CN105859584B - One kind being based on the 3 degree of functionality urethane acrylates and its preparation method and application of trihydroxy methyl second (third) alkane - Google Patents
One kind being based on the 3 degree of functionality urethane acrylates and its preparation method and application of trihydroxy methyl second (third) alkane Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33351—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group acyclic
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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
- C09D11/00—Inks
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
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Abstract
The invention discloses a kind of 3 degree of functionality urethane acrylates, are prepared via a method which to obtain：It is first reacted under the action of catalyst with ethylene oxide or propylene oxide by trimethylolethane or trimethylolpropane and trihydroxy polyethers is made, trihydroxy polyethers is reacted with isocyanates ethyl acrylate again is made 3 degree of functionality urethane acrylates.The present invention prepares urethane acrylate using isocyanates ethyl acrylate, reduce reaction step, reaction process is simple, easily controllable, it is not easy to generate gel because of side reaction, urethane acrylate product viscosity is low, it is more advantageous to construction and the application of UV formulation products, is not added with for UV sprayings or few solubilizer, satisfaction is applied to the requirement of low-viscosity dope；After the solidification of 3 degree of functionality UV curable urethane acrylates of low viscosity, there are the excellent performances such as high hardness, wear-resisting, scratch resistance, heat-resisting, weatherability, it can be in the raw material application as UV coating, ink, adhesive.
Description
Technical field
The invention belongs to Material Fields, are related to a kind of 3 degree of functionality polyurethane acroleic acids being based on trihydroxy methyl second (third) alkane
Ester and its preparation method and application, more particularly, to a kind of 3 degree of functionality polyurethane of low viscosity being based on trihydroxy methyl second (third) alkane
Acrylate and its preparation method and application.
Background technology
Stringent limitation with legislations of environmental protection to solvent with the rapid development of science and technology, UV photocuring macromolecule materials
Material is increasingly valued by people.UV photo-curing materials have the excellent performances such as quick solidifying, low energy consumption, pollutes less, is efficient,
The fields such as coating, printing and electronics industry thus are widely used in, are quickly grown in recent years.Urethane acrylate
(polyurethane acrylate, PUA) is a kind of important Photocurable oligomers, has low stimulation, curing rate fast, high
The excellent performances such as the transparency, stretch-proof, cohesive energy height, are widely used in the fields such as light-curable ink, coating, adhesive, the U.S.,
Japan, countries in Europe are widely used.In recent years, the rise with UV-curing technology in China, novel photocuring material
Expect that the raw material purposes as UV coating, ink, adhesive is more and more wider, usage amount is increasing year by year.
Applicant discloses one kind 3 in Chinese patent ZL201310146346.8 (Authorization Notice No. CN 103274967B)
Degree of functionality urethane acrylate is prepared via a method which to obtain：Under the action of catalyst by 2,2- dihydromethyl propionic acids first
Prepared by being reacted with ethylene oxide or propylene oxide trihydroxy polyether ester, trihydroxy polyether ester (are selected from diisocyanate again
One kind in HDI, IPDI, HMDI, MDI) and hydroxy-ethyl acrylate or hydroxypropyl acrylate reaction be made 3 degree of functionality polyurethane third
Olefin(e) acid ester.3 degree of functionality polyurethane propylene are prepared as a result of diisocyanate and hydroxy-ethyl acrylate or hydroxypropyl acrylate
Acid esters, reaction process step is more, relatively cumbersome, and production process is not easy to control, because the presence of side reaction will produce the risk of gel.
Light-cured resin is the matrix resin of photocureable coating, wide in variety, is widely used.With in global range to environment
The pay attention to day by day of problem, light-cured resin will be fast-developing with the development of photocureable coating.It develops more environmentally-friendly, viscous
Spend the striving direction that low, comprehensive performance is more excellent light-cured resin is WeiLai Technology personnel.
Invention content
The 3 degree of functionality polyurethane acroleic acid of one kind that the purpose of the present invention is provide Chinese patent ZL201310146346.8
Ester and its preparation method and application is improved or expands, and provides a kind of 3 function of low viscosity being based on trihydroxy methyl second (third) alkane
Spend urethane acrylate.
It is a further object of the present invention to provide the preparation methods of the 3 degree of functionality urethane acrylate of low viscosity.
It is yet another object of the invention to provide the applications of the 3 degree of functionality urethane acrylate of low viscosity.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of 3 degree of functionality urethane acrylate of low viscosity, is prepared via a method which to obtain：First by trimethylolethane
Or trimethylolpropane reacts with ethylene oxide or propylene oxide and trihydroxy polyethers is made under the action of catalyst, trihydroxy is poly-
Ether again with isocyanates ethyl acrylate (2-Isocyanatoethyl Acrylate, abbreviation AOI, No. CAS：13641-96-8,
Molecular formula：C6H7NO3, molecular weight：141.12) it reacts and 3 degree of functionality urethane acrylates is made.
Wherein,
First step reaction route is as follows：
R2Group is：-CH3Or-C2H5；R3Group is：- H or-CH3；
Work as n=2, R3For-H when, reacted with trimethylolethane or trimethylolpropane for ethylene oxide；Work as n=3, R3
For-CH3When, it is reacted with trimethylolethane or trimethylolpropane for propylene oxide；Wherein a+b+c=3~15.
The preparation of trihydroxy polyethers includes the following steps：Trimethylolethane or trimethylolpropane are in catalyst action
Under, be added dropwise ethylene oxide or propylene oxide reaction in 155 DEG C~165 DEG C in autoclave, reaction pressure control 0.2~
0.6MPa is dripped and is kept the temperature 1~3 hour again for 155 DEG C~165 DEG C after ethylene oxide or propylene oxide, be subsequently cooled to 80 DEG C with
Under, atlapulgite is added and stirs 0.5~2 hour, carries out cycle press filtration until clear, obtains trihydroxy polyethers；Wherein, described
Trimethylolethane or the amount ratio of trimethylolpropane and ethylene oxide or propylene oxide be 1mol：3~15mol, preferably
For 1mol：5~6.5mol.
The catalyst is the arbitrary ratio of the one or more in sodium formate, potassium formate, sodium benzoate, Potassium Benzoate
Example mixture, catalyst amount are trimethylolethane or trimethylolpropane and ethylene oxide or propylene oxide gross mass
0.5wt%~5wt%, preferably 1wt%~5wt%.
3 degree of functionality urethane acrylate of the present invention, obtained trihydroxy polyethers and isocyanates acrylic acid
Ethyl ester is according to amount ratio 1mol：The 3 degree of functionality polyurethane propylene are made in 60 DEG C~95 DEG C reactions in 2.8~3.1mol
Acid esters.
Preferably, obtained trihydroxy polyethers and isocyanates ethyl acrylate are according to amount ratio 1mol：2.9~
3mol stirs 3~6 hours obtained 3 degree of functionality polyurethane of insulation reaction under the action of catalyst, polymerization inhibitor in 80 DEG C~95 DEG C
Acrylate；Wherein, polymerization inhibitor can be p-hydroxyanisole or hydroquinone, and dosage is trihydroxy polyethers and isocyanates
100~5000ppm of ethyl acrylate gross mass；Catalyst is dibutyl tin laurate, dosage be trihydroxy polyethers with
100~3000ppm of isocyanates ethyl acrylate gross mass.
Second step reaction route is as follows：
Trihydroxy polyethers reacts to obtain 3 degree of functionality urethane acrylates with isocyanates ethyl acrylate：
R1For：
R2For：-CH3Or-C2H5；N=2 or 3, a+b+c=3~15；
The reaction that the first step of the present invention prepares trihydroxy polyethers is 3 hydroxyls in trimethylolethane or trimethylolpropane
The opening (anionic polymerisation) that base is carried out with epoxy third (second) alkane is well known organic chemical reactions, in the present invention
Under reaction condition, epoxy third (second) alkane is gaseous state, and continuous feed finishes, then insulation reaction 1~3 hour, until in autoclave
Pressure drops to constant, i.e., epoxy third (second) alkane reacts completely, and conversion ratio is 99.9% or more；Second step reaction is isocyanates
Isocyano in ethyl acrylate is reacted with hydroxyl, belongs to well known synthesis of polyurethane (polyurethanes) reaction.
The preparation method of 3 degree of functionality urethane acrylate of the present invention, includes the following steps：First by trihydroxy methyl
Ethane or trimethylolpropane react with ethylene oxide or propylene oxide and trihydroxy polyethers are made under the action of catalyst, three hydroxyls
Base polyethers again with isocyanates ethyl acrylate (No. CAS：13641-96-8, molecular formula：C6H7NO3, molecular weight：141.12) anti-
3 degree of functionality urethane acrylates (i.e. formula (II) compound) should be made.
Wherein, the preparation of trihydroxy polyethers includes the following steps：Trimethylolethane or trimethylolpropane are in catalyst
Under effect, ethylene oxide or propylene oxide reaction is added dropwise in 155 DEG C~165 DEG C in autoclave, reaction pressure control exists
0.2~0.6MPa drips and keeps the temperature 1~3 hour again for 155 DEG C~165 DEG C after ethylene oxide or propylene oxide, is subsequently cooled to 80
It DEG C is stirred 0.5~2 hour hereinafter, atlapulgite is added, carries out cycle press filtration until clear, obtain trihydroxy shown in formula (I)
Polyethers；Wherein, the trimethylolethane or trimethylolpropane and the amount ratio of ethylene oxide or propylene oxide are 1mol：
3~15mol, preferably 1mol：5~6.5mol.
The catalyst is the arbitrary ratio of the one or more in sodium formate, potassium formate, sodium benzoate, Potassium Benzoate
Example mixture, catalyst amount are trimethylolethane or trimethylolpropane and ethylene oxide or propylene oxide gross mass
0.5wt%~5wt%, preferably 1wt%~5wt%.
The preparation method of 3 degree of functionality urethane acrylate of the present invention, obtained trihydroxy polyethers and isocyanide
Acid esters ethyl acrylate is according to amount ratio 1mol：3 degrees of functionality are made in 60 DEG C~95 DEG C reactions in 2.8~3.1mol
Urethane acrylate.
Preferably, obtained trihydroxy polyethers and isocyanates ethyl acrylate are according to amount ratio 1mol：2.9~
3mol stirs 3~6 hours obtained 3 degree of functionality polyurethane of insulation reaction under the action of catalyst, polymerization inhibitor in 80 DEG C~95 DEG C
Acrylate；Wherein, polymerization inhibitor can be p-hydroxyanisole or hydroquinone, and dosage is trihydroxy polyethers and isocyanates
100~5000ppm of ethyl acrylate gross mass；Catalyst is dibutyl tin laurate, dosage be trihydroxy polyethers with
100~3000ppm of isocyanates ethyl acrylate gross mass.
3 degree of functionality urethane acrylate of low viscosity of the present invention is in preparing UV coating, ink or adhesive
Using.
Advantageous effect：
The present invention prepares that trihydroxy polyethers used catalyst is different from traditional method, and the catalyst used in conventional method is
Sodium hydroxide, potassium hydroxide, after polymerisation is complete, the aqueous acid that needs to phosphorate is neutralized, then high vacuum dehydration, pressure
Filter obtains trihydroxy polyethers；The present invention is using the one or more in sodium formate, potassium formate, sodium benzoate, Potassium Benzoate
Arbitrary proportion mixture after having polymerize, does not need acid adding and water is added to neutralize, and does not need high vacuum dehydration, only need to add atlapulgite mistake
Consider, filter residue passes through water-soluble, catalyst-solvent, filters out atlapulgite, and the aqueous solution of catalyst realizes recycling again through evaporative crystallization
It utilizes, reaction process belongs to green catalysis and clean manufacturing.
The present invention prepares urethane acrylate using isocyanates ethyl acrylate, reduces reaction step, reacted
Journey is simple, easily controllable, is not easy to generate gel because of side reaction, and urethane acrylate product viscosity is low, is more advantageous to construction
And the application of UV formulation products, it is not added with for UV sprayings or few solubilizer, satisfaction is applied to the requirement of low-viscosity dope；Low viscosity
After the solidification of 3 degree of functionality UV curable urethane acrylates, there are the Optimalities such as high hardness, wear-resisting, scratch resistance, heat-resisting, weatherability
Can, it can be in the raw material application as UV coating, ink, adhesive.
Specific implementation mode
Embodiment 1
1200 grams of trimethylolethanes (CAS 77-85-0, molecular formula C are put into 6L autoclaves5H12O3, molecule
120.147), 38 grams of sodium formates are warming up to 155 DEG C to amount, start that ethylene oxide (C is added dropwise2H4O, molecular weight 44) 2200 grams carry out it is anti-
It answers, 155 DEG C~165 DEG C, 0.2~0.6MPa of pressure of temperature control, is added dropwise 3~4 hours, 155 DEG C~165 DEG C heat preservations 2~3 are small after dripping off
When, 80 DEG C are subsequently cooled to hereinafter, the crude product that discharges to obtain；After the stirring 30 minutes of 40 grams of atlapulgite is added in crude product, through recycling press filtration
Obtain clear trihydroxy polyethers (C15H32O8, molecular weight 340) and 3455.4 grams, shown in structure such as formula (I), wherein：N=2, a+b+
C=5.
Trihydroxy polyethers (C obtained is put into 1000mL four-hole boiling flasks15H32O8, molecular weight 340) and 170 grams, isocyanic acid
Ester ethyl acrylate 211.5 grams (1.5mol), 0.3 gram of catalyst dibutyltin dilaurylate, polymerization inhibitor p-hydroxyanisole 1
Gram, it is to slowly warm up within 0.5~4 hour 80 DEG C~85 DEG C insulation reactions and discharges for 3~5 hours, 3 degree of functionality polyurethane acroleic acids are made
Ester, shown in structure such as formula (II), wherein：
R1For：
N=2, a+b+c=5.
Embodiment 2
1340 grams of trimethylolpropanes (CAS 77-99-6, molecular formula C are put into 6L autoclaves6H14O3, molecule
134.1736), 60 grams of potassium formates are warming up to 155 DEG C to amount, start that propylene oxide (C is added dropwise3H6O, molecular weight 58) 3480 grams carry out
Reaction, 155 DEG C~165 DEG C, pressure 0.2-0.6MPa of temperature control are added dropwise 3~4 hours, 155 DEG C~165 DEG C heat preservations 2~3 after dripping off
Hour, 80 DEG C are subsequently cooled to hereinafter, the crude product that discharges to obtain；After the stirring 30 minutes of 60 grams of atlapulgite is added in crude product, pressed through cycle
Consider to obtain clear trihydroxy polyethers (C24H50O9, molecular weight 482) and 4722.4 grams, shown in structure such as formula (I), wherein：N=3, a+
B+c=6.
Trihydroxy polyethers (C obtained is put into 1000mL four-hole boiling flasks24H50O9, molecular weight 482) and 241 grams, isocyanic acid
Ester ethyl acrylate 210 grams (1.488mol), 0.3 gram of catalyst dibutyltin dilaurylate, 1 gram of p-hydroxyanisole, 0.5~
It is to slowly warm up within 4 hours 80 DEG C~85 DEG C insulation reactions to discharge for 3~5 hours, 3 degree of functionality urethane acrylates, structure is made
As shown in formula (II), wherein：
R1For：
N=3, a+b+c=6.
Embodiment 3
3 degrees of functionality are prepared with the preparation method of the embodiment 1-2 provided in Chinese patent ZL201310146346.8
Urethane acrylate, 1-2, it is poly- to investigate 3 degrees of functionality made from 1-2 of the embodiment of the present invention and comparative example 1-2 as a comparison case
The viscosity of urethane acrylate.
Test method：NDJ-1 type rotary viscosimeters, No. 4 rotors, 60 revs/min.Concrete operation step refers to《NDJ-1
Type rotational viscometer operation instructions》.
The viscosity of 13 degree of functionality urethane acrylate of table
| Comparative example 1 | Embodiment 1 | Comparative example 2 | Embodiment 2 | |
| Viscosity | 7200mPa.s@60℃ | 3600mPa.s@60℃ | 7700mPa.s@60℃ | 3900mPa.s@60℃ |
1 product comparison ratio of embodiment, 1 product viscosity declines 60 DEG C of 3600mPa.s@, fall 50.00%.
2 product comparison ratio of embodiment, 2 product viscosity declines 60 DEG C of 3800mPa.s@, fall 49.35%.
Embodiment 4
Raw material
UV resins are 1.：3 degree of functionality aliphatic urethane acrylate of low viscosity prepared by embodiment 2 (uses 3 degree of functionality fat
The purpose of fat adoption urethane acrylate is the performances such as the hardness for increasing film, intensity, wear-resisting)；
UV resins are 2.：2 degree of functionality aliphatic urethane acrylate of low viscosity (uses 2 degree of functionality aliphatic polyurethanes third
The purpose of olefin(e) acid ester is to increase the flexibility of film, anti-riot to split, cold-resistant thermal circulation performance), preparation method is as follows：
Polycarbonate glycol (UBE Ube Industries, Ltd UH-100, molecular weight are put into 1000mL four-hole boiling flasks
1000) 500 grams, isocyanates ethyl acrylate 141 grams (1mol), 0.1 gram of catalyst dibutyltin dilaurylate, polymerization inhibitor pair
0.7 gram of hydroxyanisol is to slowly warm up to 80 DEG C~85 DEG C insulation reactions for 0.5~4 hour and discharges for 3~5 hours, such as following formula is made
2 degree of functionality polycarbonate polyurethane acrylate of shown structure.
R is：-CH2CH2CH2CH2CH2CH2, i.e., glycol monomer is 1,6- hexylene glycols in polycarbonate glycol；
N=(1000-118)/144=6.1250.
Use the viscosity determining procedure that embodiment 3 is recorded measure the viscosity of 4 degree of functionality urethane acrylates obtained for
3700mPa.s@60℃。
UV monomers：Double pentaerythritol methacrylate (DPHA, Jiangsu Litian Technology Co., Ltd.)；1,6-HD
Diacrylate (HDDA, Jiangsu profit field).
Photoinitiator：1173, Nanjing Wa Li Chemical Industry Science Co., Ltd.
Auxiliary agent：Tego432, Tego92, German enlightening are high.
Mixed solvent：Butyl acetate, toluene, methylisobutylketone in mass ratio 1：1：1 mixing.
Instrument and equipment
LT-1002 type uv cure machines, blue sky Te Deng Development Co., Ltds；QFZ type paint film adhesion analyzers, Tianjin
Ke Lian Material Testing Machine factory of city；RCA paper tape wear resistant instruments, Shanghai modern environment project research institute；Water-bath；Cold cycling is set
It is standby.
The preparation of coating
The UV resins of certain mass are weighed, UV monomers, mixed solvent, photoinitiator, auxiliary agent is then added, stirs evenly,
It is configured to coating.The proportioning of coating is shown in Table 2.
The proportioning of 2 coating of table
The preparation and solidification of film
The ABS plastic plank of 10cm × 10cm is selected, first in one layer of thermoplastic acrylic resin white bottom of its surface spraying
Paint, 60 DEG C are toasted 3h, then the UV coating prepared according to table 2 in its surface spraying, and coating thickness is about 20 μm, on photo solidification machine
Solidification, makes cured film reach surface drying, is characterized with tack method, records hardening time.
Performance test
Hardening time：Experiment uses tack method, touches coating surface with finger, if do not felt tacky, that is, thinks paint film
Surface is cured.
Pencil hardness：It is measured with reference to GB 6739-86 film pencil hardness methods.
Adhesive force：It is measured with reference to GB/T 1720-88 film adhesive measuring methods.It is divided into 7 grades, 1 grade best, and 7 grades worst.
Wearability：RCA is tested, 175g, 500 ± 50 times.
Water boiling resistance：With reference to standard GB/T/T 1733《Paint film water resistance measuring method》.
Cold-resistant thermal cycle：
(1) range and explanation：Plastic paint because moisture and hot ageing or losses of plasticizer, or both and it sometimes appear that cracking
Trend, using the degree for being alternately exposed to can to measure paint film in climate cabinet and household freezer and whether cracking and cracking.
(2) instrument：1. damp heat box, 2. household freezer, 3. colour photometer, 4. draws lattice device.
(3) assay method：1. test piece is put into relative temperature 100%, temperature be in 38 DEG C of incubator hot tank for 24 hours.
The placement of model should be with a vertical 0-30 degree angle, and plate plate is required mutually to be not in contact with each other during the test.2. after for 24 hours, standing
Model is moved to 20h in the household freezer of (- 23 ± 1.5) DEG C, 30S is at most not to be exceeded in transfer time.3. model is taken out,
4h is placed at room temperature, and so in total 48h is a cycle, during which can carry out stage evaluation.4. 15 cycles are carried out altogether, it is then right
Model appearance, color, adhesive force are tested.
(4) result indicates：Film should be without cracking, discoloration, adhesive force decline or other defects.
(5) reference standard：Unite States Standard AAMA 615-02《The industry rule of high-performance organic coating on plastic material
Model, performance requirement and test method》.(1)
Results and discussion, influence of the resin to film performance
UV resins are the main bodys of UV coating, its performance substantially determines the main performance of film after solidification.This experiment
Different formulations are formed using 3 degree of functionality aliphatic urethane acrylates and 2 degree of functionality aliphatic urethane acrylate resins,
Various composition dosage is shown in Table 2, and film performance is shown in Table 3.
33 degree of functionality urethane acrylate of table and 2 degree of functionality urethane acrylate different ratios are to coating property
It influences
Bibliography：(1) the Yu Yingying coatings industries method of inspection and the Beijing instrument complete works：Chemical Industry Press,
2007：525.
1173 explanation of attached photoinitiator：
Manufacturer：Nanjing Wa Li Chemical Industry Science Co., Ltd
Chemical name：2- hydroxy-2-methyl -1- phenyl -1- acetone
English name：2-Hydroxy-2-methyl-1-phenyl-propan-1-one
CAS NO：7473-98-5
Molecular formula：C10H12O
Molecular weight：164.2
Chemical structural formula：
Technical indicator：
Appearance：It is colourless to light yellow transparent liquid
Purity：>=99.0%
Boiling point：80-81 DEG C (degree Celsius)
Light transmittance：425nm >=99.0%；500nm >=99.3%
Fugitive constituent：≤ 0.2%
Ash：≤ 0.10%
Using：
1173 are suitable for acrylic acid photocuring varnish system, such as the varnish etc. of timber, metal, paper, plastics.1173 is special
Do not recommend in the UV-curing coating for needing to be subjected to chronic sun exposure and color inhibition, since 1173 be liquid, is highly susceptible to altogether
It is mixed, so being suitble to be used in compounding with other photoinitiators, it is proposed that additive amount is 1~4%w/w.
Claims (6)
1. a kind of 3 degree of functionality urethane acrylates based on trimethylolethane or trimethylolpropane, it is characterised in that：It is logical
Following method is crossed to be prepared：First by trimethylolethane or trimethylolpropane under the action of catalyst with ethylene oxide or ring
Ethylene Oxide reacts and trihydroxy polyethers is made, and obtained trihydroxy polyethers is with isocyanates ethyl acrylate according to amount ratio
1mol：2.9~3mol stirs 3~6 hours obtained 3 officials of insulation reaction under the action of catalyst, polymerization inhibitor in 80 DEG C~95 DEG C
Energy degree urethane acrylate；Wherein, polymerization inhibitor be p-hydroxyanisole or hydroquinone, dosage be trihydroxy polyethers with it is different
100~5000ppm of cyanate ethyl acrylate gross mass, catalyst are dibutyl tin laurate, and dosage is trihydroxy
100~3000ppm of polyethers and isocyanates ethyl acrylate gross mass.
2. 3 degree of functionality urethane acrylate according to claim 1, it is characterised in that：The preparation packet of trihydroxy polyethers
Include following steps：Trimethylolethane or trimethylolpropane under the action of catalyst, in autoclave in 155 DEG C~
165 DEG C are added dropwise ethylene oxide or propylene oxide reaction, and reaction pressure control drips ethylene oxide or ring in 0.2~0.6MPa
1~3 hour is kept the temperature again for 155 DEG C~165 DEG C, be subsequently cooled to 80 DEG C hereinafter, atlapulgite stirring 0.5~2 is added after Ethylene Oxide
Hour, cycle press filtration is carried out until clear, obtains trihydroxy polyethers；Wherein, the trimethylolethane or trihydroxy methyl
Propane is 1mol with the amount ratio of ethylene oxide or propylene oxide：3~15mol.
3. 3 degree of functionality urethane acrylate according to claim 2, it is characterised in that：The catalyst is formic acid
One or more kinds of arbitrary proportion mixtures in sodium, potassium formate, sodium benzoate, Potassium Benzoate；Catalyst amount is three hydroxyls
Methyl ethane or trimethylolpropane and ethylene oxide or 0.5wt%~5wt% of propylene oxide gross mass.
4. the preparation method of 3 degree of functionality urethane acrylate described in claim 1, it is characterised in that：Include the following steps：
It is first reacted under the action of catalyst with ethylene oxide or propylene oxide by trimethylolethane or trimethylolpropane and is made three
Hydroxy polyethers, trihydroxy polyethers is reacted with isocyanates ethyl acrylate again is made 3 degree of functionality urethane acrylates.
5. the preparation method of 3 degree of functionality urethane acrylate according to claim 4, it is characterised in that：Trihydroxy is poly-
The preparation of ether includes the following steps：Trimethylolethane or trimethylolpropane under the action of catalyst, in autoclave
Ethylene oxide is added dropwise in 155 DEG C~165 DEG C or propylene oxide reaction, reaction pressure are controlled in 0.2~0.6MPa, drips epoxy
1~3 hour is kept the temperature again for 155 DEG C~165 DEG C, be subsequently cooled to 80 DEG C and stirred hereinafter, atlapulgite is added after ethane or propylene oxide
It mixes 0.5~2 hour, carries out cycle press filtration until clear, obtains trihydroxy polyethers；Wherein, the trimethylolethane or
Trimethylolpropane is 1mol with the amount ratio of ethylene oxide or propylene oxide：3~15mol；
The catalyst is that one or more kinds of arbitrary proportions in sodium formate, potassium formate, sodium benzoate, Potassium Benzoate mix
Object, catalyst amount are trimethylolethane or trimethylolpropane and ethylene oxide or the 0.5wt% of propylene oxide gross mass
~5wt%.
6. application of the 3 degree of functionality urethane acrylate described in claim 1 in preparing UV coating, ink or adhesive.
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| CN109053994B (en) * | 2018-08-09 | 2020-11-06 | 黑龙江省科学院石油化学研究院 | Comb-shaped structure polyurethane acrylate and preparation method thereof |
| CN110204685B (en) * | 2019-05-27 | 2020-09-22 | 华南理工大学 | Tri-functionality polyurethane acrylate resin and preparation method and application thereof |
| CN110714336B (en) * | 2019-09-26 | 2022-08-05 | 江苏利田科技有限公司 | 9-functionality-degree PUA-based ultraviolet-curing coating adhesive for textile fabric and preparation method and application thereof |
| CN115612041A (en) * | 2021-07-15 | 2023-01-17 | 道生天合材料科技(上海)股份有限公司 | Resin composition, polyurethane material, polyurethane composite material and preparation method |
| CN114957645B (en) * | 2022-05-23 | 2024-01-19 | 武汉中科先进材料科技有限公司 | Photo-curing super-hydrophilic coating composition for ABS (Acrylonitrile butadiene styrene) substrate and preparation method of coating of photo-curing super-hydrophilic coating composition |
| CN115490844A (en) * | 2022-10-27 | 2022-12-20 | 句容宁武新材料股份有限公司 | Preparation method of trimethylolethane polyether polyol |
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