CN109678761A - A kind of high-modulus fluorochemical urethane acrylate and preparation method thereof - Google Patents
A kind of high-modulus fluorochemical urethane acrylate and preparation method thereof Download PDFInfo
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- CN109678761A CN109678761A CN201811560151.7A CN201811560151A CN109678761A CN 109678761 A CN109678761 A CN 109678761A CN 201811560151 A CN201811560151 A CN 201811560151A CN 109678761 A CN109678761 A CN 109678761A
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- acrylate
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- diisocyanate
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- intermediate product
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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
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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
- C07C269/04—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 amines with formation of carbamate groups
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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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 high modulus polyurethane acrylate and preparation method thereof；The resin is synthesized by " three-step approach " by diisopropanolamine (DIPA) and fluorinated acrylate, diisocyanate and hydroxy acrylate and is made；Its curing membrane performance is excellent, has the characteristics that modulus is high, hardness is big, solvent resistant.Preparation method synthesis technology of the invention is simple, easily controllable without by-product.Soft segment small volume in urethane acrylate of the invention, rigidity preferably, can reduce volume contraction in photocuring；Hydrogen in acid imide on nitrogen is easily-activated, can form chemical bond or hydrogen bond with larger bond energy with hydroxyl, the carboxyl on substrate, thus modulus can be improved., as photocureable coating matrix resin in use, the surface of light solidifying coating can be lower, modulus is higher, has great application prospect for it.
Description
Technical field
The invention belongs to photo-curing material fields, and in particular to a kind of high-modulus fluorochemical urethane acrylate and its preparation
Method.
Background technique
UV curable liquid coating is a kind of environment-friendly and energy-efficient coating of exploitation the 1960s.It has no or low
VOC emission saves the energy (the 1/10 to 1/5 of energy consumption only heat curable powder coating), solidification rate fast (0.1 to 10s), production
High-efficient, suitable flow line production, solidification temperature is low, is suitble to the advantages that coating heat-sensitive substrate material.
Photocureable coating is made of photoinitiator, reactive diluent, oligomer (resin) and various additives, wherein oligomeric
Physical performance plays a major role to the performance of coating, and oligomer must have ultraviolet curing group in structure, belongs to photoresist.
Urethane acrylate is a kind of important Photocurable oligomers, be by multicomponent isocyanate, long-chain polyhydric alcohol and hydroxyl
Acrylate is synthesized through two-step reaction and is made.
Since the MOLECULE DESIGN of urethane acrylate is more flexible, the multicomponent isocyanate of selection different structure can be passed through
And long-chain polyhydric alcohol, the functional resin with particular characteristic is synthesized, field of photo-curing coatings is widely used in.In addition, in light
Coating material solidified middle introducing fluorine-containing material, especially fluorine resin, the surface of material can be greatly reduced, so as to improve coating table
Soil resistance, weatherability and the resistance to chemical corrosion in face.At present in field of photo-curing coatings, a more prominent problem is, with
Epoxy Acrylates resin is compared, and polyurethane acrylates resin modulus is smaller, limits polyurethane acrylates resin
In the application of field of photo-curing coatings.
For this purpose, this field, which continues to need, develops a kind of high-modulus fluorochemical urethane acrylate and preparation method thereof.
Summary of the invention
The purpose of the present invention is to provide a kind of high-modulus fluorochemical urethane acrylate and preparation method thereof.The polyurethane
Soft segment small volume in acrylate, rigidity preferably, can reduce volume contraction in photocuring；Hydrogen in acid imide on nitrogen is easy
Activation, can form chemical bond or hydrogen bond with larger bond energy with hydroxyl, the carboxyl on substrate, thus modulus can be improved.
The purpose of the present invention is achieved through the following technical solutions:
According to an aspect of the invention, there is provided a kind of preparation method of high-modulus fluorochemical urethane acrylate, by
Diisopropanolamine (DIPA) and fluorinated acrylate, diisocyanate and hydroxy acrylate are synthesized by " three-step approach ", finally obtain one
Kind high-modulus photo-curing material.
Sintetics and its structure are shown below.
Preferably, the method specifically comprises the following steps:
S1, at 45~65 DEG C, the methanol that diisopropanolamine (DIPA) is added in fluorinated acrylate according to 1~1.5:1 of molar ratio is molten
In liquid system, reaction obtains intermediate product A completely；
S2, at 65~80 DEG C, hydroxy acrylate is added in diisocyanate according to 1~1.5:1 of molar ratio, completely
Reaction obtains intermediate product B；
S3, molar ratio be 1:1.5~2.5 intermediate product A and intermediate product B reacted completely at 70~80 DEG C to get
The high-modulus fluorochemical urethane acrylate.In step S3, the molar ratio of more preferable intermediate product A and intermediate product B are 1:
2。
Preferably, fluorinated acrylate is acrylic acid trifluoro ethyl ester, trifluoroethyl methacrylate, ten difluoro heptan of acrylic acid
One of ester, dodecafluoroheptyl methacrylate, hexafluorobutyl acrylate and Hexafluorobutyl mathacrylate are a variety of.
Preferably, diisocyanate is isophorone diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate, diphenylene two
One of isocyanates, tetramethyl-ring hexane diisocyanate and 1,6- hexamethylene diisocyanate are a variety of.
Preferably, hydroxy acrylate is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and methyl
One of hydroxypropyl acrylate is a variety of.
According to another aspect of the present invention, a kind of high-modulus light being prepared by above method of the present invention is additionally provided
Curing materials.
Meanwhile according to another aspect of the invention, high-modulus fluorochemical urethane propylene of the present invention is also claimed
Acid esters is preparing the application in photocureable coating.
Compared with prior art, the beneficial effects of the present invention are:
1, in terms of raw material, the method for the present invention only needs a small number of raw materials, and when generating final product, the present invention does not need that high toxicity is added
Organotin reagent；
2, in terms of process flow, method of the invention is more simple and convenient, and variable factor is less, and the quality of product is more steady
It is fixed, it is easily generalized in industrial mass production；
3, from the point of view of the product of preparation (fluorochemical urethane acrylate), product structure of the invention is very symmetrical, composition
Simply, and carbon-carbon double bond ratio is higher, and curing rate is faster；And the fluorochemical urethane acrylate being prepared in the prior art
Structure is more complex, is affected by each component；
4, high-modulus fluorochemical urethane acrylate of the invention is as photocureable coating matrix resin in use, photocuring
The surface of coating can be lower, and modulus is higher, has great application prospect.
Detailed description of the invention
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon:
Fig. 1 is the infrared spectrum of high-modulus fluorochemical urethane acrylate prepared by the embodiment of the present invention 1；
Fig. 2 is the nucleus magnetic hydrogen spectrum of high-modulus fluorochemical urethane acrylate prepared by the embodiment of the present invention 1.
Specific embodiment
The following describes the present invention in detail with reference to examples.Following embodiment will be helpful to those skilled in the art
The present invention is further understood, but the invention is not limited in any way.It should be pointed out that those skilled in the art
For, without departing from the inventive concept of the premise, it can also make certain adjustments and improvements.These belong to guarantor of the invention
Protect range.
Embodiment 1
The present embodiment is related to a kind of high-modulus fluorochemical urethane acrylate and preparation method thereof, includes the following steps:
39.9g diisopropanolamine (DIPA) and 20ml methanol solvate are added in a 250ml four-hole boiling flask, is stirred at room temperature to two different
After Propanolamine is completely dissolved, 127.4g dodecafluorhe-ptylacrylate is slowly added dropwise, then heats to 55 DEG C, stirred under nitrogen atmosphere
Reaction 5 hours, revolving remove solvent methanol, obtain a kind of light yellow liquid, i.e. intermediate product A.
133.4g isophorone diisocyanate is added in a 250ml four-hole boiling flask, 76.6g acrylic acid hydroxyl is slowly added dropwise
Ethyl ester then heats to 65 DEG C, stops reaction when reaction to isocyanates is near 11.9%, obtain intermediate product B.
Above-mentioned intermediate product A, B are added in a 500ml four-hole boiling flask, is sufficiently stirred at 75 DEG C, until in infrared spectroscopy
Isocyano characteristic peak disappear until to get arrive the high-modulus photo-curing material.Sintetics and its structure are shown below.
It can be seen that the high-modulus fluorochemical urethane acrylate structural of synthesis is very symmetrical, composition is simple, carbon in structure
Carbon double bond ratio is high, and curing rate is fast.
Further, the high-modulus fluorochemical urethane acrylate of synthesis can be using infrared spectroscopy, nucleus magnetic hydrogen spectrum to it
It is analyzed and characterized.
From the infrared spectrum (Fig. 1) of product as can be seen that 1197.6cm-1It is the absorption peak of C-F key, 703.9cm-1With
688.4cm-1It is CF3Absorption peak, 1636.5cm-1 is-CH=CH2Characteristic absorption peak, illustrate in product really containing fluorine with
And polymerizable acrylate group.
By products therefrom using deuterated chloroform as solvent, TMS carries out nucleus magnetic hydrogen spectrum analysis as internal standard, as shown in Figure 2.In conjunction with
Infrared spectrum is analyzed, and can determine to have obtained target product.
Embodiment 2
The present embodiment is related to a kind of high-modulus fluorochemical urethane acrylate and preparation method thereof, includes the following steps:
39.9g diisopropanolamine (DIPA) and 20ml methanol solvate are added in a 250ml four-hole boiling flask, is stirred at room temperature to two different
After Propanolamine is completely dissolved, 144.1g dodecafluoroheptyl methacrylate is slowly added dropwise, then heats to 60 DEG C, under nitrogen protection
It is stirred to react 4 hours, revolving removes solvent methanol, obtains a kind of light yellow liquid, i.e. intermediate product A.
104.5g Toluene-2,4-diisocyanate is added in a 250ml four-hole boiling flask, 93.7g acrylic acid is slowly added dropwise in 4- diisocyanate
Hydroxypropyl acrylate then heats to 70 DEG C, stops reaction when reaction to isocyanates is near 12.7%, obtain intermediate product B.
Above-mentioned intermediate product A, B are added in a 500ml four-hole boiling flask, is sufficiently stirred at 80 DEG C, until in infrared spectroscopy
Isocyano characteristic peak disappear until to get arrive the high-modulus photo-curing material.
Embodiment 3
The present embodiment is related to a kind of high-modulus fluorochemical urethane acrylate and preparation method thereof, includes the following steps:
39.9g diisopropanolamine (DIPA) and 20ml methanol solvate are added in a 250ml four-hole boiling flask, is stirred at room temperature to two different
After Propanolamine is completely dissolved, 92.1g hexafluorobutyl acrylate is slowly added dropwise, then heats to 50 DEG C, stirred under nitrogen atmosphere is anti-
It answers 6 hours, revolving removes solvent methanol, obtains a kind of light yellow liquid, i.e. intermediate product A.
100.9g 1 is added in a 250ml four-hole boiling flask, 101.5g first is slowly added dropwise in 6- hexamethylene diisocyanate
Base hydroxy-ethyl acrylate then heats to 65 DEG C, stops reaction when reaction to isocyanates is near 12.4%, obtain intermediate production
Object B.
Above-mentioned intermediate product A, B are added in a 500ml four-hole boiling flask, is sufficiently stirred at 70 DEG C, until in infrared spectroscopy
Isocyano characteristic peak disappear until to get arrive the high-modulus photo-curing material.
Comparative example 1
This comparative example is the method that this field routinely introduces fluorine-containing material, is included the following steps:
33.34g isophorone diisocyanate and the positive fourth of 0.05g tin dilaurate two are added in a 250ml four-hole boiling flask
149.15g fluorine-containing polyether glycol ZDOL2000 is slowly added dropwise at 45 DEG C in Ji Xi.After being added dropwise, wait react to isocyanates
When near 3.45%, 17.42g hydroxy-ethyl acrylate, 0.20g p-hydroxyanisole and 0.05g tin dilaurate two is being added just
Butyl tin, and be sufficiently stirred at 65 DEG C, the fluorine-containing poly- ammonia is arrived until isocyano characteristic peak disappears into infrared spectroscopy
Ester acrylate.
Comparative example 2
Comparative example is commercial polyurethane acrylate.
It is right in photocureable coating that products therefrom in above-described embodiment 1~3 and comparative example 1~2 is added to according to 15wt%
Curing rate, surface contact angle, viscosity and modulus are tested.As a result shown in the following table 1.
Table 1
Through each embodiment in table 1 compared with the performance data of comparative example, it can significantly find that high-modulus of the invention is fluorine-containing
Urethane acrylate has taken into account surface can lower, the higher advantage of modulus.
The preferred embodiment of the present invention has been described in detail above, but the invention be not limited to it is described
Embodiment, those skilled in the art can also make various equivalent on the premise of not violating the inventive spirit of the present invention
Variation or replacement, and apply the general principles described here to other examples without making the creative labor.Therefore,
These equivalent variation or replacement are all included in the scope defined by the claims of the present application.
Claims (7)
1. a kind of preparation method of high-modulus fluorochemical urethane acrylate, which is characterized in that diisopropanolamine (DIPA) and fluorine-containing propene
Acid esters, diisocyanate are synthesized with hydroxy acrylate by three-step approach, and the high-modulus fluorochemical urethane acrylate is obtained.
2. the method according to claim 1, wherein the method specifically comprises the following steps:
S1, at 45~65 DEG C, fluorinated acrylate is added to the methanol solution body of diisopropanolamine (DIPA) according to 1~1.5:1 of molar ratio
In system, reaction obtains intermediate product A completely；
S2, at 65~80 DEG C, hydroxy acrylate is added in diisocyanate according to 1~1.5:1 of molar ratio, is reacted completely
Obtain intermediate product B；
S3, the intermediate product A and intermediate product B that molar ratio is 1:1.5~2.5 are reacted completely at 70~80 DEG C to get described
High-modulus fluorochemical urethane acrylate.
3. according to the method described in claim 2, it is characterized in that, the fluorinated acrylate is acrylic acid trifluoro ethyl ester, first
Base acrylic acid trifluoro ethyl ester, dodecafluorhe-ptylacrylate, dodecafluoroheptyl methacrylate, hexafluorobutyl acrylate, methyl-prop
One of olefin(e) acid hexafluoro butyl ester is a variety of.
4. according to the method described in claim 2, it is characterized in that, the diisocyanate be isophorone diisocyanate,
Toluene-2,4-diisocyanate, 4- diisocyanate, diphenylene diisocyanate, tetramethyl-ring hexane diisocyanate, 1,6- hexa-methylene two
One of isocyanates is a variety of.
5. according to the method described in claim 2, it is characterized in that, the hydroxy acrylate is hydroxy-ethyl acrylate, methyl
One of hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate are a variety of.
6. a kind of high-modulus photo-curing material that method according to any one of claims 1 to 5 is prepared.
7. a kind of high-modulus photo-curing material as claimed in claim 6 is preparing the purposes in photocureable coating.
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| CN201811560151.7A CN109678761A (en) | 2018-12-19 | 2018-12-19 | A kind of high-modulus fluorochemical urethane acrylate and preparation method thereof |
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| CN201811560151.7A CN109678761A (en) | 2018-12-19 | 2018-12-19 | A kind of high-modulus fluorochemical urethane acrylate and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057462A (en) * | 2019-12-16 | 2020-04-24 | 中昊北方涂料工业研究设计院有限公司 | Ultra-low refractive index high fluorine content UV curing polyurethane acrylate coating |
| CN114163605A (en) * | 2021-12-03 | 2022-03-11 | 万华化学集团股份有限公司 | Vegetable oil-based fluorinated hydroxy resin and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057462A (en) * | 2019-12-16 | 2020-04-24 | 中昊北方涂料工业研究设计院有限公司 | Ultra-low refractive index high fluorine content UV curing polyurethane acrylate coating |
| CN114163605A (en) * | 2021-12-03 | 2022-03-11 | 万华化学集团股份有限公司 | Vegetable oil-based fluorinated hydroxy resin and preparation method and application thereof |
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Application publication date: 20190426 |