CN106957406B - A kind of calixarene type light-cured polyurethane resin and its coatings of preparation - Google Patents
A kind of calixarene type light-cured polyurethane resin and its coatings of preparation Download PDFInfo
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- CN106957406B CN106957406B CN201710330204.5A CN201710330204A CN106957406B CN 106957406 B CN106957406 B CN 106957406B CN 201710330204 A CN201710330204 A CN 201710330204A CN 106957406 B CN106957406 B CN 106957406B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of calixarene type light-cured polyurethane resin, the calixarene type light-cured polyurethane resin is made as follows: (1) preparing the prepolymer of isocyanate group sealing end；(2) prepolymer that isocyanate group half blocks is prepared；(3) calixarenes monomer is accessed in the prepolymer that isocyanate group made from step (2) half blocks, the calixarene type light-cured polyurethane is made.The groups such as photo curable cumarin, double bond are grafted on calixarenes by the present invention, are prepared for calixarene type photocuring selfreparing polyurethane resin and are substantially increased the hardness of selfreparing while guaranteeing preferable self-healing properties.
Description
Technical field
The present invention relates to photo-curing material technical fields, anti-more particularly, to a kind of calixarenes monomer and polyurethane prepolymer
Calixarene type light-cured polyurethane resin should be prepared, and its application in selfreparing.
Background technique
Coatings refer to after disruption, have self-repairing capability, or have certainly under certain external environment
The functional coating of my repair ability.Coatings can be mainly divided into two classes, and one kind is foreign aid's type selfreparing, and one kind is intrinsic
Type selfreparing；The multiple reparation that Intrinsical selfreparing is realized using the effect of reversible chemical key, overcomes foreign aid's type type selfreparing
The shortcomings that, but since the structure of its dynamic invertibity and most of coatings is all single armed or few arm configuration, it can load
Selfreparing group amount is relatively fewer, for the self-healing properties of guarantee, most of selfreparings all have a lower hardness and
A possibility that mechanical property, these problems all greatly reduce selfreparing practical application.
Calixarenes is a kind of macrocyclic compound being made of methylene-bridged phenol units, and nineteen forty-two gold gram synthesizes for the first time
It obtains, by ancient odd referred to as calixarenes due to its structure is as a wineglass.Four-c- methyl cup [4] resorcinol calixarenes are wherein
The relatively simple one kind of structure, the benzene ring structure in its structure make it have higher rigidity.Meanwhile four between-c- methyl cup [4]
Benzenediol calixarenes is a kind of multi-arm monomer, as the polyol structure of synthesis of polyurethane, can form a kind of nucleocapsid knot
Structure, and the access amount of selfreparing group can be dramatically increased, so that self-repair efficiency is obtained certain raising.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of calixarene type light-cured polyurethanes
Resin and its coatings of preparation.The groups such as photo curable cumarin, double bond are grafted on calixarenes by the present invention, system
It substantially increases and reviews one's lessons by oneself while guaranteeing preferable self-healing properties for calixarene type photocuring selfreparing polyurethane resin
The hardness of overcoating layer.
Technical scheme is as follows:
A kind of calixarene type light-cured polyurethane resin, the calixarene type light-cured polyurethane resin is as follows
It is made:
(1) diisocyanate, the dilution of catalyst dibutyltin dilaurylate are placed in reactor using anhydrous solvent,
Then the diluted dihydric alcohol of anhydrous solvent is added dropwise into reactor, 2~4h is reacted at 40~50 DEG C, isocyanate group sealing end is made
Prepolymer；
(2) photo-curing monomer is dissolved in anhydrous solvent, is added dropwise to the prepolymer of the sealing end of isocyanate group made from step (1)
In, 4~6h is reacted at 70~80 DEG C, and the prepolymer that isocyanate group half blocks is made；
(3) calixarenes monomer and triethylamine are dissolved in anhydrous solvent, are added dropwise to isocyanate group made from step (2) half and seal
In the prepolymer at end, 12~18h is reacted at 70~80 DEG C, reaction terminates, and product is precipitated in ice-water bath, filtered, vacuum is dry
It is dry, the calixarene type light-cured polyurethane is made.
Diisocyanate described in step (1) is methyl diphenylene diisocyanate, polymeric diphenylmethane diisocyanate
Ester, toluene di-isocyanate(TDI), hexamethylene diisocyanate, isophorone diisocyanate, benzene dimethylene diisocyanate
One of or it is a variety of；The dihydric alcohol be PEG-400, PEG-800, PEG-1000, PEG-2000, PEG-10000,
T5650E, T5650J, T5651, T5652, polyethylene oxide (polyethylene glycol) glycol, polypropylene oxide (polypropylene glycol) glycol,
One of polytetrahydrofuran diol, polyethylene glycol adipate glycol, polyadipate -1,4- butyl glycol ester diol are a variety of；
The molar ratio of the diisocyanate and dihydric alcohol is 2~2.2:1.
Photo-curing monomer described in step (2) is Hymecromone, 9- anthryl carbinol, 4- hydroxy-3-methoxy
Cinnamic acid, 4- hydroxyl -3,5- dimethoxy-cinnamic acid, 3,4- dihydroxycinnamic acid, hydroxyethyl methacrylate, acrylic acid hydroxyl second
One of ester is a variety of；The molar ratio of the prepolymer of the photo-curing monomer and isocyanate group sealing end is 1~1.1:1.
Calixarenes monomer described in step (3) is resorcinol calixarenes, tetramethoxy resorcinol calixarenes, to tertiary fourth
One of base calixarenes is a variety of；The molar ratio for the prepolymer that the calixarenes monomer and isocyanate group half blocks is 1~
1.1:1。
The anhydrous solvent is one of N,N-dimethylformamide, acetone, tetrahydrofuran, ethyl acetate or a variety of；
The dosage of the anhydrous solvent is the 20~30wt% of concentration for making reactant in reaction system.
A kind of application of the calixarene type light-cured polyurethane resin, the light-cured polyurethane resin can be used for selfreparing
Technical field.
A kind of coatings of the calixarene type light-cured polyurethane resin, raw material and each raw material contained by the coating
Mass percent are as follows:
Each raw material is mixed according to the above ratio, after being protected from light 30~60min of ultrasound, is spun on aluminium sheet, with a thickness of 0.1~
1mm, under the conditions of 40~100 DEG C, 60~120min of preliminary drying, then in 500-800mJ/cm2Energy under be exposed solidification,
Prepare calixarene type light-cured polyurethane coatings.
The reactive diluent is trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate
One of or it is a variety of；The photoinitiator is 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxy-cyclohexyl phenyl first
Ketone, 2- hydroxyl-4 '-(2- hydroxy ethoxy)-2- methyl phenyl ketone, 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholine-1- acetone
One of or it is a variety of；The solvent is N,N-dimethylformamide, in butanone, dimethyl acetamide, cyclohexanone, ethyl acetate
It is one or more.
The present invention is beneficial to be had the technical effect that
(1) polyurethane resin in the present invention can be grafted on calixarenes using calixarenes as stone by gradually addition
A plurality of linear type flexible polyurethane chain, forms the structure of a kind of " stone flexible arm ", and the benzene ring structure in calixarenes can greatly improve
Hardness, meanwhile, the multi-arm structure of polyurethane can not only be grafted more selfreparing groups, while can keep under heating
The mobility of chain guarantees there is preferable self-healing properties.
(2) the calixarenes monomer used in the present invention, synthesis material is simple and easy to get, and synthesis technology is mature, preparation method letter
It is single.
(3) photosensitive group that light-cured polyurethane resin molecule chain end contains in the present invention, by using solidification temperature
It is low, curing rate is fast, curing efficiency is high, easy to operate, energy-saving and environment-friendly UV-curing technology, prepare calixarene type photocuring
Polyurethane selfreparing not only simplifies traditional film-forming process, improves production efficiency, while can also be by forming cross-linked network
Come the mechanical performance enhanced.Meanwhile it can as the polyurethane resin of photosensitive group using coumarin group, anthryl group, cinnamoyl group
To carry out Light Curing under conditions of not adding photoinitiator.
Detailed description of the invention
Fig. 1 is reaction process schematic diagram of the present invention.
Fig. 2 is the comparison diagram that coatings made from embodiment 1 repair front and back.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Embodiment 1
A kind of synthesis of calixarene type light-cured polyurethane resin:
(1) use the anhydrous N,N-dimethylformamide of 12.5g (DMF) by two isocyanide of 2.445g (0.011mol) isophorone
Acid esters, the dilution of 0.015g dibutyl tin dilaurate are placed in the three-necked flask with stirring and condensation, are then burnt to three mouthfuls
The mixture of 12.5g anhydrous DMF and 2.5g (0.005mol) PCDL500 is slowly added dropwise in bottle, reacts 2h at 50 DEG C, is made different
The prepolymer of cyanic acid base sealing end；
(2) 0.881g (0.005mol) Hymecromone is dissolved in 4.4g anhydrous DMF, is added dropwise to step
(1) in the prepolymer of the sealing end of isocyanate group made from, 6h is reacted at 70 DEG C, the prepolymer that isocyanate group half blocks is made；
(3) four-c- methyl cup [4] resorcinol calixarenes of 0.341g (0.000625mol) and 0.005g triethylamine is molten
In 1.7g anhydrous DMF, it is added dropwise in the prepolymer that isocyanate group made from step (2) half blocks, reacts 12h at 80 DEG C,
Reaction terminates, and product is precipitated in ice-water bath, filters, is dried in vacuo, and the calixarene type light-cured polyurethane is made.
The DMF of calixarene type polyurethane and 40wt% prepared by the 60wt% embodiment of the present invention is mixed, and is protected from light ultrasound
It after 30min, is spun on aluminium sheet, with a thickness of 0.3mm, under the conditions of 70 DEG C, preliminary drying 120min, then in 600mJ/cm2Energy
It is exposed solidification under amount, prepares calixarene type light-cured polyurethane coatings.
After the calixarene type light-cured polyurethane coatings surface of preparation being scratched using scratching instrument, utilize heat
Air pressure gun makes the surface of coating heat 2min at 100 DEG C, and observes oneself of coating by three-dimensional super depth of field optical microscopy
Repairing performance.Coating repairs the comparison of front and back as shown in Fig. 2, the pendulum-rocker hardness (avg) of coating is 172 ± 3, and pencil hardness is
3H。
As seen from Figure 2, the scratch disappearance after coating is destroyed is more obvious, presents good selfreparing effect
Fruit.
Embodiment 2
A kind of synthesis of calixarene type light-cured polyurethane resin:
(1) use 13.5g anhydrous ethyl acetate by 3.364g (0.02mol) hexamethylene diisocyanate and 0.020g
It is added to after DBTDL dilution in the three-necked flask with stirring and condensation, the anhydrous second of 16g is then slowly added dropwise into three-necked flask
The mixture of acetoacetic ester and 4.0g (0.01mol) PEG400, reaction stir 3h at 45 DEG C, prepare the pre- of isocyanate group sealing end
Polymers；
(2) 1.301g (0.01mol) hydroxyethyl methacrylate is dissolved in 5.2g anhydrous ethyl acetate, be slowly added dropwise into
In the prepolymer of the sealing end of isocyanate group made from step (1), reaction stirs 4h at 80 DEG C, and the pre-polymerization that isocyano group half blocks is made
Object；
(3) four-c- methyl cup [4] resorcinol calixarenes of 0.681g (0.00125mol) and 0.007g triethylamine are dissolved in
In 2.7g anhydrous ethyl acetate, it is added dropwise in the prepolymer that isocyanate group made from step (2) half blocks, reaction is stirred at 75 DEG C
15h is mixed, reaction terminates, and product is added drop-wise in ice-water bath and is precipitated, and filters, and it is solid to prepare the calixarene type light for vacuum drying
Change polyurethane resin.
By the three hydroxyl first of triethoxyization of light-cured polyurethane resin prepared by the 50wt% embodiment of the present invention, 20wt%
2- hydroxy-2-methyl -1- phenyl -1- the acetone of base propane triacrylate, the ethyl acetate of 27wt% and 3wt% mixes, and keeps away
It after light ultrasound 45min, is spun on aluminium sheet, with a thickness of 0.2mm, under the conditions of 40 DEG C, preliminary drying 120min, then in 700mJ/
cm2Energy under be exposed solidification, prepare calixarene type light-cured polyurethane coatings.
Embodiment 3
A kind of synthesis of calixarene type light-cured polyurethane resin:
(1) use the anhydrous butanone of 16.5g by 5.505g (0.022mol) diphenylmethylene diisocyanate and 0.025g
It is added to after DBTDL dilution in the three-necked flask with stirring and condensation；Then the anhydrous fourth of 24g is slowly added dropwise into three-necked flask
The mixture of ketone and 8.0g (0.01mol) PCDL800, reaction stir 4h at 40 DEG C, prepare the pre-polymerization of isocyanate group sealing end
Object；
(2) 1.161g (0.01mol) hydroxy-ethyl acrylate is dissolved in the anhydrous butanone of 3.5g, is slowly added dropwise into step (1)
The prepolymer of isocyano group sealing end obtained, reaction stir 4h at 75 DEG C, and the prepolymer that isocyano group half blocks is made；
(3) four-c- methyl cup [4] resorcinol calixarenes of 0.681g (0.00125mol) and 0.009g triethylamine are dissolved in
In the anhydrous butanone of 2g, it is added dropwise in the prepolymer that isocyanate group made from step (2) half blocks, reaction stirs 18h at 70 DEG C,
Reaction terminates, and product is added drop-wise in ice-water bath and is precipitated, and filters, and the calixarene type light-solidifying poly ammonia is prepared in vacuum drying
Ester resin.
By light-cured polyurethane resin prepared in the 50wt% embodiment of the present invention, nine ethoxylation of 10wt%, three hydroxyl first
Base propane triacrylate, 38wt% ethyl acetate, the mixing of 2wt%1- hydroxy-cyclohexyl phenyl ketone, are protected from light ultrasonic 60min
Afterwards, it is spun on aluminium sheet, with a thickness of 0.15mm, under the conditions of 50 DEG C, preliminary drying 60min, then in 800mJ/cm2Energy under into
Row exposure curing prepares calixarene type light-cured polyurethane coatings.
Claims (6)
1. a kind of calixarene type light-cured polyurethane resin, it is characterised in that the calixarene type light-cured polyurethane resin passes through
Following steps are made:
(1) diisocyanate, the dilution of catalyst dibutyltin dilaurylate are placed in reactor using anhydrous solvent, then
The diluted dihydric alcohol of anhydrous solvent is added dropwise into reactor, 2~4h is reacted at 40~50 DEG C, the pre- of isocyanate group sealing end is made
Polymers；
(2) photo-curing monomer is dissolved in anhydrous solvent, is added dropwise in the prepolymer of the sealing end of isocyanate group made from step (1),
4~6h is reacted at 70~80 DEG C, and the prepolymer that isocyanate group half blocks is made；
(3) calixarenes monomer and triethylamine are dissolved in anhydrous solvent, are added dropwise to what isocyanate group made from step (2) half blocked
In prepolymer, 12~18h is reacted at 70~80 DEG C, reaction terminates, and product is precipitated in ice-water bath, filters, is dried in vacuo, system
Obtain the calixarene type light-cured polyurethane；
Photo-curing monomer described in step (2) is Hymecromone, 9- anthryl carbinol, 4- hydroxy-3-methoxy cortex cinnamomi
In acid, 4- hydroxyl -3,5- dimethoxy-cinnamic acid, 3,4- dihydroxycinnamic acid, hydroxyethyl methacrylate, hydroxy-ethyl acrylate
It is one or more；The molar ratio of the prepolymer of the photo-curing monomer and isocyanate group sealing end is 1~1.1:1；
Calixarenes monomer described in step (3) is resorcinol calixarenes, tetramethoxy resorcinol calixarenes, to tert-butyl-calix
One of aromatic hydrocarbons is a variety of；The molar ratio for the prepolymer that the calixarenes monomer and isocyanate group half block is 1~1.1:1.
2. calixarene type light-cured polyurethane resin according to claim 1, it is characterised in that two is different described in step (1)
Cyanate is methyl diphenylene diisocyanate, polymeric diphenylmethane diisocyanate, toluene di-isocyanate(TDI), hexa-methylene
One of diisocyanate, isophorone diisocyanate, benzene dimethylene diisocyanate are a variety of；The dihydric alcohol is
PEG-400, PEG-800, PEG-1000, PEG-2000, PEG-10000, T5650E, T5650J, T5651, T5652, polycyclic oxygen
Ethane diol, polypropylene oxide glycol, polytetrahydrofuran diol, polyethylene glycol adipate glycol, polyadipate -1,4- fourth two
One of alcohol esterdiol is a variety of；The molar ratio of the diisocyanate and dihydric alcohol is 2~2.2:1.
3. calixarene type light-cured polyurethane resin according to claim 1, it is characterised in that the anhydrous solvent is N,
One of dinethylformamide, acetone, tetrahydrofuran, ethyl acetate are a variety of；The dosage of the anhydrous solvent is to make instead
The concentration for answering reactant in system is 20~30wt%.
4. a kind of application of any one of claims 1 to 3 calixarene type light-cured polyurethane resin, it is characterised in that the light
Curable polyurethane resin can be used for self-repair technology field.
5. a kind of coatings containing any one of claims 1 to 3 calixarene type light-cured polyurethane resin, special
Sign is the mass percent of raw material contained by the coating and each raw material are as follows:
Each raw material is mixed according to the above ratio, after being protected from light 30~60min of ultrasound, is spun on aluminium sheet, with a thickness of 0.1~1mm,
Under the conditions of 40~100 DEG C, 60~120min of preliminary drying, then in 500-800mJ/cm2Energy under be exposed solidification, prepare
Calixarene type light-cured polyurethane coatings.
6. coatings according to claim 5, it is characterised in that the reactive diluent is trimethylolpropane tris
One of acrylate, ethoxylated trimethylolpropane triacrylate are a variety of；The photoinitiator is 2- hydroxyl -2-
Methyl-1-phenyl-1- acetone, 1- hydroxy-cyclohexyl phenyl ketone, 2- hydroxyl-4 '-(2- hydroxy ethoxy)-2- methyl phenyl ketone,
One of 2- methyl-1-(4- methyl mercapto phenyl)-2- morpholine-1- acetone is a variety of；The solvent is N, N- dimethyl formyl
One of amine, butanone, dimethyl acetamide, cyclohexanone, ethyl acetate are a variety of.
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| CN109111562B (en) * | 2018-07-23 | 2021-04-30 | 中国科学院深圳先进技术研究院 | Self-repairing polyurethane, preparation method thereof and self-repairing method thereof |
| CN109160995B (en) * | 2018-08-19 | 2021-02-23 | 南京理工大学 | Column [5] arene self-assembly elastomer material and preparation method thereof |
| CN110669188B (en) * | 2019-10-21 | 2020-10-13 | 南京林业大学 | Waterborne polyurethane coating capable of self-repairing through ultraviolet light and preparation method thereof |
| CN111234169B (en) * | 2020-03-17 | 2021-05-28 | 四川大学 | Intelligent material with controllable surface hydrophobicity/super-hydrophobicity and preparation method thereof |
| CN111607317B (en) * | 2020-05-19 | 2021-12-21 | 湖南弘擎电子材料科技有限公司 | Flame-retardant and water-resistant ultraviolet-curing adhesive and preparation method thereof |
| CN112661989A (en) * | 2020-12-22 | 2021-04-16 | 四川大学 | Ultraviolet light post-crosslinking curing polyurethane and preparation and application thereof |
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| JP2014218532A (en) * | 2013-04-30 | 2014-11-20 | 学校法人 関西大学 | Polymer and production method of the same |
| CN104356338A (en) * | 2014-10-30 | 2015-02-18 | 华南理工大学 | Self-repairing polyurethane coating and preparation method thereof |
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