CN110498898A - The cured soluble polyurethane acrylate oligomer of the ultraviolet light of one-step synthesis method and its method - Google Patents
The cured soluble polyurethane acrylate oligomer of the ultraviolet light of one-step synthesis method and its method Download PDFInfo
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- CN110498898A CN110498898A CN201910670151.0A CN201910670151A CN110498898A CN 110498898 A CN110498898 A CN 110498898A CN 201910670151 A CN201910670151 A CN 201910670151A CN 110498898 A CN110498898 A CN 110498898A
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
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- 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
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- 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
- C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to the synthetic methods that one-step method quickly prepares soluble polyurethane oligomer.Specifically, the synthesis of the cured soluble polyurethane of ultraviolet light is completed by the design of several parts: being reacted using double base isocyanates one end with the multi-functional acrylate of hydroxyl and ultraviolet light solidification characteristic part is made, it is water-soluble that the other end reacts realization with the amino of poly- alcohol and carboxylic acid, carboxylic acid is neutralized using small molecule organic amine, is finally distributed in water.This method is completed in 5 hours, and the combined coefficient of soluble polyurethane can be greatly improved, obtained ultraviolet light solidify soluble polyurethane coating film forming and stability it is all fine.
Description
Technical field
The invention belongs to ultraviolet lights to solidify oligomer preparation field, in particular to a kind of efficiently to prepare soluble polyurethane
The preparation method of the UV curable polymer of acrylic coating.
Background technique
Ultraviolet solidified aqueous coating is one and combines traditional UV-curing technology and water paint technology
New technology, have energy conservation and environmental protection, on human health without influence, safety is good many advantages, such as, grown rapidly nearly ten years
And extensive use, and an one of important directions for green coating development are had become, due to active response and meet national society
The development policies direction of environmental protection coating material, future will have huge application development space.
Ultraviolet solidified aqueous coating is by aquosity ultraviolet light prepolymer, photoinitiator, water and various additives (defoaming
Agent, levelling agent and pigments and fillers etc.) composition.Aquosity ultraviolet light prepolymer is the most important composition portion of UV-curable waterborne system
Point, which determine the mechanical property of cured film, physical mechanical property, wearability, the property such as chemical resistance and photo-curing rate
Energy.Photoinitiator is the main component of UV-curable waterborne system, under the irradiation of ultraviolet light, chemistry occurs through excitation and becomes
Change, cracking generate reactive intermediate (living radical or cation), and then in initiation system unsaturated double-bond occur polymerization and
Cross-linking reaction, it plays decisive role to the laser curing velocity of photocureable coating, and in ultraviolet solidified aqueous coating, light draws
The dosage for sending out agent is seldom, and generally 3%~5% or so, research on maximum utilized quantity is no more than 7%~10%.It is right in actual application
The final performance of cured film has certain influence.So aquosity ultraviolet light prepolymer and photoinitiator always are aquosity ultraviolet light
The research hotspot of curing system.
Aquosity ultraviolet light prepolymer mainly has aqueous polyurethane acrylate, waterborne epoxy acrylate and waterborne polyester third
Olefin(e) acid ester three classes.
Summary of the invention
The invention mainly relates to aqueous polyurethane acrylate oligomer, in response to the development of national green environmental protection coating material
Appeal, the present invention proposes that one-step method quickly prepares the synthetic method of soluble polyurethane, and the present invention favorably promotes similar coating to open
Efficiency is sent out, the production efficiency that ultraviolet light solidifies soluble polyurethane coating is improved, accelerates to promote marketization development and Optimization Progress.
The technical solution of the present invention is as follows: the cured soluble polyurethane oligomer of ultraviolet light of one-step method preparation, described low
Polymers composition are as follows:
I) double base isocyanates；
Ii) the multi-functional acrylate of hydroxyl；
Iii) polyalcohols；
Iv) amino carboxylic acid；
V) small molecule organic amine；
According to the multi-functional acrylate of double base isocyanates and hydroxyl, polyalcohols, amino carboxylic acid, small molecule organic amine
The ratio that molar ratio is 1:0.2-1.5:0.3-1.0:0.4-1.2:0.4-1.2 is stocked up；The polyfunctional group third of the hydroxyl
Olefin(e) acid ester refers to the acrylate of two functional groups or more.
The double base isocyanates refers to any in isophorone diisocyanate IPDI or toluene di-isocyanate(TDI) TDI
It is one or more.
The multi-functional acrylate of the hydroxyl refers to trihydroxy methyl diacrylate, three acrylic acid of pentaerythrite
Any one or more in ester.
The polyalcohols refers to any one or more in polyethylene glycol or polypropylene glycol, molecular weight 500-1200 it
Between；
The amino carboxylic acid is not limited to Beta-alanine, any one or more in 1- 1-aminocyclopropane-1-carboxylic acid.
The small molecule organic amine refers to any one or more in diethylamine or triethylamine.
The polymerization inhibitor is p-hydroxyanisole, and total dosage is the 0.2% of crylic acid hydroxy ester gross mass.
The preparation method of the cured soluble polyurethane oligomer of ultraviolet light of the one-step method preparation, will contain polymerization inhibitor
Double base isocyanates the multi-functional acrylate of hydroxyl is added under stiring, at 80-90 DEG C after reaction 0.5-1 hours,
Polyalcohols is added, then ammoniates yl carboxylic acid again after reaction 0.5-1 hours at 80-90 DEG C, is reacted 0.5-1 hours at 80-90 DEG C, this
When NCO=0, be added small molecule organic amine, reaction 0.5 hour after, be added deionized water, be sufficiently stirred 1 hour or more to get arriving
The urethane oligomer of water-soluble uV curable.
Beneficial effect
This method is completed in 5 hours, and the combined coefficient of soluble polyurethane can be greatly improved, and obtained polyurethane applies
Material is water-soluble, uV curable, and its film forming and stability are all fine.
Detailed description of the invention
Fig. 1: the soluble polyurethane coating synthesized controls be positive cup and cup, is displayed without precipitating；
Fig. 2: not being layered after senile experiment, illustrates qualified stability；
Fig. 3: ultraviolet light solidifies after heating, drying on glass, it is seen that has obtained cured film.
Specific embodiment
In the following, being further elaborated on by embodiment and attached drawing to the present invention.
One-step method prepares the synthetic method of the cured soluble polyurethane coating of ultraviolet light, and the oligomer is following substance
Reaction product: double base isocyanates；The multi-functional acrylate of hydroxyl；Polyalcohols；Amino carboxylic acid；Small molecule organic amine；
Polymerization inhibitor.It is characterized by: according to the multi-functional acrylate of double base isocyanates and hydroxyl, polyalcohols, aminocarboxylic
Acid, the ratio that small molecule organic amine molar ratio is 1:0.2-1.5:0.3-1.0:0.4-1.2:0.4-1.2 are stocked up, and polymerization inhibitor will be contained
Double base isocyanates the multi-functional acrylate of hydroxyl is added under stiring, at 80-90 DEG C after reaction 0.5-1 hours,
Polyalcohols is added, then ammoniates yl carboxylic acid again after reaction 0.5-1 hours at 80-90 DEG C, is reacted 0.5-1 hours at 80-90 DEG C, this
When NCO=0, small molecule organic amine is added, deionized water and other dispersing agents is added, it is small to be sufficiently stirred 1 after reaction 0.5 hour
When more than to get to the urethane oligomer of water-soluble uV curable.
The double base isocyanates refers to any in isophorone diisocyanate IPDI or toluene di-isocyanate(TDI) TDI
It is one or more；The multi-functional acrylate of the hydroxyl refers to the acrylate of two functional groups or more, is primarily referred to as
Trihydroxy methyl diacrylate, pentaerythritol triacrylate any one or more；The polyalcohols refer to polyethylene glycol or
Any one or more in polypropylene glycol, molecular weight is between 500-1200；The amino carboxylic acid, which refers to, is not limited to beta-amino
Any one or more in propionic acid, 1- 1-aminocyclopropane-1-carboxylic acid；The small molecule organic amine refers to diethylamine or triethylamine
In any one or more.
The multi-functional acrylate of double base isocyanates and hydroxyl, polyalcohols, amino carboxylic acid, small molecule organic amine mole
Than for 1:0.2-1.5:0.3-1.0:0.4-1.2:0.4-1.2.
The polymerization inhibitor is p-hydroxyanisole, and total dosage is the 0.2% of crylic acid hydroxy ester gross mass.
1 synthesis of oligonucleotides object of embodiment
It is added the isophorone diisocyanate (IPDI) of 60g, 160g season is added when temperature reaches 70 DEG C or more in heating
Penta tetrol acrylate and p-hydroxyanisole 0.32g, react half an hour between 85-90 DEG C.It is different that 60g isophorone two is added
Cyanate under stirring, is added the mixture 220g of polyethylene glycol and polypropylene glycol, reacts half an hour at same temperature.It adds
Whether Beta-alanine 300g, 85-90 DEG C of holding half an hour, test NCO are equal to 0, and then the reaction was continued for non-zero, until being zero.Add
Enter 150g diethylamine, after half an hour, 1200ml deionized water is added, after opening stirring 1 hour, discharging measures PH:7.5, viscosity
Apply four glasss 45 seconds.Obtained soluble polyurethane is well dispersed, does not settle as shown in Figure 1.It is denoted as MAP1.
2 synthesis of oligonucleotides object of embodiment
It is added the toluene di-isocyanate(TDI) (TDI) of 660g in reactor, heating is added when temperature reaches 70 DEG C or more
1500g pentaerythritol acrylate hydroxyanisol 30g, reacts half an hour between 85-90 DEG C.800g toluene diisocyanate is added
Under stirring, Macrogol 3000 g is added, in 85-90 DEG C of reaction half an hour in acid esters.Add 1- 1-aminocyclopropane-1-carboxylic acid
Whether 3000g, 85-90 DEG C of holding half an hour, test NCO are equal to 0, and then the reaction was continued for non-zero, until being zero.1800g tri- is added
After half an hour, 15000ml deionized water is added in ethamine, and after opening stirring 1 hour, discharging measures PH:7.3, and viscosity applies four glasss
38 seconds.It is denoted as MAP2.
Obtained soluble polyurethane after three days, is not layered by 80 DEG C, shows good stability, as shown in Figure 2.
3 synthesis of oligonucleotides object of embodiment
It is added the toluene di-isocyanate(TDI) (TDI) of 200g in reactor, heating is added when temperature reaches 75 DEG C or more
400g pentaerythritol acrylate and hydroxyanisol 0.8g, react half an hour between 85-90 DEG C.It is different that 120g toluene two is added
Cyanate is added with stirring polypropylene glycol 400g, in 85-90 DEG C of reaction half an hour.1- 1-aminocyclopropane-1-carboxylic acid 300g is added,
Whether 85-90 DEG C of holding half an hour, test NCO are equal to 0, and then the reaction was continued for non-zero, until being zero.200g triethylamine is added, partly
After hour, 1300ml deionized water is added, after opening stirring 1 hour, discharging measures PH:7.0, and viscosity applies four glasss 27 seconds.It is denoted as
MAP3。
4 synthesis of oligonucleotides object of embodiment
It is added the toluene di-isocyanate(TDI) (TDI) of 250g in reactor, heating is added when temperature reaches 75 DEG C or more
480g pentaerythritol acrylate and hydroxyanisol 0.96g, react half an hour between 85-90 DEG C.160g toluene two is added
Isocyanates is added with stirring polypropylene glycol 400g, in 85-90 DEG C of reaction half an hour.Add Beta-alanine 310g, 85-
90 DEG C of holding half an hour, it is slowly added to Beta-alanine 30g, prevents whether a large amount of foams, test NCO are equal to 0, non-zero is then
The reaction was continued, until being zero.180g triethylamine is added, after half an hour, 1400ml deionized water is added, after opening stirring 1 hour,
Discharging, measures PH:7.2, and viscosity applies four glasss 28 seconds.It is denoted as MAP4.
Embodiment 5 prepares the coating material solidified PUA1 of UV
| Formula | % |
| MP1 | 98.1 |
| 1173 | 1.9 |
| Total amount | 100 |
Embodiment 6 prepares the coating material solidified PUA2 of UV
| Formula | % |
| MP2 | 98 |
| 1173 | 2 |
| Total amount | 100 |
Embodiment 7 prepares the coating material solidified PUA3 of UV
| Formula | % |
| MP3 | 98 |
| 1173 | 2 |
| Total amount | 100 |
Embodiment 8 prepares the coating material solidified PUA4 of UV
| Formula | % |
| MP4 | 98 |
| 1173 | 2 |
| Total amount | 100 |
Embodiment 9
It uses spreader 100um film on glass respectively 5,6,7,8 four groups of coating of example, is kept for 15 points in 60 DEG C of baking ovens
Clock, 1000mj/cm2Solidify under ultraviolet lamp, test curing degree RAU respectively, test result is as follows:
| Sample | PUA1 | PUA2 | PUA3 | PUA4 |
| RAU% | 89 | 90 | 90 | 92 |
| Whether | It is | It is | It is | It is |
From upper table as it can be seen that several oligomer curing degrees of synthesis are relatively high, illustrate quick solidifying, and film forming is all fine.Such as
Fig. 3 show the photo after PUA5 solidifies, and presents preferable filming performance.
Claims (8)
1. the cured soluble polyurethane oligomer of ultraviolet light of one-step method preparation, it is characterised in that: the oligomer composition are as follows:
I) double base isocyanates；
Ii) the multi-functional acrylate of hydroxyl；
Iii) polyalcohols；
Iv) amino carboxylic acid；
V) small molecule organic amine；
According to the multi-functional acrylate of double base isocyanates and hydroxyl, polyalcohols, amino carboxylic acid, small molecule organic amine mole
Than the ratio stock for 1:0.2-1.5:0.3-1.0:0.4-1.2:0.4-1.2；The polyfunctional group acrylic acid of the hydroxyl
Ester refers to the acrylate of two functional groups or more.
2. the cured soluble polyurethane oligomer of ultraviolet light of one-step method preparation according to claim 1, feature exist
In: the double base isocyanates refers to any one in isophorone diisocyanate IPDI or toluene di-isocyanate(TDI) TDI
Or it is a variety of.
3. the cured soluble polyurethane oligomer of ultraviolet light of one-step method preparation according to claim 1, feature exist
Refer to trihydroxy methyl diacrylate in, the multi-functional acrylate of the hydroxyl, in pentaerythritol triacrylate
Any one or more.
4. the cured soluble polyurethane oligomer of ultraviolet light of one-step method preparation according to claim 1, feature exist
In the polyalcohols refers to any one or more in polyethylene glycol or polypropylene glycol, and molecular weight is between 500-1200.
5. the cured soluble polyurethane oligomer of ultraviolet light of one-step method preparation according to claim 1, feature exist
Beta-alanine, any one or more in 1- 1-aminocyclopropane-1-carboxylic acid are not limited in, the amino carboxylic acid.
6. the cured soluble polyurethane oligomer of ultraviolet light of one-step method preparation according to claim 1, feature exist
Refer to any one or more in diethylamine or triethylamine in, the small molecule organic amine.
7. the cured soluble polyurethane oligomer of ultraviolet light of one-step method preparation according to claim 1, feature exist
In the polymerization inhibitor is p-hydroxyanisole, and total dosage is the 0.2% of crylic acid hydroxy ester gross mass.
8. the preparation side of the cured soluble polyurethane oligomer of ultraviolet light of one-step method preparation as claimed in claim 1 to 7
Method, which is characterized in that the double base isocyanates containing polymerization inhibitor is added to the multi-functional acrylate of hydroxyl, In under stiring
80-90 DEG C after reaction 0.5-1 hours, is added polyalcohols, then ammoniates yl carboxylic acid, In again after reaction 0.5-1 hours at 80-90 DEG C
It is reacted at 80-90 DEG C 0.5-1 hours, NCO=0, is added small molecule organic amine and deionization is added after reaction 0.5 hour at this time
Water is sufficiently stirred 1 hour or more to get the urethane oligomer for arriving water-soluble uV curable.
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Citations (5)
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|---|---|---|---|---|
| EP2757118A1 (en) * | 2013-01-17 | 2014-07-23 | Allnex Belgium, S.A. | Radiation curable aqueous compositions with reversible drying. |
| CN105669938A (en) * | 2016-03-24 | 2016-06-15 | 万华化学集团股份有限公司 | Waterborne radiation-supportive curing polyurethane acrylate combination, preparation method and coating |
| CN107254250A (en) * | 2017-07-10 | 2017-10-17 | 湖南邦弗特新材料技术有限公司 | A kind of aqueous UV urethane acrylate dispersoids of high glaze and preparation method thereof |
| CN107922762A (en) * | 2015-10-28 | 2018-04-17 | 惠普发展公司，有限责任合伙企业 | Adhesive dispersion based on radiation-curable polyurethane |
| WO2018123349A1 (en) * | 2016-12-27 | 2018-07-05 | 富士フイルム株式会社 | Aqueous dispersion, method for producing same and image formation method |
-
2019
- 2019-07-24 CN CN201910670151.0A patent/CN110498898A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2757118A1 (en) * | 2013-01-17 | 2014-07-23 | Allnex Belgium, S.A. | Radiation curable aqueous compositions with reversible drying. |
| CN107922762A (en) * | 2015-10-28 | 2018-04-17 | 惠普发展公司，有限责任合伙企业 | Adhesive dispersion based on radiation-curable polyurethane |
| CN105669938A (en) * | 2016-03-24 | 2016-06-15 | 万华化学集团股份有限公司 | Waterborne radiation-supportive curing polyurethane acrylate combination, preparation method and coating |
| WO2018123349A1 (en) * | 2016-12-27 | 2018-07-05 | 富士フイルム株式会社 | Aqueous dispersion, method for producing same and image formation method |
| CN107254250A (en) * | 2017-07-10 | 2017-10-17 | 湖南邦弗特新材料技术有限公司 | A kind of aqueous UV urethane acrylate dispersoids of high glaze and preparation method thereof |
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| Title |
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| 王宁 等: "多官能度聚氨酯丙烯酸酯树脂的合成及性能研究", 《西南科技大学学报》 * |
| 苏嘉辉 等: "多官能度聚氨酯丙烯酸酯水性UV树脂的合成与性能表征", 《高分子材料科学与工程》 * |
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