CN105859586A - 2-functionality-degree makrolon urethane acrylate and preparation method and application thereof - Google Patents
2-functionality-degree makrolon urethane acrylate and preparation method and application thereof Download PDFInfo
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- CN105859586A CN105859586A CN201610235699.9A CN201610235699A CN105859586A CN 105859586 A CN105859586 A CN 105859586A CN 201610235699 A CN201610235699 A CN 201610235699A CN 105859586 A CN105859586 A CN 105859586A
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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
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/711—Monoisocyanates or monoisothiocyanates containing oxygen in addition to isocyanate oxygen
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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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
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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
- 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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Abstract
The invention discloses low-viscosity 2-functionality-degree makrolon urethane acrylate and a preparation method and application thereof. The preparation method of low-viscosity 2-functionality-degree makrolonurethane acrylate comprises the following step that polycarbonate diol and isocyanatoethyl prop-2-enoate react to obtain 2-functionality-degree makrolon urethane acrylate. The invention further discloses application of 2-functionality-degree makrolon urethane acrylate to preparation of a UV coating or ink or an adhesive. Makrolon urethane acrylate is prepared from isocyanatoethyl prop-2-enoate, the reaction process is simple and easy to control, gel is not prone to be generated through side reactions, the product viscosity is low, construction and application of UV formula products are benefited, and when 2-functionality-degree makrolon urethane acrylate is used for UV spraying, no solvent or few solvent is added, and the requirement for 2-functionality-degree makrolon urethane acrylate used for the low-viscosity coating is met. After 2-functionality-degree UV photocuring makrolon urethane acrylate is cured, excellent mechanical performance, hydrolysis resistance, thermal stability, weather fastness, durability, drug resistance and solvent resistance are achieved, and 2-functionality-degree makrolon urethane can be used as a raw material of the UV coating, the ink and the adhesive.
Description
Technical field
The invention belongs to Material Field, relate to a kind of 2 degree of functionality polycarbonate polyurethane acrylate and preparation method thereof and answer
With, especially relate to a kind of low viscosity 2 degree of functionality polycarbonate 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 more
More it is subject to people's attention.UV photo-curing material has the premium properties such as quick solidifying, energy consumption is low, pollute less, efficiency is high,
Thus it being widely used in the fields such as coating, printing and electronics industry, development in recent years is rapid.Urethane acrylate
(polyurethane acrylate, PUA) is a kind of important Photocurable oligomers, has low stimulation, curing rate fast, high thoroughly
The premium properties such as bright property, stretch-proof, cohesive energy height, are widely used in the fields such as light-curable ink, coating, adhesive, in U.S.
State, Japan, countries in Europe are widely used.In recent years, along with UV-curing technology is in the rise of China, novel light is solid
Formed material as UV coating, ink, adhesive raw material purposes increasingly wider, usage amount is increasing year by year.
Applicant discloses a kind of 3 officials at Chinese patent ZL201310146346.8 (Authorization Notice No. CN 103274967 B)
Energy degree urethane acrylate, is prepared via a method which to obtain: first by 2,2-dihydromethyl propionic acid under catalyst action with ring
Oxidative ethane or propylene oxide reaction and prepared trihydroxy polyether ester, trihydroxy polyether ester again with diisocyanate (selected from HDI,
One in IPDI, HMDI, MDI) and hydroxy-ethyl acrylate or hydroxypropyl acrylate reaction prepare 3 degree of functionality polyurethane
Acrylate.3 degree of functionality polyurethane third are prepared owing to have employed diisocyanate and hydroxy-ethyl acrylate or hydroxypropyl acrylate
Olefin(e) acid ester, course of reaction step is many, relatively cumbersome, and production process is wayward, because the existence of side reaction can produce the wind of gel
Danger.
Light-cured resin is the matrix resin of photocureable coating, wide in variety, is widely used.Along with in global range to environmental problem
Pay attention to day by day, light-cured resin will be fast-developing along with the development of photocureable coating.Develop more environmentally-friendly, viscosity
The more excellent light-cured resin of low, combination property is the striving direction of WeiLai Technology personnel.
Summary of the invention
It is an object of the invention to provide a kind of low viscosity 2 degree of functionality polycarbonate polyurethane acrylate.
It is a further object of the present invention to provide the preparation method of this low viscosity 2 degree of functionality polycarbonate polyurethane acrylate.
It is yet another object of the invention to provide the application of this low viscosity 2 degree of functionality polycarbonate 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 polycarbonate polyurethane acrylate (Polycarbonate-based Polyurethane
Acrylate), it is prepared via a method which to obtain: by PCDL (PCDL, Polycarbonate diol) and isocyanic acid
Ester ethyl acrylate (2-Isocyanatoethyl Acrylate, abbreviation AOI, No. CAS: 13641-96-8, molecular formula:
C6H7NO3, molecular weight: 141.12) and the prepared 2 degree of functionality polycarbonate polyurethane acrylate of reaction.
Reaction scheme is as follows:
PCDL and isocyanates ethyl acrylate react to obtain 2 degree of functionality polycarbonate polyurethane acrylate:
R is :-CH2CH2CH2CH2CH2CH2-, i.e. 1,6-hexylene glycol is the PCDL of monomer；Or,
R is :-CH2CH2CH2CH2CH2CH2-and-CH2CH2CH2CH2CH2-, i.e. 1,6-hexylene glycol and 1,5-PD
PCDL for monomer；Or,
R is :-CH2CH2CH2CH2CH2CH2-and-CH2CH2CH2CH2-, i.e. 1,6-hexylene glycol and BDO are single
The PCDL of body；Or,
R is:I.e. 1,4 cyclohexane dimethanol is the PCDL of monomer；Or,
R is:With-CH2CH2CH2CH2CH2CH2-, i.e. Isosorbide-5-Nitrae-hexamethylene two
Methyl alcohol and 1,6-HD are the PCDL of monomer；Or,
R is :-CH2CH2CH2CH2CH2CH2-with(m=1～
10), i.e. 1,6-hexylene glycol and polycaprolactone glycol (or 6-caprolactone) are the PCDL of monomer.
The most described PCDL is with 1,6-HD, 1,5-pentanediol, 1,4-butanediol, 1,4 cyclohexane dimethanol, gathers
In the dihydroxylic alcohols such as caprolactone diol (or 6-caprolactone) one or both for monomer copolymerization prepare, prepare PCDL
Belong to chemical reaction as well known to those skilled in the art.Have the documents below can be for reference:
1. analogy cutting edge of a knife or a sword, the optimization of synthesis [D] of aliphatic polycarbonate diol, Shanghai, East China University of Science, 2012；
2. Ma Fangfang, aliphatic polycarbonate diol synthesising process research [D], Shanghai, East China University of Science, 2013；
3. Xu Wen dragon, the synthesis of PCDL and the performance study [D] of polyurethane synthetic material thereof, Qingdao, Qingdao science and technology
University, 2014；
4. Feng Wang becomes, two step ester-interchange method synthctic fat adoption carbonate diol and Thermal Properties [D] thereof, Xiang Tan, University Of Xiangtan,
2014。
Preferably, 2 described degree of functionality polycarbonate polyurethane acrylate are by PCDL and isocyanates acrylic acid
Ethyl ester according to amount ratio 1mol:1.5～2.5mol, at 60 DEG C～95 DEG C reaction and prepare.
It is further preferred that 2 described degree of functionality polycarbonate polyurethane acrylate are by PCDL and isocyanates
Ethyl acrylate according to amount ratio 1mol:1.8～2.2mol, at 60 DEG C～95 DEG C reaction and prepare.
It is furthermore preferred that 2 described degree of functionality polycarbonate polyurethane acrylate are by PCDL and isocyanates propylene
Acetoacetic ester according to amount ratio 1mol:1.9～2mol, catalyst, polymerization inhibitor effect under stirring insulation at 80 DEG C～95 DEG C
React 3～6 hours and prepare；Wherein, catalyst is dibutyl tin laurate, and its consumption is that PCDL is with different
The 100～3000ppm of cyanate ethyl acrylate gross mass；Polymerization inhibitor can be MEHQ or hydroquinones, and it is used
Amount is PCDL and the 100～5000ppm of isocyanates ethyl acrylate gross mass.
Present invention reaction is the reaction of the isocyano in isocyanates ethyl acrylate and the hydroxyl of PCDL, belongs to known
Synthesis of polyurethane (polyurethanes) reaction.
The preparation method of 2 degree of functionality polycarbonate polyurethane acrylate of the present invention, including: PCDL is with different
The reaction of cyanate ethyl acrylate prepares 2 degree of functionality polycarbonate polyurethane acrylate (i.e. formula (I) compound).
Described PCDL is 1mol:1.5～2.5mol with the amount ratio of isocyanates ethyl acrylate, reaction temperature
It it is 60 DEG C～95 DEG C.
Preferably, described PCDL is 1mol:1.8～2.2mol with the amount ratio of isocyanates ethyl acrylate,
Reaction temperature is 60 DEG C～95 DEG C.
It is further preferred that PCDL and isocyanates ethyl acrylate are according to amount ratio 1mol:1.9～2mol,
Catalyst, polymerization inhibitor effect under in 80 DEG C～95 DEG C stirring insulation reaction 3～6 hours prepare the 2 poly-ammonia of degree of functionality Merlon
Ester acrylate；Wherein, catalyst is dibutyl tin laurate, and its consumption is PCDL and isocyanates acrylic acid
The 100～3000ppm of ethyl ester gross mass；Polymerization inhibitor can be MEHQ or hydroquinones, and its consumption is Merlon
Glycol and the 100～5000ppm of isocyanates ethyl acrylate gross mass.
Low viscosity 2 degree of functionality polycarbonate polyurethane acrylate of the present invention is at preparation UV coating, ink or adhesive
In application.
Beneficial effect:
The present invention uses isocyanates ethyl acrylate to prepare polycarbonate polyurethane acrylate, decreases reactions steps, reaction
Process is simple, easily controllable, is difficult to produce gel because of side reaction, and polycarbonate polyurethane acrylate product viscosity is low, more
Be conducive to construction and the application of UV formulation product, be not added with for UV spraying or few solubilizer, meet and be applied to low-viscosity dope
Requirement；After low viscosity 2 degree of functionality UV light-solidifying poly carbonate polyurethane acrylate cures, possesses the mechanicalness of excellence
The performances such as energy, hydrolytic resistance, heat endurance, weatherability, durability, resistance to chemical reagents and solvent resistance, it is possible to be coated with as UV
Material, ink, the raw material application of adhesive.
Detailed description of the invention
Embodiment 1
PCDL (UBE Ube Industries, Ltd UH-50, molecular weight is put in 1000mL four-hole boiling flask
500) 500 grams, isocyanates ethyl acrylate 282 grams (2mol), catalyst dibutyltin dilaurylate 0.09 gram, inhibition
Agent MEHQ 0.9 gram, is to slowly warm up to 80 DEG C～85 DEG C of insulation reaction 3～discharging in 5 hours for 0.5～4 hour, prepares
2 degree of functionality polycarbonate polyurethane acrylate of the structure that is shown below.
R is :-CH2CH2CH2CH2CH2CH2-, i.e. in PCDL, glycol monomer is 1,6-hexylene glycol；
N=(500-118)/144=2.6528.
Embodiment 2
PCDL (UBE Ube Industries, Ltd UH-100, molecular weight is put in 1000mL four-hole boiling flask
1000) 500 grams, isocyanates ethyl acrylate 141 grams (1mol), catalyst dibutyltin dilaurylate 0.1 gram, inhibition
Agent MEHQ 0.7 gram, is to slowly warm up to 80 DEG C～85 DEG C of insulation reaction 3～discharging in 5 hours for 0.5～4 hour, prepares
2 degree of functionality polycarbonate polyurethane acrylate of the structure that is shown below.
R is :-CH2CH2CH2CH2CH2CH2-, i.e. in PCDL, glycol monomer is 1,6-hexylene glycol；
N=(1000-118)/144=6.1250.
Embodiment 3
PCDL (UBE Ube Industries, Ltd UH-200, molecular weight is put in 1000mL four-hole boiling flask
2000) 500 grams, isocyanates ethyl acrylate 70.5 grams (0.5mol), catalyst dibutyltin dilaurylate 0.1 gram, resistance
Poly-agent MEHQ 0.6 gram, is to slowly warm up to 80 DEG C～85 DEG C of insulation reaction 3～discharging in 5 hours, system for 0.5～4 hour
2 degree of functionality polycarbonate polyurethane acrylate of the structure that must be shown below.
R is :-CH2CH2CH2CH2CH2CH2-, i.e. in PCDL, glycol monomer is 1,6-hexylene glycol；
N=(2000-118)/144=13.0694.
Comparative example 1
PCDL (UBE Ube Industries, Ltd UH-50, molecular weight is put in 1000mL four-hole boiling flask
500) 250 grams, IPDI (IPDI) 222 grams (1mol), catalyst dibutyltin dilaurylate 0.09
Gram, it is warmed up to 60 DEG C～65 DEG C stirring insulation reaction 2～3 hours, is subsequently adding polymerization inhibitor MEHQ 0.9 gram, urges
Agent dibutyl tin laurate 0.09 gram, hydroxy-ethyl acrylate 128 grams, within 0.5～4 hour, it is to slowly warm up to 80 DEG C～85 DEG C
Insulation reaction 3～discharging in 5 hours, prepare 2 degree of functionality polycarbonate polyurethane acrylate of the structure that is shown below.
R is :-CH2CH2CH2CH2CH2CH2-, i.e. in PCDL, glycol monomer is 1,6-hexylene glycol；
N=(500-118)/144=2.6528；
R1For:
Comparative example 2
PCDL (UBE Ube Industries, Ltd UH-100, molecular weight is put in 1000mL four-hole boiling flask
1000) 500 grams, IPDI 222 grams (1mol), catalyst dibutyltin dilaurylate 0.12 gram, it is warmed up to 60 DEG C～65 DEG C
Stirring insulation reaction 2～3 hours, is subsequently adding polymerization inhibitor MEHQ 1 gram, catalyst dibutyltin dilaurylate
0.12 gram, hydroxy-ethyl acrylate 128 grams, within 0.5～4 hour, it is to slowly warm up to 80 DEG C～85 DEG C of insulation reaction 3～goes out for 5 hours
Material, prepares 2 degree of functionality polycarbonate polyurethane acrylate of the structure that is shown below.
R is :-CH2CH2CH2CH2CH2CH2-, i.e. in PCDL, glycol monomer is 1,6-hexylene glycol；
N=(1000-118)/144=6.1250；
R1For:
Comparative example 3
PCDL (UBE Ube Industries, Ltd UH-200, molecular weight is put in 1000mL four-hole boiling flask
2000) 500 grams, IPDI 111 grams (0.5mol), catalyst dibutyltin dilaurylate 0.1 gram, be warmed up to 60 DEG C～
65 DEG C of stirring insulation reaction 2～3 hours, are subsequently adding polymerization inhibitor MEHQ 0.8 gram, catalyst dibutyltin cinnamic acid two fourth
0.1 gram of base tin, hydroxy-ethyl acrylate 64 grams, within 0.5～4 hour, it is to slowly warm up to 80 DEG C～85 DEG C of insulation reaction 3～goes out for 5 hours
Material, prepares 2 degree of functionality polycarbonate polyurethane acrylate of the structure that is shown below.
R is :-CH2CH2CH2CH2CH2CH2-, i.e. in PCDL, glycol monomer is 1,6-hexylene glycol；
N=(2000-118)/144=13.0694；
R1For:
Embodiment 4
The viscosity of the 2 degree of functionality urethane acrylates that investigation embodiment of the present invention 1-3 and comparative example 1-3 prepare.
Method of testing: NDJ-1 type is rotating turns viscosimeter, No. 4 rotors, 60 revs/min.Concrete operation step is with reference to " NDJ-1
Type rotation viscometer operation instructions ".
The viscosity of table 12 degree of functionality polycarbonate polyurethane acrylate/unit mPa.s@60 DEG C
| Comparative example 1 | Embodiment 1 | Comparative example 2 | Embodiment 2 | Comparative example 3 | Embodiment 3 | |
| Viscosity | 5400 | 2600 | 7200 | 3700 | 9300 | 4800 |
Embodiment 1 product comparison ratio 1 product viscosity declines 2800mPa.s@60 DEG C, and fall is 51.85%.
Embodiment 2 product comparison ratio 2 product viscosity declines 3500mPa.s@60 DEG C, and fall is 48.61%.
Embodiment 3 product comparison ratio 3 product viscosity declines 4500mPa.s@60 DEG C, and fall is 48.39%.
Embodiment 5
Raw material
UV resin is 1.: low viscosity 2 degree of functionality Aliphatic Polycarbonate Polyurethanes acrylate (uses 2 degree of functionality aliphatic polies
The purpose of urethane acrylate is to increase the flexibility of film, anti-riot splits, cold-hot cycle performance), prepared by embodiment 1.
UV resin is 2.: low viscosity 4 degree of functionality aliphatic urethane acrylate (uses 4 degree of functionality aliphatic polyurethane propylene
The purpose of acid esters is to increase the hardness of film, intensity, the performance such as wear-resisting), preparation method is as follows:
1361 grams of pentaerythrites (CAS 115-77-5, chemical formula C are put in 6L autoclave5H12O4, molecular weight
136.15), 50 grams of potassium formates, it is warming up to 155 DEG C, starts to drip expoxy propane (C3H6O, molecular weight 58) 3480 grams enter
Row reaction, temperature control 155 DEG C～165 DEG C, pressure 0.10～0.60MPa, drip 3～4 hours, drip off latter 155 DEG C～165 DEG C
Being incubated 2～3 hours, be subsequently cooled to less than 80 DEG C, discharging obtains crude product；Crude product adds atlapulgite 60 grams and stirs 30 minutes
After, obtain clear tetrahydroxy polyethers (C through overanxious23H48O10, molecular weight 484) and 4743.2 grams, the following institute of structure such as formula
Show,
Wherein: n=3, a+b+c+d=6；
Prepared tetrahydroxy polyethers (C is put in 1000mL four-hole boiling flask23H48O10, molecular weight 484) and 242 grams, isocyanide
Acid esters ethyl acrylate 280 grams (1.984mol), catalyst dibutyltin dilaurylate 0.25 gram, polymerization inhibitor para hydroxybenzene first
0.8 gram of ether, is to slowly warm up to 80 DEG C～85 DEG C of insulation reaction 3～discharging in 5 hours for 0.5～4 hour, prepares the 4 poly-ammonia of degree of functionality
Ester acrylate, structure such as formula is as follows,
Wherein: n=3, a+b+c+d=6.
The viscosity determining procedure using embodiment 4 to record records the viscosity of 4 prepared degree of functionality urethane acrylates
7400mPa.s@60℃。
UV monomer: double trimethylolpropane tetraacrylate (Di-TMPTA, 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 research institute；Water-bath；Cold cycling
Equipment.
The preparation of coating
Weighing the UV resin of certain mass, be subsequently adding UV monomer, mixed solvent, light trigger, auxiliary agent, stirring is all
Even, it is configured to coating.The proportioning of coating is shown 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, then the UV coating prepared according to table 2 at its surface spraying, coating thickness is about 20 μm, on photo solidification machine
Solidification, makes cured film reach surface drying, characterizes by tack method, records hardening time.
Performance test
Hardening time: experiment uses tack method, touches coating surface with finger, if do not felt tacky, i.e. think coating surface
Cured.
Pencil hardness: measure with reference to GB 6739-86 film pencil hardness method.
Adhesive force: measure with reference to GB/T 1720-88 film adhesive determination method.Being divided into 7 grades, 1 grade optimal, and 7 grades
Difference.
Wearability: RCA tests, 175g, 500 ± 50 times.
Water boiling resistance: with reference to standard GB/T/T 1733 " paint film resistance to water determination method ".
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 ftractures becomes
Gesture, uses and is alternately exposed in climate cabinet and household freezer to 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.Sample
The placement of plate with a vertical 0-30 degree angle, and should require that plate plate is not in contact with each other in process of the test mutually.2. after 24h, immediately
Model is moved to 20h in the household freezer of (-23 ± 1.5) DEG C, is at most not to be exceeded 30S transfer time.3. model is taken out,
Ambient temperatare puts 4h, and 48h is a circulation the most altogether, and period can carry out stage evaluation.Carry out 15 circulations the most altogether, so
Afterwards model outward appearance, color, adhesive force are tested.
(4) result represents: film should decline or other defect without cracking, variable color, adhesive force.
(5) reference standard: Unite States Standard AAMA 615-02 " advise on plastic material by the industry of high-performance organic coating
Model, 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 is adopted
Form different with 4 degree of functionality aliphatic urethane acrylates and 2 degree of functionality Aliphatic Polycarbonate Polyurethanes acrylates
Formula, various Ingredient Amount are shown in Table 2, and film performance is shown 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
Bibliography: (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
CAS NO:7473-98-5
Molecular formula: C10H12O
Molecular weight: 164.2
Chemical structural formula:
Technical indicator:
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 is special
Recommend needing to stand chronic sun exposure and in the UV-curable coating of color inhibition, owing to 1173 is liquid, be highly susceptible to being blended,
So being suitable for use compounding with other light trigger, it is proposed that addition is 1～4%w/w.
Claims (9)
1. a degree of functionality polycarbonate polyurethane acrylate, it is characterised in that be prepared via a method which to obtain: by gathering
Carbonate diol and isocyanates ethyl acrylate react and prepare 2 degree of functionality polycarbonate polyurethane acrylate.
2 degree of functionality polycarbonate polyurethane acrylate the most according to claim 1, it is characterised in that 2 described officials
Energy degree polycarbonate polyurethane acrylate is according to amount ratio 1mol by PCDL and isocyanates ethyl acrylate:
1.5～2.5mol, at 60 DEG C～95 DEG C reaction and prepare.
2 degree of functionality polycarbonate polyurethane acrylate the most according to claim 1, it is characterised in that 2 described officials
Energy degree polycarbonate polyurethane acrylate is according to amount ratio 1mol by PCDL and isocyanates ethyl acrylate:
1.8～2.2mol, at 60 DEG C～95 DEG C reaction and prepare.
4. according to 2 degree of functionality polycarbonate polyurethane acrylate described in any one of claim 1-3, it is characterised in that institute
The 2 degree of functionality polycarbonate polyurethane acrylate stated are according to amount ratio by PCDL and isocyanates ethyl acrylate
1mol:1.9～2mol, catalyst, polymerization inhibitor effect under at 80 DEG C～95 DEG C, stir insulation reaction 3～6 hours and make
?；Wherein, catalyst is dibutyl tin laurate, and its consumption is that PCDL is total with isocyanates ethyl acrylate
The 100～3000ppm of quality；Polymerization inhibitor can be MEHQ or hydroquinones, its consumption be PCDL with
The 100～5000ppm of isocyanates ethyl acrylate gross mass.
5. the preparation method of 2 degree of functionality polycarbonate polyurethane acrylate described in claim 1, it is characterised in that bag
Include: PCDL and isocyanates ethyl acrylate react and prepare 2 degree of functionality polycarbonate polyurethane acrylate.
The preparation method of 2 degree of functionality polycarbonate polyurethane acrylate the most according to claim 5, it is characterised in that
Described PCDL is 1mol:1.5～2.5mol with the amount ratio of isocyanates ethyl acrylate, and reaction temperature is
60 DEG C～95 DEG C.
The preparation method of 2 degree of functionality polycarbonate polyurethane acrylate the most according to claim 6, it is characterised in that
Described PCDL is 1mol:1.8～2.2mol with the amount ratio of isocyanates ethyl acrylate, and reaction temperature is
60 DEG C～95 DEG C.
8. according to the preparation method of 2 degree of functionality polycarbonate polyurethane acrylate described in any one of claim 5-7, its
Be characterised by PCDL and isocyanates ethyl acrylate according to amount ratio 1mol:1.9～2mol, in catalyst, resistance
2 degree of functionality polycarbonate polyurethane acrylic acid are prepared in 80 DEG C～95 DEG C stirring insulation reaction 3～6 hours under the effect of poly-agent
Ester；Wherein, catalyst is dibutyl tin laurate, and its consumption is PCDL and the total matter of isocyanates ethyl acrylate
The 100～3000ppm of amount；Polymerization inhibitor can be MEHQ or hydroquinones, and its consumption is that PCDL is with different
The 100～5000ppm of cyanate ethyl acrylate gross mass.
9. 2 degree of functionality polycarbonate polyurethane acrylate described in claim 1 are in preparation UV coating, ink or bonding
Application in agent.
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