CN106750130B - A kind of preparation method and application of highly filled waterborne polyurethane resin and its coating - Google Patents
A kind of preparation method and application of highly filled waterborne polyurethane resin and its coating Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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- C08G18/40—High-molecular-weight compounds
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- C08G18/44—Polycarbonates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
- C08G18/40—High-molecular-weight compounds
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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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The present invention discloses the preparation method and application of a kind of highly filled waterborne polyurethane resin and its coating.The present invention mixes poly (propylene carbonate) polyalcohol or poly (propylene carbonate) polyalcohol with other conventional polymer polyalcohols, with isocyanates, chain extender, crosslinking agent, catalyst, sulfonic acid type hydrophilic chain extender reaction, water emulsification is added later, slough solvent, up to highly filled waterborne polyurethane resin, then levelling agent is added, thickener, mill base, environment-friendly type cosolvent, the auxiliary agents such as defoaming agent, obtain the highly filled aqueous polyurethane coating prepared using poly (propylene carbonate) polyalcohol as raw material, the rate of drying that forms a film is fast, richness is high, with good adhesive force, hardness and water-fast solvent resistance.
Description
Technical field
The invention belongs to aqueous polyurethane coating field, it is related specifically to using poly (propylene carbonate) polyalcohol as wherein one
It plants the synthesis of the highly filled aqueous polyurethane emulsion of necessary component and mixes the aqueous polyurethane emulsion and other auxiliary agents
Conjunction prepares aqueous polyurethane coating and application.
Background technique
Currently, the resin for coating mainly includes the resins such as acrylic acid, alcohol acids, polyurethanes, but it is wherein big absolutely
Part is solvent type resin.Organic solvent existing for solvent based coating is inflammable, explosive, volatile, is good for environment and people
Health undoubtedly will cause extremely serious destruction.With the raising of increasingly strict and people's environmental consciousness of environmental regulation, ring is pursued
Border friendly product has become trend of the times, and solvent product will be replaced gradually by aqueous product.
Controllability of the aqueous polyurethane due to its structure, excellent combination property have been widely used for adhesive, leather
The fields such as finishing agent, automobile interior decoration, coating, but the limitation due to synthesizing Raw Materials for Waterborne Polyurethane now, so that it is prepared
Film be lacking in terms of hardness, richness, wear-resisting, water resistance and solvent resistance.
Poly (propylene carbonate) polyalcohol is a kind of aliphatic polyol as made of the copolymerization such as carbon dioxide and propylene oxide,
Compared with the polycarbonate polyol of similar performance, in addition to prepare operation it is simple, it is low in cost other than, moreover it is possible to effectively improve pair
In the comprehensive utilization of carbon dioxide, alleviate " greenhouse effects ".It is simultaneous due to the polycarbonate structure in its structure containing 31~50%
Has the good characteristic of polycarbonate and polyethers, therefore it has excellent wear-resisting, water-fast solvent resistance.So can be by using
Poly (propylene carbonate) polyalcohol is the aqueous polyurethane coating that raw material preparation has superperformance.
Another factor for restricting water-base polyurethane material application at present is exactly that solid content is lower.Aqueous poly- ammonia on the market
For the solid content of ester lotion mostly 30~40%, on the one hand traffic expense can be reduced by preparing highly filled aqueous polyurethane
With on the other hand capable of reducing subsequent baking step, reduce energy consumption.So preparing highly filled aqueous polyurethane coating
It is extremely urgent, but it is poly- to be difficult to prepare high solid content water by carboxylic acid type hydrophilic chain extender (such as dihydromethyl propionic acid) merely
Urethane lotion.Chinese patent CN 103626953 discloses a kind of synthetic method of sulfonate type water-based polyurethane emulsion, uses
Homemade sulfonic acid type polyester diol is raw material, is mixed with other polyalcohols, and the aqueous polyurethane cream of higher solids content is prepared for
Liquid, but it is complicated for operation to prepare the sulfonic acid type polyester diol, structure adjust that space is small, and usage amount is larger, and cost performance is not high.In
State patent CN102010650 discloses a kind of aqueous polyurethane coating tree prepared using poly (propylene carbonate) polyalcohol as raw material
Rouge, but the conventional method of its disclosed only resins synthesis, do not refer to the synthesis of highly filled aqueous polyurethane emulsion,
Also with no specific disclosure of its Paint preparation technology.Chinese patent CN103755911 discloses a kind of environment-friendly type poly (propylene carbonate)
The preparation of type aqueous polyurethane coating, innovative point are to use organo-bismuth as environment-friendly type catalyst, be synthesized using two-step method
The preferable aqueous polyurethane coating of stability, is not related to the synthesis of highly filled aqueous polyurethane emulsion.
Summary of the invention
It is an object of the invention in view of the deficiencies of the prior art, provide a kind of highly filled aqueous polyurethane tree
The preparation method of rouge, this method using the relatively high poly (propylene carbonate) polyalcohol of sexual valence as necessary component, by addition compared with
A kind of highly filled waterborne polyurethane resin is made in the way of rear chain extension in few dosage Sulfonate-type hydrophilic chain extender, operates
Simplicity, consumption quantity of solvent are less., the coating paint film using resin preparation has excellent hardness, richness, adhesive force and resistance to
Water solvent resistance.
A kind of preparation method of highly filled aqueous polyurethane emulsion, comprising the following steps:
Step (1), by 5~45 parts by weight poly (propylene carbonate) polyalcohols, 15~50 parts by weight isocyanates 70~90
It is reacted 2~4 hours at DEG C, obtains mixed solution A；
Preferably, other conventional polymer dihydric alcohols of 0~20 parts by weight can also be added；
0.2~7 parts by weight chain extender, 50~100 pbw acetones or fourth is added in step (2) in above-mentioned mixed solution A
Ketone is added 0.02~0.3 part by weight of catalyst, is placed at 60~70 DEG C and reacts 5~8 hours, obtain mixing molten after stirring and evenly mixing
Liquid B；
Preferably, 0~4 parts by weight of crosslinking agent can also be added；
Step (3) after above-mentioned mixed solution B is cooled to 35~60 DEG C, adds 0.1~10 parts by weight sulfonic acid type hydrophilic
Chain extender reacts 15~60 minutes, and deionized water high speed is added and emulsifies, the water of addition makes latex solids content in 45wt%
It is above, it stirs 10~20 minutes；
Step (3) products therefrom is placed on Rotary Evaporators, vacuum decompression by step (4), is removed solvent, is obtained 100 weights
Measure the highly filled aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol of part.
It is a further object to provide the highly filled aqueous polyurethanes based on poly (propylene carbonate) polyalcohol
Application of the lotion in aqueous polyurethane coating preparation, specific preparation process are as follows:
This method is by the above-mentioned preparation of 100~200 parts by weight based on the highly filled of poly (propylene carbonate) polyalcohol
Aqueous polyurethane emulsion, 0.002~1.2 parts by weight levelling agent, 0.05~4 parts by weight of thickening agent, 0.05~6 parts by weight environment-friendly type
(deionized water here is consolidated for adjusting coating for auxiliary agent, 0.003~0.1 parts by weight defoaming agent and a certain amount of deionized water
Body content and viscosity) it is added sequentially in scuffing of cylinder bore, 1~2 hour is stirred under 250~500 revs/min to get based on poly- carbonic acid
The highly filled aqueous polyurethane coating of sub- propyl ester polyalcohol.
Preferably, 0~15 parts by weight mill base can also be added.
The poly (propylene carbonate) polyalcohol refer to synthesized by carbon dioxide and propylene oxide by chemical polymerization it is simultaneous
Has the polyalcohol of polycarbonate and polyether structure, molecular weight is 1500~4000, and degree of functionality is 2~6, and preferably degree of functionality is 2
~4, most preferably degree of functionality is 2, and structure is as follows:
The conventional dihydric alcohol includes poly adipate succinic acid ester dihydric alcohol, polypropylene oxide glycol, polycyclic oxygen second
Alkane dihydric alcohol, polytetrahydrofuran ether dihydric alcohol, polycaprolactone diols and polycarbonate glycol are one such or a variety of,
Molecular weight is 1000~4000.
The isocyanates be toluene di-isocyanate(TDI) (TDI), 4,4- methyl diphenylene diisocyanate (MDI), 4,
4- dicyclohexyl methyl hydride diisocyanate (HMDI), isophorone diisocyanate (IPDI) and hexamethylene-diisocyanate
One or more of (HDI).
The chain extender is that ethylene glycol, 1,2- propylene glycol, 1,4- butanediol, neopentyl glycol, 1,6-HD and two are sweet
One or more of alcohol.
The catalyst is organotin, organo-bismuth, organic silver or organic zinc.
The crosslinking agent is one of trimethylolpropane, trimethylolethane, glycerol, pentaerythrite and castor oil
Or it is several.
The sulfonic acid type hydrophilic chain extender includes ethylenediamine base propanesulfonate (APS), ethylenediamine base ethanesulfonic acid sodium (AAS)
With Degussa A95 and its derivative.
The levelling agent is organic silicon type levelling agent, and Germany Digao TEGO 410, TEGO 425 or TEGO can be selected
450, perhaps BYK333, BYK346 or BYK378 of Germany's Bi Ke chemistry or Guangzhou Si Luoke Chemical Co., Ltd8000、8030 or8033；
The thickener is polyurethane-type thickener, the modest polyurethane-type thickener WT-102 of optional Hai Mingsi moral,
The ACRYSOL of WT-105A or WT-202 or ROHM AND HAASTMRM 8W、ACRYSOLTMRM 12W or ACRYSOLTMRM 5000；
Aqueous color paste or Suzhou Sunmun Technology Co., Ltd. of Switzerland's Clariant Corporation can be selected in the mill base
Aqueous color paste；
Ethylene glycol monobutyl ether or ethylene glycol monomethyl ether etc. can be selected in the environment-friendly type cosolvent；
The defoaming agent is organic silicon type defoaming agent, can select German Digao TEGO Foamex 1488 or TEGO
Foamex 825 or Guangzhou Si Luoke Chemical Co., Ltd4650、4680 or4800,
Or BYK 022, BYK 024 or the BYK 025 of Germany's Bi Ke chemistry.
Existing advantage is the present invention compared with prior art:
1, the raw material poly (propylene carbonate) polyalcohol that the present invention uses is total by chemistry by carbon dioxide and propylene oxide
It is poly- to form, the structure of polycarbonate and polyethers is had both, compared with the pure polycarbonate polyol that performance is closer to, the value of environmental protection
Obviously, cost performance is higher.Compared to other polyalcohols, the coating stable storing of poly (propylene carbonate) polyols preparation, property are used
Can be excellent, film adhesive force on base material is good, and hardness is high, and richness is good, while water resistance and chemical solvent resistance can be excellent.
2, the present invention innovatively carries out chemical copolymerization using with minimal amount of sulfonic acid type hydrophilic chain extender, and solid is prepared
The waterborne polyurethane resin of content higher (45% or more).
3, the water paint that the present invention is prepared is due to its solid content height, and rate of drying is exceedingly fast at normal temperature, saves energy
Source and human resources, practical application of being more convenient for.
4, the present invention not will cause the discharge of VOCs (volatilizable organic matter) during synthesizing and preparing water paint,
It is harmless for environmental and human health impacts.
5, the present invention is using the agent of minute quantity sulfonic acid type hydrophilic as chain extender, compared to utilization carboxylic acid type/sulfonic acid type hydrophilic
The waterborne polyurethane resin prepared as chain extender is blended in agent, and operating procedure is simpler, it is not necessary that alkaline matter (such as ammonia is added
Class) it is used as neutralizer；Simultaneously because the characteristic of sulfonate, lotion potential resistance to electrolyte contamination, the freeze-thaw resistance of preparation have a clear superiority；In addition
Using the coating of resin preparation, its is water-fast, solvent resistance is more excellent, is suitably applied and requires harsher high-end neck
Domain.
6, the present invention combines the aqueous polyurethane of preparation using poly (propylene carbonate) polyalcohol with sulfonic acid type hydrophilic chain extender
Lotion combines raw material advantage and process innovation.
Specific embodiment
It is for further analysis to the present invention combined with specific embodiments below.
Embodiment 1
By 70g molecular weight be 2500 poly (propylene carbonate) dihydric alcohol and 35g isoflurane chalcone diisocyanate at 90 DEG C
7g1 is added in reaction 2 hours, and the di lauric dibutyl of 0.02g is added in 4~butanediol, 1g trimethylolpropane, 70g acetone
Tin reacts 8 hours at 60 DEG C, is cooled to 45 DEG C, stirs 10 minutes, 0.5gA95 is added, 40g is added after reaction 30 minutes
Acetone rapidly joins 160g deionized water high speed and emulsifies, stirs 10 minutes；On a rotary evaporator by products therefrom, vacuum subtracts
Pressure removes solvent, obtains the highly filled aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol.
By the aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol of the above-mentioned preparation of 150g, 0.05g levelling agent
TEGO 410, thickener WT-105A, 1g aqueous color paste of 0.07g, 0.8g ethylene glycol monobutyl ether, 0.02g defoaming agent TEGO
The deionized water of Foamex 825 and surplus is added sequentially in scuffing of cylinder bore, stirs 1~2 hour under 250~500 revs/min, i.e.,
Obtain the aqueous polyurethane coating based on poly (propylene carbonate) polyalcohol.
Embodiment 2
45g molecular weight is reacted 2.5 at 80 DEG C with 20g toluene di-isocyanate(TDI) for 2000 poly (propylene carbonate) dihydric alcohols
Hour, 7g1 is added, 0.02g dibutyl tin dilaurate is added, at 60 DEG C in 6- hexylene glycol, 1g trimethylolpropane, 80g acetone
Lower reaction 5 hours, is cooled to 45 DEG C, stirs 10 minutes, and 0.6gAPS is added and 40g acetone is added, quickly after reaction 60 minutes
100g deionized water high speed is added to emulsify, stirs 10 minutes；On a rotary evaporator by products therefrom, vacuum decompression removes molten
Agent obtains the highly filled aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol.
By the aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol of the above-mentioned preparation of 150g, 0.1g levelling agent
BYK346,0.05g thickener ACRYSOLTMRM 12W, 1g aqueous color paste, 1g ethylene glycol monobutyl ether, 0.02g defoaming agent TEGO
The deionized water of Foamex 825 and surplus is added sequentially in scuffing of cylinder bore, stirs 1~2 hour under 250~500 revs/min, i.e.,
Obtain the aqueous polyurethane coating based on poly (propylene carbonate) polyalcohol.
Embodiment 3
By 40g molecular weight be 2000 poly (propylene carbonate) dihydric alcohol and 20g molecular weight be 3000 polyadipate fourth two
Alcohol ester dihydric alcohol reacts 2.5 hours with 35g isoflurane chalcone diisocyanate at 90 DEG C, and 6g diglycol, 1.5g is added
Trimethylolpropane, 90g acetone, are added the dibutyl tin dilaurate of 0.02g, react 5 hours at 60 DEG C, are cooled to 45
DEG C, it stirs 10 minutes, 0.5gA95 is added, 40g acetone is added after reaction 30 minutes, rapidly join 80g deionized water high speed
Emulsification is stirred 10 minutes；On a rotary evaporator by products therefrom, vacuum decompression removes solvent, obtains based on polymerized thylene carbonate third
The highly filled aqueous polyurethane emulsion of ester polyol.
By the aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol of the above-mentioned preparation of 150g, 0.05g levelling agent8030,0.07g thickener ACRYSOLTMRM 5000,1g aqueous color paste, 0.8g ethylene glycol monobutyl ether, 0.01g defoaming
Agent4650 and the deionized water of surplus be added sequentially in scuffing of cylinder bore, it is small that 1~2 is stirred under 250~500 revs/min
When to get the aqueous polyurethane coating based on poly (propylene carbonate) polyalcohol.
Embodiment 4
By 40g molecular weight be 3000 poly (propylene carbonate) dihydric alcohol and 20g molecular weight be 2000 polytetrahydrofuran ether
Dihydric alcohol reacts 2.5 hours with 25g isoflurane chalcone diisocyanate, 10g hexamethylene diisocyanate at 90 DEG C, and 6g is added
Ethylene glycol, 1g trimethylolpropane, 90g acetone are added 0.02g organic bismuth catalyst, react 5 hours, be cooled at 65 DEG C
It 45 DEG C, stirs 10 minutes, 0.5 part of A95 is added, 40g acetone is added after reaction 30 minutes, it is high to rapidly join 90g deionized water
Speed emulsification, is stirred 10 minutes；On a rotary evaporator by products therefrom, vacuum decompression removes solvent, obtains based on polymerized thylene carbonate
The highly filled aqueous polyurethane emulsion of propyl ester polyalcohol.
By the aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol of the above-mentioned preparation of 150g, 0.05g levelling agent
TEGO 410,0.1g thickener ACRYSOLTMRM 5000,1g aqueous color paste, 0.8g ethylene glycol monobutyl ether, 0.01g defoaming agent BYK
025 and the deionized water of surplus be added sequentially in scuffing of cylinder bore, 1~2 hour is stirred under 250~500 revs/min to get being based on
The aqueous polyurethane coating of poly (propylene carbonate) polyalcohol.
Embodiment 5
By 45g molecular weight be 2000 poly (propylene carbonate) dihydric alcohol and 20g molecular weight be 2000 polypropylene glycol binary
Alcohol reacts 2.5 hours with 20g isoflurane chalcone diisocyanate, 15g hexamethylene diisocyanate at 90 DEG C, and 5g second two is added
Alcohol, 1g trimethylolpropane, 90 parts of acetone are added 0.02g dibutyl tin dilaurate, react 5 hours, be cooled at 65 DEG C
It 45 DEG C, stirs 10 minutes, 0.5gA95 is added, 40g acetone is added after reaction 40 minutes, it is high to rapidly join 100g deionized water
Speed emulsification, is stirred 10 minutes；On a rotary evaporator by products therefrom, vacuum decompression removes solvent, obtains based on polymerized thylene carbonate
The highly filled aqueous polyurethane emulsion of propyl ester polyalcohol.
By the aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol of the above-mentioned preparation of 150g, 0.05g levelling agent
TEGO 410,0.1g thickener WT~102,1g aqueous color paste, 0.8g ethylene glycol monobutyl ether, 0.01g defoaming agent BYK 025 and remaining
The deionized water of amount is added sequentially in scuffing of cylinder bore, stirs 1~2 hour under 250~500 revs/min to get based on polymerized thylene carbonate
The aqueous polyurethane coating of propyl ester polyalcohol.
Comparative example 1
0.5g A95 in embodiment 1 is substituted for 0.25g N, N- (2- ethoxy) -2-aminoethanesulfonic acid sodium (BES-
) and 0.25g dihydromethyl propionic acid (DMPA) Na.
By the aqueous polyurethane coating based on poly (propylene carbonate) polyalcohol of above-mentioned preparation on standard testing glass plate
Film forming, air drying 7 days, thickness of dry film 40um carried out the test of following project to gained paint film.
Wherein, water-fast test is the Soak Test 240h in pure water, and acid proof test is in 5wt%H2SO4Aqueous solution in soak
For 24 hours, alkaline-resisting test is for 24 hours, salt water resistance test is 3%NaCl's to Soak Test in the aqueous solution of 5wt%NaOH for bubble test
Soak Test for 24 hours, is graded, from 1 grade to 3 grade, wherein 1 grade of expression paint film immersion portion by estimating paint film appearance in aqueous solution
Point bubble-free, without falling off, substantially unchanged, effect is best, and 2 grades of expressions paint films, which impregnate part, to be occurred slightly whitening or slight gas
Partial exfoliation occurs for bubble or paint film, and effect is placed in the middle, and 3 grades of expression paint films immersion parts large area occur and fall off, and effect is worst.
It can be seen that the aqueous polyurethane prepared using poly (propylene carbonate) polyalcohol for raw material from embodiment test result
Coating, no matter the aspect of performance such as water-fast or solvent resistant are superior to the coating using other polyols preparations.
Embodiment 6
By 5g molecular weight be 1500 poly (propylene carbonate) tetrahydroxylic alcohol and 20g molecular weight be 1000 polypropylene oxide binary
Alcohol reacts 4 hours with 15g toluene di-isocyanate(TDI) at 70 DEG C, and 7g1,2- propylene glycol, 2g trimethylolethane, 50g fourth is added
Ketone is added 0.3g lauric acid bismuth, reacts 5 hours at 70 DEG C, is cooled to 35 DEG C, stirs 10 minutes, and 0.1gAAS, reaction is added
After 40 minutes, 40g butanone is added, rapidly joins 100g deionized water high speed and emulsifies, stir 10 minutes；Products therefrom is being revolved
Turn on evaporimeter, vacuum decompression, removes solvent, obtain the highly filled aqueous polyurethane based on poly (propylene carbonate) polyalcohol
Lotion.
By the aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol of the above-mentioned preparation of 100g, 0.002g levelling agent
TEGO 425,4g thickener WT-202,0.05g aqueous color paste, 0.05g ethylene glycol monobutyl ether, 022 and of 0.003g defoaming agent BYK
The deionized water of surplus is added sequentially in scuffing of cylinder bore, stirs 1~2 hour under 250~500 revs/min to get based on poly- carbonic acid
The aqueous polyurethane coating of sub- propyl ester polyalcohol.
Embodiment 7
By 45g molecular weight be 4000 poly (propylene carbonate) hexahydroxylic alcohols and 2g molecular weight be 1000 polyethylene oxide binary
Alcohol reacts 2.5 hours with 50gMDI at 90 DEG C, and 7g neopentyl glycol, 4g glycerol, 100g acetone is added, and 0.3g tin dilaurate is added
Dibutyl tin reacts 6 hours at 65 DEG C, is cooled to 60 DEG C, stirs 20 minutes, and 10gA95 derivative is added, and reacts 40 minutes
Later, 10g acetone is added, rapidly joins 100g deionized water high speed and emulsifies, stir 10 minutes；By products therefrom in rotary evaporation
On instrument, vacuum decompression removes solvent, obtains the highly filled aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol.
By the aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol of the above-mentioned preparation of 200g, 1.2g levelling agent TEGO
425,1g thickener ACRYSOLTMRM 8W, 15g aqueous color paste, 6g ethylene glycol monobutyl ether, 0.1g defoaming agent BYK 024 and surplus
Deionized water be added sequentially in scuffing of cylinder bore, 1~2 hour is stirred under 250~500 revs/min to get based on polymerized thylene carbonate third
The aqueous polyurethane coating of ester polyol.
Embodiment 8
By 30g molecular weight be 3000 poly (propylene carbonate) pentabasis alcohol and 2g molecular weight be 1000 pla-pcl dihydric alcohol
It is reacted at 80 DEG C 3 hours with 50gHMDI, 7g diethylene glycol (DEG), 4g pentaerythrite, 100g acetone is added, 0.3g tin dilaurate is added
Dibutyl tin reacts 6 hours at 65 DEG C, is cooled to 40 DEG C, stirs 20 minutes, is added 2gAAS derivative, reaction 40 minutes it
Afterwards, 10g acetone is added, rapidly joins 100g deionized water high speed and emulsifies, stir 10 minutes；By products therefrom in Rotary Evaporators
On, vacuum decompression removes solvent, obtains the highly filled aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol.
By the aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol of the above-mentioned preparation of 130g, 0.1g levelling agent
BYK346,0.1g thickener ACRYSOLTMRM 12W, 2g aqueous color paste, 1g ethylene glycol monobutyl ether, 0.01g defoaming agent
4680 and the deionized water of surplus be added sequentially in scuffing of cylinder bore, 1~2 hour is stirred under 250~500 revs/min to get being based on
The aqueous polyurethane coating of poly (propylene carbonate) polyalcohol.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent defines.
Claims (8)
1. a kind of preparation method of highly filled waterborne polyurethane resin, it is characterised in that method includes the following steps:
Step (1), by 5~45 parts by weight poly (propylene carbonate) polyalcohols, 15~50 parts by weight isocyanates at 70~90 DEG C
Reaction 2~4 hours, obtains mixed solution A；
Step (2), chain extender 1,50~100 pbw acetones or the fourth that 0.2~7 parts by weight are added in above-mentioned mixed solution A
Ketone is added 0.02~0.3 part by weight of catalyst, is placed at 60~70 DEG C and reacts 5~8 hours, obtain mixing molten after stirring and evenly mixing
Liquid B；
Step (3) after above-mentioned mixed solution B is cooled to 35~60 DEG C, adds sulfonic acid type hydrophilic chain extender, reaction 15~60
Minute, deionized water is added and is emulsified, the water of addition makes latex solids content in 45wt% or more, stirs 10~20 points
Clock；
The mass ratio of poly (propylene carbonate) polyalcohol and sulfonic acid type hydrophilic chain extender is 70:0.5 or 45:0.6；
Step (3) products therefrom is placed on Rotary Evaporators, vacuum decompression by step (4), is removed solvent, is obtained 100 parts by weight
The highly filled aqueous polyurethane emulsion based on poly (propylene carbonate) polyalcohol；
Wherein, the poly (propylene carbonate) polyalcohol refer to synthesized by carbon dioxide and propylene oxide by chemical polymerization it is simultaneous
Has the polyalcohol of polycarbonate and polyether structure, molecular weight is 1500~4000, and degree of functionality is 2~6；
The chain extender 1 is in ethylene glycol, 1,2- propylene glycol, 1,4- butanediol, neopentyl glycol, 1,6-HD and diethylene glycol (DEG)
One or more；
The sulfonic acid type hydrophilic chain extender include ethylenediamine base propanesulfonate, ethylenediamine base ethanesulfonic acid sodium and Degussa A95 and
Its derivative.
2. the highly filled waterborne polyurethane resin obtained based on the method as described in claim 1 is in aqueous polyurethane coating
Application in preparation.
3. a kind of preparation method of highly filled aqueous polyurethane coating, it is characterised in that this method is by 100~200 weight
Highly filled aqueous polyurethane emulsion that part the method as described in claim 1 obtains, 0.002~1.2 parts by weight levelling agent,
0.05~4 parts by weight of thickening agent, 0.05~6 parts by weight environment-friend auxiliaries, 0.003~0.1 parts by weight defoaming agent and a certain amount of
Deionized water is added sequentially in scuffing of cylinder bore, stirs 1~2 hour under 250~500 revs/min to get based on poly (propylene carbonate)
The highly filled aqueous polyurethane coating of polyalcohol.
4. a kind of preparation method of highly filled waterborne polyurethane resin as described in claim 1, it is characterised in that step
(1) other conventional polymer dihydric alcohols of 0~20 parts by weight can also be added.
5. a kind of preparation method of highly filled waterborne polyurethane resin as described in claim 1, it is characterised in that step
(2) 0~4 parts by weight of crosslinking agent can also be added.
6. a kind of preparation method of highly filled aqueous polyurethane coating as claimed in claim 3, it is characterised in that may be used also
0~15 parts by weight mill base is added.
7. a kind of preparation method of highly filled waterborne polyurethane resin as described in claim 1, it is characterised in that described
Poly (propylene carbonate) polyalcohol refer to by carbon dioxide and propylene oxide by chemical polymerization synthesize have both polycarbonate with
The polyalcohol of polyether structure, molecular weight are 1500~4000, degree of functionality 2.
8. a kind of preparation method of highly filled waterborne polyurethane resin as claimed in claim 4, it is characterised in that described
Conventional polymer dihydric alcohol include poly adipate succinic acid ester dihydric alcohol, polypropylene oxide glycol, polyethylene oxide binary
Alcohol, polytetrahydrofuran ether dihydric alcohol, polycaprolactone diols and polycarbonate glycol are one such or a variety of, molecular weight
It is 1000~4000；
The isocyanates is toluene di-isocyanate(TDI), 4,4- methyl diphenylene diisocyanate, 4,4- dicyclohexyl methyl hydride
One or more of diisocyanate, isophorone diisocyanate and hexamethylene-diisocyanate；
The catalyst is organotin, organo-bismuth, organic silver or organic zinc；
The crosslinking agent is one of trimethylolpropane, trimethylolethane, glycerol, pentaerythrite and castor oil or several
Kind.
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