CN105330808A - Inner crosslinking composite polyester-polyether waterborne polyurethane emulsion and preparation method thereof - Google Patents
Inner crosslinking composite polyester-polyether waterborne polyurethane emulsion and preparation method thereof Download PDFInfo
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- CN105330808A CN105330808A CN201510765198.7A CN201510765198A CN105330808A CN 105330808 A CN105330808 A CN 105330808A CN 201510765198 A CN201510765198 A CN 201510765198A CN 105330808 A CN105330808 A CN 105330808A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
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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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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides inner crosslinking composite polyester-polyether waterborne polyurethane emulsion and a preparation method thereof. The inner crosslinking composite polyester-polyether waterborne polyurethane emulsion comprises water and waterborne polyurethane resin, wherein the waterborne polyurethane resin is prepared from diisocyanate, polyester polyol, polyether glycol, a hydrophilic chain-extending agent, a short-chain chain-extending agent and a later chain-extending agent. The preparation method of the waterborne polyurethane resin includes the following steps that after polyester polyol is dewatered, diisocyanate is added, polyether glycol is added after reaction, the hydrophilic chain-extending agent is added after reaction, temperature is lowered after reaction, and the short-chain chain-extending agent is added for reaction; the temperature is lowered again, a neutralizing agent and acetone are added during temperature keeping, discharging is performed after reaction, dispersing is performed, water and the later chain-extending agent are added while dispersing is performed, emulsification is performed, and emulsion is obtained; acetone is removed under the vacuum condition at the temperature of 50 DEG C, and the finished product emulsion is obtained. In the synthesizing process of the emulsion, no metal catalysts are contained, the content of VOC is low, and the preparation method is environmentally friendly.
Description
Technical field
The present invention relates to a kind of interior crosslinked complex polyester-polyether type aqueous polyaminoester emulsion and preparation method thereof, belong to technical field of aqueous paint.
Background technology
Urethane is the high molecular synthetic material containing more carbamate groups on a kind of main chain, generally by the oligomer polyol such as polyethers, polyester, polyisocyanates and glycol or Diamines chainextender progressively addition polymerization form, its structure can describe by " soft section " and " hard section ", the polyvalent alcohol such as polyethers, polyester forms soft section, and vulcabond, chainextender form hard section.Due to the thermodynamics uncompatibility between soft section and hard section, soft section and hard section can form independently microcell by scatter-gather, have micro phase separation structure.Soft section of elasticity providing PU material, toughness and low-temperature performance, hard section then provides hardness, the strength and modulus performance of PU material.The range of application of current urethane very extensive.
The urethane of conventional synthesis has PAUR substantially, and namely soft section adopts polyester polyol material; Polyether(poly)urethane, namely soft section have employed polyether polyol material.And PAUR has good intensity, sticking power and well physical property, but hydrolytic resistance, chemical-resistant etc. are not as polyether(poly)urethane.And polyether(poly)urethane has good submissive type, resistance to Qu Rao, hydrolytic resistance, chemical-resistant etc., but weathering resistance, glued membrane physical strength etc. are all not as PAUR.Therefore prepare compound urethane to have very important significance.
Because the consistency of polyester polyol and polyether glycol is not good, in traditional technology, polyester polyol and polyether glycol and polyisocyanates one are reacted, the polyester-polyether type aqueous polyurethane amylose regularity obtained is not high, easily in system, form PAUR and polyether(poly)urethane respectively, physical mixed splicing under high velocity agitation, and polyester portion and polyether moiety " weakness " performance separately on macromolecular chain segment cannot be avoided, so the composite polyurethane of synthesis can not embody the premium properties of PAUR and polyether(poly)urethane simultaneously, often there is more defects.
Summary of the invention
For defect of the prior art, the object of this invention is to provide a kind of interior crosslinked complex polyester-polyether type aqueous polyaminoester emulsion and preparation method thereof.
The present invention is achieved by the following technical solutions:
First aspect, the invention provides a kind of interior crosslinked complex polyester-polyether type aqueous polyaminoester emulsion, comprise water and waterborne polyurethane resin, the feedstock composition preparing described waterborne polyurethane resin comprises the following component of percentage:
If the polyester selected, polyether glycol are below or above this scope, can be difficult to reach the over-all properties simultaneously embodying PAUR advantage different from polyether(poly)urethane.
If do not select hydrophilic chain extender or lower than this scope, the impact that emulsion is turned white and stability in storage is not good can be caused; If higher than this scope, emulsion viscosity can be caused bigger than normal, levelling is poor waits detrimentally affect.
If do not select short chain chainextender or lower than this scope, urethane microphase-separated can be caused not good, be difficult to reach premium properties; If higher than this scope, degradation detrimentally affect under physicals can be caused again.
If do not select rear chainextender that emulsion shelf-stability may be caused poor, emulsion is gel in storage process easily; If higher than this scope, can cause again during emulsion dispersion and very easily occur the detrimentally affect such as gel, breakdown of emulsion.
Preferably, described vulcabond is selected from one or more in hydrogenated diphenyl methane diisocyanate, isophorone diisocyanate.
Preferably, the number-average molecular weight of described polyester polyol is 1000 ~ 5000.
Preferably, described polyester polyol is selected from poly-hexanodioic acid-butanediol ester polyvalent alcohol, polycarbonate polyol, polycaprolactone polyol etc. wherein one or more.
Preferably, the number-average molecular weight of described polyether glycol is 200 ~ 2000.
Preferably, described polyether glycol is selected from one or more in polypropylene glycol, polytetrahydrofuran diol, polyether triol.
Preferably, described hydrophilic chain extender is selected from the one in dimethylol propionic acid, dimethylolpropionic acid.
Preferably, described short chain chainextender is selected from ethylene glycol, propylene glycol, butyleneglycol wherein one or more.
Preferably, described neutralizing agent is N, N-dimethylethanolamine; Described rear chainextender is selected from quadrol, isophorone diamine, diethylene triamine, triethylene tetraamine wherein one or more.
Second aspect, present invention also offers a kind of preparation method of interior crosslinked complex polyester-polyether type aqueous polyaminoester emulsion as the aforementioned, it comprises the steps:
By polyester polyols dehydration of alcohols to water content lower than after 200ppm, add vulcabond, be incubated at 85 DEG C and react;
Add polyether glycol, at 85 DEG C, continue reaction;
Add hydrophilic chain extender, at 85 DEG C, continue reaction;
Be cooled to 75 DEG C, add short chain chainextender, be incubated at 75 DEG C and react;
Be cooled to 50 DEG C, keep stirring, adding acetone and being neutralized to pH is 5 ~ 7, reacts;
Blowing also disperses, and dispersion limit, limit adds water and is connected with rear expansion, carries out emulsification, obtains emulsion;
Under the vacuum condition of 50 DEG C, remove acetone by described, obtain finished emulsion.
The PAUR performed polymer that this resins synthesis adopts polyester polyol and isocyanic ester elder generation Reactive Synthesis regular, then add chain-extend polyether polyols and form regular complex polyester-polyether(poly)urethane macromole.And on polyether glycol, select polyfunctional group and the lower structure of molecular weight, at synthetic mesh polyurethane macromolecular simultaneously, the bad phenomenon such as system gel and viscosity surge when avoiding traditional internal crosslinker to use, and also maintains macromolecular reaction later stage enough activity.By rational raw material selection and structure design, accomplish the advantage simultaneously embodying PAUR and polyether(poly)urethane, such as synthesize chemical-resistant and physical strength good polyaminoester emulsion simultaneously, to the over-all properties promoting polyaminoester emulsion, with promotion industry development important.
Compared with prior art, the present invention has following beneficial effect:
1, the mechanical property after the form significant increase emulsion film forming of cross-linking set is adopted in the part (polyether segment) that macromolecular chain segment physicals is minimum;
2, owing to adopting height self-crosslinking structure, very fine and close after this composite emulsion film forming, chemical can be resisted and infiltrate, improving chemicals-resistant and refusing water, oil repellent energy at double;
3, good resistance to circumnutating property and glued membrane hardness can be embodied after this emulsion film forming simultaneously, be applicable to the use on differing materials surface;
4, owing to molecule segment there being polar polyester segment, macromole has again the moon/nonionic intensity, thus possesses good perviousness and the sticking power to base material;
5, this emulsion and other aqueous polyurethanes (polyester type, polyether-type), oiliness urethane, aqueous acrylic emulsion etc. mix all good consistency, for field widely after can mixing;
6, not containing metal class catalyzer in this emulsion synthesize process, low VOC, environmental protection.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
embodiment 1
The present embodiment polyaminoester emulsion adopts the raw material of following component and content to be prepared:
| A | Isophorone diisocyanate | 550g |
| B | Polyester diol (molecular weight 3000) | 600g |
| C | Polyether-tribasic alcohol (molecular weight 500) | 205g |
| D | Dimethylolpropionic acid | 118g |
| E | Butyleneglycol | 82g |
| F | N, N '-dimethyl thanomin | 64g |
| G | Diethylene triamine | 25g |
| H | Acetone | 1000g |
| I | Deionized water | 3700g |
Above-mentioned polyaminoester emulsion is by following processing step preparation:
B component is at 85 DEG C, and stir dehydration under vacuum condition, stirring velocity is 200rpm.Until after the water content in B component is less than 200ppm, terminates to vacuumize recovery normal pressure, keep 85 DEG C.Keep stirring and adding component A, keep 85 DEG C to react 2h.Add component C, 85 DEG C are continued reaction 1 hour.Add component D, 85 DEG C are continued reaction 1 hour.Be cooled to 75 DEG C, add component E, react 1.5 hours.Be cooled to 50 DEG C, add component F, continue stirring discharging after 30 minutes.By resin high speed dispersion under 1200rpm rotating speed of synthesis, add component I, treat to stir completely to be split into emulsion, add component G, keep 30min subsequently.The emulsion of synthesis poured in rotary evaporation still, 50 DEG C vacuumize down and carry out revolving steaming and remove acetone, until solid containing >=35% after terminate, obtain finished emulsion.
Performance evaluation:
| Solid content | ≥35％ |
| Temperature tolerance after emulsion film forming | Growing dim appears in >=130 DEG C of coatings |
| Hardness after emulsion film forming | ＞2H |
| The resistance to ethanol of emulsion film forming (50%, V/V) 30H | Unchanged |
| Resistance to the circumnutating property of emulsion film forming | >=50 repeatedly bend and do not ftracture |
| Emulsion stability in storage | 50 DEG C, within more than 3 months, there is not exception |
embodiment 2
The present embodiment polyaminoester emulsion adopts the raw material of following component and content to be prepared:
| A | Isophorone diisocyanate | 600g |
| B | Polyester diol (molecular weight 1000) | 438g |
| C | Polyether-tribasic alcohol (molecular weight 1000) | 305g |
| D | Dimethylolpropionic acid | 106g |
| E | Ethylene glycol | 66g |
| F | N, N '-dimethyl thanomin | 58g |
| G | Diethylene triamine | 26g |
| H | Acetone | 1000g |
| I | Deionized water | 3500g |
Above-mentioned polyaminoester emulsion is by following processing step preparation:
B component is at 85 DEG C, and stir dehydration under vacuum condition, stirring velocity is 200rpm.Until after the water content in B component is less than 200ppm, terminates to vacuumize recovery normal pressure, keep 85 DEG C.Keep stirring and adding component A, keep 85 DEG C to react 2h.Add component C, 85 DEG C are continued reaction 1 hour.Add component D, 85 DEG C are continued reaction 1 hour.Be cooled to 75 DEG C, add component E, react 1.5 hours.Be cooled to 50 DEG C, add component F, continue stirring discharging after 30 minutes.By resin high speed dispersion under 1200rpm rotating speed of synthesis, add component I, treat to stir completely to be split into emulsion, add component G, keep 30min subsequently.The emulsion of synthesis poured in rotary evaporation still, 50 DEG C vacuumize down and carry out revolving steaming and remove acetone, until solid containing >=35% after terminate, obtain finished emulsion.
Performance evaluation:
| Solid content | ≥35％ |
| Temperature tolerance after emulsion film forming | Growing dim appears in >=120 DEG C of coatings |
| The resistance to ethanol of emulsion film forming (50%, V/V) 48H | Unchanged |
| Hardness after emulsion film forming | 2H |
| Resistance to the circumnutating property of emulsion film forming | >=50 repeatedly bend and do not ftracture |
| Emulsion stability in storage | 50 DEG C, within more than 3 months, there is not exception |
embodiment 3
The present embodiment polyaminoester emulsion adopts the raw material of following component and content to be prepared:
| A | Hydrogenated diphenyl methane diisocyanate | 655g |
| B | Polyester diol (molecular weight 3000) | 708g |
| C | Polyether-tribasic alcohol (molecular weight 300) | 270g |
| D | Dimethylol propionic acid | 131g |
| E | Butyleneglycol | 27g |
| F | N, N '-dimethyl thanomin | 66g |
| G | Isophorone diamine | 48g |
| H | Acetone | 1200g |
| I | Deionized water | 3700g |
Above-mentioned polyaminoester emulsion is by following processing step preparation:
B component is at 85 DEG C, and stir dehydration under vacuum condition, stirring velocity is 200rpm.Until after the water content in B component is less than 200ppm, terminates to vacuumize recovery normal pressure, keep 85 DEG C.Keep stirring and adding component A, keep 85 DEG C to react 2h.Add component C, 85 DEG C are continued reaction 1 hour.Add component D, 85 DEG C are continued reaction 1 hour.Be cooled to 75 DEG C, add component E, react 1.5 hours.Be cooled to 50 DEG C, add component F, continue stirring discharging after 30 minutes.By resin high speed dispersion under 1200rpm rotating speed of synthesis, add component I, treat to stir completely to be split into emulsion, add component G, keep 30min subsequently.The emulsion of synthesis poured in rotary evaporation still, 50 DEG C vacuumize down and carry out revolving steaming and remove acetone, until solid containing >=35% after terminate, obtain finished emulsion.
Performance evaluation:
| Solid content | ≥35％ |
| Temperature tolerance after emulsion film forming | Growing dim appears in >=150 DEG C of coatings |
| The resistance to ethanol of emulsion film forming (50%, V/V) 40H | Unchanged |
| Hardness after emulsion film forming | ＞2H |
| Resistance to the circumnutating property of emulsion film forming | >=50 repeatedly bend and do not ftracture |
| Emulsion stability in storage | 50 DEG C, within more than 3 months, there is not exception |
comparative example 1
The present embodiment polyaminoester emulsion adopts the raw material of following component and content to be prepared:
| A | Isophorone diisocyanate | 555g |
| B | Polyester diol (molecular weight 2000) | 715g |
| C | Dimethylolpropionic acid | 100g |
| D | Ethylene glycol | 88g |
| E | N, N '-dimethyl thanomin | 54g |
| F | Diethylene triamine | 27g |
| G | Acetone | 1000g |
| H | Deionized water | 3500g |
Above-mentioned polyaminoester emulsion is by following processing step preparation:
B component is at 85 DEG C, and stir dehydration under vacuum condition, stirring velocity is 200rpm.Until after the water content in B component is less than 200ppm, terminates to vacuumize recovery normal pressure, keep 85 DEG C.Keep stirring and adding component A, keep 85 DEG C to react 2h.Add component C, 85 DEG C are continued reaction 1 hour.Add component D, 85 DEG C are continued reaction 2 hours.Be cooled to 50 DEG C, add component E, continue stirring discharging after 30 minutes.By resin high speed dispersion under 1200rpm rotating speed of synthesis, add component H, treat to stir completely to be split into emulsion, add component F, keep 30min subsequently.The emulsion of synthesis poured in rotary evaporation still, 50 DEG C vacuumize down and carry out revolving steaming and remove acetone, until solid containing >=35% after terminate, obtain finished emulsion.
Performance evaluation:
| Solid content | ≥35％ |
| Temperature tolerance after emulsion film forming | Growing dim appears in >=120 DEG C of coatings |
| The resistance to ethanol of emulsion film forming (50%, V/V) 6H | Complete swelling is broken, is partly dissolved |
| Hardness after emulsion film forming | 2H |
| Resistance to the circumnutating property of emulsion film forming | Repeatedly bend for 8 times and occur cracking |
| Emulsion stability in storage | 50 DEG C, within more than 3 months, there is not exception |
comparative example 2
The present embodiment polyaminoester emulsion adopts the raw material of following component and content to be prepared:
| A | Hydrogenated diphenyl methane diisocyanate | 548g |
| B | Polyether Glycols (molecular weight 2000) | 705g |
| C | Dimethylol propionic acid | 127g |
| D | Butyleneglycol | 59g |
| E | N, N '-dimethyl thanomin | 62g |
| F | Isophorone diamine | 51g |
| G | Acetone | 1200g |
| H | Deionized water | 3700g |
Above-mentioned polyaminoester emulsion is by following processing step preparation:
B component is at 85 DEG C, and stir dehydration under vacuum condition, stirring velocity is 200rpm.Until after the water content in B component is less than 200ppm, terminates to vacuumize recovery normal pressure, keep 85 DEG C.Keep stirring and adding component A, keep 85 DEG C to react 2h.Add component C, 85 DEG C are continued reaction 1 hour.Add component D, 85 DEG C are continued reaction 2 hours.Be cooled to 50 DEG C, add component E, continue stirring discharging after 30 minutes.By resin high speed dispersion under 1200rpm rotating speed of synthesis, add component H, treat to stir completely to be split into emulsion, add component F, keep 30min subsequently.The emulsion of synthesis poured in rotary evaporation still, 50 DEG C vacuumize down and carry out revolving steaming and remove acetone, until solid containing >=35% after terminate, obtain finished emulsion.
Performance evaluation:
| Solid content | ≥35％ |
| Temperature tolerance after emulsion film forming | Growing dim appears in < 80 DEG C of coatings |
| The resistance to ethanol of emulsion film forming (50%, V/V) 40H | Unchanged |
| Hardness after emulsion film forming | ＜HB |
| Resistance to the circumnutating property of emulsion film forming | Repeatedly bend for 40 times and occur cracking |
| Emulsion stability in storage | 50 DEG C, within more than 3 months, there is not exception |
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (10)
1. crosslinked complex polyester-polyether type aqueous polyaminoester emulsion in, comprise water and waterborne polyurethane resin, it is characterized in that, the feedstock composition preparing described waterborne polyurethane resin comprises the following component of percentage:
2. crosslinked complex polyester-polyether type aqueous polyaminoester emulsion in as claimed in claim 1, is characterized in that, described vulcabond be selected from hydrogenated diphenyl methane diisocyanate, isophorone diisocyanate one or more.
3. interior crosslinked complex polyester-polyether type aqueous polyaminoester emulsion as claimed in claim 1, it is characterized in that, the number-average molecular weight of described polyester polyol is 1000 ~ 5000.
4. in as described in claim 1 or 3, crosslinked complex polyester-polyether type aqueous polyaminoester emulsion, is characterized in that, described polyester polyol be selected from poly-hexanodioic acid-butanediol ester polyvalent alcohol, polycarbonate polyol, polycaprolactone polyol one or more.
5. interior crosslinked complex polyester-polyether type aqueous polyaminoester emulsion as claimed in claim 1, it is characterized in that, the number-average molecular weight of described polyether glycol is 200 ~ 2000.
6. in as described in claim 1 or 5, crosslinked complex polyester-polyether type aqueous polyaminoester emulsion, is characterized in that, described polyether glycol be selected from polypropylene glycol, polytetrahydrofuran diol, polyether triol one or more.
7. interior crosslinked complex polyester-polyether type aqueous polyaminoester emulsion as claimed in claim 1, it is characterized in that, described hydrophilic chain extender is selected from the one in dimethylol propionic acid, dimethylolpropionic acid.
8. crosslinked complex polyester-polyether type aqueous polyaminoester emulsion in as claimed in claim 1, is characterized in that, described short chain chainextender is selected from ethylene glycol, propylene glycol, butyleneglycol wherein one or more.
9. crosslinked complex polyester-polyether type aqueous polyaminoester emulsion in as claimed in claim 1, is characterized in that, described rear chainextender is selected from quadrol, isophorone diamine, diethylene triamine, triethylene tetraamine wherein one or more.
10. a preparation method for interior crosslinked complex polyester-polyether type aqueous polyaminoester emulsion as claimed in claim 1, is characterized in that, comprise the steps:
By polyester polyols dehydration of alcohols to water content lower than after 200ppm, add vulcabond, be incubated at 85 DEG C and react;
Add polyether glycol, at 85 DEG C, continue reaction;
Add hydrophilic chain extender, at 85 DEG C, continue reaction;
Be cooled to 75 DEG C, add short chain chainextender, be incubated at 75 DEG C and react;
Be cooled to 50 DEG C, keep stirring, adding acetone and being neutralized to pH is 5 ~ 7, reacts;
Blowing also disperses, and dispersion limit, limit adds water and rear chainextender, carries out emulsification, obtains emulsion;
Under the vacuum condition of 50 DEG C, remove acetone by described, obtain finished emulsion.
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| CN105925167A (en) * | 2016-06-23 | 2016-09-07 | 李英 | Touch oil and preparation method for touch membrane utilizing same |
| CN106243319A (en) * | 2016-07-28 | 2016-12-21 | 上海维凯光电新材料有限公司 | Aqueous polyurethane emulsion of resistance to bending and preparation method thereof |
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| CN105925167B (en) * | 2016-06-23 | 2018-05-25 | 永春豪田工艺品有限公司 | A kind of sense of touch oil and the sense of touch membrane preparation method using sense of touch oil |
| CN106243319A (en) * | 2016-07-28 | 2016-12-21 | 上海维凯光电新材料有限公司 | Aqueous polyurethane emulsion of resistance to bending and preparation method thereof |
| CN106496514A (en) * | 2016-09-22 | 2017-03-15 | 南通万顺化工科技有限公司 | A kind of waterborne polyurethane resin |
| CN106893068A (en) * | 2017-03-28 | 2017-06-27 | 广州贝高新材料有限公司 | A kind of Aqueous Polyurethane Adhesives and preparation method thereof |
| CN108912302A (en) * | 2018-05-25 | 2018-11-30 | 南京工业大学 | Waterborne polyurethane and preparation method and application thereof |
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| CN111925725A (en) * | 2020-07-07 | 2020-11-13 | 厦门三德信科技股份有限公司 | Polyurethane coating, high-transparency thermoplastic polyurethane outer anti-explosion coating and manufacturing method |
| CN111808260A (en) * | 2020-07-29 | 2020-10-23 | 四川尤博瑞新材料有限公司 | Thermosensitive condom based on waterborne polyurethane and preparation method thereof |
| CN111808260B (en) * | 2020-07-29 | 2021-05-25 | 四川尤博瑞新材料有限公司 | Thermosensitive condom based on waterborne polyurethane and preparation method thereof |
| CN112915592A (en) * | 2021-02-09 | 2021-06-08 | 天津大学 | Magnetic nano material and preparation method and application thereof |
| CN112915592B (en) * | 2021-02-09 | 2022-08-16 | 天津大学 | Magnetic nano material and preparation method and application thereof |
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