CN101928508B - Polyethylene glycol-modified epoxy acrylate coating and preparation method thereof - Google Patents
Polyethylene glycol-modified epoxy acrylate coating and preparation method thereof Download PDFInfo
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- CN101928508B CN101928508B CN 201010263021 CN201010263021A CN101928508B CN 101928508 B CN101928508 B CN 101928508B CN 201010263021 CN201010263021 CN 201010263021 CN 201010263021 A CN201010263021 A CN 201010263021A CN 101928508 B CN101928508 B CN 101928508B
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Abstract
The invention discloses a polyethylene glycol-modified epoxy acrylate coating and a preparation method thereof. The method comprises the following steps: firstly adding epoxy resin and catalyst to a reaction vessel, rising the temperature to be 105-115 DEG C under the stirring condition, adding modifier, and reacting for 2-4 hours; preparing modified resin; reducing the temperature to be 90-100 DEG C for the modified resin, adding the even mixture of catalyst, polymerization inhibitor and acrylic acid within 30-60min, and reacting for 3-5 hours at constant temperature; obtaining the polyethylene glycol-modified epoxy acrylate resin; and adding an activated monomer, photoinitiator, flatting agent and antifoaming agent to the polyethylene glycol-modified epoxy acrylate resin, and evenly stirring and mixing to obtain the polyethylene glycol-modified epoxy acrylate coating. The photocureable coating prepared by the method has the advantages of far low viscosity, excellent adhesion and storage stability; and the solidified film has the performances of excellent flexibility, luster, pencil hardness, water tolerance, acid resistance, alkali resistance and the like.
Description
Technical field
The present invention relates to a kind of epoxy acrylate coating, particularly relate to a kind of poly ethyldiol modified epoxy acrylate coating and preparation method thereof, this coating is applicable to fields such as woodenware, metallic substance.
Background technology
In recent years; World's environmental regulation is perfect day by day; Require harsh day by day; Traditional solvent based coating has been because the discharging of volatile organic matter (VOC) has received great impact, and is that the environment-friendly coating of representative becomes that people pay close attention to and the focus of research with ultraviolet-curing paint (UVCC), water-borne coatings, high solid coating and powder coating.Compare with the coating of other types, the UVCC curing speed is fast, solidification value is low, environmental protection and energy saving, coating performance excellent, can be used for the coating of thermo-sensitivity grounds such as plastics, paper and timber.
Epoxy acrylate coating strong adhesion, chemical resistance are good, the coating film gloss degree high, hardness is high, resistance toheat is excellent, inexpensive, are the maximum and most widely used light-cured resin coating of present consumption.
The epoxy acrylate coating that prior art is produced, resin viscosity is high, is semi-solid, needs to add a large amount of reactive thinners and regulates viscosity.Because reactive thinner all has special irritating smell and higher toxicity, and local environment is had pollution, and there is injury in operator; And reactive thinner costs an arm and a leg, and product cost is increased.In addition, after epoxy acrylate coating solidified, its fragility height of filming, poor in flexibility, easy to crack influenced decorative effect.
Owing to adopt the excessive mode of epoxy resin during the synthesizing epoxy propenoate at present, cause epoxide group more in the product to exist, so the package stability of resin be relatively poor; Traditional preparation process technology often adopts higher temperature of reaction, causes side reaction easily; And catalyst selectivity is not done, and causes resin viscosity to rise and degradation.
In sum, existing prescription and the existing shortcoming of preparation technology thereof of producing epoxy acrylate coating, cause shorter resin storage period, over-all properties not high, need mix more reactive monomer.Therefore epoxy acrylate is carried out modification, prolong the storage period of resin, under the situation of mixing reactive monomer less, improve the over-all properties of filming, have positive meaning reducing resin cost and toxicity.
Summary of the invention
The objective of the invention is provides poly ethyldiol modified epoxy acrylate coating of a kind of ultraviolet light polymerization and preparation method thereof in order to solve the deficiency of prior art, and the photo-cured coating for preparing through this method has low viscosity, and cured film has excellent flexibility.
The object of the invention realizes through following technical scheme:
A kind of preparation method of poly ethyldiol modified epoxy acrylate coating comprises the steps:
(1) preparation of poly ethyldiol modified Epocryl
A, in reaction vessel, add epoxy resin and catalyzer, catalyzer is the 0.3-0.4% of weight epoxy; Be warming up to 105-115 ℃ under stirring, add properties-correcting agent, the mol ratio of properties-correcting agent and epoxy resin is 0.08-0.1: 1, and temperature control and back flow reaction 2-4 hour; Make modified resin; Described properties-correcting agent is PEG 400 and/or Polyethylene Glycol-600; Described epoxy resin is bisphenol A type epoxy resin;
B, the modified resin of step a gained is cooled to 90-100 ℃, adds catalyzer, stopper and acrylic acid uniform mixture, the control mixture added isothermal reaction 3-5 hour in 30-60 minute; When the system acid number of recording was lower than 5mgKOH/g, cooling discharging got poly ethyldiol modified Epocryl; Catalyzer is the 0.6-0.8% of modified resin weight, and stopper is the 0.05-0.07% of modified resin weight; The mol ratio of vinylformic acid and modified resin epoxy group(ing) is 1.02-1.05: 1;
Catalyzer among said step a and the step b is triphenyl phosphorus and/or Tetrabutyl amonium bromide;
Described stopper is a MEHQ;
(2) preparation of the poly ethyldiol modified epoxy acrylate coating of ultraviolet light polymerization
In the poly ethyldiol modified Epocryl of step (1) gained, add reactive monomer, light trigger, flow agent and skimmer, mix, obtain the poly ethyldiol modified epoxy acrylate coating of uV curable;
Described reactive monomer is one or more in bifunctional monomer and the trifunctional monomer; Described bifunctional monomer is tripropylene glycol double methacrylate or the two Ucar 35 double methacrylate that contracts, and described trifunctional monomer is a Viscoat 295, and addition is the 8-10% of this step composition of raw materials gross weight;
Described light trigger is 2-hydroxy-2-methyl-1-phenyl-acetone and/or 1-hydroxyl-cyclohexyl benzophenone, and addition is the 3-4% of this step composition of raw materials gross weight;
Described flow agent is polyether-modified YSR 3286 interpolymer solution, and addition is the 0.3-0.5% of this step composition of raw materials gross weight;
Described skimmer is broken bubble polymkeric substance and polysiloxane solution, and addition is the 0.6-0.8% of this step composition of raw materials gross weight.
Said bisphenol A type epoxy resin is preferably epoxy resin E-51 or epoxy resin E-44.
Mixing preferably of said step (2) mixes on electric blender.
Said dropping catalyzer, stopper and acrylic acid uniform mixture preferably added in 35-45 minute.
A kind of poly ethyldiol modified epoxy acrylate coating is by method for preparing.
With respect to prior art, the present invention has following advantage and beneficial effect:
(1) the present invention introduces long soft segment by polyoxyethylene glycol and epoxy resin reaction in molecular structure, and changes the original structure of epoxy resin, has reduced the viscosity of epoxy resin preferably, and has made resin have excellent flexibility.Resin has the utmost point LV of 263cp (60 ℃), and cured film has excellent flexibility, for 1-3mm (normal temperature), improves greatly than currently available products.
(2) the present invention adopts the excessive slightly prescription condition of vinylformic acid for guaranteeing the abundant reaction of epoxide group, makes the synthetic resin that good stability arranged.
Embodiment
For better understanding the present invention, below in conjunction with embodiment the present invention is done further explanation, but the scope that the present invention requires to protect is not limited to the scope that embodiment representes.
Embodiment 1
(1) preparation of poly ethyldiol modified Epocryl
The epoxy resin E-51 and the 0.12g triphenyl phosphorus that in reaction vessel, add 39.2g stir down and are warming up to 110 ℃, add the 4g PEG 400,110 ℃ of temperature controls, and back flow reaction 3 hours, the first step reaction end; Be cooled to 95 ℃, in reaction vessel, drip 0.26g triphenyl phosphorus, 0.026g MEHQ and the acrylic acid uniform mixture of 13.22g, be controlled in the 35min and add isothermal reaction 4 hours.The system acid number of recording is lower than 5mgKOH/g, and cooling discharging gets poly ethyldiol modified Epocryl.
(2) preparation of the poly ethyldiol modified epoxy acrylate coating of ultraviolet light polymerization
Get step (1) gained binder resin 43.5g; Stir and to add 1g Irgacure1173 (2-hydroxy-2-methyl-1-phenyl-acetone), 0.5g Irgacure184 (1-hydroxyl-cyclohexyl benzophenone), 2g TPGDA (tripropylene glycol double methacrylate), 1g DPGDA (two contract Ucar 35 double methacrylate), 1.5g TMPTA (Viscoat 295), the 0.2g BYK-300 (solution of polyether-modified YSR 3286 interpolymer down; The leveling auxiliary agent of producing for German Bi Ke company) with 0.3g BYK-066N (broken polymkeric substance and the polysiloxane solution of steeping; The froth breaking auxiliary agent of producing for German Bi Ke company); On electric blender, mix, obtain the poly ethyldiol modified epoxy acrylate coating I-1 of uV curable.
Embodiment 2
(1) preparation of poly ethyldiol modified Epocryl
In reaction vessel, add 45.5g epoxy resin E-44 and 0.14g Tetrabutyl amonium bromide, be warming up to 105 ℃ under stirring, add the 4.8g Polyethylene Glycol-600, temperature control and back flow reaction 3.5 hours, the first step reaction finishes; Be cooled to 90 ℃, in reaction vessel, drip 0.3g Tetrabutyl amonium bromide, 0.035g MEHQ and the acrylic acid uniform mixture of 13.51g, be controlled in the 50min and add isothermal reaction 4.5 hours.The system acid number of recording is lower than 5mgKOH/g, and cooling discharging gets poly ethyldiol modified Epocryl.
(2) preparation of the poly ethyldiol modified epoxy acrylate coating of ultraviolet light polymerization
Get step (1) gained binder resin 42.5g; Stir and add 1g Irgacure1173,1g Irgacure184,2gTPGDA, 1.5gDPGDA, 1.5gTMPTA, 0.15gBYK-300 and 0.35gBYK-066N down; On electric blender, mix, obtain the poly ethyldiol modified epoxy acrylate coating I-2 of uV curable.
Embodiment 3
(1) preparation of poly ethyldiol modified Epocryl
In reaction vessel, add 39.2g epoxy resin E-51 and 0.14g Tetrabutyl amonium bromide, be warming up to 115 ℃ under stirring, add the 6g Polyethylene Glycol-600, temperature control and back flow reaction 4 hours, the first step reaction finishes; Be cooled to 100 ℃, in reaction vessel, drip 0.27g Tetrabutyl amonium bromide, 0.027g MEHQ and the acrylic acid uniform mixture of 13.22g, be controlled in the 40min and add isothermal reaction 3.5 hours.The system acid number of recording is lower than 5mgKOH/g, and cooling discharging gets poly ethyldiol modified Epocryl.
(2) preparation of the poly ethyldiol modified epoxy acrylate coating of ultraviolet light polymerization
Get step (1) gained binder resin 43g; Stir adding 0.5g Irgacure1173,1g Irgacure184,2g TPGDA, 1.5gDPGDA, 1.5gTMPTA, 0.25gBYK-300 and 0.3gBYK-066N down, obtain the poly ethyldiol modified epoxy acrylate coating I-3 of uV curable.
Embodiment 4
(1) preparation of poly ethyldiol modified Epocryl
In reaction vessel, add 45.5g epoxy resin E-44 and 0.14g triphenyl phosphorus, be warming up to 110 ℃ under stirring, add the 3.2g PEG 400, temperature control and back flow reaction 3 hours, the first step reaction finishes; Be cooled to 95 ℃, in reaction vessel, drip 0.29g triphenyl phosphorus, 0.029g MEHQ and the acrylic acid uniform mixture of 13.51g, be controlled in the 45min and add isothermal reaction 4 hours.The system acid number of recording is lower than 5mgKOH/g, and cooling discharging gets poly ethyldiol modified Epocryl.
(2) preparation of the poly ethyldiol modified epoxy acrylate coating of ultraviolet light polymerization
Get step (1) gained binder resin 43.45g; Stir adding 1g Irgacure1173,1g Irgacure184,1.5g TPGDA, 1.5g DPGDA, 1g TMPTA, 0.15g BYK-300 and 0.4g BYK-066N down, obtain the poly ethyldiol modified epoxy acrylate coating I-4 of uV curable.
Embodiment 5
(1) preparation of poly ethyldiol modified Epocryl
In reaction vessel, add 39.2g epoxy resin E-51 and 0.15g triphenyl phosphorus, be warming up to 108 ℃ under stirring, add the 4.8g Polyethylene Glycol-600, temperature control and back flow reaction 3 hours, the first step reaction finishes; Be cooled to 92 ℃, in reaction vessel, drip 0.27g triphenyl phosphorus, 0.023g MEHQ and the acrylic acid uniform mixture of 13.51g, be controlled in the 50min and add isothermal reaction 4.5 hours.The system acid number of recording is lower than 5mgKOH/g, and cooling discharging gets poly ethyldiol modified Epocryl.
(2) preparation of the poly ethyldiol modified epoxy acrylate coating of ultraviolet light polymerization
Get step (1) gained binder resin 43.4g; Stir adding 1g Irgacure1173,0.5g Irgacure184,2g TPGDA, 1.5g DPGDA, 1g TMPTA, 0.25g BYK-300 and 0.35g BYK-066N down, obtain the poly ethyldiol modified epoxy acrylate coating I-5 of uV curable.
Above embodiment product performance are tested, and compare with commercially available unmodified product, the result sees table 1 for details.Wherein the vast eastern agency's of trade Co., Ltd in Guangzhou 621A-80 type epoxy acrylate is adopted in the commercially available prod; Package stability for range estimation, viscosity adopt that the BrookfieldRVDL-II+ viscosity apparatus is measured, pencil hardness according to standard GB/T1730-93 test, sticking power according to GB/T1720-79 measure, flexility according to GB/T1731-93 measure, glossiness is according to GB/T1743-89, adopts that 60 ° of photoelectric glossmeters are measured, water-fast, milk acid, alkalescence is respectively according to GB/T1733-93, GB/T1763-89 mensuration.
Table 1 product of the present invention and commercially available resistance are relatively
| Sample | Package stability | Dope viscosity (cp/25 ℃) | Sticking power/level | Snappiness (mm) | Hardness | Gloss/60 ° | Water-fast, sour, alkali |
| I-1 | There is not considerable change half a year | 1007 | 0 | 3 | 6H | 91.9％ | Excellent |
| I-2 | There is not considerable change half a year | 1430 | 0 | 1 | 5H | 93.2％ | Excellent |
| I-3 | There is not considerable change half a year | 1200 | 0 | 2 | 6H | 90.5％ | Excellent |
| I-4 | There is not considerable change half a year | 1135 | 0 | 2 | 6H | 92.5％ | Excellent |
| I-5 | There is not considerable change half a year | 1350 | 0 | 1 | 5H | 92.1％ | Excellent |
| Commercially available | Half a year, viscosity became big | 4500 | 0 | More than 10 | 6H | 92.7％ | Excellent |
Table 1 result shows: modified epoxy acrylic ester coating of the present invention is keeping outside excellent pencil hardness, sticking power, gloss and water-fast, the acid-and base-resisting performance; Has extremely low viscosity; About 1000-1350cp/25 ℃ (can not adding reactive monomer fully uses) is merely about 1/4 of commercially available article; Filming after the curing has more excellent flexibility, and 1-3mm only, and commercially available article snappiness extreme difference are more than 10mm; In addition, this product shelf-stable.Prove that modified epoxy acrylic ester coating of the present invention has more performance advantage than the commercially available prod.
Claims (4)
1. the preparation method of a poly ethyldiol modified epoxy acrylate coating is characterized in that, comprises the steps:
(1) preparation of poly ethyldiol modified Epocryl
A, in reaction vessel, add epoxy resin and catalyzer, catalyzer is the 0.3-0.4% of weight epoxy; Be warming up to 105-115 ℃ under stirring, add properties-correcting agent, the mol ratio of properties-correcting agent and epoxy resin is 0.08-0.1: 1, and temperature control and back flow reaction 2-4 hour; Make modified resin; Described properties-correcting agent is PEG 400 and/or Polyethylene Glycol-600; Described epoxy resin is bisphenol A type epoxy resin; Said bisphenol A type epoxy resin is epoxy resin E-51 or epoxy resin E-44;
B, the modified resin of step a gained is cooled to 90-100 ℃, adds catalyzer, stopper and acrylic acid uniform mixture, the control mixture added isothermal reaction 3-5 hour in 30-60 minute; When the system acid number of recording was lower than 5mgKOH/g, cooling discharging got poly ethyldiol modified Epocryl; Catalyzer is the 0.6-0.8% of modified resin weight, and stopper is the 0.05-0.07% of modified resin weight; The mol ratio of vinylformic acid and modified resin epoxy group(ing) is 1.02-1.05: 1;
Catalyzer among said step a and the step b is triphenyl phosphorus and/or Tetrabutyl amonium bromide;
Described stopper is a MEHQ;
(2) preparation of the poly ethyldiol modified epoxy acrylate coating of ultraviolet light polymerization
In the poly ethyldiol modified Epocryl of step (1) gained, add reactive monomer, light trigger, flow agent and skimmer, mix, obtain the poly ethyldiol modified epoxy acrylate coating of uV curable;
Described reactive monomer is one or more in bifunctional monomer and the trifunctional monomer; Described bifunctional monomer is tripropylene glycol double methacrylate or the two Ucar 35 double methacrylate that contracts, and described trifunctional monomer is a Viscoat 295, and addition is the 8-10% of this step composition of raw materials gross weight;
Described light trigger is 2-hydroxy-2-methyl 1-phenyl-acetone and/or 1-hydroxy-cyclohexyl benzophenone, and addition is the 3-4% of this step composition of raw materials gross weight;
Described flow agent is polyether-modified YSR 3286 interpolymer solution, and addition is the 0.3-0.5% of this step composition of raw materials gross weight;
Described skimmer is broken bubble polymkeric substance and polysiloxane solution, and addition is the 0.6-0.8% of this step composition of raw materials gross weight.
2. the preparation method of poly ethyldiol modified epoxy acrylate coating according to claim 1 is characterized in that mixing of said step (2) is on electric blender, to mix.
3. the preparation method of poly ethyldiol modified epoxy acrylate coating according to claim 1 is characterized in that said dropping catalyzer, stopper and acrylic acid uniform mixture added in 35-45 minute.
4. a poly ethyldiol modified epoxy acrylate coating is characterized in that, it is by the said method preparation of claim 1.
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| CN103333321A (en) * | 2013-07-10 | 2013-10-02 | 无锡市金盛助剂厂 | Synthetic method of modified bisphenol A epoxy acrylate resin |
| CN103360576A (en) * | 2013-07-24 | 2013-10-23 | 无锡市金盛助剂厂 | Synthetic method of modified bisphenol A epoxy acrylate |
| CN103450446B (en) * | 2013-08-26 | 2016-02-03 | 江苏高博智融科技有限公司 | A kind of synthetic method of modified bisphenol A epoxy acrylate |
| CN103524712A (en) * | 2013-08-26 | 2014-01-22 | 无锡市金盛助剂厂 | Synthetic method of modified bisphenol A epoxy acrylate |
| CN103450447B (en) * | 2013-08-26 | 2016-02-03 | 江苏高博智融科技有限公司 | A kind of synthetic method of modified bisphenol A epoxy acrylate |
| CN103450449B (en) * | 2013-08-26 | 2016-02-03 | 江苏高博智融科技有限公司 | A kind of synthetic method of modified bisphenol A epoxy acrylate |
| CN103554386B (en) * | 2013-10-22 | 2016-06-01 | 北京金汇利应用化工制品有限公司 | The preparation method of a kind of self-emulsifying bicomponent epoxy resin |
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| CN105400383A (en) * | 2014-09-11 | 2016-03-16 | 洋紫荆油墨（浙江）有限公司 | Flexible ultraviolet-light-curable varnishing oil and preparation method thereof |
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