2~3, intramolecular carbonate group
Mole fraction is 0.3~0.4, and each intramolecular carboxyl number is 1~2.Side chain content is selected to have the poly (propylene carbonate) of carboxyl
The molecular weight of polyalcohol is less than 1000 or the emulsion appearance that synthesis obtains is influenced more than 3000, reduces lotion uniformity；Molecule
Interior carbonic ester group mole fraction can produce the structure and performance of final poly (propylene carbonate) polyalcohol less than 0.3 or higher than 0.4
It is raw to influence, so that the appearance of aqueous polyurethane emulsion being finally prepared is influenced, soft and hard segments skewness.
Yet further, the aliphatic isocyanates for isofoer diisocyanate, hexamethylene diisocyanate,
One or more mixtures in hydrogenated diphenyl methane diisocyanate.Aliphatic isocyanates are polynary with poly (propylene carbonate)
Hydroxyl or amino reactive polymeric the generation polyurethane of alcohol, are the primary raw material of synthesis of polyurethane, and aliphatic isocyanates will not
Quinoid structure is converted into during storage makes aqueous polyurethane emulsion turn yellow.
Yet further, the catalyst is stannous octoate, di-n-butyltin dilaurate, one kind in tin acetate or several
The mixture of kind.Catalyst shortens polyaminoester emulsion generated time, improves reaction speed and curing rate.
Yet further, the neutralizer is triethylamine, tripropyl amine (TPA), tri-n-butylamine, sodium hydroxide, one kind in ammonium hydroxide or several
The mixture of kind.Neutralizer primarily to neutralize the carboxylic poly (propylene carbonate) polyalcohol of side chain on carboxyl, formed from
It could emulsify to form lotion in water after minor structure, if neutralizer addition is more lotion can be caused unstable, addition is few
The example group of formation is insufficient to emulsify, and causes lotion unstable.
Yet further, the chain extender is one kind or several in ethylenediamine, triethylene diamine, ethylenediamine base ethyl sulfonic acid sodium
Kind mixture.Chain extender causes strand diffusion to extend with poly (propylene carbonate) polyol reaction, water-based poly- so as to fulfill generating
Urethane and curing molding.
Yet further, a kind of preparation method of the aqueous polyurethane emulsion of color inhibition, each component is weighed by formula, by with
Side weighs each component, and it is different that the poly (propylene carbonate) polyalcohol for containing carboxyl to 115~125 parts of side chains adds 18~63 parts of aliphatic
Cyanate and 0.06~0.36 part of catalyst, when reaction 2~6 is small at a temperature of 70 DEG C~90 DEG C, adding 5~20 parts of acetone reduces
Viscosity, is cooled to -10 DEG C~40 DEG C, adds 12 parts of neutralizers and reacts 10~60 minutes, adds 332 parts~460 parts deionized waters,
In -10 DEG C~5 DEG C emulsified reactions 10~60 minutes, 0.6~1.2 part of chain extender is added 10~60 minutes, removed under reduced pressure acetone,
Obtain the aqueous polyurethane emulsion of color inhibition.Preliminary polymerization carries out that reaction speed can be improved in a heated condition, and heating-up temperature is low
The purpose for improving reaction speed is not reached then in 70 DEG C, heating-up temperature then causes reaction acutely to make reaction process can not higher than 90 DEG C
Control, can ensure when isothermal reaction 2~6 is small reaction fully it is complete, avoid because react not exclusively and caused by material waste；Add third
Ketone dilute reaction solution reduces viscosity, and the neutralizer for ensureing subsequently to add can stir evenly, by reducing solution temperature to -10~40
DEG C it can prevent that temperature is excessive, reaction is too fast, causes to react uncontrollable, and poly- carbonic acid can be ensured by adding neutralizer and reacting 10~60 minutes
Carboxyl complete neutralization on sub- propyl ester polyalcohol, can be too high because of aliphatic isocyanates activity more than 60 minutes if neutralizing the time,
Cause to crosslink, influence the effect of next step emulsion reaction.It is more that neutralizer has neutralized the carboxylic poly (propylene carbonate) of side chain
Carboxyl on first alcohol, forms ionic structure, and can carry out emulsification under cryogenic after addition water forms lotion.The chain extender of addition
Contain the poly (propylene carbonate) polyol reaction of carboxyl with soft segment, be embedded in, obtain soft in the soft segment of poly (propylene carbonate) polyalcohol
The uniform and relatively good emulsion appearance of the block of hard section.
Yet further, the aliphatic isocyanates are 30~50 parts, and the acetone is 10~18 parts.
Yet further, the poly (propylene carbonate) polyalcohol that the side chain contains carboxyl is 110 DEG C~130 DEG C in temperature,
Vacuum pressure is dehydrated 3h under conditions of being -0.08MPa~-0.1MPa, is sealed after cooling stand-by.It can be added using heating, vacuum dehydration
The fast moisture evaporation and poly (propylene carbonate) polyalcohol for avoiding high temperature and causing side chain to contain carboxyl goes bad.
Compared with prior art, the advantageous effects of the invention：
Firstth, aqueous polyurethane emulsion color inhibition is prepared, block is uniform, and soft and hard segments are evenly distributed and stable quality.Tradition
It is but so meeting by introducing hydrophilic chain extender in the hard section of poly (propylene carbonate) dihydric alcohol to prepare aqueous polyurethane emulsion
Cause the polyurethane products block lack of homogeneity, soft and hard segments skewness and the emulsion appearance that finally synthesize bad, the present invention
Preparation method uses the carboxylic poly (propylene carbonate) polyalcohol of soft segment not introduce hydrophilic expansion in hard section for main Material synthesis
Chain agent, ensures that the block for the aqueous polyurethane emulsion that reaction obtains is uniform, and soft and hard segments are evenly distributed and emulsify completely, water-based poly- ammonia
Ester lotion quality stability under static conditions is good, and replaces conventional fragrant race isocyanates using aliphatic isocyanates, closes
Into aqueous polyurethane emulsion color inhibition, high intensity, and adhesive property is good.
Secondth, production process safety and environmental protection.Conventional solvent type polyurethane is needed using substantial amounts of organic in the synthesis process
Solvent, such as toluene, benzene, alkyl chloride, are producing and are producing substantial amounts of volatile organic matter in application process, inflammable and explosive,
Production process danger coefficient is higher and not environmentally.The present invention adopts water consumption substitution organic solvent, does not introduce high boiling solvent, is applying
During the organic molten material of non-volatility discharge and reduce the usage amount of low boiling point solvent, improve the safety coefficient of production process,
And using and discharging for organic solvent is reduced, it is more environmentally-friendly.
3rd, raw materials used environmentally friendly and cost is low.The poly (propylene carbonate) that the side chain that the present invention uses contains carboxyl is polynary
Alcohol is to be made using carbon dioxide and propylene oxide as raw material, has the structure of carbonate group and ether, and intensity is high, hydrolysis, into
This is low, and mass produces and will not damage to environment, and environmental protection, energy-saving and emission-reduction are had a very big significance.
4th, preparation process is simple, has actual application value.Building-up process of the present invention is brief, and preparation process is simple, holds
Production is easily promoted, there is actual application value.
Embodiment
Technical scheme is more fully understood for ease of those skilled in the art, in conjunction with embodiment to this
Invention is described further.
Embodiment 1
It is 1000 to take 120 parts of molecular weight, the carboxylic polymerized thylene carbonate third of side chain that hydroxy functionality is 2 and carboxyl functionality is 1
Ester dihydric alcohol, is 110 DEG C in temperature, after vacuum pressure is -0.08MPa dehydration, adds 53 parts of isophorone diisocyanate, and
0.24 part of stannous octoate catalyst, when reaction 4 is small at 85 DEG C, adding 10 parts of acetone reduces viscosity, is reduced to 40 DEG C, adds 12
In part triethylamine and 10 minutes, 435 parts of deionized waters are added, are emulsified 15 minutes at 5 DEG C, add chain extension after 1.2 parts of ethylenediamines
30 minutes, removed under reduced pressure acetone, obtained the aqueous polyurethane emulsion of color inhibition.
Embodiment 2
It is 1000 to take 120 parts of molecular weight, the carboxylic polymerized thylene carbonate third of side chain that hydroxy functionality is 2 and carboxyl functionality is 1
Ester dihydric alcohol, is 120 DEG C in temperature, after vacuum pressure is -0.09MPa dehydration, adds 40 parts of isophorone diisocyanate, 10
Part hexamethylene diisocyanate, and 0.24 part of stannous octoate catalyst, when reaction 4 is small at 85 DEG C, add 15 parts of acetone drops
Low viscosity, is reduced to 40 DEG C, adds in 12 parts of triethylamines and 10 minutes, adds 427 parts of deionized waters, emulsifies 15 points at 5 DEG C
Clock, adds chain extension 30 minutes after 1.2 parts of ethylenediamines, removed under reduced pressure acetone, obtains the aqueous polyurethane emulsion of color inhibition.
Embodiment 3
It is 1000 to take 120 parts of molecular weight, the carboxylic polymerized thylene carbonate third of side chain that hydroxy functionality is 2 and carboxyl functionality is 1
Ester dihydric alcohol, is 130 DEG C in temperature, after vacuum pressure is -0.095MPa dehydration, adds 63 parts of two isocyanides of hydrogenated diphenyl methane
Acid esters, and 0.36 part of stannous octoate catalyst, when reaction 5 is small at 85 DEG C, adding 20 parts of acetone reduces viscosity, is reduced to 40
DEG C, add 12 parts of triethylamines in and 10 minutes, add 460 parts of deionized waters, at 5 DEG C emulsify 15 minutes, add 1.2 parts of second two
Chain extension 30 minutes after amine, removed under reduced pressure acetone, obtains the aqueous polyurethane emulsion of color inhibition.
Embodiment 4
It is 3000 to take 120 parts of molecular weight, the carboxylic polymerized thylene carbonate third of side chain that hydroxy functionality is 2 and carboxyl functionality is 1
Ester dihydric alcohol, is 125 DEG C in temperature, after vacuum pressure is -0.1MPa dehydration, adds 18 parts of isoflurane chalcone diisocyanates, and
0.24 part of stannous octoate catalyst, when reaction 4 is small at 85 DEG C, adding 10 parts of acetone reduces viscosity, is reduced to 40 DEG C, adds 12
In part triethylamine and 10 minutes, 332 parts of deionized waters are added, are emulsified 15 minutes at 5 DEG C, add chain extension after 0.6 part of ethylenediamine
30 minutes, removed under reduced pressure acetone, obtained the aqueous polyurethane emulsion of color inhibition.
Comparative example 1
It is 3000 to take 120 parts of molecular weight, and hydroxy functionality is 2 poly (propylene carbonate) dihydric alcohol, is 120 DEG C in temperature, vacuum
After pressure is -0.09MPa dehydration, 31 parts of isoflurane chalcone diisocyanates, 4 parts of dihydromethyl propionic acids, 25 parts of N, N- diformazans are added
Base formamide, and 0.24 part of stannous octoate catalyst, when reaction 4 is small at 85 DEG C, adding 40 parts of acetone reduces viscosity, is reduced to
40 DEG C, add 3 parts of triethylamines in and 10 minutes, add 456 parts of deionized waters, at 5 DEG C emulsify 15 minutes, add 1.2 parts of second
Chain extension 30 minutes after diamines, removed under reduced pressure acetone, obtains the aqueous polyurethane emulsion of color inhibition.
Comparative example 2
It is 1000 to take 120 parts of molecular weight, the carboxylic polymerized thylene carbonate third of side chain that hydroxy functionality is 2 and carboxyl functionality is 1
Ester dihydric alcohol, is 115 DEG C in temperature, after vacuum pressure is -0.05MPa dehydration, adds 42 parts of toluene di-isocyanate(TDI)s, and 0.06
Part stannous octoate catalyst, when reaction 2 is small at 85 DEG C, adding 5 parts of acetone reduces viscosity, is reduced to 40 DEG C, adds 12 part three
Ethamine neutralizes and then is added immediately 408 parts of deionized waters, emulsifies 15 minutes at 5 DEG C, and chain extension 30 divides after adding 1.2 parts of ethylenediamines
Clock, removed under reduced pressure acetone, obtains the aqueous polyurethane emulsion of color inhibition.
Lotion made from Example 1-4 and comparative example 1-2,2 ‰ concentration is configured to deionized water, using model
Nano particle size and Zeta point the position analyzer of DelsaNano C, tests emulsion particle diameter size and particle diameter distribution index.
Lotion made from Example 1-4 and comparative example 1-2, when storage 168 is small at 80 DEG C, stability is carried out to lotion
Analysis.If emulsion-stabilizing, then it is assumed that storage cycle was more than six months, otherwise, then it is assumed that storage cycle is less than six months.
Lotion made from Example 1-4 and comparative example 1-2, is placed in Teflon mould, after air drying, obtains
To the aqueous polyurethane glued membrane of water white transparency, obtained aqueous polyurethane glued membrane is placed under sunlight and is exposed to the sun 7, records each glue
The visual condition of film, experimental result are as shown in table 1.
Product emulsion study on the stability result obtained by table 1, embodiment
| Title | Initial appearance | Appearance after being exposed to the sun 7 | Storage stability | Particle size/nm | Profile exponent |
| Embodiment 1 | Water white transparency | Water white transparency | ＞ 6 months | 34 | 0.048 |
| Embodiment 2 | Water white transparency | Water white transparency | ＞ 6 months | 37 | 0.043 |
| Embodiment 3 | Water white transparency | Water white transparency | ＞ 6 months | 32 | 0.041 |
| Embodiment 4 | It is colourless clear | It is colourless clear | ＞ 6 months | 49 | 0.077 |
| Comparative example 1 | Blueing light | Blueing light | ＞ 6 months | 75 | 0.093 |
| Comparative example 2 | Yellow transparent | Yellow transparent | ＞ 6 months | 33 | 0.044 |
To sum up, table 1 the result shows that, based on poly (propylene carbonate) polyol systems synthesis aqueous polyurethane emulsion be respectively provided with it is excellent
Storage stability and preferable particle size and its distribution.The aqueous polyurethane emulsion prepared using soft segment containing carboxyl（It is real
Apply a 1-4 and comparative example 2）The aqueous polyurethane emulsion prepared with respect to hard section containing carboxyl（Comparative example 1）, it is equal with preferable block
Even property, soft and hard segments distribution and emulsion appearance, and it is different compared with aromatic series using the aqueous polyurethane of aliphatic isocyanates synthesis
The aqueous polyurethane of cyanic acid Lipase absobed has excellent anti-yellowing property, the aqueous polyurethane breast of the color inhibition prepared by the present invention
Liquid has very big actual application value.
The foregoing is only a preferred embodiment of the present invention, not makees limitation in any form to the present invention；It is all
The those of ordinary skill of the industry can swimmingly implement the present invention by described above；But all it is familiar with this professional technology people
Member without departing from the scope of the present invention, a little change, the modification made using disclosed above technology contents
It is equivalent embodiment of the invention with the equivalent variations of differentiation；Meanwhile all substantial technologicals according to the present invention are implemented to more than
Variation, modification and evolution of any equivalent variations for being made of example etc., still fall within technical scheme protection domain it
It is interior.
Claims (10)
1. a kind of aqueous polyurethane emulsion of color inhibition, it is characterised in that include the component of following quality proportioning：Side chain contains carboxylic
0.06~0.36 part of 18~63 parts of 115~125 parts of poly (propylene carbonate) polyalcohol, aliphatic isocyanates, the catalyst of base, in
With 0.6~1.2 part of 12 parts of agent, 5~20 parts of acetone, 332~460 parts of deionized water and chain extender.
2. the aqueous polyurethane emulsion of color inhibition according to claim 1, it is characterised in that including following quality proportioning
Component：Side chain contains 30~50 parts of 115~125 parts of poly (propylene carbonate) polyalcohol, aliphatic isocyanates, the catalyst of carboxyl
0.6~1.2 part of 0.06~0.36 part, 12 parts of neutralizer, 10~18 parts of acetone, 332~460 parts of deionized water and chain extender.
3. the aqueous polyurethane emulsion of the color inhibition according to claim 1 or claim 2, it is characterised in that：The side
The poly (propylene carbonate) polyalcohol that chain contains carboxyl be using poly (propylene carbonate) polyalcohol and the glycol of small molecule containing carboxyl as raw material,
Under the action of catalyst, ester exchange reaction occurs and is made, the side chain contains point of the poly (propylene carbonate) polyalcohol of carboxyl
Son amount is 1000~3000, and hydroxy functionality is 2~3, and the mole fraction of intramolecular carbonate group is 0.3~0.4, Mei Gefen
Carboxyl number is 1~2 in son.
4. the aqueous polyurethane emulsion of the color inhibition according to claim 1 or claim 2, it is characterised in that：The fat
Fat race isocyanates is isofoer diisocyanate, hexamethylene diisocyanate, hydrogenated diphenyl methane diisocyanate
In one or more mixtures.
5. the aqueous polyurethane emulsion of the color inhibition according to claim 1 or claim 2, it is characterised in that：It is described to urge
Agent is stannous octoate, one or more of mixtures in di-n-butyltin dilaurate, tin acetate.
6. the aqueous polyurethane emulsion of the color inhibition according to claim 1 or claim 2, it is characterised in that：In described
It is triethylamine with agent, one or more of mixtures in tripropyl amine (TPA), tri-n-butylamine, sodium hydroxide, ammonium hydroxide.
7. the aqueous polyurethane emulsion of the color inhibition according to claim 1 or claim 2, it is characterised in that：The expansion
Chain agent is ethylenediamine, one or more of mixtures in triethylene diamine, ethylenediamine base ethyl sulfonic acid sodium.
A kind of 8. preparation of the aqueous polyurethane emulsion of color inhibition according to claim 1 to 7 any one claim
Method, it is characterised in that：Each component is weighed by formula, 115~125 parts of side chains are contained to the poly (propylene carbonate) polyalcohol of carboxyl
After dehydration, 18~63 parts of aliphatic diisocyanates and 0.06~0.36 part of catalyst are added, it is anti-at a temperature of 70 DEG C~90 DEG C
Answer 2~6 it is small when, adding 5~20 parts of acetone reduces viscosity, is cooled to -10 DEG C~40 DEG C, adds 12 parts of neutralizers reactions 10~60
Minute, add 332 parts~460 parts deionized waters, -10 DEG C~5 DEG C it is emulsified reaction 10~60 minutes, add 0.6~1.2 part
Chain extender 10~60 minutes, removed under reduced pressure acetone, obtains the aqueous polyurethane emulsion of color inhibition.
9. the preparation method of the aqueous polyurethane emulsion of color inhibition according to claim 8, it is characterised in that：The fat
Race's isocyanates is 30~50 parts, and the acetone is 10~18 parts.
10. the preparation method of the aqueous polyurethane emulsion of color inhibition according to claim 8, it is characterised in that：The side
It is 110 DEG C~130 DEG C that chain, which contains the poly (propylene carbonate) polyalcohol of carboxyl in temperature, vacuum pressure for -0.08MPa~-
3h is dehydrated under conditions of 0.1MPa, is sealed after cooling stand-by.
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