CN110092883A - Corrosion-resistant aqueous supermolecule polyurethane resin of one kind and the preparation method and application thereof - Google Patents
Corrosion-resistant aqueous supermolecule polyurethane resin of one kind and the preparation method and application thereof Download PDFInfo
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- CN110092883A CN110092883A CN201910337722.9A CN201910337722A CN110092883A CN 110092883 A CN110092883 A CN 110092883A CN 201910337722 A CN201910337722 A CN 201910337722A CN 110092883 A CN110092883 A CN 110092883A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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Abstract
The invention discloses a kind of corrosion-resistant aqueous supermolecule polyurethane resins and the preparation method and application thereof.Preparation method includes: that polymeric dihydric alcohol and the hydrophilic dihydric alcohol of carboxylic acid type are uniformly mixed by (1), and diisocyanate and catalyst is then added, and using solvent as reaction medium, 55~85 DEG C are reacted 2~3 hours, obtains mix products I；(2) 50~70 DEG C are cooled to, cyclodextrin or derivatives thereof is added into mix products I and is cooled to 25~40 DEG C after reaction 6~7 hours, neutralizes, obtains mix products II；(3) water is added into mix products II to be emulsified, corrosion inhibiter is added and is uniformly mixed, removes solvent, obtains corrosion-resistant aqueous supermolecule polyurethane resin.The present invention, which is made in resin structure, contains cyclodextrin, and solubility, the bioavilability of compound, mechanical performance and the stability of oiliness corrosion inhibiter in water can be improved, and environmental protection as the base resin of water-based anticorrosive paint and adhesive, is with a wide range of applications.
Description
Technical field
The invention belongs to technical field of polymer, and in particular to the corrosion-resistant aqueous supermolecule polyurethane resin of one kind and its system
Preparation Method and application.
Background technique
It is surprising for corroding to loss caused by the mankind, and wherein copper and alloy are highly susceptible to corruption in corrosive media
Erosion every year because of huge economic loss caused by corroding to the whole world, therefore greatly develops anticorrosion technique and has become reduction corrosion damage
Lose, promote it is resource-effective there is an urgent need to.In numerous corrosion resistant etching methods, coating protection is common preventive means.
Raising and national laws regulation due to current people's environmental consciousness is to volatile organic matter (VOC), You Haikong
The control of gas pollutant (HAPs) is increasingly strict, and solvent borne polyurethane is gradually replaced aqueous polyurethane.Aqueous supermolecule is poly-
Urethane resin is with the new polyurethane system of water substitution organic solvent dispersion media.Anti-corrosion polyurethane coating is anti-after other
Most general coating variety after rotten coating, dosage are only second to phthalic resin coating.Aqueous polyurethane is due to excellent
Physical property and the chemical properties such as excellent resistance to strong acid, resistance to highly basic, ageing-resistant, salt water resistance, obtained in water-based anticorrosive paint field
To rapid development.But in aqueous polyurethane preparation process, due to the introducing of hydrophilic radical, leads to the reduction of its water resistance, compare
It is low in solvent borne polyurethane crosslink density, it is unfavorable for that corrosion sex factor is stopped to enter inside substrate, therefore researcher is by various
Method is modified it.In 2015, Chinese patent (CN105505164A) disclosed a kind of water of corrosion-resistant high adhesion force
Property polyurethane coating, but added raw material is complex, to influence its application field.
Summary of the invention
To solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of corrosion-resistant aqueous
Supermolecule polyurethane resin, the aqueous supermolecule resin stability is good, to human body and environmentally friendly.
Another object of the present invention is to provide the preparation methods of the corrosion-resistant aqueous supermolecule polyurethane resin of above-mentioned one kind.
A further object of the present invention is to provide the applications of the corrosion-resistant aqueous supermolecule polyurethane resin of above-mentioned one kind.
The object of the invention is achieved through the following technical solutions:
A kind of corrosion-resistant aqueous supermolecule polyurethane resin, has structural formula as shown in Equation 1:
Wherein, n value refers to the number of repeat unit of the upper unsaturated bond of monosubstituted cyclodextrin or derivatives thereof, value range is 8~
10。
R1Selected from-OCH3,-OH and-OCH2CH(CH3)CH2One of OH.
R2Selected from one of alpha-cyclodextrin (α-CD), beta-cyclodextrin (β-CD) and gamma-cyclodextrin (γ-CD)；The ring
Dextrin molecular formula is as shown in Equation 2, and wherein corresponding to m value in α-CD, β-CD and γ-CD molecular formula is respectively 6,7 and 8,
R3It is selected from identical or differently One or more of；Wherein, wave indicates and 1 structural formula of formula
The link position of middle imino group.
R4Selected from polymeric dihydric alcohol；It is selected from polyethylene glycol, polytetrahydrofuran ether glycol, poly-epsilon-caprolactone identical or differently
One or more of dihydric alcohol, polycarbonate glycol and polyethylene glycol adipate dihydric alcohol.
R5It is selected from one of dihydromethyl propionic acid, dimethylolpropionic acid and dyhydrobutanedioic acid or several identical or differently
Kind.
R6Identical or differently in triethylamine, tripropyl amine (TPA), triethanolamine, diethylenetriamine and dimethylethanolamine
It is one or more of.
R7Identical or differently in benzotriazole, 2-mercaptobenzothiazole, octadecylamine and methyl benzotriazazole
One or more, the R7Due to being included in cyclodextrin cavity by hydrophobic effect with hydrophobicity, then pasted with ring
It was proficient in hydrogen bond to connect with electrostatic interaction.
The preparation method of the above-mentioned corrosion-resistant aqueous supermolecule polyurethane resin of one kind, comprising the following steps:
(1) polymeric dihydric alcohol and the hydrophilic dihydric alcohol of carboxylic acid type are uniformly mixed, diisocyanate and catalyst are then added,
Using solvent as reaction medium, 55~85 DEG C are reacted 2~3 hours, obtain mix products I；
(2) 50~70 DEG C are cooled to, cyclodextrin or derivatives thereof is added into mix products I, after reaction 6~7 hours, drop
Temperature is added neutralizer and neutralizes, obtain mix products II to 25~40 DEG C；
(3) water is added into mix products II to be emulsified, corrosion inhibiter is added and is uniformly mixed, removes solvent, obtains corrosion resistant
Lose aqueous supermolecule polyurethane resin.
Total hydroxyl in isocyano and polymeric dihydric alcohol and the hydrophilic dihydric alcohol of carboxylic acid type in step (1) described diisocyanate
The molar ratio R value of base is 1:1~5, wherein R=n (- NCO)/n (- OH).
The hydrophilic dihydric alcohol of the polymeric dihydric alcohol, carboxylic acid type, diisocyanate, cyclodextrin or derivatives thereof, neutralizer and
The molar ratio of corrosion inhibiter is 2.50:(2.51~3.75): (10.94~20.00): 1:(2.51~3.75): (1~2)；More preferably
For 2.50:(2.51~3.33): (10.94~15.21): 1:(2.51~3.33): (1~2).
Step (1) described polymeric dihydric alcohol is preferably polyethylene glycol, polytetrahydrofuran ether glycol, poly-epsilon-caprolactone binary
One or more of alcohol, polycarbonate glycol and polyethylene glycol adipate dihydric alcohol；The hydrophilic dihydric alcohol of carboxylic acid type
Preferably one or more of dihydromethyl propionic acid, dimethylolpropionic acid and dyhydrobutanedioic acid.
Step (1) described diisocyanate is preferably aliphatic diisocyanate and aromatic diisocyanate；More preferably
For isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) and cyclohexanedimethyleterephthalate diisocyanate
One or more of (HXDI).
Step (1) described catalyst is preferably dibutyl tin dilaurate and/or organic bismuth catalyst.
Step (1) catalyst amount is preferably accounted for by polymeric dihydric alcohol, the hydrophilic dihydric alcohol of carboxylic acid type and diisocyanate
The 0.01~0.1% of the reactant gross mass of ester composition.
Step (1) described solvent is preferably acetone and/or butanone.
Step (1) solvent is reacted with what is be made of polymeric dihydric alcohol, the hydrophilic dihydric alcohol of carboxylic acid type and diisocyanate
Object total mass ratio is 1:(1~1.5).
Step (1) described reaction temperature is preferably 70~85 DEG C.
Step (1) and (2) described reaction carry out in inert gas or nitrogen atmosphere.
Step (2) cyclodextrin is alpha-cyclodextrin (α-CD), in beta-cyclodextrin (β-CD) and gamma-cyclodextrin (γ-CD)
One or more；The cyclodextrine derivatives are methyl flamprop and/or hydroxypropyl cyclodextrin.
Step (2) described reaction temperature is preferably 55~65 DEG C；The temperature of the neutralization is preferably 30~40 DEG C；When neutralization
Between preferably 0.5~1 hour.
Step (2) described neutralizer is preferably triethylamine, tripropyl amine (TPA), triethanolamine, diethylenetriamine and dimethyl ethanol
One or more of amine.
Step (3) corrosion inhibiter is oiliness corrosion inhibiter, preferably benzotriazole, 2-mercaptobenzothiazole, octadecylamine
One or more of with methyl benzotriazazole.
Step (3) mixing is preferably 20~30min of ultrasonic mixing.
Step (3) the emulsification revolving speed is preferably 1300~1500r/min；Emulsification times are preferably 10~40min.
Resulting lotion after step (3) described emulsification, also needs stewing process 6~24 hours.The purpose of the stewing process
It is whether the lotion that observation is formed is stable, if there is precipitating to generate.
Step (3) method for removing solvent is preferably revolving method.
The dosage of step (3) described water is according to the solid content of aqueous supermolecule polyurethane resin corrosion-resistant in lotion after emulsification
Depending on, wherein the solid content of corrosion-resistant aqueous supermolecule polyurethane resin is preferably 5~40%, more preferably 30~35%.
With PCL1000 (poly-epsilon-caprolactone glycol), IPDI (isophorone diisocyanate), DMPA (dihydroxymethyl third
Acid), for benzotriazole and methyl flamprop, reaction equation of the invention is as shown in following formula 3:
Wherein benzotriazole is to include it in cyclodextrin cavity by hydrophobic effect since it is with hydrophobicity
It is interior, then it is connect with cyclodextrin by hydrogen bond and electrostatic interaction.
Application of the above-mentioned corrosion-resistant aqueous supermolecule polyurethane resin of one kind in coating and adhesive field.
The coating is preferably water paint, and the adhesive is preferably Aqueous Adhesives.
The application method are as follows: corrosion-resistant aqueous supermolecule polyurethane resin, which is configured to water paint or adhesive, to be made
With.
The solid content of corrosion-resistant aqueous supermolecule polyurethane resin is preferably 5~40% in the water paint, more preferably
It is 30~35%.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) one of raw material of the present invention natural cyclodextrin improves the solubility of oiliness corrosion inhibiter in water and improves compound
Bioavilability, polymer had not only maintained the ability of the original inclusion of cyclodextrin, sustained release and identification, but also to have both high polymer good
Good mechanical performance, stability etc..
(2) corrosion-resistant aqueous supermolecule polyurethane resin provided by the invention is a kind of poly- ammonia of novel introducing supermolecule
Ester, anti-corrosion effect is good, no pollution to the environment, avoids harm of the organic solvent of ketone to human body.
(3) the application can simply include hydrophobic corrosion inhibiter using cyclodextrin cavity, and raw material is easy to get, and effect is bright
It is aobvious.
(4) corrosion-resistant aqueous supermolecule polyurethane resin prepared by the present invention introduces oil-soluble inhibitor, by " non-total
Corrosion inhibiter inclusion is entered cyclodextrin cavity and forms supermolecule waterborne polyurethane resin by valence link " effect, to improve resin
Corrosion resistance enhances the thermal stability of aqueous polyurethane.The present invention can be used as the base of water-based anticorrosive paint and adhesive
Plinth resin, is with a wide range of applications.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
1,25.0 mMs of poly-epsilon-caprolactone dihydric alcohol and 33.3 mMs of dihydromethyl propionic acids are added to 500ml tri-
It is stirred in mouth flask, then 152.1 mMs of isophorone diisocyanate is dissolved in 63.3g acetone, is added into
In three-necked flask, 1~2 drop dibutyl tin dilaurate is added, heating stirring is reacted 3 hours at 80 DEG C；
2,60 DEG C are cooled to, 10 mMs of methyl flamprop is added into reaction flask, reaction was cooled to 35 after 6 hours
DEG C, it is added in 33.3 mMs of triethylamines and 1 hour；
3, the emulsification of deionized water high-speed stirred (1500r/min is emulsified 30 minutes) is added on the basis of step 2, stands overnight
Afterwards, after emulsion-stabilizing, 10 mMs of benzotriazole, ultrasonic 30min are added, revolving removes excessive solvent, adjusts corrosion resistant
Aqueous supermolecule polyurethane resin solid content 30% is lost, corrosion-resistant aqueous supermolecule ester-polyurethane resin emulsion is obtained, it is entire to react
Process leads to inert gas.
Embodiment 2
1,25.0 mMs of poly-epsilon-caprolactone dihydric alcohol and 33.3 mMs of dihydromethyl propionic acids are added to 500ml tri-
It is stirred in mouth flask, then 152.1 mMs of isophorone diisocyanate is dissolved in 63.3g acetone, is added into
In three-necked flask, 1~2 drop dibutyl tin dilaurate is added, heating stirring is reacted 3 hours at 80 DEG C；
2,60 DEG C are cooled to, 10 mMs of methyl flamprop is added into reaction flask, reaction was cooled to 35 after 6 hours
DEG C, it is added in 33.3 mMs of triethylamines and 1 hour；
3, the emulsification of deionized water high-speed stirred (1500r/min is emulsified 30 minutes) is added on the basis of step 2, stands overnight
Afterwards, after emulsion-stabilizing, 20 mMs of benzotriazole, ultrasonic 30min are added, revolving removes excessive solvent, adjusts corrosion resistant
Aqueous supermolecule polyurethane resin solid content 30% is lost, corrosion-resistant aqueous supermolecule ester-polyurethane resin emulsion, as corrosion resistant are obtained
Aqueous supermolecule polyurethane resin coating is lost, entire reaction process leads to inert gas.
Embodiment 3
1,25.0 mMs of poly-epsilon-caprolactone dihydric alcohol and 26.2 mMs of dihydromethyl propionic acids are added to 500ml tri-
It is stirred in mouth flask, then 109.4 mMs of isophorone diisocyanate is dissolved in 52.8g acetone, is added into
In three-necked flask, 1~2 drop dibutyl tin dilaurate is added, heating stirring is reacted 3 hours at 80 DEG C；
2,60 DEG C are cooled to, 10 mMs of methyl flamprop is added into reaction flask, reaction was cooled to 35 after 6 hours
DEG C, it is added in 26.2 mMs of triethylamines and 1 hour；
3, the emulsification of deionized water high-speed stirred (1500r/min is emulsified 30 minutes) is added on the basis of step 2, stands overnight
Afterwards, after emulsion-stabilizing, 10 mMs of benzotriazole, ultrasonic 30min are added, revolving removes excessive solvent, adjusts corrosion resistant
Aqueous supermolecule polyurethane resin solid content 30% is lost, corrosion-resistant aqueous supermolecule ester-polyurethane resin emulsion, as corrosion resistant are obtained
Aqueous supermolecule polyurethane resin coating is lost, entire reaction process leads to inert gas.
Embodiment 4
1,25.0 mMs of poly-epsilon-caprolactone dihydric alcohol and 26.2 mMs of dihydromethyl propionic acids are added to 500ml tri-
It is stirred in mouth flask, then 109.4 mMs of isophorone diisocyanate is dissolved in 52.8g acetone, is added into
In three-necked flask, 1~2 drop dibutyl tin dilaurate is added, heating stirring is reacted 3 hours at 80 DEG C；
2,60 DEG C are cooled to, 10 mMs of methyl flamprop is added into reaction flask, reaction was cooled to 35 after 6 hours
DEG C, it is added in 26.2 mMs of triethylamines and 1 hour；
3, the emulsification of deionized water high-speed stirred (1500r/min is emulsified 30 minutes) is added on the basis of step 2, stands overnight
Afterwards, after emulsion-stabilizing, 20 mMs of benzotriazole, ultrasonic 30min are added, revolving removes excessive solvent, adjusts corrosion resistant
Aqueous supermolecule polyurethane resin solid content 30% is lost, corrosion-resistant aqueous supermolecule ester-polyurethane resin emulsion, as corrosion resistant are obtained
Aqueous supermolecule polyurethane resin coating is lost, entire reaction process leads to inert gas.
Embodiment 5
1,25.0 mMs of poly-epsilon-caprolactone dihydric alcohol and 25.1 mMs of dihydromethyl propionic acids are added to 500ml tri-
It is stirred in mouth flask, then 117.2 mMs of isophorone diisocyanate is dissolved in 54.4g acetone, is added into
In three-necked flask, 1~2 drop dibutyl tin dilaurate is added, heating stirring is reacted 3 hours at 80 DEG C；
2,60 DEG C are cooled to, 10 mMs of methyl flamprop is added into reaction flask, reaction was cooled to 35 after 6 hours
DEG C, it is added in 25.1 mMs of triethylamines and 1 hour；
3, the emulsification of deionized water high-speed stirred (1500r/min is emulsified 30 minutes) is added on the basis of step 2, stands overnight
Afterwards, after emulsion-stabilizing, 10 mMs of benzotriazole, ultrasonic 30min are added, revolving removes excessive solvent, adjusts corrosion resistant
Aqueous supermolecule polyurethane resin solid content 30% is lost, corrosion-resistant aqueous supermolecule ester-polyurethane resin emulsion, as corrosion resistant are obtained
Aqueous supermolecule polyurethane resin coating is lost, entire reaction process leads to inert gas.
Embodiment 6
1,25.0 mMs of poly-epsilon-caprolactone dihydric alcohol and 25.1 mMs of dihydromethyl propionic acids are added to 500ml tri-
It is stirred in mouth flask, then 117.2 mMs of isophorone diisocyanate is dissolved in 54.4g acetone, is added into
In three-necked flask, 1~2 drop dibutyl tin dilaurate is added, heating stirring is reacted 3 hours at 80 DEG C；
2,60 DEG C are cooled to, 10 mMs of methyl flamprop is added into reaction flask, reaction was cooled to 35 after 6 hours
DEG C, it is added in 25.1 mMs of triethylamines and 1 hour；
3, the emulsification of deionized water high-speed stirred (1500r/min is emulsified 30 minutes) is added on the basis of step 2, stands overnight
Afterwards, after emulsion-stabilizing, 20 mMs of benzotriazole, ultrasonic 30min are added, revolving removes excessive solvent, adjusts corrosion resistant
Aqueous supermolecule polyurethane resin solid content 30% is lost, corrosion-resistant aqueous supermolecule ester-polyurethane resin emulsion, as corrosion resistant are obtained
Aqueous supermolecule polyurethane resin coating is lost, entire reaction process leads to inert gas
Embodiment 7
1,25.0 mMs of poly-epsilon-caprolactone dihydric alcohol and 37.5 mMs of dihydromethyl propionic acids are added to 500ml tri-
It is stirred in mouth flask, then 200.0 mMs of isophorone diisocyanate is dissolved in 74.5g acetone, is added into
In three-necked flask, 1~2 drop dibutyl tin dilaurate is added, heating stirring is reacted 3 hours at 80 DEG C；
2,60 DEG C are cooled to, 10 mMs of methyl flamprop is added into reaction flask, reaction was cooled to 35 after 6 hours
DEG C, it is added in 37.5 mMs of triethylamines and 1 hour；
3, the emulsification of deionized water high-speed stirred (1500r/min is emulsified 30 minutes) is added on the basis of step 2, stands overnight
Afterwards, after emulsion-stabilizing, 10 mMs of benzotriazole, ultrasonic 30min are added, revolving removes excessive solvent, adjusts corrosion resistant
Aqueous supermolecule polyurethane resin solid content 30% is lost, corrosion-resistant aqueous supermolecule ester-polyurethane resin emulsion, as corrosion resistant are obtained
Aqueous supermolecule polyurethane resin coating is lost, entire reaction process leads to inert gas.
Embodiment 8
1,25.0 mMs of poly-epsilon-caprolactone dihydric alcohol and 37.5 mMs of dihydromethyl propionic acids are added to 500ml tri-
It is stirred in mouth flask, then 200.0 mMs of isophorone diisocyanate is dissolved in 74.5g acetone, is added into
In three-necked flask, 1~2 drop dibutyl tin dilaurate is added, heating stirring is reacted 3 hours at 80 DEG C；
2,60 DEG C are cooled to, 10 mMs of methyl flamprop is added into reaction flask, reaction was cooled to 35 after 6 hours
DEG C, it is added in 37.5 mMs of triethylamines and 1 hour；
3, the emulsification of deionized water high-speed stirred (1500r/min is emulsified 30 minutes) is added on the basis of step 2, stands overnight
Afterwards, after emulsion-stabilizing, 20 mMs of benzotriazole, ultrasonic 30min are added, revolving removes excessive solvent, adjusts corrosion resistant
Aqueous supermolecule polyurethane resin solid content 30% is lost, corrosion-resistant aqueous supermolecule ester-polyurethane resin emulsion, as corrosion resistant are obtained
Aqueous supermolecule polyurethane resin coating is lost, entire reaction process leads to inert gas.
Embodiment 9
1,25.0 mMs of poly-epsilon-caprolactone dihydric alcohol and 27.6 mMs of dihydromethyl propionic acids are added to 500ml tri-
It is stirred in mouth flask, then 139.0 mMs of isophorone diisocyanate is dissolved in 55.9g acetone, is added into
In three-necked flask, 1~2 drop dibutyl tin dilaurate is added, heating stirring is reacted 3 hours at 80 DEG C；
2,60 DEG C are cooled to, 10 mMs of methyl flamprop is added into reaction flask, reaction was cooled to 35 after 6 hours
DEG C, it is added in 27.6 mMs of triethylamines and 1 hour；
3, the emulsification of deionized water high-speed stirred (1500r/min is emulsified 30 minutes) is added on the basis of step 2, stands overnight
Afterwards, after emulsion-stabilizing, 10 mMs of benzotriazole, ultrasonic 30min are added, revolving removes excessive solvent, adjusts corrosion resistant
Aqueous supermolecule polyurethane resin solid content 30% is lost, corrosion-resistant aqueous supermolecule ester-polyurethane resin emulsion, as corrosion resistant are obtained
Aqueous supermolecule polyurethane resin coating is lost, entire reaction process leads to inert gas.
Embodiment 10
1,25.0 mMs of poly-epsilon-caprolactone dihydric alcohol and 27.6 mMs of dihydromethyl propionic acids are added to 500ml tri-
It is stirred in mouth flask, then 139.0 mMs of isophorone diisocyanate is dissolved in 55.9g acetone, is added into
In three-necked flask, 1~2 drop dibutyl tin dilaurate is added, heating stirring is reacted 3 hours at 80 DEG C；
2,60 DEG C are cooled to, 10 mMs of methyl flamprop is added into reaction flask, reaction was cooled to 35 after 6 hours
DEG C, it is added in 27.6 mMs of triethylamines and 1 hour；
3, the emulsification of deionized water high-speed stirred (1500r/min is emulsified 30 minutes) is added on the basis of step 2, stands overnight
Afterwards, after emulsion-stabilizing, 20 mMs of benzotriazole, ultrasonic 30min are added, revolving removes excessive solvent, adjusts corrosion resistant
Aqueous supermolecule polyurethane resin solid content 30% is lost, corrosion-resistant aqueous supermolecule ester-polyurethane resin emulsion, as corrosion resistant are obtained
Aqueous supermolecule polyurethane resin coating is lost, entire reaction process leads to inert gas.
Comparative example 1
This comparative example is a kind of commercially available waterborne polyurethane resin AH-1610A product, solid content 30%, directly by it
It is used as waterborne polyurethane resin AH-1610A coating.
It is aqueous poly- in the corrosion-resistant aqueous supermolecule polyurethane resin coating and comparative example 1 that Example 1~10 obtains
Urethane Resin A H-1610A coating pours into Teflon mould respectively, is subsequently placed in 70 DEG C of baking ovens and dries for 24 hours, can obtain
The coating smooth to surface, is tested for the property, and the detection quasi- specification of gloss scale is GB/T 9754-2007, detection attachment
Power specification is GB/T 9286-1998, and detection resistance to salt water standard specification is ASTM B117-03, obtains performance as shown in Table 1
Test result.
The performance test results of the corrosion-resistant aqueous supermolecule polyurethane resin coating of table 1
According to table 1, corrosion-resistant aqueous supermolecule polyurethane resin provided by the invention is that a kind of novel introducing is super
The polyurethane of molecule, compared to commercially available aqueous polyurethane, adhesive force, corrosion resistance, glossiness performance are all improved significantly.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of corrosion-resistant aqueous supermolecule polyurethane resin, which is characterized in that have structural formula as shown in Equation 1:
Wherein, n value refers to that the number of repeat unit of the upper unsaturated bond of monosubstituted cyclodextrin or derivatives thereof, value range are 8~10；
R1Selected from-OCH3,-OH and-OCH2CH(CH3)CH2One of OH；
R2Selected from one of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin；The cyclodextrin molecular formula is as shown in Equation 2, wherein
Corresponding to m value in α-CD, β-CD and γ-CD molecular formula is respectively 6,7 and 8,
R7Identical or differently selected from one of benzotriazole, 2-mercaptobenzothiazole, octadecylamine and methyl benzotriazazole
Or several, the R7It is included in cyclodextrin cavity by hydrophobic effect, then passes through hydrogen bond and electrostatic interaction with cyclodextrin
Connection.
2. a kind of corrosion-resistant aqueous supermolecule polyurethane resin according to claim 1, which is characterized in that
R3It is selected from identical or differently One or more of；Wherein, wave indicates and 1 structural formula of formula
The link position of middle imino group；
R4It is selected from polyethylene glycol, polytetrahydrofuran ether glycol, poly-epsilon-caprolactone dihydric alcohol, polycarbonate binary identical or differently
One or more of pure and mild polyethylene glycol adipate dihydric alcohol；
R5Identical or differently selected from one or more of dihydromethyl propionic acid, dimethylolpropionic acid and dyhydrobutanedioic acid；
R6Identical or differently selected from one of triethylamine, tripropyl amine (TPA), triethanolamine, diethylenetriamine and dimethylethanolamine
Or it is several.
3. the preparation method of any one of the claim 1~2 corrosion-resistant aqueous supermolecule polyurethane resin of one kind, feature exist
In, comprising the following steps:
(1) polymeric dihydric alcohol and the hydrophilic dihydric alcohol of carboxylic acid type are uniformly mixed, diisocyanate and catalyst are added, then with molten
As reaction medium, 55~85 DEG C are reacted 2~3 hours for agent, obtain mix products I；
(2) 50~70 DEG C are cooled to, cyclodextrin or derivatives thereof is added into mix products I and is cooled to after reaction 6~7 hours
25~40 DEG C, neutralizer is added and neutralizes, obtains mix products II；
(3) water is added into mix products II to be emulsified, corrosion inhibiter is added and is uniformly mixed, removes solvent, obtains corrosion-resistant water
Property supermolecule polyurethane resin.
4. a kind of preparation method of corrosion-resistant aqueous supermolecule polyurethane resin according to claim 3, which is characterized in that step
Suddenly the molar ratio of the isocyano in (1) described diisocyanate and hydroxyl total in polymeric dihydric alcohol and the hydrophilic dihydric alcohol of carboxylic acid type
R value is 1:1~5.
5. a kind of preparation method of corrosion-resistant aqueous supermolecule polyurethane resin according to claim 4, which is characterized in that institute
State rubbing for the hydrophilic dihydric alcohol of polymeric dihydric alcohol, carboxylic acid type, diisocyanate, cyclodextrin or derivatives thereof, neutralizer and corrosion inhibiter
You are than being 2.50:(2.51~3.75): (10.94~20.00): 1:(2.51~3.75): (1~2)；
The hydrophilic dihydric alcohol of the polymeric dihydric alcohol, carboxylic acid type, diisocyanate, cyclodextrin or derivatives thereof, neutralizer and inhibition
The molar ratio of agent is 2.50:(2.51~3.33): (10.94~15.21): 1:(2.51~3.33): (1~2).
6. according to the preparation method of the corrosion-resistant aqueous supermolecule polyurethane resin of the described one kind of claim 3 or 5, feature exists
In step (2) cyclodextrin is one or more of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin；The cyclodextrin spreads out
Biology is methyl flamprop and/or hydroxypropyl cyclodextrin；
Step (3) corrosion inhibiter is one in benzotriazole, 2-mercaptobenzothiazole, octadecylamine and methyl benzotriazazole
Kind is several.
7. according to the preparation method of the corrosion-resistant aqueous supermolecule polyurethane resin of the described one kind of claim 3 or 5, feature exists
In step (1) diisocyanate is aliphatic diisocyanate and aromatic diisocyanate；The diisocyanate is
One of isophorone diisocyanate, hexamethylene diisocyanate and cyclohexanedimethyleterephthalate diisocyanate are several
Kind；
The polymeric dihydric alcohol is polyethylene glycol, polytetrahydrofuran ether glycol, poly-epsilon-caprolactone dihydric alcohol, polycarbonate glycol
One or more of with polyethylene glycol adipate dihydric alcohol；The hydrophilic dihydric alcohol of carboxylic acid type is dihydromethyl propionic acid, two
One or more of hydroxymethylbutyrate and dyhydrobutanedioic acid；
The catalyst is dibutyl tin dilaurate and/or organic bismuth catalyst；
Step (2) neutralizer is one in triethylamine, tripropyl amine (TPA), triethanolamine, diethylenetriamine and dimethylethanolamine
Kind is several.
8. according to the preparation method of the corrosion-resistant aqueous supermolecule polyurethane resin of the described one kind of claim 3 or 5, feature exists
In step (1) reaction temperature is 70~85 DEG C；The solvent is acetone and/or butanone；
Step (1) and (2) described reaction carry out in inert gas or nitrogen atmosphere；Step (2) reaction temperature is 55
~65 DEG C；The neutralization temperature is 30~40 DEG C, and neutralizing the time is 0.5~1 hour.
9. according to the preparation method of the corrosion-resistant aqueous supermolecule polyurethane resin of the described one kind of claim 3 or 5, feature exists
In step (1) solvent and the total matter of reactant being made of polymeric dihydric alcohol, the hydrophilic dihydric alcohol of carboxylic acid type and diisocyanate
Amount is than being 1:(1~1.5)；
The catalyst amount accounts for the total matter of reactant being made of polymeric dihydric alcohol, the hydrophilic dihydric alcohol of carboxylic acid type and diisocyanate
The 0.01~0.1% of amount.
10. any one of the claim 1~2 corrosion-resistant aqueous supermolecule polyurethane resin of one kind is in coating and adhesive field
In application.
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| CN111171265A (en) * | 2020-01-20 | 2020-05-19 | 中科院广州化学有限公司 | Water-based polyurethane resin containing pyrimidone structure and preparation method and application thereof |
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