CN106700022A - Cationic waterborne polyurethane, preparation method thereof, coating composition and preparation method thereof - Google Patents
Cationic waterborne polyurethane, preparation method thereof, coating composition and preparation method thereof Download PDFInfo
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- CN106700022A CN106700022A CN201710037658.3A CN201710037658A CN106700022A CN 106700022 A CN106700022 A CN 106700022A CN 201710037658 A CN201710037658 A CN 201710037658A CN 106700022 A CN106700022 A CN 106700022A
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- NFJPEKRRHIYYES-UHFFFAOYSA-N C=C1CCCC1 Chemical compound C=C1CCCC1 NFJPEKRRHIYYES-UHFFFAOYSA-N 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N CC1CCCC1 Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- SVKBXBWZZHJALI-UHFFFAOYSA-N CCC(CC(C)C1)(CC1([N]#C)[N]#C)[N]#C Chemical compound CCC(CC(C)C1)(CC1([N]#C)[N]#C)[N]#C SVKBXBWZZHJALI-UHFFFAOYSA-N 0.000 description 1
- ZTQCWRZJWGMGCH-UHFFFAOYSA-N CCCC1CC(CC)CC1 Chemical compound CCCC1CC(CC)CC1 ZTQCWRZJWGMGCH-UHFFFAOYSA-N 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N OC(C(F)(F)F)=O Chemical compound OC(C(F)(F)F)=O DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- OEOMCOHOAWRANW-UHFFFAOYSA-N OC([ClH](Cl)(Cl)Cl)=O Chemical compound OC([ClH](Cl)(Cl)Cl)=O OEOMCOHOAWRANW-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6622—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/28—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides cationic waterborne polyurethane with a structure shown as a formula (I) and a preparation method thereof. Phosphoryl triphenylcarbinol (PTMA) is used as a reactive flame retardant to participate in chain segment reaction of polyurethane, endows good flame retardant performance to polyurethane, also serves as a crosslinking point of the polyurethane, the phosphoryl triphenylcarbinol is introduced to a polyurethane molecular chain, then poly(carbonate-ether)glycol is used as polyester glycol, the polyester glycol has a polyester structure, also has a polyether structure and has hydrolysis resistance, oxidation resistance and good mechanical properties, and the carbon dioxide based flame-retardant waterborne polyurethane is obtained. The cationic waterborne polyurethane has high flame-retardant performance and good water resistance performance, resin performance is excellent, and the dependence on fossil resources can be also reduced by adopting the waterborne polyurethane.
Description
Technical field
The present invention relates to polyurethanes technology field, it is related to a kind of cation aqueous polyurethane and preparation method thereof, coating group
Compound and preparation method thereof, more particularly to a kind of cation aqueous polyurethane with fire resistance and preparation method thereof, have
Coating composition of fire resistance and preparation method thereof.
Background technology
Polyurethane with its soft durometer adjustable extent it is wide, low temperature resistant, pliability is good, adhesive force is strong the advantages of be widely used in
The fields such as leather finish, coating, adhesive.However as the appearance of various countries' Environmental security laws and regulations, many countries have limited
The application of solvent borne polyurethane.
Aqueous polyurethane is to replace organic solvent as the new polyurethane system of decentralized medium using water, and also referred to as moisture dissipates poly-
Urethane, aqueous polyurethane or water-based polyurethane.Aqueous polyurethane is water due to its continuous phase, is easy to safely preserve and store, and
Low cost easy to use, more completely remains the characteristic of solvent borne polyurethane, additionally, due to being deposited in aqueous polyurethane strand
In the effect of Coulomb force and hydrogen bond, it is set to be better than solvent borne polyurethane in some performances.
Therefore, aqueous polyurethane has the advantages that small toxicity, low stain, energy-conservation, safe, and it is developed and is subject to generation with production
The attention of various countries of boundary, and significant progress is all achieved, the Water-borne modification of polyurethane resin progressively replaces solvent-borne type, as poly-
The important directions of urethane industrial development, and be widely used in coating, adhesive, fabric coating and finishing agent, leather finishing agent,
Many technical fields such as sheet surface treating agent and fiber strength agent.
In the preparation of aqueous polyurethane, in order to obtain the polyaminoester emulsion of stabilization, need to be in the performed polymer molecule of polyurethane
Middle introducing hydrophilic radical, makes it be emulsified in water.Group institute charging property is introduced according to it different, by aqueous polyurethane be divided into sun from
Subtype, anionic, nonionic and mixed type watersoluble polyurethane.At present, anion is more common in the research of aqueous polyurethane
The aqueous polyurethane of type, its product also has been achieved with industrialization, and the report of cation-type water-thinned polyurethane is less.Cationic
It is positively charged on aqueous polyurethane strand, there is good wellability to base material, and meanwhile it is insensitive to the hardness of water, can be in acid
Used under the conditions of property, therefore it is with a wide range of applications in fields such as weaving, adhesive, leather and papermaking.
With the extensive use and fast development of aqueous polyurethane, each downstream application field also proposes more property to it
Can require, such as fabric, leather finish, coating, adhesive, construction material field, these materials are all combustible material, generally all
It is required that carrying out flame retardant treatment to raw material.
Therefore, a kind of aqueous polyurethane with fire resistance how is obtained, while also there is preferable combination property,
As widely one of the focus of attention of many forward-looking researchers in field.
The content of the invention
Present invention solves the technical problem that being to provide a kind of cation aqueous polyurethane and preparation method thereof, Coating material composition
Thing and preparation method thereof, particularly a kind of cation aqueous polyurethane with fire resistance and preparation method thereof, with fire-retardant
Coating composition of performance and preparation method thereof, the cation aqueous polyurethane that the present invention is provided not only has fire resistance, and
And also there is more preferable combination property.
The invention provides a kind of cation aqueous polyurethane, with the structure shown in formula (I)；
Wherein, a is 1~5；
R1As shown in formula (2)~(6) any one：
R2As shown in formula (7)：
Wherein, m is that 1~30, n is 1~35；
R3As shown in formula (8)~(10) any one：
R4As shown in formula (12)~(14) any one：
It is the invention provides a kind of preparation method of the cation aqueous polyurethane described in above-mentioned technical proposal including following
Step：
1) under conditions of protective gas, by water removal after poly- (carbonic ester-ether) dihydroxylic alcohols and diisocyanate having
Reacted in machine solvent, obtain polyurethane prepolymer one of the end with NCO group；
2) under catalyst action, polyurethane prepolymer one and the hydrophilic chain extender that above-mentioned steps are obtained are reacted,
Obtain prepolymer two；
3) prepolymer two, the methyl alcohol of phosphoryl three and the dihydroxylic alcohols for obtaining above-mentioned steps secondary response again, obtain prepolymer three；
4) after the prepolymer three for obtaining above-mentioned steps is neutralized, then emulsified, obtained cation aqueous polyurethane.
Preferably, the diisocyanate includes that toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1,6- six are sub-
One or more in methyl diisocyanate, isoflurane chalcone diisocyanate and dicyclohexyl methyl hydride diisocyanate；
The organic solvent includes one or more in butanone, acetone and cyclohexanone；
The catalyst includes dibutyl tin laurate；
The hydrophilic chain extender includes in N methyldiethanol amine, N butyl diethanol amine and N- phenyldiethanol-amines
Plant or various；
The dihydroxylic alcohols includes one or more in ethylene glycol, propane diols, butanediol, pentanediol and hexylene glycol.
Preferably, the molecular weight of poly- (carbonic ester-ether) dihydroxylic alcohols is 1500~5000 dalton；
Poly- (carbonic ester-ether) dihydroxylic alcohols is (125~238) with the mass ratio of the diisocyanate：(36~76)；
The hydrophilic chain extender is (6.46~16.65) with the mass ratio of poly- (carbonic ester-ether) dihydroxylic alcohols：(125~
238)；
The dihydroxylic alcohols is (3.50~7.0) with the mass ratio of poly- (carbonic ester-ether) dihydroxylic alcohols：(125~238).
Preferably, it is described to neutralize to add acid to neutralize；
The acid includes one or more in trifluoroacetic acid, trichloroacetic acid, acetate and hydrochloride；
The emulsification is addition water emulsification.
Preferably, the step 1) in, the temperature of the reaction is 70~80 DEG C；The time of the reaction is 1.5~3 small
When；
The step 2) in, the temperature of the reaction is 30~40 DEG C；The time of the reaction is 1~2 hour；
The step 3) in, the temperature of the secondary response again is 45~80 DEG C；The time of the secondary response again is 1.5~2
Hour.
The invention provides a kind of coating composition, including cation aqueous polyurethane described in above-mentioned technical proposal or on
State the cation aqueous polyurethane prepared by technical scheme any one.
Preferably, also include：
The cation aqueous polyurethane is 100~220 weight portions.
Preferably, the water-based thickener includes one or more in BENAQUA 4000, WT-113 and WT115；
The aqueous levelling agent includes one or more in BYK-350, BYK-359 and BYK-381；
The aqueous defoamer includes one or more in BYK-019, BYK-021 and BYK-A 500；
The aqueous wetting agent includes one or more in BYK-187, BYK-3400 and BYK-3410；
The aqueous cosolvent includes isopropanol, butyl glycol ether, butyl, propylene glycol monomethyl ether, propane diols fourth
One or more in ether and dipropylene；
The waterborne curing agent includes aqueous polyisocyanates.
Present invention also offers a kind of preparation method of the coating composition as described in above-mentioned technical scheme any one, bag
Include following steps：
A () enters cation aqueous polyurethane, water-based thickener, aqueous defoamer, aqueous levelling agent and aqueous wetting agent
After row mixing, mixture is obtained；
In b mixture that () is obtained to above-mentioned steps, aqueous cosolvent and waterborne curing agent are added, after mixing again, obtained
To coating composition.
The cation aqueous polyurethane with the structure shown in (containing) formula (I) and its preparation side the invention provides one kind
Method.Compared with prior art, the present invention is directed to existing common water borne polyurethane flame-proof poor performance, and common water borne polyurethane
Oligomer polyol used is mainly polyester-type and polyether-type, and PAUR hydrolytic resistance is poor, EU
Resistance to oxidation and the poor many defects of mechanical performance.The present invention is joined by the use of the methyl alcohol of phosphoryl three (PTMA) as reactive flame retardant
In the segment reaction to polyurethane, both assigned polyurethane good fire resistance, the crosslinking points of polyurethane had been act as again, by phosphorus
The methyl alcohol of acyl group three (PTMA) is incorporated into polyurethane molecular chain, reuses poly- (carbonic ester-ether) dihydroxylic alcohols as polyester diol,
The dihydroxylic alcohols had not only had polyester construction but also had had polyether structure, had hydrolysis, resistance to oxidation and preferable mechanical performance concurrently, obtained
Carbon dioxide-base flame-retardant aqueous polyurethane, is a kind of cationic water with fire resistance and preferable water resistance higher
Property polyurethane resin, resin property is excellent, and the aqueous polyurethane can also reduce the dependence to fossil resources.
Test result indicate that, aqueous polyurethane prepared by the flame retardant type cation aqueous polyurethane provided using the present invention is applied
Film, limited oxygen index can reach 26.8, and it is only 8.9% that water absorption rate is minimum.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the aqueous polyurethane that the embodiment of the present invention 1 is prepared；
Fig. 2 is the infrared spectrum of the aqueous polyurethane that the embodiment of the present invention 2 is prepared.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The all raw materials of the present invention, originate to it and are not particularly limited, commercially buying or according to people in the art
Known to member prepared by conventional method.
The present invention is not particularly limited, with painting well known to those skilled in the art to the raw materials used trade mark to its implication
The raw material of the trade mark of production firm's production of the conventional trade mark or routine in material field.
The all raw materials of the present invention, are not particularly limited to its purity, present invention preferably employs the pure or aqueous polyurethane of analysis
The conventional purity that field uses.
The invention discloses a kind of cation aqueous polyurethane, with the structure shown in formula (I)；
Wherein, a is 1~5；
R1As shown in formula (2)~(6) any one：
R2As shown in formula (7)：
Wherein, m is that 1~30, n is 1~35；
R3As shown in formula (8)~(10) any one：
R4As shown in formula (12)~(14) any one：
The present invention is to the cation aqueous polyurethane with structure shown in formula (I) without other special limitations, ability
Knowable to field technique personnel, the cation aqueous polyurethane can be the structural formula, it is also possible to fragment or official containing the structure
Fragment, the wave shown in formula (I) can be rolled into a ballSegment before representative can be repeat unit, for repeat unit
Number (degree of polymerization), the present invention is not particularly limited.
A of the present invention is 1~5, preferably 2~4, most preferably 3；M of the present invention be 1~30, preferably 5~
25, more preferably 10~20, most preferably 12~18；Of the present invention is 1~35, preferably 5~30, more preferably 10~
25, most preferably 15~20.
It is the invention provides a kind of preparation method of the cation aqueous polyurethane described in above-mentioned technical proposal including following
Step：
1) under conditions of protective gas, by water removal after poly- (carbonic ester-ether) dihydroxylic alcohols and diisocyanate having
Reacted in machine solvent, obtain polyurethane prepolymer one of the end with NCO group；
2) under catalyst action, polyurethane prepolymer one and the hydrophilic chain extender that above-mentioned steps are obtained are reacted,
Obtain prepolymer two；
3) prepolymer two, the methyl alcohol of phosphoryl three and the dihydroxylic alcohols for obtaining above-mentioned steps secondary response again, obtain prepolymer three；
4) after the prepolymer three for obtaining above-mentioned steps is neutralized, then emulsified, obtained cation aqueous polyurethane.
The present invention is selected the raw material in the preparation method and preferred scope, preferably with aforesaid cations aqueous polyurethane
In corresponding group selection and preferred scope correspond, this is no longer going to repeat them.
The present invention first under conditions of protective gas, by water removal after poly- (carbonic ester-ether) dihydroxylic alcohols and two isocyanides
Acid esters reacts in organic solvent, obtains polyurethane prepolymer one of the end with NCO group.
The present invention is not particularly limited to the protective gas, is with protective gas well known to those skilled in the art
Can, those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement, the present invention
The protective gas is preferably nitrogen or inert gas, more preferably nitrogen.
The no spy in source of poly- (carbonic ester-ether) dihydroxylic alcohols (compound formula (7) shown in) of the present invention for being used
Do not limit, prepared with the preparation method of poly- (carbonic ester-ether) dihydroxylic alcohols well known to those skilled in the art or commercially available purchase,
Those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement, and the present invention is excellent
According to patent 201210086834.X or disclosed in patent 201110231493.6 prepared by method for choosing；
M is 1~30, preferably 10~25；N is 1~35, preferably 5~30.
No other the special limitations of parameter of the present invention to poly- (carbonic ester-ether) dihydroxylic alcohols, with people in the art
The parameter of poly- (carbonic ester-ether) dihydroxylic alcohols known to member, those skilled in the art can be according to actual experiment situation, product
It is required that and quality requirement selected and adjusted, the molecular weight of poly- (carbonic ester-ether) dihydroxylic alcohols of the present invention is preferably 1500
~5000 dalton, more preferably 2000~4500 dalton, more preferably 2500~4000 dalton, most preferably 3000~
3500 dalton.
The present invention is to the water removal mode and parameter of poly- (carbonic ester-ether) dihydroxylic alcohols with formula (7) structure without spy
Do not limit, with the water removal mode and parameter of such compound well known to those skilled in the art, those skilled in the art can
Selected and adjusted with according to actual experiment situation, product requirement and quality requirement, water removal of the present invention is preferably is depressurized
Distillation water removal, the temperature of the water removal is preferably 105~115 DEG C, more preferably 108~113 DEG C；The time of the water removal is preferred
It is 50~70 minutes, more preferably 55~65 minutes.
The present invention is not particularly limited to the diisocyanate, is with diisocyanate well known to those skilled in the art
Can, those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement, the present invention
The diisocyanate preferably includes toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, the isocyanide of 1,6- hexa-methylenes two
One or more in acid esters, isoflurane chalcone diisocyanate and dicyclohexyl methyl hydride diisocyanate, more preferably toluene
Diisocyanate, methyl diphenylene diisocyanate, 1,6- hexamethylene diisocyanates, isoflurane chalcone diisocyanate or two
Diphenylmethane diisocyanate, most preferably toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1,6- hexa-methylenes
Diisocyanate or dicyclohexyl methyl hydride diisocyanate.
The present invention is not particularly limited to the organic solvent, with the organic of such reaction well known to those skilled in the art
Solvent, those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement,
Organic solvent of the present invention preferably includes one or more in butanone, acetone and cyclohexanone, more preferably butanone or acetone,
Most preferably butanone.
The present invention to the water removal after poly- (carbonic ester-ether) dihydroxylic alcohols and diisocyanate additional proportion without special
Limitation, with the conventional ratio of such compound well known to those skilled in the art, those skilled in the art can be according to reality
Border experimental conditions, product requirement and quality requirement are selected and adjusted, poly- (carbonic ester-ether) dihydroxylic alcohols of the present invention and institute
State the mass ratio preferably (125~238) of diisocyanate：(36~76), more preferably (150~213)：(46~66), most
Preferably (175~183)：(51~61).
The present invention is not particularly limited to the condition of the reaction, with the normal of such reaction well known to those skilled in the art
Rule condition, those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement
Whole, the temperature of reaction of the present invention is preferably 70~80 DEG C, most preferably more preferably 72~78 DEG C, 74~76 DEG C；It is described
The time of reaction is preferably 1.5~3 hours, more preferably 1.8~2.7 hours, most preferably 2.0~2.5 hours.
Of the invention subsequent under catalyst action, polyurethane prepolymer one and the hydrophilic chain extender that above-mentioned steps are obtained enter
Row reaction, obtains prepolymer two.
The present invention is not particularly limited to the catalyst, with the catalyst of such reaction well known to those skilled in the art
, those skilled in the art can be selected and be adjusted, this hair according to actual experiment situation, product requirement and quality requirement
The bright catalyst is preferably dibutyl tin laurate.
The present invention is not particularly limited to the hydrophilic chain extender, conventional with such reaction well known to those skilled in the art
Hydrophilic chain extender, those skilled in the art can be selected according to actual experiment situation, product requirement and quality requirement
Select and adjust, hydrophilic chain extender of the present invention preferably includes N methyldiethanol amine, N butyl diethanol amine and N- phenyl two
One or more in monoethanolamine, more preferably N methyldiethanol amine, N butyl diethanol amine or N- phenyldiethanol-amines.
The present invention is not particularly limited to the additional proportion of the hydrophilic chain extender, with it is well known to those skilled in the art this
The conventional ratio of class compound, those skilled in the art can be according to actual experiment situation, product requirement and quality requirement
Selected and adjusted, hydrophilic chain extender of the present invention is preferably with the mass ratio of poly- (carbonic ester-ether) dihydroxylic alcohols
(6.46~16.65)：(125~238), more preferably (8.46~14.65)：(150~213), most preferably (10.46~
12.65)：(175~183).
The present invention is not particularly limited to the condition of the reaction, with the normal of such reaction well known to those skilled in the art
Rule condition, those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement
Whole, the temperature of reaction of the present invention is preferably 30~40 DEG C, most preferably more preferably 32~38 DEG C, 34~36 DEG C；It is described
The time of reaction is preferably 1~2 hour, more preferably 1.2~1.8 hours, most preferably 1.4~1.6 hours.
Hydrophilic chain extender of the present invention is preferably added dropwise in polyurethane prepolymer one of the end with NCO group, described
The time of dropwise addition is preferably controlled to 1h completion of dropping.
The present invention and then the prepolymer two, the methyl alcohol of phosphoryl three (PTMA) and the dihydroxylic alcohols that obtain above-mentioned steps are anti-again
Should, obtain prepolymer three.
The present invention is not particularly limited to the dihydroxylic alcohols, with conventional dihydroxylic alcohols well known to those skilled in the art,
Those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement, institute of the present invention
One or more during dihydroxylic alcohols preferably includes ethylene glycol, propane diols, butanediol, pentanediol and hexylene glycol is stated, is more preferably wrapped
Include ethylene glycol, propane diols, butanediol, pentanediol or hexylene glycol, most preferably butanediol.
The present invention is not particularly limited to the additional proportion of the dihydroxylic alcohols, with conventional ratio well known to those skilled in the art
Example, those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement, this
The dihydroxylic alcohols is invented to be preferably (3.5~7.0) with the mass ratio of poly- (carbonic ester-ether) dihydroxylic alcohols：(125~238), more
Preferably (4.0~6.5)：(150~213), most preferably (4.5~6.0)：(175~183).
The present invention is not particularly limited to the condition of the secondary response again, with such reaction well known to those skilled in the art
Normal condition, those skilled in the art can be selected according to actual experiment situation, product requirement and quality requirement
And adjustment, the temperature of secondary response again of the present invention is preferably 45~80 DEG C, more preferably 55~75 DEG C, most preferably 60~70
℃；The time of the secondary response again is preferably 1.5~2 hours, and more preferably 1.6~1.9 hours, most preferably 1.7~1.8 is small
When.
After the last prepolymer three for obtaining above-mentioned steps of the invention is neutralized, then emulsified, obtained cation water-based poly-
Urethane resin.
The present invention is not particularly limited to the condition of the neutralization, with such reaction well known to those skilled in the art
With condition, those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement
Whole, it is 6~7 that the condition of neutralization of the present invention is preferably and is neutralized to pH.The present invention is not limited especially the mode of the neutralization
System, in the neutralization mode of such reaction well known to those skilled in the art, those skilled in the art can be according to actual reality
Test situation, product requirement and quality requirement to be selected and adjusted, the mode of neutralization of the present invention is preferably sour neutralization.This hair
Bright sour one or more be preferably in trifluoroacetic acid, trichloroacetic acid, acetic acid and hydrochloric acid, more preferably trifluoroacetic acid,
Trichloroacetic acid, acetic acid or hydrochloric acid.
The present invention is not particularly limited to the condition of the emulsification, with the breast of such reaction well known to those skilled in the art
Change condition, those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement
Whole, the condition of emulsification of the present invention is preferably stirring and emulsifying.The speed of stirring of the present invention is preferably 1200~
1800rpm, more preferably 1300~1700rpm, most preferably 1400~1600rpm；The time of the stirring is preferably 0.5~
2h, more preferably 1.0~1.5h.
The present invention is not particularly limited to the mode of the emulsification, with the breast of such reaction well known to those skilled in the art
Change mode, those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement
Whole, the mode of emulsification of the present invention is preferably addition water and is emulsified, and more preferably adds deionized water to be emulsified.
The present invention is the integrality and operability of raising reaction scheme, also includes removing the step of solvent after the emulsification
Suddenly.The present invention is not particularly limited to the mode of the removing solvent, with going for such reaction well known to those skilled in the art
Solvent mode, those skilled in the art can be selected according to actual experiment situation, product requirement and quality requirement and
Adjustment, removing solvent of the present invention is preferably vacuum distillation and removes solvent.
Present invention also offers a kind of coating composition, including cation aqueous polyurethane described in above-mentioned technical proposal or
Cation aqueous polyurethane prepared by above-mentioned technical proposal any one.
Selection of the present invention to the cation aqueous polyurethane in the coating composition and preferred scope, preferably with it is foregoing
Selection and preferred scope in cation aqueous polyurethane and preparation method thereof are corresponded, and this is no longer going to repeat them.
The present invention is not particularly limited to the coating composition, with such water paint well known to those skilled in the art
Composition, those skilled in the art can be selected and be adjusted according to actual experiment situation, product requirement and quality requirement
Whole, coating composition of the present invention can be only above-mentioned cation aqueous polyurethane, it is also possible to including above-mentioned cation water-based
Polyurethane, the present invention is the practicality and range of application of raising coating composition, and the coating composition preferably also includes：
Wherein, the cation aqueous polyurethane is 100~220 weight portions.
The consumption of cation aqueous polyurethane of the present invention is preferably 100~220 weight portions, more preferably 120~200
Weight portion, most preferably 140~180 weight portions.
The addition of water-based thickener of the present invention is preferably 0.6~1.8 weight portion, more preferably 0.8~1.6 weight
Part, most preferably 1.0~1.4 weight portions.The present invention is not particularly limited to the specifically chosen of the water-based thickener, with ability
Aqueous coating thickener known to field technique personnel, those skilled in the art can be according to practical situations, product
It is required that and quality requirement selected and adjusted, the specific marque of water-based thickener of the present invention is preferably included
One or more in BENAQUA 4000, WT-113 and WT115, more preferably BENAQUA 4000, WT-113 or WT115.
The addition of aqueous levelling agent of the present invention is preferably 0.1~0.3 weight portion, more preferably 0.14~0.26 weight
Amount part, most preferably 0.18~0.22 weight portion.The present invention is not particularly limited to the specifically chosen of the aqueous levelling agent, with
Aqueous coating levelling agent well known to those skilled in the art, those skilled in the art can according to practical situations,
Product requirement and quality requirement are selected and adjusted, and the specific marque of aqueous levelling agent of the present invention is preferably included
One or more in BYK-350, BYK-359 and BYK-381, more preferably BYK-350, BYK-359 or BYK-381.
The addition of aqueous defoamer of the present invention is preferably 0.6~1.8 weight portion, more preferably 0.8~1.6 weight
Part, most preferably 1.0~1.4 weight portions.The present invention is not particularly limited to the specifically chosen of the aqueous defoamer, with ability
Aqueous coating defoamer known to field technique personnel, those skilled in the art can be according to practical situations, product
It is required that and quality requirement selected and adjusted, the specific marque of aqueous defoamer of the present invention preferably includes BYK-
019th, one or more in BYK-021 and BYK-A 500, more preferably BYK-019, BYK-021 or BYK-A 500.
The addition of aqueous wetting agent of the present invention is preferably 0.3~0.7 weight portion, more preferably 0.35~0.65 weight
Amount part, most preferably 0.4~0.6 weight portion.The present invention is not particularly limited to the specifically chosen of the aqueous wetting agent, with this
Aqueous coating wetting agent known to art personnel, those skilled in the art can be according to practical situations, product
Product requirement and quality requirement are selected and adjusted, and the specific marque of aqueous wetting agent of the present invention preferably includes BYK-
187th, one or more in BYK-3400 and BYK-3410, more preferably BYK-187, BYK-3400 or BYK-3410.
The addition of aqueous cosolvent of the present invention is preferably 6~8 weight portions, more preferably 6.4~7.6 weight portions,
Most preferably 6.8~7.2 weight portions.The present invention is not particularly limited to the specifically chosen of aqueous cosolvent, with this area
Aqueous coating cosolvent known to technical staff, those skilled in the art can want according to practical situations, product
Ask and quality requirement is selected and adjusted, aqueous cosolvent of the present invention preferably includes isopropanol, butyl glycol ether, diethyl
One or more in glycol butyl ether, propylene glycol monomethyl ether, propandiol butyl ether and dipropylene, more preferably isopropanol, second
Glycol butyl ether, butyl, propylene glycol monomethyl ether, propandiol butyl ether or dipropylene.
The addition of waterborne curing agent of the present invention is preferably 2~6 weight portions, more preferably 3~5 weight portions, optimal
Elect 3.5~4.5 weight portions as.The present invention is not particularly limited to the specifically chosen of the waterborne curing agent, with art technology
Aqueous coating curing agent known to personnel, those skilled in the art can according to practical situations, product requirement and
Quality requirement is selected and adjusted, and waterborne curing agent of the present invention preferably includes aqueous polyisocyanates, its specific commodity
Model is preferably included3100、The Hes of XP 2487/1In XP 2451 one
Plant or various, most preferably3100、XP 2487/1 orXP 2451。
Present invention also offers a kind of preparation method of the coating composition as described in above-mentioned technical scheme any one, bag
Include following steps：
A () enters cation aqueous polyurethane, water-based thickener, aqueous defoamer, aqueous levelling agent and aqueous wetting agent
After row mixing, mixture is obtained；
In b mixture that () is obtained to above-mentioned steps, aqueous cosolvent and waterborne curing agent are added, after mixing again, obtained
To coating composition, i.e. carbon dioxide-base aqueous polyurethane coating.
The present invention is not particularly limited to the mode of the mixing, is with hybrid mode well known to those skilled in the art
Can, those skilled in the art can be selected and be adjusted according to practical condition, product requirement and quality requirement, the present invention
The mixing is preferably stirring mixing.The present invention is not particularly limited to the time of the mixing, ripe with those skilled in the art
The incorporation time known, those skilled in the art can be selected according to practical condition, product requirement and quality requirement
Select and adjust, the time of mixing of the present invention is preferably 2~3 hours, more preferably 2.2~2.8 hours, most preferably 2.4
~2.6 hours.
The present invention is not particularly limited to the mode for mixing again, with hybrid mode well known to those skilled in the art
, those skilled in the art can be selected and be adjusted, this hair according to practical condition, product requirement and quality requirement
The bright mixing again is preferably stirring mixing.The present invention is not particularly limited to the time for mixing again, with this area
Incorporation time known to technical staff, those skilled in the art can be according to practical condition, product requirement and quality
It is required that being selected and being adjusted, the time for mixing again of the present invention is preferably 0.3~2 hour, more preferably 0.4~1.5
Hour, most preferably 0.5~1 hour.
Include cation aqueous polyurethane of structure shown in formula (I) and preparation method thereof, painting the invention provides one kind
Feed composition and preparation method thereof.The present invention participates in polyurethane by the use of the methyl alcohol of phosphoryl three (PTMA) as reactive flame retardant
Segment reaction in, both assigned polyurethane good fire resistance, the crosslinking points of polyurethane are act as again, by the methyl alcohol of phosphoryl three
(PTMA) it is incorporated into polyurethane molecular chain, reuses poly- (carbonic ester-ether) dihydroxylic alcohols as polyester diol, the dihydroxylic alcohols was both
There is polyether structure again with polyester construction, hydrolysis, resistance to oxidation and preferable mechanical performance is had concurrently, carbon dioxide-base has been obtained
Flame-retardant aqueous polyurethane, is a kind of cation aqueous polyurethane tree with fire resistance and preferable water resistance higher
Fat, resin property is excellent, and the aqueous polyurethane can also reduce the dependence to fossil resources.
Test result indicate that, aqueous polyurethane prepared by the flame retardant type cation aqueous polyurethane provided using the present invention is applied
Film, limited oxygen index can reach 26.8, and it is only 8.9% that water absorption rate is minimum.
In order to further illustrate the present invention, a kind of cation aqueous polyurethane for providing the present invention with reference to embodiments
And preparation method thereof, coating composition and preparation method thereof has been described in detail, but it is to be understood that these embodiments be
Implemented under premised on technical solution of the present invention, given detailed implementation method and specific operating process, be simply
The features and advantages of the present invention are further illustrated, rather than limiting to the claimed invention, protection scope of the present invention
It is not limited to following embodiments.
Embodiment 1
Method according to patent 201210086834.X disclosed embodiments 11 prepares number-average molecular weight for 1500 roads
Poly- (carbonic ester-ether) dihydroxylic alcohols that you pause.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 125 grams of molecular weight for preparing are 1500 dalton is added in there-necked flask,
110 DEG C are heated to, are dehydrated 1 hour under -0.98MPa, be cooled to 75 DEG C, under nitrogen protection, add 195 grams of butanone and 76 grams
Methyl diphenylene diisocyanate reacts 2 hours, is then cooled to 35 DEG C, and 0.0020 gram of dropwise addition is dibutyltindilaurate catalyzed
Agent, adds 9.78 grams of N butyl diethanol amines, addition to be reacted 1 hour after finishing in three batches, then heats to 70 DEG C, adds 2.45
Gram methyl alcohol of phosphoryl three and 5.45 grams of butanediols, react 2 hours, add in glacial acetic acid and pH is to 7, be subsequently adding 250 grams go from
Sub- water, 1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtain a kind of cation aqueous polyurethane resin.
Infrared detection, testing result are carried out as shown in figure 1, Fig. 1 to the aqueous polyurethane that the embodiment of the present invention 1 is prepared
It is the infrared spectrum of the aqueous polyurethane that the embodiment of the present invention 1 is prepared, as shown in Figure 1, infrared spectrum：3334cm-1,
2951cm-1,1747cm-1,1533cm-1,1457cm-1,1379cm-1,1245cm-1,1131cm-1,1061cm-1,981cm-1,
846cm-1,789cm-1、481cm-1。
Embodiment 2
Method according to the disclosed embodiment 17 of patent 201110231493.6 prepares number-average molecular weight for 3500 roads
Poly- (carbonic ester-ether) dihydroxylic alcohols that you pause.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 195 grams of molecular weight for preparing are 3500 dalton is added in there-necked flask,
110 DEG C are heated to, are dehydrated 1 hour under -0.98MPa, be cooled to 78 DEG C, under nitrogen protection, add 158 grams of butanone and 36 grams
1, hexamethylene-diisocyanate reacts 2 hours, is then cooled to 32 DEG C, and 0.0014 gram of dibutyltin dilaurate catalyst is added dropwise,
Add 6.68 grams of N methyldiethanol amines, addition to be reacted 1 hour after finishing in three batches, then heat to 75 DEG C, add 1.60 grams
The methyl alcohol of phosphoryl three and 3.52 grams of butanediols, are reacted 2 hours, and 320 grams of deionizations are subsequently adding to 7 with pH in addition glacial acetic acid
Water, 1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtain a kind of cation aqueous polyurethane resin.
Infrared detection, testing result are carried out as shown in Fig. 2 Fig. 2 to the aqueous polyurethane that the embodiment of the present invention 2 is prepared
It is the infrared spectrum of the aqueous polyurethane that the embodiment of the present invention 2 is prepared, infrared spectrum as shown in Figure 2：3336cm-1,
2951cm-1,1747cm-1,1532cm-1,1457cm-1,1366cm-1,1245cm-1,1131cm-1,1060cm-1,981cm-1,
846cm-1,789cm-1、478cm-1。
Embodiment 3
Method according to patent 201210086834.X disclosed embodiments 9 prepares number-average molecular weight for 2000 dongles
Poly- (carbonic ester-ether) dihydroxylic alcohols for pausing.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 200 grams of molecular weight for preparing are 2000 dalton is added in there-necked flask,
110 DEG C are heated to, are dehydrated 1 hour under -0.98MPa, be cooled to 75 DEG C, under nitrogen protection, add 100 grams of butanone and 100
Gram dicyclohexyl methyl hydride diisocyanate reacts 2 hours, is then cooled to 38 DEG C, and 0.0025 gram of dibutyl tin laurate is added dropwise
Catalyst, adds 12.60 grams of N methyldiethanol amines, addition to be reacted 1 hour after finishing in three batches, then heats to 72 DEG C, plus
Enter 3.15 grams of methyl alcohol of phosphoryl three and 7.0 grams of butanediols, react 2 hours, 350 grams are subsequently adding to 7 with pH in addition glacial acetic acid
Deionized water, 1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtain a kind of cation aqueous polyurethane resin.
Infrared detection is carried out to the aqueous polyurethane that the embodiment of the present invention 3 is prepared, testing result is implemented for the present invention
The infrared spectrum of the aqueous polyurethane that example 3 is prepared：3335cm-1,2950cm-1,1748cm-1,1534cm-1,1456cm-1,
1378c m-1,1246cm-1,1132cm-1,1062cm-1,980cm-1,846cm-1,788cm-1、480cm-1。
Embodiment 4
Method according to patent 201210086834.X disclosed embodiments 4 prepares number-average molecular weight for 5000 dongles
Poly- (carbonic ester-ether) dihydroxylic alcohols for pausing.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 238 grams of molecular weight for preparing are 5000 dalton is added in there-necked flask,
110 DEG C are heated to, are dehydrated 1 hour under -0.98MPa, be cooled to 72 DEG C, under nitrogen protection, add 300 grams of butanone and 40.5
Gram IPDI reacts 2 hours, is then cooled to 34 DEG C, be added dropwise 0.0020 gram it is dibutyltindilaurate catalyzed
Agent, adds 6.46 grams of N butyl diethanol amines, addition to be reacted 1 hour after finishing in three batches, then heats to 76 DEG C, adds 1.50
Gram methyl alcohol of phosphoryl three and 3.50 grams of butanediols, react 2 hours, add in glacial acetic acid and pH is to 7, be subsequently adding 450 grams go from
Sub- water, 1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtain a kind of cation aqueous polyurethane resin.
Infrared detection is carried out to the aqueous polyurethane that the embodiment of the present invention 4 is prepared, testing result is implemented for the present invention
The INFRARED SPECTRUM of the aqueous polyurethane that example 4 is prepared：3336cm-1,2952cm-1,1748cm-1,1535cm-1,1459cm-1,
1376cm-1,1249cm-1,1135cm-1,1066cm-1,985cm-1,848cm-1,785cm-1、481cm-1。
Embodiment 5
Method according to patent 201210086834.X disclosed embodiments 9 prepares number-average molecular weight for 2000 dongles
Poly- (carbonic ester-ether) dihydroxylic alcohols for pausing.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 138 grams of molecular weight for preparing are 2000 dalton is added in there-necked flask,
110 DEG C are heated to, are dehydrated 1 hour under -0.98MPa, be cooled to 80 DEG C, under nitrogen protection, add 115 grams of butanone and 42.4
Gram toluene di-isocyanate(TDI) reacts 2 hours, is then cooled to 32 DEG C, and 0.0015 gram of dibutyltin dilaurate catalyst is added dropwise,
Add 8.20 grams of N methyldiethanol amines, addition to be reacted 1 hour after finishing in three batches, then heat to 75 DEG C, add 2.13 grams
The methyl alcohol of phosphoryl three and 4.20 grams of butanediols, are reacted 2 hours, and 200 grams of deionizations are subsequently adding to 7 with pH in addition glacial acetic acid
Water, 1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtain a kind of cation aqueous polyurethane resin.
Infrared detection is carried out to the aqueous polyurethane that the embodiment of the present invention 5 is prepared, testing result is implemented for the present invention
The infrared spectrum of the aqueous polyurethane that example 5 is prepared：3339cm-1,2951cm-1,1746cm-1,1532cm-1,1457cm-1,
1366cm-1,1245cm-1,1131cm-1,1062cm-1,985cm-1,846cm-1,785cm-1、481cm-1。
Embodiment 6
Method according to patent 201210086834.X disclosed embodiments 8 prepares number-average molecular weight for 2800 dongles
Poly- (carbonic ester-ether) dihydroxylic alcohols for pausing.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 218 grams of molecular weight for preparing are 2800 dalton is added in there-necked flask,
110 DEG C are heated to, are dehydrated 1 hour under -0.98MPa, be cooled to 74 DEG C, under nitrogen protection, add 250 grams of butanone and 49 grams
Toluene di-isocyanate(TDI) reacts 2 hours, is then cooled to 36 DEG C, and 0.0014 gram of dibutyltin dilaurate catalyst is added dropwise, point
Three batches of additions, 13.65 grams of N- phenyldiethanol-amines, addition is reacted 1 hour after finishing, and then heats to 78 DEG C, adds 2.38 grams of phosphorus
The methyl alcohol of acyl group three and 5.20 grams of butanediols, are reacted 2 hours, and 330 grams of deionized waters are subsequently adding to 7 with pH in addition glacial acetic acid,
1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtain a kind of cation aqueous polyurethane resin.
Infrared detection is carried out to the aqueous polyurethane that the embodiment of the present invention 6 is prepared, testing result is implemented for the present invention
The infrared spectrum of the aqueous polyurethane that example 6 is prepared：3338cm-1,2953cm-1,1748cm-1,1532cm-1,1456cm-1,
1368cm-1,1247cm-1,1130cm-1,1064cm-1,984cm-1,846cm-1,787cm-1、481cm-1。
Comparative example 1
Waterborne polyurethane resin synthesizes
Preparation method is same as Example 1, only changes the methyl alcohol of phosphoryl three into butanediol.
Embodiment 7
By the material ratio of table 1, carbon dioxide-base aqueous polyurethane coating is prepared in accordance with the following methods：
(1) referring to table 1, table 1 is aqueous polyurethane coating material composition and ratio provided in an embodiment of the present invention
Table 1
According to the proportioning of table 1 by carbon dioxide-base flame-retardant aqueous polyurethane, water-based thickener, aqueous cosolvent, aqueous
Defoamer, aqueous levelling agent and aqueous wetting agent add agitating device, are stirred with speed, and mixture was obtained through 2~3 hours；
(2) to waterborne curing agent is added in the mixture, stirring obtains carbon dioxide-base after 1 hour flame-retardant aqueous poly-
Urethane coating.The coating that will be obtained is designated as WPU1, WPU2, WPU3, WPU4, WPU5, WPU6 and DB1 respectively.Respectively by dioxy
Change carbon-based aqueous polyurethane coating WPU1, WPU2, WPU3, WPU4, WPU5, WPU6 and DB1 are coated uniformly on polytetrafluoroethylene (PTFE)
In disk, 150~200um of thickness, after room temperature is placed 5 days, after 8 hours at 50 DEG C of vacuum drying oven are completely dried, to the film for obtaining
Carry out tensile property test, limited oxygen index and water resistance test.2 are the results are shown in Table, table 2 is the embodiment of the present invention and comparative example system
Standby aqueous polyurethane film performance test result.
Table 2
| Project | WAD1 | WAD2 | WAD3 | WAD4 | WAD5 | WAD6 | DB1 |
| Elongation at break (%) | 500 | 510 | 490 | 510 | 540 | 550 | 460 |
| Tensile strength (MPa) | 37 | 35 | 41 | 39 | 40 | 42 | 28 |
| Limited oxygen index | 26.3 | 23.9 | 25.6 | 24.7 | 26.8 | 25.1 | 21.0 |
| Water absorption rate (%) | 9.5 | 10.2 | 8.9 | 9.5 | 9.4 | 9.9 | 13.8 |
Wherein, the water resistance test of film：The film of drying is made dumbbell shaped batten weighs and be designated as W0, place at room temperature
Weighed after 24 hours in deionized water and be designated as W1, water absorption rate (%)=(W1-W0)/W0* 100%.
A kind of cation aqueous polyurethane with fire resistance and preparation method thereof for there is provided the present invention above, have
Coating composition of fire resistance and preparation method thereof is described in detail, and specific case used herein is to the present invention
Principle and implementation method be set forth, the explanation of above example is only intended to help and understands the method for the present invention and its core
Thought is thought, including best mode, and also causes that any person skilled in the art can put into practice the present invention, including manufacture and
Using any device or system, and the method for implementing any combination.It should be pointed out that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, these improve and repair
Decorations are also fallen into the protection domain of the claims in the present invention.The scope of patent protection of the present invention is defined by the claims, and
May include those skilled in the art it is conceivable that other embodiment.If these other embodiments have is not different from right
It is required that the structural element of character express, or if they include being equal to knot without essence difference with the character express of claim
Structure key element, then these other embodiments also should be comprising within the scope of the claims.
Claims (10)
1. a kind of cation aqueous polyurethane, it is characterised in that with the structure shown in formula (I)；
Wherein, a is 1~5；
R1As shown in formula (2)~(6) any one：
R2As shown in formula (7)：
Wherein, m is that 1~30, n is 1~35；
R3As shown in formula (8)~(10) any one：
R4As shown in formula (12)~(14) any one：
2. a kind of preparation method of cation aqueous polyurethane as claimed in claim 1, it is characterised in that including following step
Suddenly：
1) under conditions of protective gas, by water removal after poly- (carbonic ester-ether) dihydroxylic alcohols and diisocyanate organic molten
Reacted in agent, obtain polyurethane prepolymer one of the end with NCO group；
2) under catalyst action, polyurethane prepolymer one and the hydrophilic chain extender that above-mentioned steps are obtained are reacted, and are obtained
Prepolymer two；
3) prepolymer two, the methyl alcohol of phosphoryl three and the dihydroxylic alcohols for obtaining above-mentioned steps secondary response again, obtain prepolymer three；
4) after the prepolymer three for obtaining above-mentioned steps is neutralized, then emulsified, obtained cation aqueous polyurethane.
3. preparation method according to claim 2, it is characterised in that the diisocyanate includes toluene diisocynate
Ester, methyl diphenylene diisocyanate, 1,6- hexamethylene diisocyanates, isoflurane chalcone diisocyanate and dicyclohexyl
One or more in methane diisocyanate；
The organic solvent includes one or more in butanone, acetone and cyclohexanone；
The catalyst includes dibutyl tin laurate；
The hydrophilic chain extender include N methyldiethanol amine, N butyl diethanol amine and N- phenyldiethanol-amines in one kind or
It is various；
The dihydroxylic alcohols includes one or more in ethylene glycol, propane diols, butanediol, pentanediol and hexylene glycol.
4. preparation method according to claim 2, it is characterised in that the molecular weight of poly- (carbonic ester-ether) dihydroxylic alcohols
It is 1500~5000 dalton；
Poly- (carbonic ester-ether) dihydroxylic alcohols is (125~238) with the mass ratio of the diisocyanate：(36~76)；
The hydrophilic chain extender is (6.46~16.65) with the mass ratio of poly- (carbonic ester-ether) dihydroxylic alcohols：(125~
238)；
The dihydroxylic alcohols is (3.50~7.0) with the mass ratio of poly- (carbonic ester-ether) dihydroxylic alcohols：(125~238).
5. preparation method according to claim 2, it is characterised in that the neutralization is neutralized to add acid；
The acid includes one or more in trifluoroacetic acid, trichloroacetic acid, acetate and hydrochloride；
The emulsification is addition water emulsification.
6. the preparation method according to claim 2~5 any one, it is characterised in that the step 1) in, the reaction
Temperature be 70~80 DEG C；The time of the reaction is 1.5~3 hours；
The step 2) in, the temperature of the reaction is 30~40 DEG C；The time of the reaction is 1~2 hour；
The step 3) in, the temperature of the secondary response again is 45~80 DEG C；The time of the secondary response again is 1.5~2 hours.
7. a kind of coating composition, it is characterised in that including cation aqueous polyurethane or claim described in claim 1
Cation aqueous polyurethane prepared by 2~6 any one.
8. coating composition according to claim 7, it is characterised in that also include：
The cation aqueous polyurethane is 100~220 weight portions.
9. coating composition according to claim 8, it is characterised in that the water-based thickener include BENAQUA4000,
One or more in WT-113 and WT115；
The aqueous levelling agent includes one or more in BYK-350, BYK-359 and BYK-381；
The aqueous defoamer includes one or more in BYK-019, BYK-021 and BYK-A500；
The aqueous wetting agent includes one or more in BYK-187, BYK-3400 and BYK-3410；
The aqueous cosolvent include isopropanol, butyl glycol ether, butyl, propylene glycol monomethyl ether, propandiol butyl ether and
One or more in dipropylene；
The waterborne curing agent includes aqueous polyisocyanates.
10. a kind of preparation method of coating composition as claimed in claim 8 or 9, it is characterised in that comprise the following steps：
A () is mixed cation aqueous polyurethane, water-based thickener, aqueous defoamer, aqueous levelling agent and aqueous wetting agent
After conjunction, mixture is obtained；
In b mixture that () is obtained to above-mentioned steps, aqueous cosolvent and waterborne curing agent are added, after mixing again, applied
Feed composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN109880145A (en) * | 2019-03-07 | 2019-06-14 | 中国科学院长春应用化学研究所 | A kind of fire-retardant Polyimide foams of low smell and preparation method thereof |
| CN110105531A (en) * | 2019-05-16 | 2019-08-09 | 浙江恒川新材料有限公司 | A kind of preparation method of paper antimicrobial coating |
| CN111004568A (en) * | 2019-11-18 | 2020-04-14 | 广东东方一哥新材料股份有限公司 | Preparation method of water-based transparent primer without drying in low-temperature high-humidity environment |
| CN111533875A (en) * | 2020-05-07 | 2020-08-14 | 合肥科天水性科技有限责任公司 | Preparation method of cationic waterborne polyurethane, leather bottom sealing resin and leather coating |
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