CN105860026A - Hexa-functionality urethane acrylate based on dipentaerythritol and preparation method and application of hexa-functionality urethane acrylate - Google Patents
Hexa-functionality urethane acrylate based on dipentaerythritol and preparation method and application of hexa-functionality urethane acrylate Download PDFInfo
- Publication number
- CN105860026A CN105860026A CN201610234875.7A CN201610234875A CN105860026A CN 105860026 A CN105860026 A CN 105860026A CN 201610234875 A CN201610234875 A CN 201610234875A CN 105860026 A CN105860026 A CN 105860026A
- Authority
- CN
- China
- Prior art keywords
- degree
- functionality
- functionality urethane
- urethane acrylate
- hexa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G18/48—Polyethers
- C08G18/4829—Polyethers containing at least three hydroxy groups
-
- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses hexa-functionality urethane acrylate based on dipentaerythritol. A preparation method of hexa-functionality urethane acrylate comprises the steps of firstly, making dipentaerythritol react with ethylene oxide or epoxypropane under the action of a catalyst, so that hexa-hydroxy polyether is obtained; then making hexa-hydroxy polyether react with 2-isocyanatoethyl acrylate, so that hexa-functionality urethane acrylate is obtained. The invention further discloses application of low-viscosity hexa-functionality urethane acrylate to preparation of UV coating or printing ink or adhesive. According to hexa-functionality urethane acrylate and the preparation method and application thereof, urethane acrylate is prepared from 2-isocyanatoethyl acrylate, the reaction process is simple and easy to control, gel is not generated easily due to side reactions, a urethane acrylate product is low in viscosity, the requirement of applying hexa-functionality urethane acrylate to a low-viscosity coating is met, and no or little solvent is added when hexa-functionality urethane acrylate is used for UV coating; after low-viscosity hexa-functionality urethane acrylate UV photocuring urethane acrylate is cured, the excellent performance such as high hardness, abrasion resistance, scratch resistance, heat resistance and weather resistance is achieved, and hexa-functionality urethane acrylate can be applied as a raw material of the UV coating, printing ink and adhesive.
Description
Technical field
The invention belongs to Material Field, relate to a kind of 6 degree of functionality urethane acrylate and preparation sides thereof based on bipentaerythrite
Method and application, be specifically related to a kind of low viscosity based on bipentaerythrite 6 degree of functionality urethane acrylate and preparation method thereof 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 6 officials at Chinese patent ZL 201310143291.5 (Authorization Notice No. CN 103224603 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 the prepared 6 degree of functionality polyurethane propylene of trimethylolpropane diacrylate reaction
Acid esters.6 degree of functionality urethane acrylates are prepared, instead owing to have employed diisocyanate and trimethylolpropane diacrylate
Answering process steps many, relatively cumbersome, 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 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
The one 6 degree of functionality urethane acrylate provided for Chinese patent ZL 201310143291.5 is provided
And its preparation method and application improve or expand, it is provided that a kind of low viscosity 6 degree of functionality polyurethane third based on bipentaerythrite
Olefin(e) acid ester.
It is a further object of the present invention to provide the preparation method of this low viscosity 6 degree of functionality urethane acrylate.
It is yet another object of the invention to provide the application of this low viscosity 6 degree of functionality urethane acrylate.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of low viscosity 6 degree of functionality urethane acrylate, is prepared via a method which to obtain: first by bipentaerythrite in catalysis
Under agent effect with oxirane or propylene oxide reaction and prepare PH, PH again with isocyanates acrylic acid second
(2-Isocyanatoethyl Acrylate is called for short AOI, No. CAS: 13641-96-8, molecular formula: C to ester6H7NO3, molecule
Amount: 141.12) the prepared 6 degree of functionality urethane acrylates of reaction.
Wherein,
First step reaction scheme is as follows:
Work as n=2, R when being-H, react with bipentaerythrite for oxirane；Working as n=3, R is-CH3Time, for expoxy propane
React with bipentaerythrite；Wherein a+b+c+d+e+f=6～30.
The preparation of PH comprises the following steps: bipentaerythrite under catalyst action, in autoclave in
155 DEG C～165 DEG C dropping oxirane or propylene oxide reaction, reaction pressure controls, 0.1～0.6MPa, to drip epoxy second
After alkane or expoxy propane, 155 DEG C～165 DEG C are incubated 1～3 hour again, are subsequently cooled to less than 80 DEG C, add atlapulgite stirring
0.5～2 hour, be circulated press filtration until clear, must as shown in formula (I) PH；Wherein, described double
Pentaerythrite is 1mol:6～30mol, preferably 1mol:8～11mol with the amount ratio of oxirane or expoxy propane.
Described catalyst is that one or more arbitrary proportions in sodium formate, potassium formate, Sodium Benzoate, Potassium Benzoate mix
And thing, catalyst amount is bipentaerythrite and oxirane or 0.5wt%～5wt% of expoxy propane gross mass, is preferably
0.5wt%～1wt%.
Atlapulgite consumption is bipentaerythrite and oxirane or 0.5wt%～5wt% of expoxy propane gross mass.
Obtained PH and isocyanates ethyl acrylate according to amount ratio 1mol:5.8～6.1mol, in 60 DEG C～
95 DEG C are reacted and prepare 6 described degree of functionality urethane acrylates.
Preferably, obtained PH and isocyanates ethyl acrylate according to amount ratio 1mol:5.9～6mol,
Catalyst, polymerization inhibitor effect under in 80 DEG C～95 DEG C stirring insulation reaction 3～6 hours prepare 6 degree of functionality polyurethane acroleic acids
Ester.Wherein, polymerization inhibitor can be MEHQ or hydroquinones, and its consumption is PH and isocyanates acrylic acid
The 100～5000ppm of ethyl ester gross mass；Catalyst is dibutyl tin laurate, and its consumption is PH and isocyanic acid
The 100～3000ppm of ester ethyl acrylate gross mass.
Second step reaction scheme is as follows:
PH and isocyanates ethyl acrylate react to obtain 6 degree of functionality urethane acrylates:
R1For:
N=2 or 3, a+b+c+d+e+f=6～30.
It is that 6 hydroxyls in bipentaerythrite are carried out with epoxy third (second) alkane that the first step of the present invention prepares the reaction of 6 hydroxy polyethers
Opening (anionic polymerisation), for known organic chemical reactions, under the conditions of the reaction according to the invention, epoxy third
(second) alkane is gaseous state, and continuous feed is complete, then insulation reaction 1～3 hours, drops to perseverance to high pressure reacting kettle inner pressure
Fixed, i.e. epoxy third (second) alkane reacts completely, and conversion ratio is more than 99.9%；Second step reaction is isocyanates ethyl acrylate
In the reaction of isocyano and hydroxyl, belong to known synthesis of polyurethane (polyurethanes) reaction.
The preparation method of 6 degree of functionality urethane acrylates of the present invention, comprises the following steps: first existed by bipentaerythrite
Under catalyst action with oxirane or propylene oxide reaction and prepare PH, PH again with isocyanates propylene
Acetoacetic ester reaction prepares 6 degree of functionality urethane acrylates (i.e. formula (II) compound).
Wherein, the preparation of PH comprises the following steps: bipentaerythrite is under catalyst action, in autoclave
In 155 DEG C～165 DEG C dropping oxirane or propylene oxide reaction, reaction pressure controls, 0.1～0.6MPa, to drip epoxy
After ethane or expoxy propane, 155 DEG C～165 DEG C are incubated 1～3 hour again, are subsequently cooled to less than 80 DEG C, add atlapulgite and stir
Mix 0.5～2 hour, be circulated press filtration until clear, obtain PH (formula (I))；Wherein, described double seasons
Penta tetrol is 1mol:6～30mol, preferably 1mol:8～11mol with the amount ratio of oxirane or expoxy propane.
Described catalyst is that one or more arbitrary proportions in sodium formate, potassium formate, Sodium Benzoate, Potassium Benzoate mix
And thing, catalyst amount is bipentaerythrite and oxirane or 0.5wt%～5wt% of expoxy propane gross mass, is preferably
0.5wt%～1wt%.
The preparation method of 6 degree of functionality urethane acrylates of the present invention, obtained PH and isocyanates third
Olefin(e) acid ethyl ester, according to amount ratio 1mol:5.8～6.1mol, prepares 6 described degree of functionality polyurethane in 60 DEG C～95 DEG C reactions
Acrylate.
Preferably, obtained PH and isocyanates ethyl acrylate according to amount ratio 1mol:5.9～6mol,
Catalyst, polymerization inhibitor effect under in 80 DEG C～95 DEG C stirring insulation reaction 3～6 hours prepare 6 degree of functionality polyurethane acroleic acids
Ester；Wherein, polymerization inhibitor can be MEHQ or hydroquinones, and its consumption is PH and isocyanates acrylic acid
The 100～5000ppm of ethyl ester gross mass；Catalyst is dibutyl tin laurate, and its consumption is PH and isocyanic acid
The 100～3000ppm of ester ethyl acrylate gross mass.
Low viscosity 6 degree of functionality urethane acrylate of the present invention answering in preparing UV coating, ink or adhesive
With.
Beneficial effect:
It is different from traditional method that the present invention prepares polyethers used catalyst, and the catalyst used by conventional method is NaOH, hydrogen
Potassium oxide, after polymerisation is complete, needs to add phosphate aqueous solution and is neutralized process, and then high vacuum dehydration, press filtration are gathered
Ether；The present invention uses one or more arbitrary proportions in sodium formate, potassium formate, Sodium Benzoate, Potassium Benzoate to mix
Thing, after being polymerized, it is not necessary to acid adding adds water neutralization, it is not necessary to high vacuum is dehydrated, and only need to add atlapulgite overanxious, and filter residue passes through
Water-soluble, catalyst-solvent, filter out atlapulgite, the aqueous solution of catalyst is through evaporative crystallization, it is achieved recycling, reaction
Process belongs to green catalysis and cleaning produces.
The present invention uses isocyanates ethyl acrylate to prepare urethane acrylate, decreases reactions steps, course of reaction letter
Single, easily controllable, it is difficult to produce gel because of side reaction, urethane acrylate product viscosity is low, meets and is applied to low viscosity
Coating, is not added with for UV spraying or few solubilizer；This low viscosity 6 degree of functionality UV curable urethane acrylate solidifies
After, there is the premium properties such as hardness is high, wear-resisting, scratch resistance, heat-resisting, weatherability, it is possible to as UV coating, ink, viscous
The raw material application of mixture.
Detailed description of the invention
Embodiment 1
2542 grams of bipentaerythrites (CAS 126-58-9, chemical formula C are put in 6L autoclave10H22O7, point
Son amount 254.28), 56 grams of sodium formates, it is warming up to 155 DEG C, starts to drip oxirane (C2H4O, molecular weight 44) 3520
Gram react, temperature control 155 DEG C～165 DEG C, pressure 0.10～0.40MPa, drip 3～4 hours, drip off rear 155 DEG C～
165 DEG C are incubated 2～3 hours, are subsequently cooled to less than 80 DEG C, and discharging obtains crude product；Crude product adds atlapulgite 50 grams stirring 30
After minute, obtain clear PH (C through overanxious26H54O15, molecular weight 606) and 5938.2 grams, structure such as formula
(I) shown in, wherein: n=2, a+b+c+d+e+f=8.
Prepared PH (C is put in 1000mL four-hole boiling flask26H54O15, molecular weight 606) and 303 grams, isocyanide
Acid esters ethyl acrylate 423 grams (3mol), catalyst dibutyltin dilaurylate 0.33 gram, polymerization inhibitor MEHQ
1.2 grams, within 0.5～4 hour, it is to slowly warm up to 80 DEG C～85 DEG C of insulation reaction 3～discharging in 5 hours, prepares 6 degree of functionality polyurethane
Acrylate, shown in structure such as formula (II), wherein:
R1For:
N=2, a+b+c+d+e+f=8.
Embodiment 2
2542 grams of bipentaerythrites (CAS 126-58-9, chemical formula C are put in 6L autoclave10H22O7, point
Son amount 254.28), 65 grams of potassium formates, it is warming up to 155 DEG C, starts to drip expoxy propane (C3H6O, molecular weight 58) 5800
Gram react, temperature control 155 DEG C～165 DEG C, pressure 0.10～0.40MPa, drip 3～4 hours, drip off rear 155 DEG C～
165 DEG C are incubated 2～3 hours, are subsequently cooled to less than 80 DEG C, and discharging obtains crude product；Crude product adds atlapulgite 60 grams stirring 30
After minute, obtain clear PH (C through overanxious40H82O17, molecular weight 834) and 5170.2 grams, structure such as formula
(I) shown in, wherein: n=3, a+b+c+d+e+f=10.
Prepared PH (C is put in 1000mL four-hole boiling flask40H82O17, molecular weight 834) and 417 grams, isocyanide
Acid esters ethyl acrylate 423 grams (3mol), catalyst dibutyltin dilaurylate 0.4 gram, polymerization inhibitor MEHQ 1.5
Gram, within 0.5～4 hour, it is to slowly warm up to 80 DEG C～85 DEG C of insulation reaction 3～discharging in 5 hours, prepares 6 degree of functionality polyurethane propylene
Acid esters, shown in structure such as formula (II), wherein:
R1For:
N=3, a+b+c+d+e+f=10.
Embodiment 3
6 degree of functionality polyurethane acroleic acids are prepared with reference to the preparation method of embodiment 1-2 in Chinese patent ZL201310143291.5
Ester, the 6 degree of functionality polyurethane third prepared respectively as comparative example 1-2, investigation embodiment of the present invention 1-2 and comparative example 1-2
The viscosity of olefin(e) acid ester.
Method of testing: NDJ-1 type rotary 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 16 degree of functionality urethane acrylate
| Comparative example 1 | Embodiment 1 | Comparative example 2 | Embodiment 2 | |
| Viscosity | 14000mPa.s@60℃ | 7100mPa.s@60℃ | 16000mPa.s@60℃ | 8200mPa.s@60℃ |
Embodiment 1 product comparison ratio 1 product viscosity declines 6900mPa.s@60 DEG C, and fall is 49.29%.
Embodiment 2 product comparison ratio 2 product viscosity declines 7800mPa.s@60 DEG C, and fall is 48.75%.
Embodiment 4
Raw material
UV resin is 1.: the low viscosity 6 degree of functionality aliphatic urethane acrylate of embodiment 1 preparation (uses 6 degree of functionality fat
The purpose of fat adoption urethane acrylate is to increase the hardness of film, intensity, the performance such as wear-resisting)；
UV resin is 2.: low viscosity 2 degree of functionality aliphatic urethane acrylate (uses 2 degree of functionality aliphatic polyurethane propylene
The purpose of acid esters is to increase the flexibility of film, anti-riot splits, cold-hot cycle performance), preparation method is as follows:
PTMEG (Chongqing Chi Yuan Chemical Co., Ltd., PTMG is put in 1000mL four-hole boiling flask
PTMEG2000, molecular weight 2000) 500 grams, isocyanates ethyl acrylate 70.5 grams (0.5mol), catalyst dibutyltin cinnamic acid
Dibutyl tin 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 of insulation reaction
Discharging in 3～5 hours, prepares 2 degree of functionality polycaprolactone polyurethane acrylate of the structure that is shown below.
R is: (CH2CH2CH2CH2O)nCH2CH2CH2CH2—；
N=(2000-90)/72=26.5278.
The viscosity determining procedure using embodiment 3 records the viscosity of 2 prepared degree of functionality polycaprolactone polyurethane acrylate
3600mPa.s@60℃。
UV monomer: trimethylolpropane trimethacrylate (TMPTA, profit field, Jiangsu)；1,6 hexanediol diacrylate
(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
Different formulations is formed, respectively with 6 degree of functionality aliphatic urethane acrylates and 2 degree of functionality aliphatic urethane acrylate resins
Planting Ingredient Amount and be shown in Table 2, film performance is shown in Table 3.
Table 36 official's urethane acrylate and the impact on coating property of the 2 official's 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 (10)
1. 6 degree of functionality urethane acrylates based on bipentaerythrite, it is characterised in that: 6 described degrees of functionality are gathered
Urethane acrylate is prepared via a method which to obtain: first by bipentaerythrite under catalyst action with oxirane or epoxy third
Alkane reacts and prepares PH, and PH reacts with isocyanates ethyl acrylate and prepares 6 degree of functionality polyurethane third
Olefin(e) acid ester.
6 degree of functionality urethane acrylates the most according to claim 1, it is characterised in that: the preparation of PH
Comprise the following steps: bipentaerythrite, under catalyst action, drips epoxy second in 155 DEG C～165 DEG C in autoclave
Alkane or propylene oxide reaction, reaction pressure controls 0.1～0.6MPa, drip after oxirane or expoxy propane 155 DEG C～
165 DEG C are incubated 1～3 hour again, are subsequently cooled to less than 80 DEG C, add atlapulgite and stir 0.5～2 hour, are circulated
Press filtration, until clear, obtains PH；Wherein, described bipentaerythrite and oxirane or the consumption of expoxy propane
Ratio is 1mol:6～30mol.
6 degree of functionality urethane acrylates the most according to claim 2, it is characterised in that: described catalyst is first
One or more arbitrary proportion mixtures in acid sodium, potassium formate, Sodium Benzoate, Potassium Benzoate, catalyst amount is double
Pentaerythrite and oxirane or 0.5wt%～5wt% of expoxy propane gross mass.
6 degree of functionality urethane acrylates the most according to claim 1, it is characterised in that: obtained hexahydroxy gathers
Ether and isocyanates ethyl acrylate according to amount ratio 1mol:5.8～6.1mol, prepare described in 60 DEG C～95 DEG C reactions
6 degree of functionality urethane acrylates.
6 degree of functionality urethane acrylates the most according to claim 4, it is characterised in that: obtained hexahydroxy gathers
Ether and isocyanates ethyl acrylate according to amount ratio 1mol:5.9～6mol, catalyst, polymerization inhibitor effect under in
80 DEG C～95 DEG C stirring insulation reaction 3～6 hours prepared 6 degree of functionality urethane acrylates；Wherein, polymerization inhibitor is to hydroxyl
Methyl phenyl ethers anisole or hydroquinones, its consumption is the 100～5000ppm of PH and isocyanates ethyl acrylate gross mass；
Catalyst is dibutyl tin laurate, its consumption be PH with the 100 of isocyanates ethyl acrylate gross mass～
3000ppm。
6. the preparation method of 6 degree of functionality urethane acrylates described in claim 1, it is characterised in that: include following step
Rapid: first by bipentaerythrite under catalyst action with oxirane or propylene oxide reaction and prepare PH, hexahydroxy
Polyethers reacts with isocyanates ethyl acrylate and prepares 6 degree of functionality urethane acrylates.
The preparation method of 6 degree of functionality urethane acrylates the most according to claim 6, it is characterised in that: hexahydroxy
The preparation of polyethers comprises the following steps: bipentaerythrite is under catalyst action, in 155 DEG C～165 DEG C in autoclave
Dropping oxirane or propylene oxide reaction, reaction pressure controls, 0.1～0.6MPa, to drip oxirane or expoxy propane
Latter 155 DEG C～165 DEG C are incubated 1～3 hour again, are subsequently cooled to less than 80 DEG C, add atlapulgite stirring 0.5～2 little
Time, it is circulated press filtration until clear, obtains PH；Wherein, described bipentaerythrite and oxirane or ring
The amount ratio of Ethylene Oxide is 1mol:6～30mol；
Described catalyst is that one or more arbitrary proportions in sodium formate, potassium formate, Sodium Benzoate, Potassium Benzoate mix
And thing, catalyst amount is bipentaerythrite and oxirane or 0.5wt%～5wt% of expoxy propane gross mass.
The preparation method of 6 degree of functionality urethane acrylates the most according to claim 6, it is characterised in that: obtained
PH and isocyanates ethyl acrylate according to amount ratio 1mol:5.8～6.1mol, in 60 DEG C～95 DEG C reactions
Prepare 6 described degree of functionality urethane acrylates.
The preparation method of 6 degree of functionality urethane acrylates the most according to claim 8, it is characterised in that: obtained
PH and isocyanates ethyl acrylate according to amount ratio 1mol:5.9～6mol, at catalyst, the work of polymerization inhibitor
6 degree of functionality urethane acrylates are prepared in 80 DEG C～95 DEG C stirring insulation reaction 3～6 hours under with；Wherein, polymerization inhibitor is
MEHQ or hydroquinones, its consumption be PH with the 100 of isocyanates ethyl acrylate gross mass～
5000ppm；Catalyst is dibutyl tin laurate, and its consumption is PH and isocyanates ethyl acrylate gross mass
100～3000ppm.
10. the answering in preparing UV coating, ink or adhesive of 6 degree of functionality urethane acrylates described in claim 1
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610234875.7A CN105860026A (en) | 2016-04-15 | 2016-04-15 | Hexa-functionality urethane acrylate based on dipentaerythritol and preparation method and application of hexa-functionality urethane acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610234875.7A CN105860026A (en) | 2016-04-15 | 2016-04-15 | Hexa-functionality urethane acrylate based on dipentaerythritol and preparation method and application of hexa-functionality urethane acrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105860026A true CN105860026A (en) | 2016-08-17 |
Family
ID=56632156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610234875.7A Pending CN105860026A (en) | 2016-04-15 | 2016-04-15 | Hexa-functionality urethane acrylate based on dipentaerythritol and preparation method and application of hexa-functionality urethane acrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105860026A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018181710A1 (en) | 2017-03-31 | 2018-10-04 | 三井化学株式会社 | Multifunctional monomer for dental material, and hydroxyl group-containing monomer for dental material |
| CN116396474A (en) * | 2023-04-10 | 2023-07-07 | 宜兴市江山生物科技有限公司 | Hyperbranched polyether ester with multiple purposes and preparation method thereof |
-
2016
- 2016-04-15 CN CN201610234875.7A patent/CN105860026A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018181710A1 (en) | 2017-03-31 | 2018-10-04 | 三井化学株式会社 | Multifunctional monomer for dental material, and hydroxyl group-containing monomer for dental material |
| US11406571B2 (en) | 2017-03-31 | 2022-08-09 | Mitsui Chemicals, Inc. | Dental polyfunctional monomers and dental hydroxyl group-containing monomers |
| EP3603607B1 (en) * | 2017-03-31 | 2023-09-20 | Mitsui Chemicals, Inc. | Multifunctional monomer for dental material, and hydroxyl group-containing monomer for dental material |
| US11786444B2 (en) | 2017-03-31 | 2023-10-17 | Mitsui Chemicals, Inc. | Dental polyfunctional monomers and dental hydroxyl group-containing monomers |
| CN116396474A (en) * | 2023-04-10 | 2023-07-07 | 宜兴市江山生物科技有限公司 | Hyperbranched polyether ester with multiple purposes and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105859584B (en) | One kind being based on the 3 degree of functionality urethane acrylates and its preparation method and application of trihydroxy methyl second (third) alkane | |
| CN103274967B (en) | Tri-functional polyurethane acrylate, and preparation method and application thereof | |
| CN103224603B (en) | Urethane acrylate with six functionalities as well as preparation method and application thereof | |
| CN105801829B (en) | 2 degree of functionality polycaprolactone polyurethane acrylate of one kind and its preparation method and application | |
| CN105859586A (en) | 2-functionality-degree makrolon urethane acrylate and preparation method and application thereof | |
| CN103242508B (en) | A kind of 4 functionality urethane acrylates and its preparation method and application | |
| CN105859585B (en) | A kind of 3 degree of functionality urethane acrylates based on glycerine and its preparation method and application | |
| CN105859587B (en) | A kind of 4 degree of functionality urethane acrylates based on pentaerythrite and its preparation method and application | |
| CN103214649B (en) | 9-functionality-degree polyurethane acrylate as well as preparation method and application thereof | |
| CN107254251A (en) | A kind of aqueous UV urethane acrylate dispersoids with self-initiating function and preparation method thereof | |
| CN105859997A (en) | 3-functionality-degree polycaprolactone urethane acrylate and preparation method and application thereof | |
| CN105801807A (en) | 2-functionality-degree polyether urethane acrylate and preparation method and application thereof | |
| CN105860028A (en) | Tri-functionality urethane acrylate based on 2, 2-dimethylolpropionic acid/2, 2-dimethylolbutanoic acid and preparation method and application of tri-functionality urethane acrylate | |
| CN106750140A (en) | A kind of amine modified urethane acrylate light-cured resin and preparation method thereof | |
| CN101967341A (en) | Waterborne wear-resisting ultraviolet-cured glazing oil and preparation method thereof | |
| CN105505197B (en) | Ultraviolet-curing paint and preparation method thereof | |
| CN105820063B (en) | A kind of 4 degree of functionality urethane acrylates based on anhydrous citric acid and its preparation method and application | |
| CN107189032A (en) | A kind of multifunctional UV solidification polyurethane vegetable oil acid esters prepolymers and its preparation method and application | |
| CN107903372A (en) | A kind of UV photocurings flexibility ultra-branched polyurethane acrylate resin and preparation method and application | |
| CN103193953B (en) | Urethane acrylate with functionality of 12 as well as preparation method and application thereof | |
| CN101274977A (en) | Curing agent 1,6- hexamethylene diisocyanate prepolymer and preparation thereof | |
| CN105801791B (en) | A kind of castor oil-base UV cured polyurethane acrylates and its preparation method and application | |
| CN106995655A (en) | No-solvent type UV cure coating compositions and coating | |
| CN105860027A (en) | 2-functionality-degree polyester-based urethane acrylate and preparation method and application thereof | |
| CN105884655B (en) | A kind of 4 degree of functionality urethane acrylates based on double trimethylolpropane and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160817 |