CN106519180A - High-temperature self-repairing polyurethane emulsion and preparation method thereof - Google Patents
High-temperature self-repairing polyurethane emulsion and preparation method thereof Download PDFInfo
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- CN106519180A CN106519180A CN201610950098.6A CN201610950098A CN106519180A CN 106519180 A CN106519180 A CN 106519180A CN 201610950098 A CN201610950098 A CN 201610950098A CN 106519180 A CN106519180 A CN 106519180A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
-
- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
Abstract
The invention discloses a high-temperature self-repairing polyurethane emulsion and a preparation method thereof. The emulsion comprises water and a resin component, wherein the resin component comprises the following raw materials in percentage by weight: 20-40% of hexamethylene diisocyanate, 5-11% of aromatic diisocyanate, 30-50% of polyester polyol, 9-15% of hydrophilic chain extender, 3-6% of short-chain chain extender and 1-5% of rear chain extender. In the invention, by matching the hexamethylene diisocyanate of a highly symmetric structure with the polyester polyol of high molecular weight, the polyurethane material obtains relatively good resilience and fast crystallinity after high-temperature softening; and by adding the aromatic diisocyanate, the physical properties such as hardness and temperature resistance of polyurethane are improved. When the temperature is higher than or equal to 40 DEG C, the prepared polyurethane material is gradually softened and rebounds to realize self-repairing of the scratches on the surface; and after being cooled to room temperature, the polyurethane material is crystallized fast to recover the material shape.
Description
Technical field
The invention belongs to technical field of coatings, and in particular to a kind of high temperature selfreparing polyaminoester emulsion and preparation method thereof.
Background technology
Polyurethane (PU) is a kind of high molecular synthetic material of performance between rubber and plastics, due to its backbone structure
In " soft section " and " hard section " there is microphase-separated so that polyurethane can not only possess rubber elasticity but also have the hardness of plastics, and
And as raw material variety is various, the backbone structure adjustment free degree is big, causes polyurethane be prepared into the product of different shape, should
With extensive.
When synthesis of polyurethane applies to soft or rigid package face coat, in line flow procedure, stretching, clot and cutting
Stage, the coating of unavoidable meeting surface scratch cause defect rate to be lifted.And finished product is in use, as the reason such as contact
Cause coating surface cut to increase, affect product attractive in appearance even with the life-span.Therefore coating itself is allowed to possess under certain condition
Self-reparing capability, significant, but polyurethane selfreparing cut performance, existing document is rarely reported.
The content of the invention
It is an object of the invention to overcome the shortcomings of that above-mentioned prior art is present, there is provided a kind of high temperature selfreparing polyurethane breast
Liquid and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：
The present invention relates to a kind of high temperature selfreparing polyaminoester emulsion, including water and resin Composition, by accounting for resin Composition gross weight
Weight percent content meter, the resin Composition includes following each raw material components：
In the emulsion system of the present invention, the corresponding weight percent for accounting for resin Composition gross weight of six methylene diisocyanates
It is 20～40% than content, if synthesising stability can be caused to decline higher than this scope, and final polyurethane resin heatproof is too low；If
Synthetic material self-reparing capability can be caused poor less than this scope.
Preferably, the aromatic diisocyanate is toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate
(MDI) one or two in.In the emulsion system of the present invention, its corresponding weight percent content for accounting for resin Composition gross weight
For 5～11%, if synthesising stability can be caused poor higher than this scope, easily gel；If synthetic resin can be caused less than this scope
Physical property is not good, it is difficult to use as coating.
Preferably, the PEPA includes polyadipate-butanediol ester polyalcohol, polycarbonate polyol, gathers oneself
Lactone polyols etc. are therein one or more；The number-average molecular weight of the PEPA is 3000～6000g/mol.At this
In the system of invention, if the molecular weight of its PEPA can cause the poor properties of synthesis of polyurethane higher than this scope；If being less than
This scope can cause selfreparing cut less able.
Preferably, the hydrophilic chain extender is dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid (DMBA) therein
Kind.In the emulsion system of the present invention, its corresponding weight percent content for accounting for resin Composition gross weight is 9～15%, if being higher than
This scope can cause to synthesize viscosity greatly, and emulsion is admittedly containing low；If stability of emulsion can be caused poor less than this scope, levelling is deteriorated.This
In the emulsion system of invention, its corresponding weight percent content for accounting for resin Composition gross weight is 9～15%, if being higher than this scope
Final emulsion viscosity can be caused excessive, admittedly containing low；If can cause less than this scope, stability of emulsion is poor, and film forming is poor.
Preferably, the short chain chain extender is one or more therein of ethylene glycol, butanediol, neopentyl glycol etc..This
In bright emulsion system, its corresponding weight percent content for accounting for resin Composition gross weight is 3～6%, if being higher or lower than this
Scope can cause emulsion synthesising stability poor.
Preferably, the rear chain extender be ethylenediamine, IPD (IPDA), diethylene triamine (DETA), three
Ethene urotropine (TETA) is therein one or more.In the emulsion system of the present invention, which is corresponding to account for resin Composition gross weight
Weight percent content is 1～5%, if emulsification can be caused difficult higher than this scope；If emulsion-stabilizing can be caused less than this scope
Property be deteriorated.
Preferably, the nertralizer be N, the one kind or several in N '-dimethyl monoethanolamine, triethylamine, diisopropylethylamine
Kind.In the emulsion system of the present invention, the corresponding weight percent content for accounting for resin Composition gross weight of nertralizer is 3～10%, if
Final emulsion viscosity can be caused big higher than this scope, smell weight；If stability of emulsion can be caused poor less than this scope, easily precipitate.
The invention further relates to a kind of method for preparing afore-said hot selfreparing polyaminoester emulsion, methods described includes following step
Suddenly：
, at 70-90 DEG C, stirring under vacuum condition is dehydrated, and mixing speed is 100-200rpm for S1, the PEPA selected,
After the water content in PEPA is less than 200ppm, vacuum is gone to reach normal pressure；
S2, aromatic diisocyanate is kept stirring for and is added, be incubated to 50-65 DEG C of reaction 0.8-1.2h；
S3, six methylene diisocyanates are kept stirring for and are added, be warming up to 75-85 DEG C and insulation reaction 0.8-
1.2h；
S4, hydrophilic chain extender is kept stirring for and adds, 80-85 DEG C is continued reaction 0.8-1.2 hours, is added when viscosity is larger
Acetone dilutes viscosity reduction；
S5,70-80 DEG C is cooled to, is kept stirring for and adds, add short chain chain extender, be incubated 70-75 DEG C of reaction 1.2-
1.8h, adds acetone dilution viscosity reduction when viscosity is larger；
S6 ,≤50 DEG C being cooled to, be kept stirring for, it is 6.5-7.5 to add nertralizer to adjust pH value, viscosity is 200～
1000cp, reacts 0.3-0.7h；
The resin of synthesis is disperseed under high speed dispersor by S7, discharging, rotating speed 1000-1500rpm, while dispersion
Add water and rear chain extender, emulsion dispersion 0.3-0.7h；
After S8, emulsion end of synthesis, emulsion is poured in distillation still, vacuumize and be heated to 45-55 DEG C, desolvation third
Finished emulsion is obtained after ketone.
With high degree of symmetry structure six methylene diisocyanates are coordinated macromolecule PEPA by the present invention
Use, give polyurethane material after hot mastication, preferable resilience and rapid crystallization, and pass through to add aromatic series isocyanide
Acid esters lifts the physical property such as the hardness and heatproof of polyurethane.By rational structure design so that polyurethane material is warm at >=40 DEG C
Under degree, can gradually soften and resilience, review one's lessons by oneself the cut of complex surface, after cooling to room temperature the proterties of rapid crystallization restorer.
When the polyurethane resin is used as soft or rigid package face coat, the surface scratch that product is accumulated in production line balance,
(40-50 DEG C) the storage stage of curing chamber, it is possible to realize cut selfreparing, to the technique for improving yield rate and polyurethane industrial
Optimization, important in inhibiting.
Compared with prior art, the present invention has the advantages that：
1) composite of this resin as coating, in following process and routine use, the new cut for producing also may be used
Soften which by arbitrary mode of heating, and cut is repaired rapidly, be cooled to after room temperature just restorability shape；
2) this resin also to injured and is weighed wounded, has certain self-reparing capability；
3) due to having a large amount of polarity segments and negative ion intensities on molecule segment, thus possesses preferable base material adhesive force；
4) this resin is mixed with other aqueous polyurethanes (polyester-type, polyether-type), oiliness polyurethane, aqueous acrylic emulsion etc.
Conjunction has good compatibility, can be used for wider field after mixing.
5) metal-based catalysts, low VOC, environmental protection are not contained in this resin synthesis process.
Specific embodiment
With reference to embodiment, the present invention is described in detail.Following examples will be helpful to those skilled in the art
The present invention is further understood, but the invention is not limited in any way.It should be pointed out that to one of ordinary skill in the art
For, without departing from the inventive concept of the premise, can also make certain adjustments and improvements.These belong to the guarantor of the present invention
Shield scope.
Embodiment 1
The present embodiment polyaminoester emulsion is prepared using the raw material of following components and content：
| a | PCDL (molecular weight 3000g/mol) | 288g |
| b | Toluene di-isocyanate(TDI) | 45g |
| c | Six methylene diisocyanates | 241g |
| d | Dihydromethyl propionic acid | 101g |
| e | Butanediol | 24.8g |
| f | N, N '-dimethyl monoethanolamine | 76g |
| g | Diethylene triamine | 24.7g |
| h | Acetone | 700g |
| i | Deionized water | 1575g |
Above-mentioned polyaminoester emulsion is prepared in following processing steps：
1) at 85 DEG C, stirring under vacuum condition is dehydrated component a, and mixing speed is 200rpm.Water content in component a
After 200ppm, end vacuumizes recovery normal pressure, is reduced to 65 DEG C.
2) component b is kept stirring for and is added, 65 DEG C of reaction 1h are kept.
3) 85 DEG C are warming up to, component c is kept stirring for and adds, 85 DEG C of reaction 1.5h are kept.
4) component d is kept stirring for and adds, 85 DEG C are continued reaction 1 hour.Constituent part h dilution drops are added when viscosity is larger
It is viscous.
5) 75 DEG C are cooled to, component e is added, are reacted 2 hours.Remaining constituent part h dilutions drop is added when viscosity is larger
It is viscous.
6) 50 DEG C are cooled to, it is 7 or so to add component f to adjust pH value, and viscosity is 200～1000cp, continues 30 points of stirring
Discharge after clock.
7) resin of synthesis is disperseed under 1200rpm rotating speeds at a high speed, adds component i, treat that stirring is split into emulsion completely, plus
Enter component g, subsequently keep 30min.The emulsion of synthesis is poured in rotary evaporation kettle, 50 DEG C vacuumize down carry out revolving removing third
Ketone, terminates after containing >=35% admittedly, obtains finished emulsion.
Performance evaluation：
Embodiment 2
The present embodiment polyaminoester emulsion is prepared using the raw material of following components and content：
| a | Polyadipate-butanediol type dihydroxylic alcohols (molecular weight 4000g/mol) | 352g |
| b | Toluene di-isocyanate(TDI) | 61g |
| c | Six methylene diisocyanates | 204g |
| d | Dihydromethyl propionic acid | 73.7g |
| e | Neopentyl glycol | 45.7g |
| f | N, N '-dimethyl monoethanolamine | 44g |
| g | IPD | 37.4g |
| h | Acetone | 700g |
| i | Deionized water | 1692g |
Above-mentioned polyaminoester emulsion is prepared in following processing steps：
1) at 85 DEG C, stirring under vacuum condition is dehydrated component a, and mixing speed is 200rpm.Water content in component a
After 200ppm, end vacuumizes recovery normal pressure, is reduced to 65 DEG C.
2) component b is kept stirring for and is added, 65 DEG C of reaction 1h are kept.
3) 85 DEG C are warming up to, component c is kept stirring for and adds, 85 DEG C of reaction 1.5h are kept.
4) component d is kept stirring for and adds, 85 DEG C are continued reaction 1 hour.Constituent part h dilution drops are added when viscosity is larger
It is viscous.
5) 75 DEG C are cooled to, component e is added, are reacted 2 hours.Remaining constituent part h dilutions drop is added when viscosity is larger
It is viscous.
6) 50 DEG C are cooled to, it is 7 or so to add component f to adjust pH value, and viscosity is 200～1000cp, continues 30 points of stirring
Discharge after clock.
7) resin of synthesis is disperseed under 1200rpm rotating speeds at a high speed, adds component i, treat that stirring is split into emulsion completely, plus
Enter component g, subsequently keep 30min.The emulsion of synthesis is poured in rotary evaporation kettle, 50 DEG C vacuumize down carry out revolving removing third
Ketone, terminates after containing >=35% admittedly, obtains finished emulsion.
Performance evaluation：
| Solid content | >=35% |
| Temperature tolerance after emulsion film forming | Growing dim occur in >=120 DEG C of coatings |
| 40 DEG C of cut extinction times | ＜ 20h |
| 60 DEG C of cut extinction times | ＜ 2h |
| 80 DEG C of cut extinction times | ＜ 10s |
| Emulsion film forming hardness | ≥HB |
| Emulsion storage stability | 50 DEG C, there is not exception within more than 3 months |
Embodiment 3
The present embodiment polyaminoester emulsion is prepared using the raw material of following components and content：
Above-mentioned polyaminoester emulsion is prepared in following processing steps：
1) at 85 DEG C, stirring under vacuum condition is dehydrated component a, and mixing speed is 200rpm.Water content in component a
After 200ppm, end vacuumizes recovery normal pressure, is reduced to 65 DEG C.
2) component b is kept stirring for and is added, 65 DEG C of reaction 1h are kept.
3) 85 DEG C are warming up to, component c is kept stirring for and adds, 85 DEG C of reaction 1.5h are kept.
4) component d is kept stirring for and adds, 85 DEG C are continued reaction 1 hour.Constituent part h dilution drops are added when viscosity is larger
It is viscous.
5) 75 DEG C are cooled to, component e is added, are reacted 2 hours.Remaining constituent part h dilutions drop is added when viscosity is larger
It is viscous.
6) 50 DEG C are cooled to, it is 7 or so to add component f to adjust pH value, and viscosity is 200～1000cp, continues 30 points of stirring
Discharge after clock.
7) resin of synthesis is disperseed under 1200rpm rotating speeds at a high speed, adds component i, treat that stirring is split into emulsion completely, plus
Enter component g, subsequently keep 30min.The emulsion of synthesis is poured in rotary evaporation kettle, 50 DEG C vacuumize down carry out revolving removing third
Ketone, terminates after containing >=35% admittedly, obtains finished emulsion.
Performance evaluation：
| Solid content | >=35% |
| Temperature tolerance after emulsion film forming | Growing dim occur in >=120 DEG C of coatings |
| 40 DEG C of cut extinction times | ＜ 24h |
| 60 DEG C of cut extinction times | ＜ 6h |
| 80 DEG C of cut extinction times | ＜ 10s |
| Emulsion film forming hardness | ≥HB |
| Emulsion storage stability | 50 DEG C, there is not exception within more than 3 months |
Comparative example 1
The polyaminoester emulsion of this comparative example is prepared using the raw material of following components and content：
Above-mentioned polyaminoester emulsion is prepared in following processing steps：
1) at 85 DEG C, stirring under vacuum condition is dehydrated component a, and mixing speed is 200rpm.Water content in component a
After 200ppm, end vacuumizes recovery normal pressure, is reduced to 65 DEG C.
2) component b is kept stirring for and is added, 65 DEG C of reaction 1h are kept.
3) 85 DEG C are warming up to, component c is kept stirring for and adds, 85 DEG C of reaction 1.5h are kept.
4) component d is kept stirring for and adds, 85 DEG C are continued reaction 1 hour.Constituent part h dilution drops are added when viscosity is larger
It is viscous.
5) 75 DEG C are cooled to, component e is added, are reacted 2 hours.Remaining constituent part h dilutions drop is added when viscosity is larger
It is viscous.
6) 50 DEG C are cooled to, it is 7 or so to add component f to adjust pH value, and viscosity is 200～1000cp, continues 30 points of stirring
Discharge after clock.
7) resin of synthesis is disperseed under 1200rpm rotating speeds at a high speed, adds component i, treat that stirring is split into emulsion completely, plus
Enter component g, subsequently keep 30min.The emulsion of synthesis is poured in rotary evaporation kettle, 50 DEG C vacuumize down carry out revolving removing third
Ketone, terminates after containing >=35% admittedly, obtains finished emulsion.
Performance evaluation：
| Solid content | >=35% |
| Temperature tolerance after emulsion film forming | Growing dim occur in >=140 DEG C of coatings |
| 40 DEG C of cut extinction times | Cannot recover |
| 60 DEG C of cut extinction times | Cannot recover |
| 80 DEG C of cut extinction times | ＞ 24h recover part |
| Emulsion film forming hardness | ≥2H |
| Emulsion storage stability | 50 DEG C, there is not exception within more than 3 months |
Comparative example 2
The polyaminoester emulsion of this comparative example is prepared using the raw material of following components and content：
| a | PCDL (molecular weight 1500g/mol) | 288g |
| b | Toluene di-isocyanate(TDI) | 45g |
| c | Six methylene diisocyanates | 241g |
| d | Dihydromethyl propionic acid | 101g |
| e | Butanediol | 24.8g |
| f | N, N '-dimethyl monoethanolamine | 76g |
| g | Diethylene triamine | 24.7g |
| h | Acetone | 700g |
| i | Deionized water | 1575g |
Above-mentioned polyaminoester emulsion is prepared in following processing steps：
1) at 85 DEG C, stirring under vacuum condition is dehydrated component a, and mixing speed is 200rpm.Water content in component a
After 200ppm, end vacuumizes recovery normal pressure, is reduced to 65 DEG C.
2) component b is kept stirring for and is added, 65 DEG C of reaction 1h are kept.
3) 85 DEG C are warming up to, component c is kept stirring for and adds, 85 DEG C of reaction 1.5h are kept.
4) component d is kept stirring for and adds, 85 DEG C are continued reaction 1 hour.Constituent part h dilution drops are added when viscosity is larger
It is viscous.
5) 75 DEG C are cooled to, component e is added, are reacted 2 hours.Remaining constituent part h dilutions drop is added when viscosity is larger
It is viscous.
6) 50 DEG C are cooled to, it is 7 or so to add component f to adjust pH value, and viscosity is 200～1000cp, continues 30 points of stirring
Discharge after clock.
7) resin of synthesis is disperseed under 1200rpm rotating speeds at a high speed, adds component i, treat that stirring is split into emulsion completely, plus
Enter component g, subsequently keep 30min.The emulsion of synthesis is poured in rotary evaporation kettle, 50 DEG C vacuumize down carry out revolving removing third
Ketone, terminates after containing >=35% admittedly, obtains finished emulsion.
Performance evaluation：
| Solid content | >=35% |
| Temperature tolerance after emulsion film forming | Growing dim occur in >=130 DEG C of coatings |
| 40 DEG C of cut extinction times | ＞ 72h |
| 60 DEG C of cut extinction times | 24h recovers part |
| 80 DEG C of cut extinction times | ＜ 1h |
| Emulsion film forming hardness | ≥H |
| Emulsion storage stability | 50 DEG C, there is not exception within more than 3 months |
Six methylene diisocyanates are not added as can be seen that working as by comparative example 1 in system, but adopts unsymmetrical knot
During the IPDI of structure, though macromolecular PEPA is also adopted by as soft section, but the polyurethane tree for synthesizing
Fat, the ability for almost not having selfreparing cut, this is due to lacking the poly- of a large amount of high symmetry " six methylene " units
Urethane main chain does not possess enough resiliences, and softening point can be caused to rise using harder isocyanates.Can be with from comparative example 2
Find out, only use six methylene diisocyanates, do not use macromolecular PEPA, although also possess certain resilience
Property, but selfreparing cut not only the time required to it is long, cannot also recover completely.This be due to low molecular weight polyester polyalcohol toughness compared with
Difference reduces resilience, and rapid crystallization ability is weak so that product is through hot mastication and after cooling, it is impossible to by segment again
Integration reaches the purpose for recovering proterties.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various modifications or modification within the scope of the claims, this not shadow
Ring the flesh and blood of the present invention.
Claims (8)
1. a kind of high temperature selfreparing polyaminoester emulsion, including water and resin Composition, it is characterised in that by accounting for resin Composition gross weight
Weight percent content meter, the resin Composition include following each raw material components：
2. high temperature selfreparing polyaminoester emulsion as claimed in claim 1, it is characterised in that the aromatic diisocyanate is
One or two in toluene di-isocyanate(TDI), methyl diphenylene diisocyanate.
3. high temperature selfreparing polyaminoester emulsion as claimed in claim 1, it is characterised in that the PEPA includes gathering oneself
One or more in diacid-butanediol ester polyalcohol, polycarbonate polyol, polycaprolactone polyol；The polyester polyols
The number-average molecular weight of alcohol is 3000～6000g/mol.
4. high temperature selfreparing polyaminoester emulsion as claimed in claim 1, it is characterised in that the hydrophilic chain extender is dihydroxy first
Base propionic acid or dimethylolpropionic acid.
5. high temperature selfreparing polyaminoester emulsion as claimed in claim 1, it is characterised in that the short chain chain extender is second two
One or more in alcohol, butanediol, neopentyl glycol.
6. high temperature selfreparing polyaminoester emulsion as claimed in claim 1, it is characterised in that the rear chain extender be ethylenediamine,
One or more in IPD, diethylene triamine, triethylene tetraamine.
7. high temperature selfreparing polyaminoester emulsion as claimed in claim 1, it is characterised in that the nertralizer is N, N '-diformazan
One or more in ethylethanolamine, triethylamine, diisopropylethylamine.
8. a kind of preparation method of the high temperature selfreparing polyaminoester emulsion as any one of claim 1～6, its feature exist
In methods described comprises the steps：
, at 70-90 DEG C, stirring under vacuum condition is dehydrated, and mixing speed is 100-200rpm for S1, the PEPA selected, until
After water content in PEPA is less than 200ppm, vacuum is gone to reach normal pressure；
S2, aromatic diisocyanate is kept stirring for and is added, be incubated to 50-65 DEG C of reaction 0.8-1.2h；
S3, six methylene diisocyanates are kept stirring for and are added, be warming up to 75-85 DEG C and insulation reaction 0.8-1.2h；
S4, hydrophilic chain extender is kept stirring for and adds, 80-85 DEG C is continued reaction 0.8-1.2 hours, and acetone is added when viscosity is larger
Dilution viscosity reduction；
S5,70-80 DEG C is cooled to, is kept stirring for and adds, add short chain chain extender, be incubated 70-75 DEG C of reaction 1.2-1.8h, glue
Acetone dilution viscosity reduction is added when spending larger；
S6 ,≤50 DEG C are cooled to, are kept stirring for, it is 6.5-7.5 to add nertralizer to adjust pH value, and viscosity is 200～1000cp, instead
Answer 0.3-0.7h；
The resin of synthesis is disperseed under high speed dispersor by S7, discharging, and rotating speed 1000-1500rpm is added while dispersion
Water and rear chain extender, emulsion dispersion 0.3-0.7h；
After S8, emulsion end of synthesis, emulsion is poured in distillation still, vacuumize and be heated to 45-55 DEG C, after desolvation acetone
Obtain finished emulsion.
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| CN117659339A (en) * | 2024-01-31 | 2024-03-08 | 中天科盛科技股份有限公司 | Self-repairing yellowing-resistant high-transparency aliphatic polyurethane elastomer and preparation method thereof |
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| CN116622279A (en) * | 2023-05-17 | 2023-08-22 | 恒昌涂料（惠阳）有限公司 | Polyurethane matte varnish capable of self-repairing scratches and preparation method thereof |
| CN116622279B (en) * | 2023-05-17 | 2024-03-15 | 恒昌涂料（惠阳）有限公司 | Polyurethane matte varnish capable of self-repairing scratches and preparation method thereof |
| CN117659339A (en) * | 2024-01-31 | 2024-03-08 | 中天科盛科技股份有限公司 | Self-repairing yellowing-resistant high-transparency aliphatic polyurethane elastomer and preparation method thereof |
| CN117659339B (en) * | 2024-01-31 | 2024-04-12 | 中天科盛科技股份有限公司 | Self-repairing yellowing-resistant high-transparency aliphatic polyurethane elastomer and preparation method thereof |
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