CN105801829A - 2-functionality-degree polycaprolactone urethane acrylate and preparation method and application thereof - Google Patents
2-functionality-degree polycaprolactone urethane acrylate and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to 2-functionality-degree polycaprolactone urethane acrylate and a preparation method and application thereof, and discloses low-viscosity 2-functionality-degree polycaprolactone urethane acrylate. The preparation method comprises the step that polycaprolactone glycol and isocyanate ethyl acrylate react to prepare 2-functionality-degree polycaprolactone urethane acrylate. The invention further discloses application of 2-functionality-degree polycaprolactone urethane acrylate to preparation of UV coatings or ink or adhesives. Isocyanate ethyl acrylate is adopted for preparing polycaprolactone urethane acrylate, the reaction process is simple and easy to control, the situation that gel is generated due to side reactions is not likely to happen, the polycaprolactone urethane acrylate product is low in viscosity and is beneficial to construction and application to UV formula products, when polycaprolactone urethane acrylate is used for UV spraying, no solvent or little solvent is added, and the requirement for application to the low-viscosity coatings is met. After low-viscosity 2-functionality-degree UV photocuring polycaprolactone urethane acrylate is cured, the excellent performance of good flexibility, good toughness, heat resistance, weather fastness and the like is achieved, and 2-functionality-degree polycaprolactone urethane acrylate can be applied as a raw material of the UV coatings, the ink and the adhesives.
Description
Technical field
The invention belongs to Material Field, relate to a kind of 2 degree of functionality polycaprolactone polyurethane acrylate and its preparation method and application, especially relate to a kind of low viscosity 2 degree of functionality polycaprolactone polyurethane acrylate and its preparation method and application.
Background technology
Along with the strict of solvent is limited by developing rapidly of science and technology with legislations of environmental protection, UV photocuring macromolecular material is increasingly subject to people's attention.The premium properties such as UV photo-curing material has quick solidifying, energy consumption is low, pollute less, efficiency is high, thus it is widely used in the fields such as coating, printing and electronics industry, development in recent years is rapid.Urethane acrylate (polyurethaneacrylate, PUA) it is a kind of important Photocurable oligomers, the premium properties such as have that low stimulation, curing rate be fast, high transparent, stretch-proof, cohesive energy are high, it is widely used in the fields such as light-curable ink, coating, adhesive, is widely used at the U.S., Japan, countries in Europe.In recent years, along with UV-curing technology is in the rise of China, novel photo-curing material as UV coating, ink, binding agent raw material purposes increasingly wider, make consumption increase year by year.
Applicant discloses a kind of 3 degree of functionality urethane acrylates at Chinese patent ZL201310146346.8 (Authorization Notice No. CN103274967B), it is prepared via a method which to obtain: first by 2,2-dihydromethyl propionic acid under catalyst action with oxirane or propylene oxide reaction and prepared trihydroxy polyether ester, trihydroxy polyether ester reacts prepare 3 degree of functionality urethane acrylates with diisocyanate (one in HDI, IPDI, HMDI, MDI) and 2-(Acryloyloxy)ethanol or Hydroxypropyl acrylate again.Preparing 3 degree of functionality urethane acrylates owing to have employed diisocyanate and 2-(Acryloyloxy)ethanol or Hydroxypropyl acrylate, course of reaction step is many, relatively cumbersome, and production process is wayward, because the existence of side reaction can produce the risk of gel.
Light-cured resin is the matrix resin of photocureable coating, wide in variety, is widely used.Along with pay attention to day by day to environmental problem in global range, light-cured resin will be fast-developing along with the development of photocureable coating.Develop striving direction more environmentally-friendly, that viscosity is low, combination property is more excellent light-cured resin is WeiLai Technology personnel.
Summary of the invention
It is an object of the invention to for a kind of low viscosity 2 degree of functionality polycaprolactone polyurethane acrylate.
The preparation method that it is a further object of the present invention to provide this low viscosity 2 degree of functionality polycaprolactone polyurethane acrylate.
It is yet another object of the invention to provide the application of this low viscosity 2 degree of functionality polycaprolactone polyurethane acrylate.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of low viscosity 2 degree of functionality polycaprolactone polyurethane acrylate (Polycaprolactone-basedPolyurethaneAcrylate), it is prepared via a method which to obtain: by polycaprolactone glycol (Polycaprolactoneglycol) and isocyanates ethyl acrylate (2-IsocyanatoethylAcrylate, it is called for short AOI, No. CAS: 13641-96-8, molecular formula: C6H7NO3, molecular weight: 141.12) and the prepared 2 degree of functionality polycaprolactone polyurethane acrylate of reaction.
Reaction scheme is as follows:
Polycaprolactone glycol and isocyanates ethyl acrylate react to obtain 2 degree of functionality polycaprolactone polyurethane acrylate:
R is :-CH2CH2OCH2CH2-、-CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2CH2CH2CH2-。
Namely described polycaprolactone glycol be with 6-caprolactone monomer (No. CAS: 502-44-3, molecular formula: C6H10O2, molecular weight: 114.14), initiator such as diethylene glycol, ethylene glycol, neopentyl glycol, BDO, the dihydroxylic alcohols such as 1,6-hexanediol, under the organo-metallic catalyst effects such as zinc acetate, titanate esters, organotin, ring-opening polymerisation prepares.Preparation polycaprolactone glycol belongs to chemical reaction as well known to those skilled in the art.
Preferably, 2 described degree of functionality polycaprolactone polyurethane acrylate are according to amount ratio 1mol:1.5～2.5mol by polycaprolactone glycol and isocyanates ethyl acrylate, reaction at 60 DEG C～95 DEG C and prepare.
It is further preferred that 2 described degree of functionality polycaprolactone polyurethane acrylate are according to amount ratio 1mol:1.8～2.2mol by polycaprolactone glycol and isocyanates ethyl acrylate, reaction at 60 DEG C～95 DEG C and prepare.
Preferred, 2 described degree of functionality polycaprolactone polyurethane acrylate are according to amount ratio 1mol:1.9～2mol by polycaprolactone glycol and isocyanates ethyl acrylate, catalyst, polymerization inhibitor effect under at 80 DEG C～95 DEG C, stir insulation reaction 3～6 hours and prepare；Wherein, catalyst is dibutyl tin laurate, and its consumption is 100～3000ppm of polycaprolactone glycol and isocyanates ethyl acrylate gross mass；Polymerization inhibitor can be MEHQ or hydroquinone, and its consumption is 100～5000ppm of polycaprolactone glycol and isocyanates ethyl acrylate gross mass.
Present invention reaction is the reaction of the isocyano in isocyanates ethyl acrylate and the hydroxyl of polycaprolactone glycol, belongs to known synthesis of polyurethane (polyurethanes) reaction.
The preparation method of 2 degree of functionality polycaprolactone polyurethane acrylate of the present invention, including: polycaprolactone glycol and isocyanates ethyl acrylate react and prepare 2 degree of functionality polycaprolactone polyurethane acrylate (i.e. formula (I) compound).
The amount ratio of described polycaprolactone glycol and isocyanates ethyl acrylate is 1mol:1.5～2.5mol, and reaction temperature is 60 DEG C～95 DEG C.
Preferably, the amount ratio of described polycaprolactone glycol and isocyanates ethyl acrylate is 1mol:1.8～2.2mol, and reaction temperature is 60 DEG C～95 DEG C.
It is preferred that, polycaprolactone glycol and isocyanates ethyl acrylate according to amount ratio 1mol:1.9～2mol, catalyst, polymerization inhibitor effect under react 3～6 hours in 80 DEG C～95 DEG C insulated and stirred and to prepare 2 degree of functionality polycaprolactone polyurethane acrylate；Wherein, catalyst is dibutyl tin laurate, and its consumption is 100～3000ppm of polycaprolactone glycol and isocyanates ethyl acrylate gross mass；Polymerization inhibitor can be MEHQ or hydroquinone, and its consumption is 100～5000ppm of polycaprolactone glycol and isocyanates ethyl acrylate gross mass.
The low viscosity 2 degree of functionality polycaprolactone polyurethane acrylate of the present invention application in preparing UV coating, ink or binding agent.
Beneficial effect:
The present invention adopts isocyanates ethyl acrylate to prepare polycaprolactone polyurethane acrylate, decrease reactions steps, course of reaction is simple, easily controllable, gel is not easily produced because of side reaction, polycaprolactone polyurethane acrylate product viscosity is low, it is more beneficial for the application of construction and UV formulation product, is not added with for UV spraying or few solubilizer, meets the requirement being applied to low-viscosity dope；After low viscosity 2 degree of functionality UV light-solidifying poly caprolactone urethane acrylate solidifies, there is the premium properties such as flexible, good toughness, heat-resisting, weatherability, it is possible to the raw material as UV coating, ink, binding agent is applied.
Detailed description of the invention
Embodiment 1
1000mL four-hole boiling flask puts into polycaprolactone glycol (Bai Situo CAPA2054, molecular weight 550) 550 grams, isocyanates ethyl acrylate 282 grams (2mol), catalyst dibutyltin dilaurylate 0.1 gram, polymerization inhibitor MEHQ 0.9 gram, within 0.5～4 hour, it is to slowly warm up to 80 DEG C～85 DEG C insulated and stirred reaction dischargings in 3～5 hours, prepares 2 degree of functionality polycaprolactone polyurethane acrylate of the structure that is shown below.
R is :-CH2CH2OCH2CH2-, namely in polycaprolactone glycol, dihydroxylic alcohols initiator is diethylene glycol；
A+b=(550-106)/114=3.8947.
Embodiment 2
1000mL four-hole boiling flask puts into polycaprolactone glycol (Bai Situo CAPA2100, molecular weight 1000) 500 grams, isocyanates ethyl acrylate 141 grams (1mol), catalyst dibutyltin dilaurylate 0.1 gram, polymerization inhibitor MEHQ 0.7 gram, within 0.5～4 hour, it is to slowly warm up to 80 DEG C～85 DEG C insulated and stirred reaction dischargings in 3～5 hours, prepares 2 degree of functionality polycaprolactone polyurethane acrylate of the structure that is shown below.
R is:Namely in polycaprolactone glycol, dihydroxylic alcohols initiator is neopentyl glycol；
A+b=(1000-104)/114=7.8596.
Embodiment 3
1000mL four-hole boiling flask puts into polycaprolactone glycol (Bai Situo CAPA2209, molecular weight 2000) 500 grams, isocyanates ethyl acrylate 70.5 grams (0.5mol), catalyst dibutyltin dilaurylate 0.1 gram, polymerization inhibitor MEHQ 0.6 gram, within 0.5～4 hour, it is to slowly warm up to 80 DEG C～85 DEG C insulated and stirred reaction dischargings in 3～5 hours, prepares 2 degree of functionality polycaprolactone polyurethane acrylate of the structure that is shown below.
R is: 1,2-ethylidene (-CH2CH2-), namely in polycaprolactone glycol, dihydroxylic alcohols initiator is ethylene glycol；
A+b=(2000-62)/114=17.
Comparative example 1
1000mL four-hole boiling flask puts into polycaprolactone glycol (Bai Situo CAPA2054, molecular weight 550) 275 grams, isophorone diisocyanate (IPDI) 222 grams (1mol), catalyst dibutyltin dilaurylate 0.1 gram, it is warmed up to 60 DEG C～65 DEG C stirring insulation reaction 2～3 hours, it is subsequently adding polymerization inhibitor MEHQ 0.9 gram, catalyst dibutyltin dilaurylate 0.1 gram, 2-(Acryloyloxy)ethanol 128 grams, within 0.5～4 hour, it is to slowly warm up to the discharging in 3～5 hours of 80 DEG C～85 DEG C insulation reaction, prepare 2 degree of functionality polycaprolactone polyurethane acrylate of the structure that is shown below.
R is :-CH2CH2OCH2CH2-, namely in polycaprolactone glycol, dihydroxylic alcohols initiator is diethylene glycol；
A+b=(550-106)/114=3.8947；
R1For:
Comparative example 2
1000mL four-hole boiling flask puts into polycaprolactone glycol (Bai Situo CAPA2100, molecular weight 1000) 500 grams, IPDI222 gram (1mol), catalyst dibutyltin dilaurylate 0.12 gram, it is warmed up to 60 DEG C～65 DEG C stirring insulation reaction 2～3 hours, it is subsequently adding polymerization inhibitor MEHQ 1 gram, catalyst dibutyltin dilaurylate 0.12 gram, 2-(Acryloyloxy)ethanol 128 grams, within 0.5～4 hour, it is to slowly warm up to the discharging in 3～5 hours of 80 DEG C～85 DEG C insulation reaction, prepares 2 degree of functionality polycaprolactone polyurethane acrylate of the structure that is shown below.
R is:Namely in polycaprolactone glycol, dihydroxylic alcohols initiator is neopentyl glycol；
A+b=(1000-104)/114=7.8596；
R1For:
Comparative example 3
1000mL four-hole boiling flask puts into polycaprolactone glycol (Bai Situo CAPA2209, molecular weight 2000) 500 grams, IPDI111 gram (0.5mol), catalyst dibutyltin dilaurylate 0.1 gram, it is warmed up to 60 DEG C～65 DEG C stirring insulation reaction 2～3 hours, it is subsequently adding polymerization inhibitor MEHQ 0.8 gram, catalyst dibutyltin dilaurylate 0.1 gram, 2-(Acryloyloxy)ethanol 64 grams, within 0.5～4 hour, it is to slowly warm up to the discharging in 3～5 hours of 80 DEG C～85 DEG C insulation reaction, prepares 2 degree of functionality polycaprolactone polyurethane acrylate of the structure that is shown below.
R is: 1,2-ethylidene (-CH2CH2-), namely in polycaprolactone glycol, dihydroxylic alcohols initiator is ethylene glycol；
A+b=(2000-62)/114=17；
R1For:
Embodiment 4
Investigate the viscosity of embodiment of the present invention 1-3 and the comparative example 1-3 2 degree of functionality urethane acrylates prepared.
Method of testing: NDJ-1 type is rotating turns viscometer, No. 4 rotors, 60 revs/min.Concrete operation step is with reference to " NDJ-1 type rotating cylinder viscometer operation instructions ".
The viscosity of table 12 degree of functionality polycaprolactone polyurethane acrylate/unit mPa.s60 DEG C
| Comparative example 1 | Embodiment 1 | Comparative example 2 | Embodiment 2 | Comparative example 3 | Embodiment 3 | |
| Viscosity | 4600 | 2200 | 6000 | 2900 | 8100 | 4100 |
Embodiment 1 product comparison ratio 1 product viscosity decline 2400mPa.s60 DEG C, fall is 52.17%.
Embodiment 2 product comparison ratio 2 product viscosity decline 3100mPa.s60 DEG C, fall is 51.67%.
Embodiment 3 product comparison ratio 3 product viscosity decline 4000mPa.s60 DEG C, fall is 49.38%.
Embodiment 5
Raw material
UV resin is 1.: low viscosity 2 degree of functionality aliphatic poly caprolactone urethane acrylate (purpose adopting 2 degree of functionality aliphatic urethane acrylates is to increase the flexibility of film, anti-riot splits, cold-hot cycle performance), prepared by embodiment 2.
UV resin is 2.: low viscosity 4 degree of functionality aliphatic urethane acrylate (purpose adopting 4 degree of functionality aliphatic urethane acrylates is to increase the hardness of film, intensity, the performance such as wear-resisting), and preparation method is as follows:
6L autoclave puts into 1920 grams of anhydrous citric acid (C6H8O7, molecular weight 192), 60 grams of potassium formates, it is warming up to 155 DEG C, starts to drip expoxy propane (C3H6O, molecular weight 58) 3480 grams react, temperature control 155 DEG C～165 DEG C, pressure 0.10～0.40MPa, drip 3～4 hours, drip off latter 155 DEG C～165 DEG C and be incubated 2～3 hours, be subsequently cooled to less than 80 DEG C, discharging obtains crude product；After crude product adds active hargil 60 grams stirring 30 minutes, obtain clear tetrahydroxy citric acid polyether ester (C through overanxious24H44O13, molecular weight 540) and 5292 grams, structure is shown below.
Wherein: n=3, a+b+c+d=6.
1000mL four-hole boiling flask puts into prepared tetrahydroxy citric acid polyether ester (C24H44O13Molecular weight 540) 270 grams, isocyanates ethyl acrylate 280 grams (1.984mol), catalyst dibutyltin dilaurylate 0.3 gram, polymerization inhibitor MEHQ 1 gram, within 0.5～4 hour, being to slowly warm up to the discharging in 3～5 hours of 80 DEG C～85 DEG C insulation reaction, prepare 4 degree of functionality urethane acrylates, structure is shown below.
Wherein: n=3, a+b+c+d=6.
The viscosity that the viscosity determining procedure identical with embodiment 4 records 4 degree of functionality aliphatic urethane acrylates is adopted to be 8000mPa.s60 DEG C.
UV monomer: pentaerythritol triacrylate (PETA, Jiangsu Litian Technology Co., Ltd.)；1,6-hexanediyl ester (HDDA, profit field, Jiangsu).
Light trigger: 1173, Nanjing Wa Li Chemical Industry Science Co., Ltd.
Auxiliary agent: Tego432, Tego92, Germany's enlightening is high.
Mixed solvent: butyl acetate, toluene, methylisobutylketone mix for 1:1:1 in mass ratio.
Instrument and equipment
LT-1002 type uv cure machine, blue sky Te Deng Development Co., Ltd；QFZ type paint film adhesion analyzer, Tianjin Ke Lian Material Testing Machine factory；RCA paper tape wear resistant instrument, Shanghai modern environment project institute；Water-bath；Cold cycling equipment.
The preparation of coating
Weigh the UV resin of certain mass, be subsequently adding UV monomer, mixed solvent, light trigger, auxiliary agent, stir, be configured to coating.The proportioning of coating is in Table 2.
The proportioning of table 2 coating
The preparation of film and solidification
Select the ABS plastic sheet material of 10cm × 10cm, first at one layer of thermoplastic acrylic resin white primer of its surface spraying, 60 DEG C of baking 3h, the UV coating prepared according to table 2 at its surface spraying again, coating thickness is about 20 μm, solidifies, make cured film reach surface drying on photo solidification machine, touch dry method with finger to characterize, record hardening time.
Performance test
Hardening time: experiment adopts finger to touch dry method, touches coating surface with finger, if do not felt tacky, namely thinks that coating surface is cured.
Pencil hardness: measure with reference to GB6739-86 film pencil hardness method.
Adhesive force: measure with reference to GB/T1720-88 film adhesive algoscopy.Being divided into 7 grades, 1 grade of the best, 7 grades worst.
Wearability: RCA tests, 175g, 500 ± 50 times.
Water boiling resistance: with reference to standard GB/T/T1733 " paint film resistance to water algoscopy ".
Cold-hot circulates:
(1) scope and explanation: plastic paint is because of moisture and hot ageing or losses of plasticizer, or both hold concurrently it sometimes appear that the trend of cracking, adopt and are alternately exposed in climate cabinet and household freezer can measure the degree whether paint film ftractures and ftracture.
(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 is 24h in the incubator hot tank of 38 DEG C.The placement of model should become 0-30 degree angle with vertical direction, and requires that plate plate is not in contact with each other mutually in process of the test.2. after 24h, model moving to 20h immediately in the household freezer of (-23 ± 1.5) DEG C, transfer time is not to be exceeded at most 30S.3. taking out model, at room temperature place 4h, 48h is a circulation so altogether, and period can carry out stage evaluation.4. carry out 15 circulations altogether, then model outward appearance, color, adhesive force are tested.
(4) result represents: film should without cracking, variable color, loss of adhesion or other defect.
(5) reference standard: Unite States Standard AAMA615-02 " on plastic material the industry standard of high-performance organic coating, performance requirement and test method ".(1)
Result and discussion, the resin impact on film performance
UV resin is the main body of UV coating, and its performance substantially determines the main performance of film after solidification.This experiment adopts 4 degree of functionality aliphatic urethane acrylates and 2 degree of functionality aliphatic poly caprolactone polyurethane acrylate resins composition different formulations, and various Ingredient Amount are in Table 2, and film performance is in Table 3.
Table 34 degree of functionality urethane acrylate and the impact on coating property of the 2 degree of functionality urethane acrylate different ratio
List of references: (1) Yu Yingying. the coatings industry method of inspection is complete works of with instrument. Beijing: Chemical Industry Press, 2007:525.
Attached light trigger 1173 illustrates:
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
CASNO:7473-98-5
Molecular formula: C10H12O
Molecular weight: 164.2
Chemical structural formula:
Technical specification:
Outward appearance: 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%
Application:
1173 are applicable to acrylic acid photocuring varnish system, such as the varnish etc. of timber, metal, paper, plastics etc..1173 special recommendations are needing to stand chronic sun exposure and in the UV-curable coating of color inhibition, owing to 1173 is liquid, are highly susceptible to blended, so being suitable for and the composite use of other light trigger, it is proposed that addition is 1～4%w/w.
Claims (9)
1. a degree of functionality polycaprolactone polyurethane acrylate, it is characterised in that it is prepared via a method which to obtain: reacted by polycaprolactone glycol and isocyanates ethyl acrylate and prepare 2 degree of functionality polycaprolactone polyurethane acrylate.
2. 2 degree of functionality polycaprolactone polyurethane acrylate according to claim 1, it is characterized in that 2 described degree of functionality polycaprolactone polyurethane acrylate are according to amount ratio 1mol:1.5～2.5mol by polycaprolactone glycol and isocyanates ethyl acrylate, reaction at 60 DEG C～95 DEG C and prepare.
3. 2 degree of functionality polycaprolactone polyurethane acrylate according to claim 2, it is characterized in that 2 described degree of functionality polycaprolactone polyurethane acrylate are according to amount ratio 1mol:1.8～2.2mol by polycaprolactone glycol and isocyanates ethyl acrylate, reaction at 60 DEG C～95 DEG C and prepare.
4. 2 degree of functionality polycaprolactone polyurethane acrylate according to any one of claim 1-3, it is characterized in that 2 described degree of functionality polycaprolactone polyurethane acrylate are according to amount ratio 1mol:1.9～2mol by polycaprolactone glycol and isocyanates ethyl acrylate, catalyst, polymerization inhibitor effect under at 80 DEG C～95 DEG C, stir insulation reaction 3～6 hours and prepare；Wherein, catalyst is dibutyl tin laurate, and its consumption is 100～3000ppm of polycaprolactone glycol and isocyanates ethyl acrylate gross mass；Polymerization inhibitor can be MEHQ or hydroquinone, and its consumption is 100～5000ppm of polycaprolactone glycol and isocyanates ethyl acrylate gross mass.
5. the preparation method of 2 degree of functionality polycaprolactone polyurethane acrylate described in claim 1, it is characterised in that including: polycaprolactone glycol and isocyanates ethyl acrylate react and prepare 2 degree of functionality polycaprolactone polyurethane acrylate.
6. the preparation method of 2 degree of functionality polycaprolactone polyurethane acrylate according to claim 5, it is characterised in that the amount ratio of described polycaprolactone glycol and isocyanates ethyl acrylate is 1mol:1.5～2.5mol, and reaction temperature is 60 DEG C～95 DEG C.
7. the preparation method of 2 degree of functionality polycaprolactone polyurethane acrylate according to claim 6, it is characterised in that the amount ratio of described polycaprolactone glycol and isocyanates ethyl acrylate is 1mol:1.8～2.2mol, and reaction temperature is 60 DEG C～95 DEG C.
8. the preparation method of 2 degree of functionality polycaprolactone polyurethane acrylate according to any one of claim 5-7, it is characterized in that polycaprolactone glycol and isocyanates ethyl acrylate are according to amount ratio 1mol:1.9～2mol, catalyst, polymerization inhibitor effect under react 3～6 hours in 80 DEG C～95 DEG C insulated and stirred and to prepare 2 degree of functionality polycaprolactone polyurethane acrylate；Wherein, catalyst is dibutyl tin laurate, and its consumption is 100～3000ppm of polycaprolactone glycol and isocyanates ethyl acrylate gross mass；Polymerization inhibitor can be MEHQ or hydroquinone, and its consumption is 100～5000ppm of polycaprolactone glycol and isocyanates ethyl acrylate gross mass.
9. the application in preparing UV coating, ink or binding agent of the low viscosity 2 degree of functionality polycaprolactone polyurethane acrylate described in claim 1.
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| EP3603607B1 (en) * | 2017-03-31 | 2023-09-20 | Mitsui Chemicals, Inc. | Multifunctional monomer for dental material, and hydroxyl group-containing monomer for dental material |
| CN108441157A (en) * | 2018-03-28 | 2018-08-24 | 西安近代化学研究所 | A kind of end alkenyl polycaprolactone adhesive and its synthetic method |
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| CN110699969B (en) * | 2019-09-26 | 2022-05-20 | 江苏利田科技股份有限公司 | Ultraviolet-curing coating adhesive for textile fabric based on polyfunctional polyurethane acrylate, and preparation method and application thereof |
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