CN105820063B - A kind of 4 degree of functionality urethane acrylates based on anhydrous citric acid and its preparation method and application - Google Patents

A kind of 4 degree of functionality urethane acrylates based on anhydrous citric acid and its preparation method and application Download PDF

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CN105820063B
CN105820063B CN201610236643.5A CN201610236643A CN105820063B CN 105820063 B CN105820063 B CN 105820063B CN 201610236643 A CN201610236643 A CN 201610236643A CN 105820063 B CN105820063 B CN 105820063B
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citric acid
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tetrahydroxy
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functionality urethane
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CN105820063A (en
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胡剑飞
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JIANGSU LITIAN TECHNOLOGY CO LTD
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JIANGSU LITIAN TECHNOLOGY Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (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 a kind of degree of functionality urethane acrylate of low viscosity 4, it is prepared via a method which to obtain：First reacted by anhydrous citric acid under catalyst action with oxirane or expoxy propane and tetrahydroxy citric acid polyether ester is made, tetrahydroxy citric acid polyether ester reacts with isocyanates ethyl acrylate again is made 4 degree of functionality urethane acrylates.The present invention is prepared using isocyanates ethyl acrylate during urethane acrylate, course of reaction is simple, easily controllable, is not easy to produce gel because of side reaction, urethane acrylate product viscosity is low, satisfaction is applied to low-viscosity dope, is not added with for UV sprayings or lacks solubilizer；After the degree of functionality UV curable urethane acrylates of low viscosity 4 solidification, there is the premium properties such as high hardness, wear-resisting, scratch resistance, heat-resisting, weatherability, can be in the raw material application as UV coating, ink, adhesive.

Description

A kind of 4 degree of functionality urethane acrylates and its preparation side based on anhydrous citric acid Method and application
Technical field
The invention belongs to Material Field, be related to a kind of 4 degree of functionality urethane acrylates based on anhydrous citric acid and its Preparation method and application, and in particular to a kind of the degree of functionality urethane acrylate of low viscosity 4 and its system based on anhydrous citric acid Preparation Method and application.
Background technology
With the rapid development of science and technology with strict limitation of the legislations of environmental protection to solvent, UV photocuring macromolecule materials Material is increasingly valued by people.UV photo-curing materials have quick solidifying, energy consumption be low, pollution less, the premium properties such as efficiency height, The fields such as coating, printing and electronics industry thus are widely used in, are quickly grown in recent years.Urethane acrylate (polyurethane acrylate, PUA) is a kind of important Photocurable oligomers, has low stimulation, curing rate fast, high The premium properties such as the transparency, stretch-proof, cohesive energy height, are widely used in the fields such as light-curable ink, coating, adhesive, the U.S., Japan, countries in Europe are widely used.In recent years, with rise of the UV-curing technology in China, new photocuring material Expect that the raw material purposes as UV coating, ink, adhesive is more and more wider, usage amount is increasing year by year.
Applicant discloses one kind in Chinese patent ZL 201310143167.9 (B of Authorization Notice No. CN 103242508) 4 degree of functionality urethane acrylates, are prepared via a method which to obtain：First by anhydrous citric acid under catalyst action with epoxy Prepared by ethane or expoxy propane react tetrahydroxy citric acid polyether ester, tetrahydroxy citric acid polyether ester again with diisocyanate The reaction of (one kind in HDI, IPDI, HMDI, MDI) and hydroxy-ethyl acrylate or hydroxypropyl acrylate is made 4 degrees of functionality and gathered Urethane acrylate.The poly- ammonia of 4 degrees of functionality is prepared as a result of diisocyanate and hydroxy-ethyl acrylate or hydroxypropyl acrylate Ester acrylate, course of reaction step is more, relatively cumbersome, and production process is difficult to control, because the presence of side reaction can produce gel Risk.
Light-cured resin is the matrix resin of photocureable coating, wide in variety, is widely used.With in global range to environment The pay attention to day by day of problem, light-cured resin will be fast-developing with the development of photocureable coating.Develop more environmentally-friendly, viscous Spend the striving direction that low, combination property is more excellent light-cured resin is WeiLai Technology personnel.
The content of the invention
The purpose of the present invention is the degree of functionality polyurethane third of one kind 4 provided for Chinese patent ZL 201310143167.9 Olefin(e) acid ester and its preparation method and application is improved, there is provided a kind of degree of functionality polyurethane of low viscosity 4 based on anhydrous citric acid Acrylate.
It is a further object of the present invention to provide the preparation method of the degree of functionality urethane acrylate of low viscosity 4.
It is yet another object of the invention to provide the application of the degree of functionality urethane acrylate of low viscosity 4.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of degree of functionality urethane acrylate of low viscosity 4, is prepared via a method which to obtain：First existed by anhydrous citric acid Reacted under catalyst action with oxirane or expoxy propane and tetrahydroxy citric acid polyether ester is made, tetrahydroxy lemon polyether acid Ester again with isocyanates ethyl acrylate (2-Isocyanatoethyl Acrylate, abbreviation AOI, No. CAS：13641-96-8, Molecular formula：C6H7NO3, molecular weight：141.12) react and 4 degree of functionality urethane acrylates are made.
Wherein,
First step reaction scheme is as follows：
Work as n=2 ,-R is oxirane and citric acid reactions when being-H；Work as n=3 ,-R is-CH3When be expoxy propane and lemon Lemon acid reaction；Wherein a+b+c+d=5~8.
The preparation of tetrahydroxy citric acid polyether ester comprises the following steps：Anhydrous citric acid is under catalyst action, in high pressure Oxirane or expoxy propane reaction is added dropwise in reactor in 155 DEG C~165 DEG C, reaction pressure control is in 0.1~0.6MPa, drop Add after oxirane or expoxy propane 155 DEG C~165 DEG C and be incubated 1~3 hour again, be subsequently cooled to less than 80 DEG C, add and live Property carclazyte stir 0.5~2 hour, circulate press filtration until clear, obtain the tetrahydroxy lemon polyether acid as shown in formula (I) Ester；Wherein, the amount ratio of described anhydrous citric acid and oxirane or expoxy propane is 1mol：5~8mol.
Described catalyst is any ratio of the one or more in sodium formate, potassium formate, sodium benzoate, Potassium Benzoate Example mixture, catalyst amount are anhydrous citric acid and oxirane or 0.5wt%~5wt% of expoxy propane gross mass, excellent Elect 0.5wt%~3wt% as.
Atlapulgite dosage is anhydrous citric acid and oxirane or 0.9wt%~5wt% of expoxy propane gross mass.
Obtained tetrahydroxy citric acid polyether ester is with isocyanates ethyl acrylate according to amount ratio 1mol：3.8~ 4.1mol, 4 described degree of functionality urethane acrylates are made in 60 DEG C~95 DEG C reactions.
Preferably, obtained tetrahydroxy citric acid polyether ester and isocyanates ethyl acrylate are according to amount ratio 1mol： 3.9~4mol, 3~6 hours obtained 4 degrees of functionality of insulation reaction are stirred in 80 DEG C~95 DEG C in the presence of catalyst, polymerization inhibitor Urethane acrylate；Wherein, polymerization inhibitor can be MEHQ or hydroquinones, and its dosage is that tetrahydroxy citric acid gathers Ether-ether and 100~5000ppm of isocyanates ethyl acrylate gross mass；Catalyst is dibutyl tin laurate, its dosage For tetrahydroxy citric acid polyether ester and 100~3000ppm of isocyanates ethyl acrylate gross mass.
Second step reaction scheme is as follows：
Tetrahydroxy citric acid polyether ester reacts to obtain 4 degree of functionality urethane acrylates with isocyanates ethyl acrylate：
R1For：
N=2 or 3, a+b+c+d=5~8.
The reaction that the first step of the present invention prepares 4 hydroxycitric acid polyether esters be 3 carboxyls in citric acid and 1 hydroxyl with The opening (anionic polymerisation) that epoxy third (second) alkane is carried out, for known organic chemical reactionses, reacted in the present invention Under the conditions of, epoxy third (second) alkane is gaseous state, and continuous feed finishes, then insulation reaction 1~3 hour, to high pressure reacting kettle inner pressure Drop to constant, i.e., epoxy third (second) alkane reacts completely, and conversion ratio is more than 99.9%；Second step reaction is isocyanates propylene The reaction of isocyano and hydroxyl in acetoacetic ester, synthesis of polyurethane (polyurethanes) known to category react.
The preparation method of 4 degree of functionality urethane acrylate of the present invention, comprises the following steps：First by anhydrous lemon Acid reacts with oxirane or expoxy propane under catalyst action and tetrahydroxy citric acid polyether ester is made, tetrahydroxy citric acid Polyether ester reacts with isocyanates ethyl acrylate again is made 4 degree of functionality urethane acrylates (i.e. formula (II) compound).
Wherein, the preparation of tetrahydroxy citric acid polyether ester comprises the following steps：Anhydrous citric acid under catalyst action, Be added dropwise oxirane or expoxy propane reaction in autoclave in 155 DEG C~165 DEG C, reaction pressure control 0.1~ 0.6MPa, drip after oxirane or expoxy propane 155 DEG C~165 DEG C and be incubated 1~3 hour again, be subsequently cooled to 80 DEG C with Under, add atlapulgite and stir 0.5~2 hour, carry out circulating press filtration until clear, obtains tetrahydroxy citric acid polyether ester (formula (I)), wherein, the amount ratio of described anhydrous citric acid and oxirane or expoxy propane is 1mol：5~8mol.
Described catalyst is any ratio of the one or more in sodium formate, potassium formate, sodium benzoate, Potassium Benzoate Example mixture, catalyst amount are anhydrous citric acid and oxirane or 0.5wt%~5wt% of expoxy propane gross mass, excellent Elect 0.5wt%~3wt% as.
The preparation method of 4 degree of functionality urethane acrylate of the present invention, obtained tetrahydroxy lemon polyether acid Ester is with isocyanates ethyl acrylate according to amount ratio 1mol：3.8~4.1mol, it is made described in 60 DEG C~95 DEG C reactions 4 degree of functionality urethane acrylates.
Preferably, obtained tetrahydroxy citric acid polyether ester and isocyanates ethyl acrylate are according to amount ratio 1mol： 3.9~4mol, 3~6 hours obtained 4 degrees of functionality of insulation reaction are stirred in 80 DEG C~95 DEG C in the presence of catalyst, polymerization inhibitor Urethane acrylate；Wherein, polymerization inhibitor can be MEHQ or hydroquinones, and its dosage is that tetrahydroxy citric acid gathers Ether-ether and 100~5000ppm of isocyanates ethyl acrylate gross mass；Catalyst is dibutyl tin laurate, its dosage For tetrahydroxy citric acid polyether ester and 100~3000ppm of isocyanates ethyl acrylate gross mass.
The degree of functionality urethane acrylate of low viscosity 4 of the present invention is in UV coating, ink or adhesive is prepared Using.
Beneficial effect：
The present invention prepares that polyether ester used catalyst is different from traditional method, and the catalyst used in conventional method is hydrogen-oxygen Change sodium, potassium hydroxide, it is necessary to which the aqueous acid that phosphorates carries out neutralisation treatment after polymerisation is complete, then high vacuum dehydration, press filtration obtains To polyether ester；The present invention is using one or more kinds of arbitrary proportions in sodium formate, potassium formate, sodium benzoate, Potassium Benzoate Mixture, after having polymerize, it is not necessary to which acid adding adds water to neutralize, it is not necessary to which high vacuum is dehydrated, and only atlapulgite need to be added overanxious, filter residue warp Water-soluble, catalyst-solvent is crossed, filters out atlapulgite, the aqueous solution of catalyst is realized recycling, reacted through evaporative crystallization Process belongs to green catalysis and clean manufacturing.Using anhydrous citric acid, course of reaction reclaimed water and oxirane or epoxy are avoided Propane reacts, and produces accessory substance ethylene glycol or propane diols.
The present invention prepares urethane acrylate using isocyanates ethyl acrylate, reduces reactions steps, reacted Journey is simple, easily controllable, is not easy to produce gel because of side reaction, and urethane acrylate product viscosity is low, meets applied to low Viscous coating material, it is not added with for UV sprayings or lacks solubilizer；The degree of functionality UV curable urethane acrylates of low viscosity 4 solidify Afterwards, there is the premium properties such as hardness is high, wear-resisting, scratch resistance, heat-resisting, weatherability, can be as UV coating, ink, adhesive Raw material application.
Embodiment
Embodiment 1
1920 grams of anhydrous citric acid (C are put into 6L autoclaves6H8O7, molecular weight 192), 40 grams of sodium formates, heating To 155 DEG C, start that oxirane (C is added dropwise2H4O, molecular weight 44) 2200 grams reacted, 155 DEG C~165 DEG C of temperature control, pressure 0.10~0.40MPa, it is added dropwise 3~4 hours, 155 DEG C~165 DEG C are incubated 2~3 hours after dripping off, and are subsequently cooled to less than 80 DEG C, Discharge to obtain crude product；After crude product adds the stirring 30 minutes of 40 grams of atlapulgite, clear tetrahydroxy lemon polyether acid is obtained through overanxious Ester (C16H28O12, molecular weight 412) and 4037.6 grams, shown in structure such as formula (I), wherein：N=2, a+b+c+d=5.
The tetrahydroxy citric acid polyether ester (C made from input in 1000mL four-hole boiling flasks16H28O12, molecular weight 412) and 206 Gram, isocyanates ethyl acrylate 282.24 grams (2mol), 0.3 gram of catalyst dibutyltin dilaurylate, polymerization inhibitor is to hydroxyl 1 gram of methyl phenyl ethers anisole, it is to slowly warm up within 0.5~4 hour 80 DEG C~85 DEG C insulation reactions and discharges for 3~5 hours, the poly- ammonia of 4 degrees of functionality is made Ester acrylate, shown in structure such as formula (II), wherein：
R1For：
N=2, a+b+c+d=5.
Embodiment 2
1920 grams of anhydrous citric acid (C are put into 6L autoclaves6H8O7, molecular weight 192), 60 grams of potassium formates, heating To 155 DEG C, start that expoxy propane (C is added dropwise3H6O, molecular weight 58) 3480 grams reacted, 155 DEG C~165 DEG C of temperature control, pressure 0.10~0.40MPa, it is added dropwise 3~4 hours, 155 DEG C~165 DEG C are incubated 2~3 hours after dripping off, and are subsequently cooled to less than 80 DEG C, Discharge to obtain crude product；After crude product adds the stirring 30 minutes of 60 grams of atlapulgite, clear tetrahydroxy lemon polyether acid is obtained through overanxious Ester (C24H44O13, molecular weight 540) and 5292 grams, shown in structure such as formula (I), wherein：N=3, a+b+c+d=6.
The tetrahydroxy citric acid polyether ester (C made from input in 1000mL four-hole boiling flasks24H44O13, molecular weight 540) and 270 Gram, isocyanates ethyl acrylate 280 grams (1.984mol), 0.3 gram of catalyst dibutyltin dilaurylate, polymerization inhibitor is to hydroxyl 1 gram of methyl phenyl ethers anisole, it is to slowly warm up within 0.5~4 hour 80 DEG C~85 DEG C insulation reactions and discharges for 3~5 hours, the poly- ammonia of 4 degrees of functionality is made Ester acrylate, shown in structure such as formula (II), wherein：
R1For：
N=3, a+b+c+d=6.
Embodiment 3
4 degree of functionality polyurethane third are made with reference to the preparation method of embodiment 1-2 in Chinese patent ZL201310143167.9 Olefin(e) acid ester, respectively as comparative example 1-2, investigate 4 degree of functionality polyurethane made from 1-2 of the embodiment of the present invention and comparative example 1-2 The viscosity of acrylate.
Method of testing：NDJ-1 type rotary viscosimeters, No. 4 rotors, 60 revs/min.Concrete operation step refers to《NDJ-1 Type rotation viscometer operation instructions》.
The viscosity of the degree of functionality urethane acrylate of table 14
Comparative example 1 Embodiment 1 Comparative example 2 Embodiment 2
Viscosity 12000mPa.s@60℃ 6200mPa.s@60℃ 15000mPa.s@60℃ 8000mPa.s@60℃
The product viscosity of 1 product comparison ratio of embodiment 1 declines 60 DEG C of 5800mPa.s@, fall 48.33%.
The product viscosity of 2 product comparison ratio of embodiment 2 declines 60 DEG C of 7000mPa.s@, fall 46.67%.
Embodiment 4
Raw material
UV resins are 1.：The degree of functionality aliphatic urethane acrylate of low viscosity 4 prepared by embodiment 1 (uses 4 degree of functionality fat The purpose of fat adoption urethane acrylate is to increase the performance such as the hardness of film, intensity, wear-resisting)；
UV resins are 2.：The degree of functionality aliphatic urethane acrylate of low viscosity 2 (uses 2 degree of functionality aliphatic polyurethanes third The purpose of olefin(e) acid ester is to increase the flexibility of film, anti-riot to split, cold-resistant thermal circulation performance), preparation method is as follows：
500 grams of polycaprolactone glycol (Bai Situo CAPA2209, molecular weight 2000) is put into 1000mL four-hole boiling flasks, it is different Cyanate ethyl acrylate 70.5 grams (0.5mol), 0.1 gram of catalyst dibutyltin dilaurylate, polymerization inhibitor MEHQ 0.6 gram, it is to slowly warm up within 0.5~4 hour 80 DEG C~85 DEG C insulation reactions and discharges for 3~5 hours, the structure that is shown below is made 2 degree of functionality polycaprolactone polyurethane acrylate.
R is 1,2- ethylidene：—CH2CH2-, i.e., dihydric alcohol initiator is ethylene glycol in polycaprolactone glycol；
A+b=(2000-62)/114=17.
Use with the viscosity determining procedure of embodiment 3 measure the viscosity of 2 degree of functionality polycaprolactone polyurethane acrylate for 4100mPa.s@60℃。
UV monomers：Double pentaerythritol methacrylate (DPHA, Jiangsu profit field)；1,6- hexanediyl ester (HDDA, Jiangsu profit field).
Light trigger：1173, Nanjing Wa Li Chemical Industry Science Co., Ltd.
Auxiliary agent：Tego432, Tego92, German enlightening are high.
Mixed solvent：Butyl acetate, toluene, methylisobutylketone are 1 in mass ratio：1：1 mixing.
Instrument and equipment
LT-1002 type uv cure machines, blue sky Te Deng Development Co., Ltds；QFZ type paint film adhesion analyzers, Tianjin Ke Lian Material Testing Machine factory of city；RCA paper tape wear resistant instruments, Shanghai modern environment project research institute；Water-bath；Cold cycling is set It is standby.
The preparation of coating
The UV resins of certain mass are weighed, UV monomers, mixed solvent, light trigger, auxiliary agent is then added, stirs, It is configured to coating.The proportioning of coating is shown in Table 2.
The proportioning of the coating of table 2
The preparation and solidification of film
From 10cm × 10cm ABS plastic sheet material, first at one layer of thermoplastic acrylic resin white bottom of its surface spraying Paint, 60 DEG C of baking 3h, then the UV coating prepared in its surface spraying according to table 2, coating thickness is about 20 μm, on photo solidification machine Solidification, makes cured film reach surface drying, is characterized with tack method, records hardening time.
Performance test
Hardening time：Experiment uses tack method, touches coating surface with finger, if do not felt tacky, that is, thinks paint film Surface is cured.
Pencil hardness：With reference to GB 6739-86 films pencil hardness method measure.
Adhesive force：With reference to GB/T 1720-88 film adhesives determination method measure.It is divided into 7 grades, 1 grade optimal, and 7 grades worst.
Wearability：RCA is tested, 175g, 500 ± 50 times.
Water boiling resistance：With reference to standard GB/T/T 1733《Paint film water resistance determination method》.
Cold-resistant thermal cycle：
(1) scope and explanation：Plastic paint because moisture and hot ageing or losses of plasticizer, or both and it sometimes appear that cracking Trend, using the degree for being alternately exposed to can to determine paint film in climate cabinet and household freezer and whether ftractureing and ftractureing.
(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 38 DEG C of incubator hot tank. The placement of model should be with a vertical 0-30 degree angle, and requires that plate plate is mutually not in contact with each other during experiment.2. after 24h, stand Model is moved to 20h in the household freezer of (- 23 ± 1.5) DEG C, 30S is at most not to be exceeded in transfer time.3. model is taken out, 4h is placed at room temperature, and so altogether 48h is a circulation, during which can carry out stage evaluation.4. 15 circulations are carried out altogether, it is then right Model outward appearance, color, adhesive force are tested.
(4) result represents：Film should be without cracking, discoloration, adhesive force decline or other defects.
(5) reference standard：Unite States Standard AAMA 615-02《The industry rule of high-performance organic coating on plastic material Model, performance requirement and test method》.(1)
As a result with discussion, influence of the resin to film performance
UV resins are the main bodys of UV coating, and its performance substantially determines the main performance of film after solidification.This experiment Different formulations are formed using 4 degree of functionality aliphatic urethane acrylates and 2 degree of functionality aliphatic urethane acrylate resins, Various composition dosage is shown in Table 2, and film performance is shown in Table 3.
The influence of the official's urethane acrylate of table 34 and 2 official's urethane acrylate different ratios to coating property
Bibliography：(1) the Yu Yingying coatings industries method of inspection and instrument complete works 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：It is colourless to light yellow transparent liquid
Purity：>=99.0%
Boiling point：80-81 DEG C (degree Celsius)
Light transmittance：425nm >=99.0%；500nm >=99.3%
Fugitive constituent：≤ 0.2%
Ash：≤ 0.10%
Using：
1173 are applied to acrylic acid photocuring varnish system, such as varnish of timber, metal, paper, plastics etc..1173 is special Do not recommend needing to be subjected in the UV-curable coating of chronic sun exposure and color inhibition, because 1173 be liquid, be highly susceptible to altogether It is mixed, so being adapted to and other light trigger compounding uses, it is proposed that addition is 1~4%w/w.

Claims (10)

  1. A kind of 1. 4 degree of functionality urethane acrylates based on anhydrous citric acid, it is characterised in that：The described poly- ammonia of 4 degrees of functionality Ester acrylate is prepared via a method which to obtain：First by anhydrous citric acid under catalyst action with oxirane or epoxy third Alkane is reacted and tetrahydroxy citric acid polyether ester is made, and tetrahydroxy citric acid polyether ester reacts with isocyanates ethyl acrylate again to be made Obtain 4 degree of functionality urethane acrylates.
  2. 2. 4 degree of functionality urethane acrylate according to claim 1, it is characterised in that：Tetrahydroxy citric acid polyether ester Preparation comprise the following steps：Anhydrous citric acid is under catalyst action, in 155 DEG C~165 DEG C dropwise additions in autoclave Oxirane or expoxy propane reaction, reaction pressure control is in 0.1~0.6MPa, after dripping 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, carry out Press filtration is circulated until clear, obtains tetrahydroxy citric acid polyether ester；Wherein, described anhydrous citric acid and oxirane or ring The amount ratio of Ethylene Oxide is 1mol：5~8mol.
  3. 3. 4 degree of functionality urethane acrylate according to claim 2, it is characterised in that：Described catalyst is formic acid One or more kinds of arbitrary proportion mixtures in sodium, potassium formate, sodium benzoate, Potassium Benzoate, catalyst amount are anhydrous Citric acid and oxirane or 0.5wt%~5wt% of expoxy propane gross mass.
  4. 4. 4 degree of functionality urethane acrylate according to claim 1, it is characterised in that：Obtained tetrahydroxy lemon Polyether acid ester is with isocyanates ethyl acrylate according to amount ratio 1mol：3.8~4.1mol, it is made in 60 DEG C~95 DEG C reactions 4 described degree of functionality urethane acrylates.
  5. 5. 4 degree of functionality urethane acrylate according to claim 4, it is characterised in that：Obtained tetrahydroxy lemon Polyether acid ester is with isocyanates ethyl acrylate according to amount ratio 1mol：3.9~4mol, in the presence of catalyst, polymerization inhibitor Insulation reaction is stirred in 80 DEG C~95 DEG C and 4 degree of functionality urethane acrylates are made within 3~6 hours.Wherein polymerization inhibitor is to hydroxyl Methyl phenyl ethers anisole or hydroquinones, its dosage be tetrahydroxy citric acid polyether ester and isocyanates ethyl acrylate gross mass 100~ 5000ppm；Catalyst is dibutyl tin laurate, and its dosage is tetrahydroxy citric acid polyether ester and isocyanates acrylic acid second 100~3000ppm of ester gross mass.
  6. 6. the preparation method of 4 degree of functionality urethane acrylates described in claim 1, it is characterised in that：Comprise the following steps： First reacted by anhydrous citric acid under catalyst action with oxirane or expoxy propane and tetrahydroxy citric acid polyether ester be made, Tetrahydroxy citric acid polyether ester reacts with isocyanates ethyl acrylate again is made 4 degree of functionality urethane acrylates.
  7. 7. the preparation method of 4 degree of functionality urethane acrylate according to claim 6, it is characterised in that：Tetrahydroxy lemon The preparation of lemon polyether acid ester comprises the following steps：Anhydrous citric acid under catalyst action, in autoclave in 155 DEG C~ 165 DEG C of dropwise addition oxirane or expoxy propane reaction, reaction pressure are controlled in 0.1~0.6MPa, drip oxirane or ring 155 DEG C~165 DEG C are incubated 1~3 hour again after Ethylene Oxide, are subsequently cooled to less than 80 DEG C, add atlapulgite stirring 0.5~2 Hour, carry out circulating press filtration until clear, obtains tetrahydroxy citric acid polyether ester；Wherein, described anhydrous citric acid and ring The amount ratio of oxidative ethane or expoxy propane is 1mol：5~8mol；
    Described catalyst is that one or more kinds of arbitrary proportions in sodium formate, potassium formate, sodium benzoate, Potassium Benzoate mix And thing, catalyst amount are anhydrous citric acid and oxirane or 0.5wt%~5wt% of expoxy propane gross mass.
  8. 8. the preparation method of 4 degree of functionality urethane acrylate according to claim 6, it is characterised in that：Obtained Tetrahydroxy citric acid polyether ester is with isocyanates ethyl acrylate according to amount ratio 1mol：3.8~4.1mol, in 60 DEG C~95 DEG C React and 4 described degree of functionality urethane acrylates are made.
  9. 9. the preparation method of 4 degree of functionality urethane acrylate according to claim 8, it is characterised in that：Obtained Tetrahydroxy citric acid polyether ester is with isocyanates ethyl acrylate according to amount ratio 1mol：3.9~4mol, in catalyst, inhibition Insulation reaction is stirred in 80 DEG C~95 DEG C 4 degree of functionality urethane acrylates are made in 3~6 hours in the presence of agent；Wherein, inhibit Agent is MEHQ or hydroquinones, and its dosage is tetrahydroxy citric acid polyether ester and the total matter of isocyanates ethyl acrylate 100~5000ppm of amount；Catalyst is dibutyl tin laurate, and its dosage is tetrahydroxy citric acid polyether ester and isocyanic acid 100~3000ppm of ester ethyl acrylate gross mass.
  10. 10. application of the 4 degree of functionality urethane acrylates in UV coating, ink or adhesive is prepared described in claim 1.
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