CN109694456A - A kind of high rigidity, aqueous polyurethane emulsion of resistance to ethyl alcohol and preparation method thereof - Google Patents
A kind of high rigidity, aqueous polyurethane emulsion of resistance to ethyl alcohol and preparation method thereof Download PDFInfo
- Publication number
- CN109694456A CN109694456A CN201811624154.2A CN201811624154A CN109694456A CN 109694456 A CN109694456 A CN 109694456A CN 201811624154 A CN201811624154 A CN 201811624154A CN 109694456 A CN109694456 A CN 109694456A
- Authority
- CN
- China
- Prior art keywords
- reaction
- product
- added
- preparation
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3212—Polyhydroxy compounds containing cycloaliphatic 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3228—Polyamines 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
- C08G18/28—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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6651—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention belongs to technical field of fine more particularly to a kind of high rigidity, the aqueous polyurethane emulsion of resistance to ethyl alcohol and preparation method thereof.The present invention provides a kind of high rigidity, the preparation method of the aqueous polyurethane emulsion of resistance to ethyl alcohol, the following steps are included: a) under the effect of the catalyst by poly (propylene carbonate) polyalcohol, diisocyanate and hydrophilic chain extender, the first reaction is carried out, the first product is obtained；B) crosslinking agent and non-hydrophilic preceding chain extender are added in the first product, carries out the second reaction, obtains the second product；C) silane coupling agent is added in the second product, carries out third reaction, obtains third product；D) after neutralizer progress neutralization reaction is added in third product, deionized water is added and carries out emulsion reaction, obtains the 4th product；E) nano silica is added in the 4th product, obtains aqueous polyurethane emulsion.The result shows that the film that aqueous polyurethane emulsion of the present invention is formed has excellent hardness and resistance to alcohol performance.
Description
Technical field
The invention belongs to the aqueous polyurethane emulsions of technical field of fine more particularly to a kind of high rigidity, resistance to ethyl alcohol
And preparation method thereof.
Background technique
Aqueous polyurethane is a kind of environmental friendly material, coating, adhesive, in terms of have and widely answer
With.However simple aqueous polyurethane is due to the presence of hydrophilic group, water resistance and resistance to alcohol repellency usually poor and hydrophilic
The presence meeting of base is so that aqueous polyurethane mechanical properties decrease, hardness are lower.Wooden furniture paint and water-based industrial paint can often connect
Touch ethyl alcohol so that there are resistance to alcohol repellency demands for aqueous polyurethane, and at present the performance of aqueous polyurethane make its application field by
Limit.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of high rigidity, the aqueous polyurethane emulsion of resistance to ethyl alcohol and its systems
Preparation Method, for solving the problems, such as that existing aqueous polyurethane is resistance to alcohol repellency and hardness is poor.
The specific technical solution of the present invention is as follows:
A kind of high rigidity, resistance to ethyl alcohol aqueous polyurethane emulsion preparation method, comprising the following steps:
A) under the effect of the catalyst by poly (propylene carbonate) polyalcohol, diisocyanate and hydrophilic chain extender, the is carried out
One reaction, obtains the first product；
B) crosslinking agent and non-hydrophilic preceding chain extender are added in first product, carries out the second reaction, obtains the second production
Object；
C) silane coupling agent is added in second product, carries out third reaction, obtains third product；
D) after neutralizer progress neutralization reaction is added in the third product, deionized water is added and carries out emulsion reaction,
Obtain the 4th product；
E) nano silica is added in the 4th product, obtains aqueous polyurethane emulsion.
Preparation method of the present invention uses poly (propylene carbonate) polyalcohol and diisocyanate for primary raw material, through nano-silica
SiClx and silane coupling agent are dual modified, obtain aqueous polyurethane emulsion, utilize the highly polar, high of poly (propylene carbonate) polyalcohol
Cohesive energy and the low polarity of silane coupling agent, the difference of low cohesive energy, so that aqueous polyurethane is in film forming, the low cohesive energy of low polarity
Silane coupling agent be enriched in surface layer, surface can reduce so that the resistance to alcohol performance of film is substantially improved, nano silica tool
There are skin effect and small-size effect, hardness of film can be greatly improved, to obtain the aqueous polyurethane of high rigidity, resistance to ethyl alcohol
Product.
Preferably, the temperature of first reaction is 70 DEG C~90 DEG C；
The time of first reaction is 2h~6h.
Preferably, the temperature of second reaction is 60 DEG C~75 DEG C；
The time of second reaction is 1h~2h.
Preferably, the temperature of the third reaction is 45 DEG C~50 DEG C；
The time of the third reaction is 10min~60min.
In the present invention, after step d) carries out emulsion reaction, before obtaining the 4th product, further includes: be added it is non-hydrophilic after
Chain extender carries out chain extending reaction.
The temperature of chain extending reaction is -10 DEG C~25 DEG C；
The time of chain extending reaction is 10min~60min.
In the present invention, step b) is carried out before the second reaction, further includes: acetone is added；
Step d) is added after non-hydrophilic rear chain extender carries out chain extending reaction, before obtaining the 4th product, further includes: remove
Acetone.
In the present invention, acetone, which is added, can reduce the second reaction, third reaction, neutralization reaction, emulsion reaction and chain extending reaction
Reaction mass viscosity, conducive to the progress of reaction.
In the present invention, after step a), before step b), further includes: reduce temperature to 50 DEG C~60 DEG C.
Step b) is carried out before the second reaction, further includes: increases temperature to 70 DEG C~75 DEG C.
After step b), before step c), further includes: reduce temperature to 40 DEG C~50 DEG C.
After step c), before step d), further includes: reduce temperature to 30 DEG C~40 DEG C.
It is specially that acetone is removed under reduced pressure that step d), which removes the acetone,.
Step e) nano silica is sonicated nano silicon dioxide dispersion, nano silicon dioxide dispersion
Mass concentration be 2%~10%, preferably 5%.
Step e) is specially that nano silicon dioxide dispersion is added in the 4th product, is dispersed, is obtained aqueous
Polyaminoester emulsion.
Preferably, the poly (propylene carbonate) polyalcohol, the diisocyanate, the hydrophilic chain extender, the crosslinking
Agent, the non-hydrophilic preceding chain extender, the nano silica and the silane coupling agent mass ratio be 60:(18~63):
(2~10): (0.1~3): (5~15): (0.1~1): (0.1~5).
In the present invention, poly (propylene carbonate) polyalcohol, non-hydrophilic rear chain extender, catalyst, neutralizer, acetone and deionization
The mass ratio of water is 60:(0.1~3): (0.06~0.36): (2~10): (5~40): (100~300).
In the present invention, the additional amount of silane coupling agent is relatively low, contains a large amount of end NCO group when emulsification in system
Molecule carries out chain extension to uncapped polyurethane molecular, is further promoted and produced by the way that non-hydrophilic rear chain extender is added after emulsification
The molecular weight of product promotes the mechanical property and patience of product.
In the present invention, poly (propylene carbonate) polyalcohol is initiator to be added, with epoxy third using carbon dioxide as starting material
Alkane carries out catalysis reaction copolymerization, and mechanical property is good, at low cost, and large-scale production consumption carbon dioxide gas can alleviate section
Greenhouse effects, while the energy such as petroleum are saved, environmental protection, energy-saving and emission-reduction are had a very big significance.In addition, polymerized thylene carbonate third
Ester contains more carbonic acid ester bond, and cohesive energy is larger, and polarity is stronger, and silane coupling agent cohesive energy is low, and polarity is low, thus lotion at
Organosilicon is easier to be pushed to surface in membrane process, and the infiltration and corrosion to ethyl alcohol have better hindrance function.
In the present invention, nano-silica surface contains great amount of hydroxy group, and good hydrophilic property can be very good to be dispersed in lotion
In, and it forms certain hydrogen bond with silane coupling agent, therefore can settle to avoid silica autohemagglutination, lotion has good
Good stability.In addition, silane coupling agent is easy to migrate to surface when emulsion film forming, nano silica is taken to film coated surface,
To which film has higher surface hardness and better hydrophobicity.
Preferably, the molecular weight of the poly (propylene carbonate) polyalcohol is 1000~3000；
The hydroxy functionality of the poly (propylene carbonate) polyalcohol is 2~3；
The mole fraction of carbonate group is 0.3~0.4 in the poly (propylene carbonate) polyol molecule.
In the present invention, poly (propylene carbonate) polyalcohol is added initiator and be catalyzed instead using carbon dioxide as starting material
Should be with epoxypropane copolymerization at obtaining, initiator is small molecule polyol, and the second catalyst is bimetallic class catalyst.Poly- carbon
Sour Asia propyl ester polyalcohol is made using carbon dioxide and propylene oxide as raw material, and at low cost, can be mass-produced can't be to environment
It causes damages, alleviation greenhouse effects and energy-saving and emission-reduction is had a very big significance.
Diisocyanate of the present invention is aliphatic diisocyanate, the resistance to Huang of film that may make aqueous polyurethane emulsion to be formed
Performance is good.
Preferably, the diisocyanate is selected from isophorone diisocyanate, hexamethylene diisocyanate or hydrogenation
Methyl diphenylene diisocyanate.
Preferably, the hydrophilic chain extender is selected from ethylenediamine base ethanesulfonic acid sodium, dihydromethyl propionic acid or dimethylolpropionic acid；
The non-hydrophilic preceding chain extender is neopentyl glycol and/or 1,4 cyclohexane dimethanol.
The non-hydrophilic rear chain extender is ethylenediamine and/or isophorone diamine.
It is furthermore preferred that hydrophilic chain extender is dihydromethyl propionic acid；
Non-hydrophilic rear chain extender is ethylenediamine.
Preferably, the catalyst is selected from stannous octoate, di-n-butyltin dilaurate or tin acetate；
The neutralizer is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, sodium hydroxide or ammonium hydroxide.
In the present invention, crosslinking agent is preferably trimethylolpropane, and silane coupling agent is preferably aminopropyl triethoxysilane
(KH-550)。
In conclusion the present invention provides a kind of preparation method of the aqueous polyurethane emulsion of resistance to ethyl alcohol, including following step
It is rapid: a) under the effect of the catalyst by poly (propylene carbonate) polyalcohol, diisocyanate and hydrophilic chain extender, it is anti-to carry out first
It answers, obtains the first product；B) crosslinking agent and non-hydrophilic preceding chain extender are added in first product, carries out the second reaction, obtains
To the second product；C) silane coupling agent is added in second product, carries out third reaction, obtains third product；D) institute
It states after neutralizer progress neutralization reaction is added in third product, deionized water is added and carries out emulsion reaction, obtains the 4th product；e)
Nano silica is added in the 4th product, obtains aqueous polyurethane emulsion.The result shows that aqueous polyurethane of the present invention
The film that lotion is formed has excellent hardness and resistance to alcohol performance.
Specific embodiment
The purpose of the present invention is to provide a kind of high rigidity, the aqueous polyurethane emulsion of resistance to ethyl alcohol and preparation method thereof.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
In terms of mass parts, take 60 parts of molecular weight be 3000, hydroxy functionality be 2 poly (propylene carbonate) dihydric alcohol, 53 parts
Isophorone diisocyanate, 5 parts of dihydromethyl propionic acids carry out 4h first under the action of 0.12 part of stannous octoate at 85 DEG C
Reaction reduces temperature to 60 DEG C, 1.3 parts of trimethylolpropanes, 3.1 parts of neopentyl glycols, 4.3 parts of 1,4-CHDMs is added
With 10 parts of acetone, 75 DEG C of progress 1h second reactions are warming up to, reduce temperature to 50 DEG C, 20 parts of acetone, which are added, reduces viscosity, is added
3.9 parts of KH-550 carry out the reaction of 30min third, reduce temperature to 40 DEG C, and 3.8 parts of triethylamines are added and carry out 5min neutralization reaction,
Then 250 parts of deionized waters are added and carry out 15min emulsion reaction in 1500r/min, add 2.56 parts of ethylenediamines in 800r/
Min carries out 30min chain extending reaction, is warming up to 50 DEG C of removed under reduced pressure acetone, obtains the 4th product.Take 5 parts of water and 0.15 part of nanometer
Silica is made into nano silicon dioxide dispersion ultrasound 10min, then nano silicon dioxide dispersion is added to 95 part the 4th
In product, disperses 30min in 500r/min, aqueous polyurethane emulsion is made.
Embodiment 2
In terms of mass parts, take 60 parts of molecular weight be 3000, hydroxy functionality be 2 poly (propylene carbonate) dihydric alcohol, 53 parts
Isophorone diisocyanate, 5 parts of dihydromethyl propionic acids carry out 4h first under the action of 0.12 part of stannous octoate at 85 DEG C
Reaction reduces temperature to 60 DEG C, 1.3 parts of trimethylolpropanes, 3.1 parts of neopentyl glycols, 4.3 parts of 1,4-CHDMs is added
With 10 parts of acetone, 75 DEG C of progress 1h second reactions are warming up to, reduce temperature to 50 DEG C, 20 parts of acetone, which are added, reduces viscosity, is added
3.9 parts of KH-550 carry out the reaction of 30min third, reduce temperature to 40 DEG C, and 3.8 parts of triethylamines are added and carry out 5min neutralization reaction,
Then 250 parts of deionized waters are added and carry out 15min emulsion reaction in 1500r/min, add 2.56 parts of ethylenediamines in 800r/
Min carries out 30min chain extending reaction, is warming up to 50 DEG C of removed under reduced pressure acetone, obtains the 4th product.Take 5 parts of water and 0.3 part of nanometer two
Silica is made into nano silicon dioxide dispersion ultrasound 10min, then nano silicon dioxide dispersion is added to 95 part of the 4th production
In object, disperses 30min in 500r/min, aqueous polyurethane emulsion is made.
Embodiment 3
In terms of mass parts, take 60 parts of molecular weight be 3000, hydroxy functionality be 2 poly (propylene carbonate) dihydric alcohol, 53 parts
Isophorone diisocyanate, 5 parts of dihydromethyl propionic acids carry out 4h first under the action of 0.12 part of stannous octoate at 85 DEG C
Reaction reduces temperature to 60 DEG C, 1.3 parts of trimethylolpropanes, 3.1 parts of neopentyl glycols, 4.3 parts of 1,4-CHDMs is added
With 10 parts of acetone, 75 DEG C of progress 1h second reactions are warming up to, reduce temperature to 50 DEG C, 20 parts of acetone, which are added, reduces viscosity, is added
3.9 parts of KH-550 carry out the reaction of 30min third, reduce temperature to 40 DEG C, and 3.8 parts of triethylamines are added and carry out 5min neutralization reaction,
Then 250 parts of deionized waters are added and carry out 15min emulsion reaction in 1500r/min, add 2.56 parts of ethylenediamines in 800r/
Min carries out 30min chain extending reaction, is warming up to 50 DEG C of removed under reduced pressure acetone, obtains the 4th product.Take 5 parts of water and 0.45 part of nanometer
Silica is made into nano silicon dioxide dispersion ultrasound 10min, then nano silicon dioxide dispersion is added to 95 part the 4th
In product, disperses 30min in 500r/min, aqueous polyurethane emulsion is made.
Embodiment 4
In terms of mass parts, take 60 parts of molecular weight be 3000, hydroxy functionality be 2 poly (propylene carbonate) dihydric alcohol, 53 parts
Isophorone diisocyanate, 5 parts of dihydromethyl propionic acids carry out 4h first under the action of 0.12 part of stannous octoate at 85 DEG C
Reaction reduces temperature to 60 DEG C, 1.3 parts of trimethylolpropanes, 3.1 parts of neopentyl glycols, 4.3 parts of 1,4-CHDMs is added
With 10 parts of acetone, 75 DEG C of progress 1h second reactions are warming up to, reduce temperature to 50 DEG C, 20 parts of acetone, which are added, reduces viscosity, is added
3.9 parts of KH-550 carry out the reaction of 30min third, reduce temperature to 40 DEG C, and 3.8 parts of triethylamines are added and carry out 5min neutralization reaction,
Then 250 parts of deionized waters are added and carry out 15min emulsion reaction in 1500r/min, add 2.56 parts of ethylenediamines in 800r/
Min carries out 30min chain extending reaction, is warming up to 50 DEG C of removed under reduced pressure acetone, obtains the 4th product.Take 5 parts of water and 0.6 part of nanometer two
Silica is made into nano silicon dioxide dispersion ultrasound 10min, then nano silicon dioxide dispersion is added to 95 part of the 4th production
In object, disperses 30min in 500r/min, aqueous polyurethane emulsion is made.
Comparative example 1
In terms of mass parts, take 60 parts of molecular weight be 3000, hydroxy functionality be 2 poly (propylene carbonate) dihydric alcohol, 53 parts
Isophorone diisocyanate, 5 parts of dihydromethyl propionic acids carry out 4h first under the action of 0.12 part of stannous octoate at 85 DEG C
Reaction reduces temperature to 60 DEG C, 1.3 parts of trimethylolpropanes, 3.1 parts of neopentyl glycols, 4.3 parts of 1,4-CHDMs is added
With 10 parts of acetone, 75 DEG C of progress 1h second reactions are warming up to, reduce temperature to 40 DEG C, 3.8 parts of triethylamines are added and carry out in 5min
And reaction, 250 parts of deionized waters are then added in 1500r/min and carry out 15min emulsion reaction, adds 2.56 parts of ethylenediamines and exists
800r/min carries out 30min chain extending reaction, is warming up to 50 DEG C of removed under reduced pressure acetone, obtains aqueous polyurethane emulsion.
Comparative example 2
In terms of mass parts, take 60 parts of molecular weight be 3000, hydroxy functionality be 2 poly (propylene carbonate) dihydric alcohol, 53 parts
Isophorone diisocyanate, 5 parts of dihydromethyl propionic acids carry out 4h first under the action of 0.12 part of stannous octoate at 85 DEG C
Reaction reduces temperature to 60 DEG C, 1.3 parts of trimethylolpropanes, 3.1 parts of neopentyl glycols, 4.3 parts of 1,4-CHDMs is added
With 10 parts of acetone, 75 DEG C of progress 1h second reactions are warming up to, reduce temperature to 50 DEG C, 20 parts of acetone, which are added, reduces viscosity, is added
3.9 parts of KH-550 carry out the reaction of 30min third, reduce temperature to 40 DEG C, and 3.8 parts of triethylamines are added and carry out 5min neutralization reaction,
Then 250 parts of deionized waters are added and carry out 15min emulsion reaction in 1500r/min, add 2.56 parts of ethylenediamines in 800r/
Min carries out 30min chain extending reaction, is warming up to 50 DEG C of removed under reduced pressure acetone, obtains aqueous polyurethane emulsion.
Comparative example 3
In terms of mass parts, take 60 parts of molecular weight be 3000, hydroxy functionality be 2 poly (propylene carbonate) dihydric alcohol, 53 parts
Isophorone diisocyanate, 5 parts of dihydromethyl propionic acids carry out 4h first under the action of 0.12 part of stannous octoate at 85 DEG C
Reaction reduces temperature to 60 DEG C, 1.3 parts of trimethylolpropanes, 3.1 parts of neopentyl glycols, 4.3 parts of 1,4-CHDMs is added
With 10 parts of acetone, 75 DEG C of progress 1h second reactions are warming up to, reduce temperature to 50 DEG C, 20 parts of acetone, which are added, reduces viscosity, reduces
Temperature is added 3.8 parts of triethylamines and carries out 5min neutralization reactions to 40 DEG C, be then added 250 parts of deionized waters 1500r/min into
Row 15min emulsion reaction adds 2.56 parts of ethylenediamines in 800r/min and carries out 30min chain extending reaction, is warming up to 50 DEG C of decompressions
Acetone is removed, the 4th product is obtained.5 parts of water and 0.6 part of nano silica are taken to be made into nano silicon dioxide dispersion ultrasound
10min, then nano silicon dioxide dispersion is added in 95 part of the 4th product, disperse 30min in 500r/min, is made aqueous
Polyaminoester emulsion.
Embodiment 5
Aqueous polyurethane emulsion made from Example 1~4 and comparative example 1~3 is respectively with four sides on black glass plate
Spreader scratches 200 μm of wet films, and dry in 50 DEG C of baking ovens taking-up is placed at room temperature for 1h for 24 hours, and filter paper is placed on film, is dripped
Add 50% (volume fraction) ethanol solution, covered with cup, cup and filter paper are taken away after 1h, towel is used after water cleaning, sees
Film coated surface cosmetic variation is examined, the results are shown in Table 1.
Lotion aqueous polyurethane emulsion made from Example 1~4 and comparative example 1~3 is respectively with four sides on tinplate
Spreader scratches 100 μm of wet films, and room temperature for 24 hours, tests its pencil hardness (scratch), the results are shown in Table 1.
Lotion aqueous polyurethane emulsion made from Example 1~4 and comparative example 1~3 is placed in Teflon mould,
Air drying for 24 hours, then at 80 DEG C is dried for 24 hours in baking oven, and aqueous polyurethane glue film is made, is placed under sunlight and shines 7 days, observes glue
Film outward appearance variation, the results are shown in Table 1.
Table 1 the result shows that, (implemented using nano silica and the aqueous polyurethane of the dual modified preparation of silane coupling agent
Example 1~4), good resistance to alcohol repellency and hardness is had both, appearance is unchanged after 50% ethyl alcohol 1h test, and hardness reaches 2H, phase
To the aqueous polyurethane (comparative example 1) of simple PPC type, the aqueous polyurethane (comparative example 2) of KH550 modification, nano silica
Modified aqueous polyurethane (comparative example 3) has superior hardness and resistance to alcohol repellency, and anti-yellowing property is good, can be used for
The coating industries such as aqueous woodware paint.
The performance test results of aqueous polyurethane emulsion made from 1 Examples 1 to 4 of table and comparative example 1~3
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the aqueous polyurethane emulsion of high rigidity, resistance to ethyl alcohol, which comprises the following steps:
A) under the effect of the catalyst by poly (propylene carbonate) polyalcohol, diisocyanate and hydrophilic chain extender, it is anti-to carry out first
It answers, obtains the first product；
B) crosslinking agent and non-hydrophilic preceding chain extender are added in first product, carries out the second reaction, obtains the second product；
C) silane coupling agent is added in second product, carries out third reaction, obtains third product；
D) after neutralizer progress neutralization reaction is added in the third product, deionized water is added and carries out emulsion reaction, obtains
4th product；
E) nano silica is added in the 4th product, obtains aqueous polyurethane emulsion.
2. preparation method according to claim 1, which is characterized in that the temperature of first reaction is 70 DEG C~90 DEG C；
The time of first reaction is 2h~6h.
3. preparation method according to claim 1, which is characterized in that the temperature of second reaction is 60 DEG C~75 DEG C；
The time of second reaction is 1h~2h.
4. preparation method according to claim 1, which is characterized in that the temperature of the third reaction is 45 DEG C~50 DEG C；
The time of the third reaction is 10min~60min.
5. preparation method according to claim 1, which is characterized in that the poly (propylene carbonate) polyalcohol, described two different
Cyanate, the hydrophilic chain extender, the crosslinking agent, the non-hydrophilic preceding chain extender, the nano silica and the silicon
The mass ratio of alkane coupling agent is 60:(18~63): (2~10): (0.1~3): (5~15): (0.1~1): (0.1~5).
6. preparation method according to claim 1, which is characterized in that the molecular weight of the poly (propylene carbonate) polyalcohol is
1000~3000；
The hydroxy functionality of the poly (propylene carbonate) polyalcohol is 2~3；
The mole fraction of carbonate group is 0.3~0.4 in the poly (propylene carbonate) polyol molecule.
7. preparation method according to claim 1, which is characterized in that the diisocyanate is selected from different two isocyanide of Fu Er ketone
Acid esters, hexamethylene diisocyanate or hydrogenated diphenyl methane diisocyanate.
8. preparation method according to claim 1, which is characterized in that the hydrophilic chain extender is selected from ethylenediamine base ethanesulfonic acid
Sodium, dihydromethyl propionic acid or dimethylolpropionic acid；
The non-hydrophilic preceding chain extender is neopentyl glycol and/or 1,4 cyclohexane dimethanol.
9. preparation method according to claim 1, which is characterized in that the catalyst is selected from stannous octoate, tin dilaurate
Di-n-butyl tin or tin acetate；
The neutralizer is selected from triethylamine, tripropyl amine (TPA), tri-n-butylamine, sodium hydroxide or ammonium hydroxide.
10. aqueous polyurethane emulsion made from preparation method described in claim 1 to 9 any one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811624154.2A CN109694456A (en) | 2018-12-28 | 2018-12-28 | A kind of high rigidity, aqueous polyurethane emulsion of resistance to ethyl alcohol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811624154.2A CN109694456A (en) | 2018-12-28 | 2018-12-28 | A kind of high rigidity, aqueous polyurethane emulsion of resistance to ethyl alcohol and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109694456A true CN109694456A (en) | 2019-04-30 |
Family
ID=66232293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811624154.2A Pending CN109694456A (en) | 2018-12-28 | 2018-12-28 | A kind of high rigidity, aqueous polyurethane emulsion of resistance to ethyl alcohol and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109694456A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317530A (en) * | 2019-07-24 | 2019-10-11 | 重庆绿涂腾科技有限公司 | A kind of anti-stone of graphene oxide aqueous polyurethane hits anticorrosive paint and preparation method thereof |
| CN111440500A (en) * | 2020-05-09 | 2020-07-24 | 山东百特新材料有限公司 | Chain-like silica sol modified water-borne wood paint and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231209A (en) * | 2014-09-26 | 2014-12-24 | 江苏日出化工有限公司 | Preparation method for high-hardness waterborne polyurethane dispersion |
| CN105482068A (en) * | 2015-12-28 | 2016-04-13 | 广东工业大学 | Water-based polypropylene carbonate polyurethane emulsion and preparation method thereof |
| CN108794717A (en) * | 2018-07-02 | 2018-11-13 | 广东工业大学 | A kind of modified aqueous polyurethane emulsion and its preparation method and application |
-
2018
- 2018-12-28 CN CN201811624154.2A patent/CN109694456A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231209A (en) * | 2014-09-26 | 2014-12-24 | 江苏日出化工有限公司 | Preparation method for high-hardness waterborne polyurethane dispersion |
| CN105482068A (en) * | 2015-12-28 | 2016-04-13 | 广东工业大学 | Water-based polypropylene carbonate polyurethane emulsion and preparation method thereof |
| CN108794717A (en) * | 2018-07-02 | 2018-11-13 | 广东工业大学 | A kind of modified aqueous polyurethane emulsion and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317530A (en) * | 2019-07-24 | 2019-10-11 | 重庆绿涂腾科技有限公司 | A kind of anti-stone of graphene oxide aqueous polyurethane hits anticorrosive paint and preparation method thereof |
| CN111440500A (en) * | 2020-05-09 | 2020-07-24 | 山东百特新材料有限公司 | Chain-like silica sol modified water-borne wood paint and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109721707A (en) | It is a kind of with enhanced water resistance, resistance to alcohol repellency aqueous polyurethane emulsion and preparation method thereof | |
| CN105504215B (en) | A kind of aqueous polyurethane emulsion of color inhibition and preparation method thereof | |
| CN106381043B (en) | Water-based two-component polyurethane primer coating and preparation method thereof | |
| CN107974156B (en) | A kind of environment-friendly water-based stripping lacquer of automobile and its preparation method and application | |
| CN109694456A (en) | A kind of high rigidity, aqueous polyurethane emulsion of resistance to ethyl alcohol and preparation method thereof | |
| JP2010001457A (en) | Aqueous composite resin composition, coating agent containing the same and laminate using the coating agent | |
| CN103666236B (en) | A kind of VOC free organic-silicon-modified waterbased urethane nano hybridization coating and preparation method thereof | |
| CN103333314A (en) | Cation photocuring fluorinated polyurethane resin and preparation method thereof | |
| WO2020062970A1 (en) | Organosilicon modified polyether polyol as well as preparation method therefor and application thereof | |
| CN103709884B (en) | Organic-silicon-modified waterbased urethane priming paint of a kind of VOC free and preparation method thereof | |
| CN112898895B (en) | Self-repairing transparent anti-fouling coating and preparation method and application thereof | |
| KR101629674B1 (en) | Two-Coats type Super-hydrophobic Coating paint and forming method for Super-hydrophobic coating film | |
| CN103666179A (en) | VOC (volatile organic compound)-free epoxy modified water-borne PU (polyurethane) finish paint and preparation method thereof | |
| CN108329342A (en) | A kind of organo-silicon coupling agent and its preparation method and application | |
| JP5760304B2 (en) | Aqueous composite resin composition and coating agent | |
| CN113549392B (en) | Polyurethane dispersion, method for the production thereof and use thereof | |
| CN107033761A (en) | A kind of aqueous floride-free anti-fingerprint antifouling polymeric composite coating and its application method | |
| CN106318192A (en) | Water-based waterproof base film for wallpaper and preparation method of water-based waterproof base film | |
| CN109824850A (en) | A kind of dual-component aqueous polyurethane and its preparation method and application | |
| JP4488123B1 (en) | Coating agent for plastic substrate and laminate using the same | |
| CN110563923A (en) | Water-dispersible isocyanate curing agent composition with high water resistance and preparation method thereof | |
| CN111019082B (en) | Nonionic photo-curing polyurethane aqueous dispersion resin composition with excellent compatibility and preparation method and application thereof | |
| CN108499826B (en) | Spraying and curing process of water-based UV (ultraviolet) coating | |
| JP2010138274A (en) | Aqueous coating agent | |
| JP5760306B2 (en) | Aqueous composite resin composition and coating agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190430 |