CN105801829B - 2 degree of functionality polycaprolactone polyurethane acrylate of one kind and its preparation method and application - Google Patents
2 degree of functionality polycaprolactone polyurethane acrylate of one kind and its preparation method and application Download PDFInfo
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Abstract
2 degree of functionality polycaprolactone polyurethane acrylate of one kind and its preparation method and application.The invention discloses a kind of 2 degree of functionality polycaprolactone polyurethane acrylate of low viscosity, are prepared via a method which to obtain：It is reacted with isocyanates ethyl acrylate by polycaprolactone glycol and 2 degree of functionality polycaprolactone polyurethane acrylate is made.The invention also discloses the application of the 2 degree of functionality polycaprolactone polyurethane acrylate in preparing UV coating, ink or adhesive.The present invention prepares polycaprolactone polyurethane acrylate using isocyanates ethyl acrylate, reaction process is simple, easily controllable, it is not easy to generate gel because of side reaction, polycaprolactone polyurethane acrylate product viscosity is low, be conducive 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；After the solidification of 2 degree of functionality UV light-solidifying poly caprolactone urethane acrylates of low viscosity, there are the excellent performances such as flexible, good toughness, heat-resisting, weatherability, it can be as the raw material application of UV coating, ink, adhesive.
Description
Technical field
The invention belongs to Material Fields, are related to 2 degree of functionality polycaprolactone polyurethane acrylate of one kind and preparation method thereof
And application, more particularly, to a kind of 2 degree of functionality polycaprolactone polyurethane acrylate of low viscosity 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 (103274967 B of Authorization Notice No. CN)
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 purpose of the present invention is for a kind of 2 degree of functionality polycaprolactone polyurethane acrylate of low viscosity.
It is a further object of the present invention to provide the preparation sides of the 2 degree of functionality polycaprolactone polyurethane acrylate of low viscosity
Method.
It is yet another object of the invention to provide the applications of the 2 degree of functionality polycaprolactone polyurethane acrylate of low viscosity.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of 2 degree of functionality polycaprolactone polyurethane acrylate (Polycaprolactone-based of low viscosity
Polyurethane Acrylate), it is prepared via a method which to obtain：By polycaprolactone glycol (Polycaprolactone
Glycol) with isocyanates ethyl acrylate (2-Isocyanatoethyl Acrylate, abbreviation AOI, No. CAS：13641-
96-8, molecular formula：C6H7NO3, molecular weight：141.12) it reacts and 2 degree of functionality polycaprolactone polyurethane acrylate is made.
Reaction route is as follows：
Polycaprolactone glycol reacts to obtain 2 degree of functionality polycaprolactone polyurethane acrylate with isocyanates ethyl acrylate：
R is：-CH2CH2OCH2CH2-、-CH2CH2-、-CH2CH2CH2CH2-、-
CH2CH2CH2CH2CH2CH2-。
The i.e. described polycaprolactone glycol is with 6- caprolactone monomers (No. CAS：502-44-3, molecular formula：C6H10O2, point
Son amount：114.14), the dihydric alcohols such as initiator such as diethylene glycol, ethylene glycol, neopentyl glycol, 1,4-butanediol, 1,6- hexylene glycols,
Under the effect of the organo-metallic catalysts such as zinc acetate, titanate esters, organotin made from ring-opening polymerisation.Prepare polycaprolactone glycol category
Chemical reaction well known to those skilled in the art.
Preferably, the 2 degree of functionality polycaprolactone polyurethane acrylate are by polycaprolactone glycol and isocyanates
Ethyl acrylate is according to amount ratio 1mol：1.5~2.5mol, prepared by reaction at 60 DEG C~95 DEG C.
It is further preferred that the 2 degree of functionality polycaprolactone polyurethane acrylate be by polycaprolactone glycol with it is different
Cyanate ethyl acrylate is according to amount ratio 1mol：1.8~2.2mol, prepared by reaction at 60 DEG C~95 DEG C.
It is furthermore preferred that the 2 degree of functionality polycaprolactone polyurethane acrylate are by polycaprolactone glycol and isocyanic acid
Ester ethyl acrylate is according to amount ratio 1mol：1.9~2mol is stirred under the action of catalyst, polymerization inhibitor at 80 DEG C~95 DEG C
Prepared by mixing insulation reaction 3~6 hours；Wherein, catalyst is dibutyl tin laurate, and dosage is polycaprolactone glycol
With 100~3000ppm of isocyanates ethyl acrylate gross mass；Polymerization inhibitor can be p-hydroxyanisole or hydroquinone,
Its dosage is 100~5000ppm of polycaprolactone glycol and isocyanates ethyl acrylate gross mass.
Present invention reaction is reacting for isocyano and the hydroxyl of polycaprolactone glycol in isocyanates ethyl acrylate,
Belong to well known synthesis of polyurethane (polyurethanes) reaction.
The preparation method of 2 degree of functionality polycaprolactone polyurethane acrylate of the present invention, including：Polycaprolactone glycol
It is reacted with isocyanates ethyl acrylate and 2 degree of functionality polycaprolactone polyurethane acrylate (i.e. formula (I) compound) is made.
The amount ratio of the polycaprolactone glycol and isocyanates ethyl acrylate is 1mol：1.5~2.5mol, reaction
Temperature is 60 DEG C~95 DEG C.
Preferably, the amount ratio of the polycaprolactone glycol and isocyanates ethyl acrylate is 1mol：1.8~
2.2mol, reaction temperature are 60 DEG C~95 DEG C.
It is further preferred that polycaprolactone glycol and isocyanates ethyl acrylate are according to amount ratio 1mol：1.9~
2mol gathers in 80 DEG C~95 DEG C insulated and stirreds reactions, 3~6 hours obtained 2 degrees of functionality in oneself under the action of catalyst, polymerization inhibitor
Ester polyurethane acrylate；Wherein, catalyst is dibutyl tin laurate, and dosage is polycaprolactone glycol and isocyanates
100~3000ppm of ethyl acrylate gross mass；Polymerization inhibitor can be p-hydroxyanisole or hydroquinone, and dosage is poly-
100~5000ppm of caprolactone diol and isocyanates ethyl acrylate gross mass.
2 degree of functionality polycaprolactone polyurethane acrylate of low viscosity of the present invention is preparing UV coating, ink or is gluing
Application in mixture.
Advantageous effect：
The present invention prepares polycaprolactone polyurethane acrylate using isocyanates ethyl acrylate, reduces reaction step
Suddenly, reaction process is simple, easily controllable, is not easy to generate gel because of side reaction, and polycaprolactone polyurethane acrylate product is viscous
It spends low, is more advantageous to construction and the application of UV formulation products, be not added with for UV sprayings or few solubilizer, meet and be applied to low viscosity
The requirement of coating；After the solidification of 2 degree of functionality UV light-solidifying poly caprolactone urethane acrylates of low viscosity, there is flexible, toughness
The excellent performances such as good, heat-resisting, weatherability, can be as the raw material application of UV coating, ink, adhesive.
Specific implementation mode
Embodiment 1
550 grams of polycaprolactone glycol (Bai Situo CAPA2054, molecular weight 550) is put into 1000mL four-hole boiling flasks, it is different
Cyanate ethyl acrylate 282 grams (2mol), 0.1 gram of catalyst dibutyltin dilaurylate, polymerization inhibitor p-hydroxyanisole 0.9
Gram, it is to slowly warm up within 0.5~4 hour 80 DEG C~85 DEG C insulated and stirreds and reacts discharging in 3~5 hours, the structure that is shown below is made
2 degree of functionality polycaprolactone polyurethane acrylate.
R is：-CH2CH2OCH2CH2, i.e., dihydric alcohol initiator is diethylene glycol in polycaprolactone glycol；
A+b=(550-106)/114=3.8947.
Embodiment 2
500 grams of polycaprolactone glycol (Bai Situo CAPA2100, molecular weight 1000) is put into 1000mL four-hole boiling flasks, it is different
Cyanate ethyl acrylate 141 grams (1mol), 0.1 gram of catalyst dibutyltin dilaurylate, polymerization inhibitor p-hydroxyanisole 0.7
Gram, it is to slowly warm up within 0.5~4 hour 80 DEG C~85 DEG C insulated and stirreds and reacts discharging in 3~5 hours, the structure that is shown below is made
2 degree of functionality polycaprolactone polyurethane acrylate.
R is：Dihydric alcohol initiator is neopentyl glycol i.e. in polycaprolactone glycol；
A+b=(1000-104)/114=7.8596.
Embodiment 3
500 grams of polycaprolactone glycol (Bai Situo CAPA2209, molecular weight 2000) is put into 1000mL four-hole boiling flasks, it is different
Cyanate ethyl acrylate 70.5 grams (0.5mol), 0.1 gram of catalyst dibutyltin dilaurylate, polymerization inhibitor p-hydroxyanisole
It 0.6 gram, is to slowly warm up within 0.5~4 hour 80 DEG C~85 DEG C insulated and stirreds and reacts discharging in 3~5 hours, the knot that is shown below is made
2 degree of functionality polycaprolactone polyurethane acrylate of structure.
R is：1,2- ethylidene (- CH2CH2), i.e., dihydric alcohol initiator is ethylene glycol in polycaprolactone glycol；
A+b=(2000-62)/114=17.
Comparative example 1
275 grams of polycaprolactone glycol (Bai Situo CAPA2054, molecular weight 550) is put into 1000mL four-hole boiling flasks, it is different
Isophorone diisocyanate (IPDI) 222 grams (1mol), 0.1 gram of catalyst dibutyltin dilaurylate are warming up to 60 DEG C~65
DEG C stirring insulation reaction 2~3 hours, is then added 0.9 gram of polymerization inhibitor p-hydroxyanisole, catalyst dibutyltin dilaurylate
0.1 gram, 128 grams of hydroxy-ethyl acrylate 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, system
2 degree of functionality polycaprolactone polyurethane acrylate of the structure that must be shown below.
R is：-CH2CH2OCH2CH2, i.e., dihydric alcohol initiator is diethylene glycol in polycaprolactone glycol；
A+b=(550-106)/114=3.8947；
R1For：
Comparative example 2
500 grams of polycaprolactone glycol (Bai Situo CAPA2100, molecular weight 1000) is put into 1000mL four-hole boiling flasks,
IPDI 222 grams (1mol), 0.12 gram of catalyst dibutyltin dilaurylate, be warming up to 60 DEG C~65 DEG C stirring insulation reactions 2~
3 hours, 1 gram of polymerization inhibitor p-hydroxyanisole, 0.12 gram of catalyst dibutyltin dilaurylate, hydroxy-ethyl acrylate is then added
It 128 grams, is to slowly warm up within 0.5~4 hour 80 DEG C~85 DEG C insulation reactions and discharges for 3~5 hours, the structure that is shown below is made
2 degree of functionality polycaprolactone polyurethane acrylate.
R is：Dihydric alcohol initiator is neopentyl glycol i.e. in polycaprolactone glycol；
A+b=(1000-104)/114=7.8596；
R1For：
Comparative example 3
500 grams of polycaprolactone glycol (Bai Situo CAPA2209, molecular weight 2000) is put into 1000mL four-hole boiling flasks,
IPDI 111 grams (0.5mol), 0.1 gram of catalyst dibutyltin dilaurylate are warming up to 60 DEG C~65 DEG C stirring insulation reactions 2
~3 hours, 0.8 gram of polymerization inhibitor p-hydroxyanisole, 0.1 gram of catalyst dibutyltin dilaurylate, acrylic acid hydroxyl is then added
64 grams of ethyl ester 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, the knot that is shown below is made
2 degree of functionality polycaprolactone polyurethane acrylate of structure.
R is：1,2- ethylidene (- CH2CH2), i.e., dihydric alcohol initiator is ethylene glycol in polycaprolactone glycol；
A+b=(2000-62)/114=17；
R1For：
Embodiment 4
Investigate the viscosity of 2 degree of functionality urethane acrylates made from 1-3 of the embodiment of the present invention and comparative example 1-3.
Test method：NDJ-1 types are rotating to turn viscosimeter, No. 4 rotors, 60 revs/min.Concrete operation step refers to《NDJ-1
Type rotational viscometer operation instructions》.
Viscosity/60 DEG C of unit mPa.s@of 12 degree of functionality polycaprolactone polyurethane acrylate of table
| Comparative example 1 | Embodiment 1 | Comparative example 2 | Embodiment 2 | Comparative example 3 | Embodiment 3 | |
| Viscosity | 4600 | 2200 | 6000 | 2900 | 8100 | 4100 |
1 product comparison ratio of embodiment, 1 product viscosity declines 60 DEG C of 2400mPa.s@, fall 52.17%.
2 product comparison ratio of embodiment, 2 product viscosity declines 60 DEG C of 3100mPa.s@, fall 51.67%.
3 product comparison ratio of embodiment, 3 product viscosity declines 60 DEG C of 4000mPa.s@, fall 49.38%.
Embodiment 5
Raw material
UV resins are 1.：2 degree of functionality aliphatic poly caprolactone urethane acrylate of low viscosity (uses 2 degree of functionality aliphatic
The purpose of urethane acrylate is to increase the flexibility of film, anti-riot to split, cold-resistant thermal circulation performance), it is prepared by embodiment 2.
UV resins are 2.：4 degree of functionality aliphatic urethane acrylate of low viscosity (uses 4 degree of functionality aliphatic polyurethanes third
The purpose of olefin(e) acid ester is the performances such as the hardness for increasing film, intensity, wear-resisting), preparation method is as follows：
1920 grams of anhydrous citric acid (C are put into 6L autoclaves6H8O7, molecular weight 192), 60 grams of potassium formates, heating
To 155 DEG C, start that propylene oxide (C is added dropwise3H6O, molecular weight 58) 3480 grams reacted, 155 DEG C~165 DEG C of temperature control, pressure
0.10~0.40MPa, be added dropwise 3~4 hours, drip off after 155 DEG C~165 DEG C keep the temperature 2~3 hours, be subsequently cooled to 80 DEG C hereinafter,
Discharge to obtain crude product；After the stirring 30 minutes of 60 grams of atlapulgite is added in crude product, clear tetrahydroxy lemon polyether acid is obtained through overanxious
Ester (C24H44O13, molecular weight 540) and 5292 grams, structure is shown below.
Wherein：N=3, a+b+c+d=6.
Tetrahydroxy citric acid polyether ester (C obtained is put into 1000mL four-hole boiling flasks24H44O13, molecular weight 540) and 270
Gram, isocyanates ethyl acrylate 280 grams (1.984mol), 0.3 gram of catalyst dibutyltin dilaurylate, polymerization inhibitor is to hydroxyl
1 gram of methyl phenyl ethers anisole 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, the poly- ammonia of 4 degrees of functionality is made
Ester acrylate, structure are shown below.
Wherein：N=3, a+b+c+d=6.
The viscosity of 4 degree of functionality aliphatic urethane acrylates is measured using viscosity determining procedure same as Example 4
For 60 DEG C of 8000mPa.s@.
UV monomers：Pentaerythritol triacrylate (PETA, Jiangsu Litian Technology Co., Ltd.)；1,6-HD two
Acrylate (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 are 1 in mass ratio：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
It is formed using 4 degree of functionality aliphatic urethane acrylates and 2 degree of functionality aliphatic poly caprolactone polyurethane acrylate resins
Different formulations, various composition dosage are shown in Table 2, and film performance is shown in Table 3.
34 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 (3)
1. a kind of 2 degree of functionality polycaprolactone polyurethane acrylate, it is characterised in that it is prepared via a method which to obtain：By gathering
Caprolactone diol is with isocyanates ethyl acrylate according to amount ratio 1mol：1.9~2mol, in the effect of catalyst, polymerization inhibitor
Under prepared by insulation reaction 3~6 hours is stirred at 80 DEG C~95 DEG C；Wherein, catalyst is dibutyl tin laurate,
Dosage is 100~3000ppm of polycaprolactone glycol and isocyanates ethyl acrylate gross mass；Polymerization inhibitor is para hydroxybenzene first
Ether or hydroquinone, dosage are 100~5000ppm of polycaprolactone glycol and isocyanates ethyl acrylate gross mass.
2. the preparation method of 2 degree of functionality polycaprolactone polyurethane acrylate described in claim 1, it is characterised in that including：
Polycaprolactone glycol is with isocyanates ethyl acrylate according to amount ratio 1mol：1.9~2mol, in catalyst, the work of polymerization inhibitor
It is reacted 3~6 hours in 80 DEG C~95 DEG C insulated and stirreds under and 2 degree of functionality polycaprolactone polyurethane acrylate is made；Wherein, it urges
Agent is dibutyl tin laurate, dosage is polycaprolactone glycol with the 100 of isocyanates ethyl acrylate gross mass~
3000ppm；Polymerization inhibitor is p-hydroxyanisole or hydroquinone, and dosage is polycaprolactone glycol and isocyanates acrylic acid second
100~5000ppm of ester gross mass.
3. 2 degree of functionality polycaprolactone polyurethane acrylate described in claim 1 is in preparing UV coating, ink or adhesive
Application.
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