Summary of the invention
The objective of the invention is the above-mentioned deficiency at prior art, a kind of 3 functionality urethane acrylates are provided.
Another object of the present invention provides the preparation method of this 3 functionality urethane acrylate.
Another purpose of the present invention provides the application of this 3 functionality urethane acrylate.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of 3 functionality urethane acrylates, prepare by the following method: earlier by 2, the trihydroxy-polyether ester that the 2-dimethylol propionic acid makes with oxyethane or propylene oxide reaction under catalyst action, trihydroxy-polyether ester make 3 functionality urethane acrylates with vulcabond and Hydroxyethyl acrylate or Propylene glycol monoacrylate reaction again.
Wherein,
The first step reaction scheme is as follows:
Work as n=2 ,-R is oxyethane and 2 during for-H, and the 2-dimethylol propionic acid reacts; Work as n=3 ,-R is-CH
3The time be the reaction of propylene oxide and 2,2-dimethylol propionic acid; A+b+c=4~8 wherein.
The preparation of trihydroxy-polyether ester may further comprise the steps: 1mol2, the 2-dimethylol propionic acid is under catalyst action, in autoclave, drip 4~8mol oxyethane or propylene oxide reaction in 155 ℃~165 ℃, reaction pressure control is at 0.2-0.6MPa, drip behind oxyethane or the propylene oxide 155 ℃~165 ℃ and be incubated 1~3 hour again, be cooled to then below 80 ℃, add atlapulgite and stirred 30 minutes, circulate press filtration until clear, get the trihydroxy-polyether ester.
Described catalyzer is one or both or the two or more arbitrary proportion miscellany in sodium formiate, potassium formiate, Sodium Benzoate, the potassium benzoate, and catalyst levels is the 1wt%~5wt% of 2,2-dimethylol propionic acid and oxyethane or propylene oxide total mass.The consumption of atlapulgite is the 1wt%~5wt% of 2,2-dimethylol propionic acid and oxyethane or propylene oxide total mass.
3 functionality urethane acrylates of the present invention, the preferred prepared trihydroxy-polyether ester of 1mol and 3~3.5mol vulcabond and 3~5mol Hydroxyethyl acrylate or Propylene glycol monoacrylate make described 3 functionality urethane acrylates in 60 ℃~95 ℃ reactions.
3 functionality urethane acrylates of the present invention, the further preferred prepared trihydroxy-polyether ester of 1mol and 3~3.5mol vulcabond are warmed up to 60 ℃~65 ℃ stirring insulation reaction and got intermediate formula (III) compound in 2~3 hours under the catalysis of catalyzer dibutyl tin laurate, intermediate formula (III) compound is at stopper, slowly be warming up to 80 ℃~85 ℃ insulation reaction in 0.5~1 hour with 3~5mol Hydroxyethyl acrylate or Propylene glycol monoacrylate under the effect of catalyzer dibutyl tin laurate and made 3 functionality urethane acrylates in 4~5 hours.Wherein stopper can be MEHQ or Resorcinol, and its consumption is 100-5000ppm, and the each consumption of catalyzer dibutyl tin laurate is 100-3000ppm.
Described vulcabond is selected from a kind of among TDI, HDI, IPDI, HMDI, the MDI.
The second step reaction scheme is as follows:
Trihydroxy-polyether ester and di-isocyanate reaction get intermediate:
(intermediate (III))
Intermediate and Hydroxyethyl acrylate react 3 functionality urethane acrylates:
(intermediate (III))
The present invention wherein the first step reaction for preparing the trihydroxy-polyether ester is 2, the opening (anionoid polymerization) that 1 carboxyl in the 2-dimethylol propionic acid and 2 hydroxyls and epoxy third (second) alkane carry out, be known organic chemical reactions, under reaction conditions of the present invention, epoxy third (second) alkane is gaseous state, and continuously feeding finishes, insulation reaction 1-3 hour again, drop to the high pressure reacting kettle inner pressure constant, i.e. epoxy third (second) alkane complete reaction, transformation efficiency is more than 99.9%; The reaction of second step is the isocyano in the vulcabond and the reaction of hydroxyl, belongs to known synthesis of polyurethane (polyurethane(s)) reaction.
The preparation method of 3 functionality urethane acrylates of the present invention, prepare by the following method: earlier by 2, the trihydroxy-polyether ester that the 2-dimethylol propionic acid makes with oxyethane or propylene oxide reaction under catalyst action, trihydroxy-polyether ester make 3 functionality urethane acrylates (being formula (II) compound) with vulcabond and Hydroxyethyl acrylate or Propylene glycol monoacrylate reaction again.
Wherein, the preparation of trihydroxy-polyether ester may further comprise the steps: 1mol2, the 2-dimethylol propionic acid is under catalyst action, in autoclave, drip 4~8mol oxyethane or propylene oxide reaction in 155 ℃~165 ℃, reaction pressure control is at 0.2-0.6MPa, drip behind oxyethane or the propylene oxide 155 ℃~165 ℃ and be incubated 1~3 hour again, be cooled to then below 80 ℃, adding atlapulgite stirred 30 minutes, circulate press filtration until clear, get trihydroxy-polyether ester (formula (I)).
Described catalyzer is one or both or the two or more arbitrary proportion miscellany in sodium formiate, potassium formiate, Sodium Benzoate, the potassium benzoate, and catalyst levels is the 0.5wt%~3wt% of 2,2-dimethylol propionic acid and oxyethane or propylene oxide total mass.
The preparation method of 3 functionality urethane acrylates of the present invention, the prepared trihydroxy-polyether ester of 1mol and 3~3.5mol vulcabond and 3~5mol Hydroxyethyl acrylate or Propylene glycol monoacrylate make described 3 functionality urethane acrylates in 60 ℃~95 ℃ reactions; A kind of among the preferred TDI of described vulcabond, HDI, IPDI, HMDI, the MDI.
The application of 3 functionality urethane acrylates of the present invention in preparation UV coating, printing ink or tackiness agent.
Beneficial effect:
It is different with traditional method that the present invention prepares the polyether ester catalyst system therefor, and the used catalyzer of traditional method is sodium hydroxide, potassium hydroxide, after polyreaction is intact, need adds phosphate aqueous solution and carry out neutralizing treatment, and high vacuum dehydration then, press filtration obtain polyether ester; The present invention adopts one or both or the two or more arbitrary proportion miscellany in sodium formiate, potassium formiate, Sodium Benzoate, the potassium benzoate, after polymerization is intact, do not need to add acid and add the water neutralization, do not need the high vacuum dehydration, it is overanxious only need to add atlapulgite, filter residue is through water-soluble, catalyst-solvent filters out atlapulgite, and the aqueous solution of catalyzer is through evaporative crystallization, realize recycling, reaction process belongs to green catalysis and cleaner production.
The present invention discloses a kind of 3 new functionality UV light-cured polyurethane acrylate and preparation method thereof.After this 3 functionality UV light-cured polyurethane acrylate solidified, it was good to have hardness height, wear-resisting, scratch resistance, heat-resisting, weathering resistance etc., can use at the raw material as UV coating, printing ink, tackiness agent.
Embodiment
Embodiment 1:
In the 6L autoclave, drop into 1340 grams, 2,2-dimethylol propionic acid (C
5H
10O
4, molecular weight 134), 40 gram sodium formiates are warming up to 155 ℃, begin to drip oxyethane (C
2H
4O, molecular weight 44) 2200 grams react, 155 ℃~165 ℃ of temperature controls, and pressure 0.2~0.6MPa dripped 3~4 hours, dripped off back 155 ℃~165 ℃ and was incubated 2~3 hours, was cooled to then below 80 ℃, and discharging gets crude product; Crude product adds atlapulgite 40 grams and stirs after 30 minutes, gets clear trihydroxy-polyether ester (C through the circulation press filtration
15H
30O
9, molecular weight 354) and 3469.2 grams, structure is suc as formula shown in (I), wherein: n=2, a+b+c=5.
In the 3000mL four-hole boiling flask, drop into trihydroxy-polyether ester (C
15H
30O
9Molecular weight 354) 177 grams, IPDI333 restrains (1.5mol), catalyzer dibutyl tin laurate 0.2 gram, be warmed up to 60 ℃~65 ℃ and stirred insulation reaction 2~3 hours, add stopper MEHQ 1 gram then, catalyzer dibutyl tin laurate 0.2 gram, Hydroxyethyl acrylate 185 grams, 0.5 slowly be warming up to the discharging in 4~5 hours of 80 ℃~85 ℃ insulation reaction in~1 hour, make 3 functionality urethane acrylates, structure is suc as formula shown in (II), wherein:
R
1For:
n=2,a+b+c=5,
R
2For:
Embodiment 2:
In the 6L autoclave, drop into 1340 grams, 2,2-dimethylol propionic acid (C
5H
10O
4, molecular weight 134), 60 gram potassium formiates are warming up to 155 ℃, begin to drip propylene oxide (C
3H
6O, molecular weight 58) 3480 grams react, 155 ℃~165 ℃ of temperature controls, and pressure 0.2~0.6MPa dripped 3-4 hour, dripped off back 155 ℃~165 ℃ and was incubated 2-3 hour, was cooled to then below 80 ℃, and discharging gets crude product; Crude product adds atlapulgite 60 grams and stirs after 30 minutes, through circulation press consider clear trihydroxy-polyether ester (C
23H
46O
10, molecular weight 482) and 4723.6 grams, structure is suc as formula shown in (I), wherein: n=3, a+b+c=6.
In the 3000mL four-hole boiling flask, drop into trihydroxy-polyether ester (C
23H
46O
10, molecular weight 482) and 241 grams, the TDI(tolylene diisocyanate, molecular weight 174) 261 grams, catalyzer dibutyl tin laurate 0.2 gram is warmed up to 60 ℃~65 ℃ and stirred insulation reaction 2~3 hours, adds MEHQ 1 gram then, catalyzer dibutyl tin laurate 0.2 gram, Hydroxyethyl acrylate 185 grams slowly were warming up to the discharging in 4~5 hours of 80 ℃~85 ℃ insulation reaction, and made 3 functionality urethane acrylates in 0.5~1 hour, structure is suc as formula shown in (II), wherein:
R
1For:
n=3,a+b+c=6,
R
2For:
Embodiment 3
Starting material
3 functional group's aliphatic urethane acrylates of UV resin: embodiment 1 preparation; Two functional group's aliphatic urethane acrylates (F5202, sharp field, Jiangsu science and technology).
UV monomer: double pentaerythritol methacrylate (DPHA, sharp field, Jiangsu); 1,6 hexanediol diacrylate (HDDA, sharp field, Jiangsu).
Light trigger: 1173, Nanjing Wa Li Chemical Industry Science Co., Ltd.
Auxiliary agent: Tego432, Tego92, German enlightening height.
Mixed solvent: N-BUTYL ACETATE, toluene, mibk are that 1:1:1 mixes by mass ratio.
Instrument and equipment
LT-1002 type uv cure machine, the special lamp in blue sky Development Co., Ltd; QFZ type paint film adhesion determinator, connection material-testing machine factory of Tianjin section; RCA paper tape wear resistant instrument, Shanghai modern environment engineering and technological research institute; Water-bath; Cold cycling equipment.The preparation of coating
Take by weighing the UV resin of certain mass, add UV monomer, light trigger, auxiliary agent then, stir, be mixed with coating.The proportioning of coating sees Table l.
Table 1: the proportioning of coating
The preparation of filming and curing
Select the ABS plastic sheet material of 10cm * 10cm for use, earlier at its surface spraying one deck thermoplastic acrylic resin white primer, 60 ℃ of baking 3h, again at its surface spraying UV finish paint, coating thickness is about 20 μ m, solidifies at photo solidification machine, makes cured film reach surface drying, with referring to that touching dry method characterizes, and records set time.
Performance test
Set time: experiment is adopted and is referred to touch dry method, touches coating surface with finger, is clamminess as not feeling, thinks that namely coating surface solidifies.
Pencil hardness: measure with reference to the GB6739-86 pencil hardness method of filming.
Sticking power: measure with reference to GB/T1720-88 film adhesive assay method.Be divided into 7 grades, 1 grade of the best, 7 grades are the poorest.
Wear resistance: RCA test, 175g, 500 ± 50 times.
Water boiling resistance: with reference to standard GB/T1733 " paint film water tolerance assay method ".
Cold-resistant thermal cycling:
(1) scope and explanation: plastic paint is because of damp and hot circulation or losses of plasticizer, and perhaps both hold concurrently and occur the trend of cracking sometimes, adopt alternately to be exposed in climate cabinet and the refrigerated tank and can measure the degree whether paint film ftractures and ftracture.
(2) instrument: 1. damp and hot case, 2. refrigerated tank, 3. 4. color measurement instrument draws the lattice device.
(3) measuring method: 1. test piece is put into relative temperature 100%, temperature and be 38 ℃ the hot case 24h of incubator.The placement of model should become 0-30 degree angle with vertical direction, and requires the plate plate not contact mutually in process of the test.2. behind the 24h, immediately model is moved to 20h in the refrigerated tank of (23 ± 1.5) ℃, should not surpass 30S transfer time at most.3. take out model, at room temperature place 4h, 48h is a circulation so altogether, during can carry out stage evaluation.4. carry out 15 circulations altogether, then model outward appearance, color, sticking power are tested.
(4) result represents: film should not have cracking, variable color, loss of adhesion or other defective.
(5) reference standard: USS AAMA615-02 " industry standard, performance requriements and the test method that are used for high-performance organic coating on the plastic material ".
(1)
Result and discussion, resin is to the influence of film performance
The UV resin is the main body of UV coating, the salient features that its performance has been filmed after having determined basically to solidify.This experiment adopts 3 functional group's aliphatic urethane acrylates and two functional group's aliphatic urethane acrylate resins to form different ingredients, and various composition consumptions see Table 1, and film performance sees Table 2.
Table 2:3 functional polyurethane acrylate and the influence of the different proportionings of two functional polyurethane acrylate to coating property
Reference:
(1) Yu Yingying. the coatings industry method of inspection and instrument complete works. Beijing: Chemical Industry Press, 2007:525.
Attached light trigger 1173 explanations:
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 ℃ (degree centigrade)
Transmittance: 425nm 〉=99.0%; 500nm 〉=99.3%
Fugitive constituent :≤0.2%
Ash :≤0.10%
Use:
1173 are applicable to vinylformic acid photocuring varnish system, as varnish of timber, metal, paper, plastics etc. etc.1173 special recommendations needs stand the UV-of long-term Exposure to Sunlight and anti-xanthochromia coating material solidified in because 1173 be liquid, be highly susceptible to blend, so be fit to and the composite use of other light trigger, the suggestion addition is 1-4%w/w.