CN103333318A - Preparation method of polyurea acrylic ester - Google Patents
Preparation method of polyurea acrylic ester Download PDFInfo
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- CN103333318A CN103333318A CN2013102285006A CN201310228500A CN103333318A CN 103333318 A CN103333318 A CN 103333318A CN 2013102285006 A CN2013102285006 A CN 2013102285006A CN 201310228500 A CN201310228500 A CN 201310228500A CN 103333318 A CN103333318 A CN 103333318A
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Abstract
The invention discloses a preparation method of polyurea acrylic ester. The preparation method has the following steps of: 1) mixing acrylic acid with polyether amine, then reacting with diisocyanate, wherein the reaction time lasts for 0.5-2 hours, and the temperature of the reaction system is 40-60 DEG C; and 2) at 40-60 DEG C, adding a catalyst and hydroxyl-containing (methyl) acrylic ester into the system, increasing the temperature to 75-85 DEG C for sufficiently reacting. The synthesized polyurea acrylic ester resin is relatively stronger in dilution resistance capability, and can keep higher viscosity under the condition of adding more reactive diluents. After the synthesized polyurea acrylic ester resin is cured into films, the hardness, wear resistance and water resistance can be greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method of polyureas acrylate.
Background technology
Generally all use a certain proportion of resin as the film forming main raw in coating, printing ink, the adhesive formulation, and improve performance.Higher coating, printing ink, the tackiness agent of most performances is based on resin and participates in chemical reaction, the mechanism of experience curing cross-linking reaction, the curing cross-linked process utilizes the polymerizable activity of resin to carry out mostly, namely under certain condition, part functional group on the resin forms the solidify material with superior performance according to the mode generation chemically crosslinked of polyreaction.This polymerization crosslinking process can be that hot radical causes mode, also can be the light initiation polymerization crosslinking method.The mode that causes hot radical need heat usually with accelerated reaction and solidify, in the existing a lot of practical applications of industrial circle, as bicomponent polyurethane coating, anaerobic glue, Vinylite industrial coating, the resin-bonded material of rostone etc.They are a common shortcoming all, and the pot-life or the engineering time that are exactly material are shorter, and prolongs the engineering time, causes curing efficiency to descend again.And photocuring technology has overcome above-mentioned deficiency, and lucifuge can be preserved for a long time, be coated with install after, see light crosslinking curing film forming immediately.
Photo-cured coating, printing ink, tackiness agent all use this key component of light-cured resin, light-cured resin mainly comprises epoxy acrylate, urethane acrylate, this three major types of polyester acrylate, can satisfy the requirement of most photocuring application performance substantially.The light-cured resin that these are classical, except the Raolical polymerizable by acrylate group forms the cross-linking chemistry network, other secondary crosslinking structure based on strong physical action is very few, though it is certain secondary crosslinked that the ammonia ester bond in the urethane acrylate can form by ammonia ester hydrogen bond, its hydrogen bond action and imperfection.Thereby based on the photocurable formulation of above-mentioned traditional light-cured resin, behind the experience film-forming, the parts that still have some deficits such as its mechanical property, water tolerance, sticking power are especially for some particular application.Therefore, be necessary that the light-cured resin of redesign synthesizing new is to satisfy the harsh requirement of mechanical property, water tolerance and sticking power from strengthening the angle of the secondary crosslinked action of resin.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polyureas acrylate.
The technical solution used in the present invention is:
A kind of preparation method of polyureas acrylate may further comprise the steps:
1) with vinylformic acid with after polyetheramine mixes again with the vulcabond hybrid reaction, the reaction times is 0.5-2h, the temperature of reaction system is 40-60 ℃;
2) under 40-60 ℃, add (methyl) acrylate of catalyzer and hydroxyl in the above-mentioned system, be warming up to 75-85 ℃ again and fully react and get final product.
Step 2) in, fully the index of reaction be in the system-the infrared spectrum characteristic peak of NCO group disappears.
The mol ratio of described vulcabond and polyether diamine is 2:1～3:2; (methyl) acrylate of described hydroxyl is 1.2-2 times of vulcabond mole number, and the mol ratio of described vinylformic acid and vulcabond is 1:(6-30).
Described vulcabond is tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethanediisocyanate, hydrogenated diphenyl methane diisocyanate, xylylene diisocyanate, 2,2,4-trimethylammonium-1, hexamethylene-diisocyanate, hexamethylene diisocyanate, the dimethyl diphenyl vulcabond, PPDI, Toluene-2,4-diisocyanate, the 4-vulcabond, 1, hexamethylene-diisocyanate, 1, the 5-naphthalene diisocyanate, 4,4-vulcabond dicyclohexyl methyl hydride, the O-phthalic group diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate, 3,3-dichloro-biphenyl-4, at least a in the 4-vulcabond.
The molecular weight of described polyether diamine is 230-4000.
In (methyl) acrylate of described hydroxyl, (methyl) acrylate group is 1～3.
Described catalyzer is organotin catalysts.
The invention has the beneficial effects as follows: the anti-dilution capacity of polyureas acrylate resin that 1) is synthesized is stronger relatively, adding under more reactive thinner conditions, still can keep higher viscosity.
2) hardness, wear resistance, water tolerance behind the polyureas acrylate resin film-forming that is synthesized improve a lot.
Embodiment
A kind of preparation method of polyureas acrylate may further comprise the steps:
1) with vinylformic acid with after polyetheramine mixes again with the vulcabond hybrid reaction, the reaction times is 0.5-2h, the temperature of reaction system is 40-60 ℃;
2) under 40-60 ℃, add (methyl) acrylate of catalyzer and hydroxyl in the above-mentioned system, be warming up to 75-85 ℃ again and fully react and get final product.
Step 2) in, fully the index of reaction be in the system-the infrared spectrum characteristic peak of NCO group disappears.
The mol ratio of described vulcabond and polyether diamine is 2:1～3:2; (methyl) acrylate of described hydroxyl is 1.2-2 times of vulcabond mole number, and the mol ratio of described vinylformic acid and vulcabond is 1:(6-30).
Described vulcabond is tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethanediisocyanate, hydrogenated diphenyl methane diisocyanate, xylylene diisocyanate, 2,2,4-trimethylammonium-1, hexamethylene-diisocyanate, hexamethylene diisocyanate, the dimethyl diphenyl vulcabond, PPDI, Toluene-2,4-diisocyanate, the 4-vulcabond, 1, hexamethylene-diisocyanate, 1, the 5-naphthalene diisocyanate, 4,4-vulcabond dicyclohexyl methyl hydride, the O-phthalic group diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate, 3,3-dichloro-biphenyl-4, at least a in the 4-vulcabond.
The molecular weight of described polyether diamine is 230-4000.
In (methyl) acrylate of described hydroxyl, (methyl) acrylate group is 1～3.
Described catalyzer is organotin catalysts.
Ultimate principle of the present invention is:
The resin that is synthesized is (methyl) acrylate functional resin that contains the urea bond structure, form comparatively firm chemically crosslinked network except quick photocuring takes place (methyl) acrylate group, its urea key also can form hydrogen bond action more closely each other, in the secondary crosslinking structure of the intersegmental formation of cross-linked network medium chain, make apparent crosslinking improve, coating hardness improves; The raising of coating compactness has also improved its barrier to water.But secondary crosslinked hydrogen bond action has reversibility, when being subjected to environmental impact, the part hydrogen bond can taking place disintegrate to spread and come, simultaneously, the chemical structure of cross-linked network can be injury-free, and after the foreign impacts, coating network medium chain section is movable and to form hydrogen bond again crosslinked again.Therefore, this is a kind of comparatively advanced coated material construction design method.Generally, can make light solidifying coating shock resistance, hardness, wear resistance, water tolerance, and aspect such as sticking power be significantly improved.
The present invention is described further below in conjunction with specific embodiment:
Embodiment 1:
1mol IPDI is joined in the 1000ml three-necked bottle, dispel the heat with water-cooling pattern in the outside, in 0.5mol Jeffamine D-230, add 0.05mol vinylformic acid, again adding there is acrylic acid polyetheramine to join among the IPDI under the whipped state in the dropping mode, 0.5 hour dropwise, the control temperature of reaction system is no more than 60 ℃, after the dropping polyetheramine is finished, continue stirring reaction 10 minutes, drip the 1.2mol vinylformic acid-2-hydroxyl ethyl ester that contains 3 DBTL catalyzer, dropwised in 40 minutes, hierarchy of control temperature is no more than 60 ℃ therebetween, then, continue to stir and heat temperature raising to 75 ℃, reacted 3～6 hours, and detected with the sampling infrared spectra and determine 2270cm
-1Near NCO group characteristic peak completely dissolve is for finishing the foundation of reaction.The rotary viscosity design determining resin is 6410cps 60 ℃ of following viscosity.
Embodiment 2:
0.6mol TDI is joined in the 1000ml three-necked bottle, dispel the heat with water-cooling pattern in the outside, in 0.4mol Jeffamine ED-900, add 0.02mol vinylformic acid, again adding there is acrylic acid polyetheramine to join among the TDI under the whipped state in the dropping mode, dropwised in 1 hour, the control temperature of reaction system is no more than 60 ℃, after the dropping polyetheramine is finished, continue stirring reaction 10 minutes, drip the 0.8mol vinylformic acid-3-hydroxypropyl acrylate that contains 3 DBTL catalyzer, dropwised in 1 hour, hierarchy of control temperature is no more than 60 ℃ during this time, then, continue to stir and heat temperature raising to 75 ℃, reacted 2～4 hours, and detected with the sampling infrared spectra and determine 2270cm
-1Near NCO group characteristic peak completely dissolve is for finishing the foundation of reaction.The rotary viscosity design determining resin is 10760cps 60 ℃ of following viscosity.
Embodiment 3:
The 0.2mol liquefied mdi is joined in the 1000ml three-necked bottle, dispel the heat with water-cooling pattern in the outside, in 0.1mol Jeffamine D-4000, add 0.03mol vinylformic acid, again adding there is acrylic acid polyetheramine to join among the MDI under the whipped state in the dropping mode, dropwised in 1 hour, the control temperature of reaction system is no more than 60 ℃, after the dropping polyetheramine is finished, continue stirring reaction 10 minutes, drip the 0.4mol pentaerythritol triacrylate that contains 3 DBTL catalyzer, dropwised in 40 minutes, hierarchy of control temperature is no more than 60 ℃ during this time, then, continue to stir and heat temperature raising to 75 ℃, reacted 3～6 hours, and detected with the sampling infrared spectra and determine 2270cm
-1Near NCO group characteristic peak completely dissolve is for finishing the foundation of reaction.The rotary viscosity design determining resin is 9270cps 60 ℃ of following viscosity.
Embodiment 4:
The 0.4mol liquefied mdi is joined in the 1000ml three-necked bottle, dispel the heat with water-cooling pattern in the outside, in 0.2mol Jeffamine D-2000, add 0.03mol vinylformic acid, again adding there is acrylic acid polyetheramine to join among the MDI under the whipped state in the dropping mode, dropwised in 1 hour, the control temperature of reaction system is no more than 60 ℃, after the dropping polyetheramine is finished, continue stirring reaction 10 minutes, drip the 0.8mol vinylformic acid-2-hydroxypropyl acrylate that contains 3 DBTL catalyzer, dropwised in 40 minutes, hierarchy of control temperature is no more than 60 ℃ during this time, then, continue to stir and heat temperature raising to 75 ℃, reacted 3～6 hours, and detected with the sampling infrared spectra and determine 2270cm
-1Near NCO group characteristic peak completely dissolve is for finishing the foundation of reaction.The rotary viscosity design determining resin is 7750cps 60 ℃ of following viscosity.
Embodiment 5:
The 0.4mol liquefied mdi is joined in the 1000ml three-necked bottle, dispel the heat with water-cooling pattern in the outside, in 0.2mol Jeffamine D-2000, add 0.03mol vinylformic acid, again adding there is acrylic acid polyetheramine to join among the MDI under the whipped state in the dropping mode, dropwised in 1 hour, the control temperature of reaction system is no more than 60 ℃, after the dropping polyetheramine is finished, continue stirring reaction 10 minutes, drip the 0.8mol 2-hydroxyethyl methacrylate that contains 3 DBTL catalyzer, dropwised in 40 minutes, hierarchy of control temperature is no more than 60 ℃ during this time, then, continue to stir and heat temperature raising to 75 ℃, reacted 3～6 hours, and detected with the sampling infrared spectra and determine 2270cm
-1Near NCO group characteristic peak completely dissolve is for finishing the foundation of reaction.The rotary viscosity design determining resin is 7640cps 60 ℃ of following viscosity.
Embodiment 6:
The 0.4mol liquefied mdi is joined in the 1000ml three-necked bottle, dispel the heat with water-cooling pattern in the outside, in 0.2mol Jeffamine D-2000, add 0.03mol vinylformic acid, again adding there is acrylic acid polyetheramine to join among the MDI under the whipped state in the dropping mode, dropwised in 1 hour, the control temperature of reaction system is no more than 60 ℃, after the dropping polyetheramine is finished, continue stirring reaction 10 minutes, drip the 0.8mol pentaerythritol triacrylate that contains 3 DBTL catalyzer, dropwised in 40 minutes, hierarchy of control temperature is no more than 60 ℃ during this time, then, continue to stir and heat temperature raising to 75 ℃, reacted 3～6 hours, and detected with the sampling infrared spectra and determine 2270cm
-1Near NCO group characteristic peak completely dissolve is for finishing the foundation of reaction.The rotary viscosity design determining resin is 8790cps 60 ℃ of following viscosity.
To be reactive thinner sell urethane acrylate EB270 to institute's synthetic resins and merchant dilutes comparative study with tripropylene glycol diacrylate TPGDA, add respectively after 30g TPGDA mixes, measure viscosity down and calculate it with respect to the viscosity drop low amplitude of unmodified resin at 50 ℃.The results are shown in table 1:
Table 1:
This shows to show that the anti-dilution of the polyureas light-cured resin that the present invention synthesized obviously is better than classical resin EB270.
Be reactive thinner with TPGDA, Viscoat 295 TMPTA, Darocure1173 is light trigger, choosing
Select embodiment 1～6 synthetic resins, and standard epoxy acrylate B102, EB270 join according to following as light-cured resin
More coating material solidified than light modulated, fill a prescription as table 2:
Table 2:
The paint formulation roller coat is on the tinplate sheet of handling, 25 microns of control thickness, solidified in 10 seconds with 2000W medium pressure mercury lamp irradiation, measure cured film resistance to impact shock, pencil hardness, wear resistance (Taber method, 100g load, turnery 300 circle back coating losss of weight), hundred lattice method sticking power (5B the bests respectively, 0B is the poorest), (the coating sample soaks after 30 minutes in 80 ℃ of hot water water tolerance, oven dry is measured hundred lattice sticking power and is changed), the results are shown in Table 3:
Table 3:
Claims (7)
1. the preparation method of a polyureas acrylate is characterized in that: may further comprise the steps:
1) with vinylformic acid with after polyetheramine mixes again with the vulcabond hybrid reaction, the reaction times is 0.5-2h, the temperature of reaction system is 40-60 ℃;
2) under 40-60 ℃, add (methyl) acrylate of catalyzer and hydroxyl in the above-mentioned system, be warming up to 75-85 ℃ again and fully react and get final product.
2. the preparation method of a kind of polyureas acrylate according to claim 1 is characterized in that: step 2) in, fully the index of reaction be in the system-the infrared spectrum characteristic peak of NCO group disappears.
3. the preparation method of a kind of polyureas acrylate according to claim 1, it is characterized in that: the mol ratio of described vulcabond and polyether diamine is 2:1 ~ 3:2; (methyl) acrylate of described hydroxyl is 1.2-2 times of vulcabond mole number, and the mol ratio of described vinylformic acid and vulcabond is 1:(6-30).
4. the preparation method of a kind of polyureas acrylate according to claim 1, it is characterized in that: described vulcabond is tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethanediisocyanate, hydrogenated diphenyl methane diisocyanate, xylylene diisocyanate, 2,2,4-trimethylammonium-1, hexamethylene-diisocyanate, hexamethylene diisocyanate, the dimethyl diphenyl vulcabond, PPDI, Toluene-2,4-diisocyanate, the 4-vulcabond, 1, hexamethylene-diisocyanate, 1, the 5-naphthalene diisocyanate, 4,4-vulcabond dicyclohexyl methyl hydride, the O-phthalic group diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate, 3,3-dichloro-biphenyl-4, at least a in the 4-vulcabond.
5. the preparation method of a kind of polyureas acrylate according to claim 1, it is characterized in that: the molecular weight of described polyether diamine is 230-4000.
6. the preparation method of a kind of polyureas acrylate according to claim 1, it is characterized in that: in (methyl) acrylate of described hydroxyl, (methyl) acrylate group is 1 ~ 3.
7. the preparation method of a kind of polyureas acrylate according to claim 1, it is characterized in that: described catalyzer is organotin catalysts.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103641962A (en) * | 2013-11-25 | 2014-03-19 | 汕头市东和机械有限公司 | Polyuria-acrylate emulsion and aqueous gravure ink prepared from same |
| CN106749942A (en) * | 2016-12-15 | 2017-05-31 | 深圳飞扬兴业科技有限公司 | A kind of 3D printing ultraviolet photocureable material and preparation method thereof |
| CN110205006A (en) * | 2019-06-24 | 2019-09-06 | 江苏凯伦建材股份有限公司 | Photocuring single-component polyurea water-repellent paint and its preparation process |
| CN112279998A (en) * | 2020-11-06 | 2021-01-29 | 广州市嵩达新材料科技有限公司 | Photo-cured polyurea nanoparticles and preparation method and application thereof |
| CN113583211A (en) * | 2021-07-30 | 2021-11-02 | 浙江大学 | Polyurea acrylate oligomer and preparation method and application method thereof |
| CN114806360A (en) * | 2021-02-04 | 2022-07-29 | 江苏凯伦建材股份有限公司 | Waterproof material |
| CN117247524A (en) * | 2023-09-21 | 2023-12-19 | 南昌航空大学 | Waterborne photo-curing multiple reversible room temperature self-repairing elastomer and preparation method and application thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641962A (en) * | 2013-11-25 | 2014-03-19 | 汕头市东和机械有限公司 | Polyuria-acrylate emulsion and aqueous gravure ink prepared from same |
| CN103641962B (en) * | 2013-11-25 | 2016-05-04 | 汕头市东和机械有限公司 | The water-base gravure ink of a kind of polyureas-acrylic acid ester emulsion and preparation thereof |
| CN106749942A (en) * | 2016-12-15 | 2017-05-31 | 深圳飞扬兴业科技有限公司 | A kind of 3D printing ultraviolet photocureable material and preparation method thereof |
| CN106749942B (en) * | 2016-12-15 | 2019-03-12 | 深圳飞扬兴业科技有限公司 | A kind of 3D printing ultraviolet photocureable material and preparation method thereof |
| CN110205006A (en) * | 2019-06-24 | 2019-09-06 | 江苏凯伦建材股份有限公司 | Photocuring single-component polyurea water-repellent paint and its preparation process |
| CN112279998A (en) * | 2020-11-06 | 2021-01-29 | 广州市嵩达新材料科技有限公司 | Photo-cured polyurea nanoparticles and preparation method and application thereof |
| CN112279998B (en) * | 2020-11-06 | 2022-04-05 | 广州市嵩达新材料科技有限公司 | Photo-cured polyurea nanoparticles and preparation method and application thereof |
| CN114806360A (en) * | 2021-02-04 | 2022-07-29 | 江苏凯伦建材股份有限公司 | Waterproof material |
| CN113583211A (en) * | 2021-07-30 | 2021-11-02 | 浙江大学 | Polyurea acrylate oligomer and preparation method and application method thereof |
| CN117247524A (en) * | 2023-09-21 | 2023-12-19 | 南昌航空大学 | Waterborne photo-curing multiple reversible room temperature self-repairing elastomer and preparation method and application thereof |
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