CN107383980B - A kind of activity ultraviolet absorbing agent and its application method - Google Patents
A kind of activity ultraviolet absorbing agent and its application method Download PDFInfo
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- CN107383980B CN107383980B CN201710478509.0A CN201710478509A CN107383980B CN 107383980 B CN107383980 B CN 107383980B CN 201710478509 A CN201710478509 A CN 201710478509A CN 107383980 B CN107383980 B CN 107383980B
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- hydroxyl
- chlorobenzotriazole
- ultraviolet absorbing
- phenyl
- absorbing agent
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Classifications
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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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)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a kind of active ultraviolet absorbing agents, including 2-(2 '-hydroxyl -4 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzotriazole and/or 2-(2 '-hydroxyl -5 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzotriazole.Active ultraviolet absorbing agent resistance to migration of the invention and safety are more preferable, compared with the active ultraviolet absorber of other reports, there is wider array of applicability, more easily Adding Way, can directly be added in coating, adhesive formulation.
Description
Technical field
The present invention relates to technical field of fine, especially a kind of active ultraviolet absorbing agent and its application method.
Background technique
It is well known that having sightless ultraviolet light (290-380 nm) in natural light, it is to lead to organic material that energy is high
One of an important factor for expecting degradation with aging.So the material under being typically exposed to UV needs to be added certain ultraviolet absorber or light
Stabilizer.In paint solidification layer, when being polluted by sunlight, greasy dirt etc., the chain rupture of dope layer interior polymer, free radical may be made to produce
Raw, configuration change etc., until making coating material gloss decline, turn to be yellow, fade, become fragile even dusting etc..Or when for varnish, UV
The protected substrate of direct irradiation makes to be declined by protection materials gloss, turn to be yellow, fade etc. to occur.To solve this problem, generally exist
Light stabilizer, such as ultraviolet absorber are added in material.Although general light stabilizer persistence in organic system is preferable,
Under rugged environment, the light stabilizer of addition is still that can migrate out.It has been reported that research shows that ultraviolet absorber is in fat
It moves out in class organomimetic phenomenon；The amount of dissolution increases with the extension of time, and migration initial stage migration rate is very fast, centainly
Transition process can reach dynamic equilibrium after time；Temperature is higher, and migration rate is faster, and the time for reaching balance is shorter, the amount of moving out
It is higher；The material the thin more is easy to moving out for ultraviolet absorber.Ultraviolet absorber is moved out, and organic layer light stability is on the one hand made
Decline, reduce its service life, on the other hand, if for food, medicine aspect when, to its safety generate damage.
In the development of material high additive value, high-weatherability, safety demand also increasingly deepen, therefore to ultraviolet light
The raising of absorbent properties proposes needs.Response type ultraviolet light vapor receipts are not easy to be vaporized and dissolve out, and obtain high security and length
Phase stable high-weatherability polymer material.
At present had part response type ultraviolet absorption agent report, the research of response type ultraviolet absorption agent had at nearly 20 years compared with
More article, patent and products, for example, great Zhong chemical company, Japan production RUVA-100, Norameo company production
The Cyasorb-416 of Norbloc 7966 and the production of CYTEC company, patent CN105348131, CN103321041,
CN102584727(for textile material arrange), CN100552125(for textile material arrangement) etc..
It is existing problem be its reactivity, applicability not comprehensively.Such as RUVA-100, Norbloc 7966, Cyasorb-
The product reactivity reported in 416 and patent CN105348131 is based on acryloyl group, reactivity be confined to have double bond from
By the reaction of base, reaction needs initiator, and when being added in current material formula, initiator residual plays opposite with light stabilizer
Effect, so be generally aggregated in resin in advance in the form of copolymerization, be not easy in (coating, adhesive) formula directly plus
Enter.For another example, ultraviolet absorber (2,4-DihydroxyBenzophenone, 2- hydroxybenzotriazole), on hydroxyl can with containing activity it is different
Cyano is reacted and is fixed, and still, 2 hydroxyls destroy original excited state intramolecular proton transfer (by photon after being reacted
Energy absorption is simultaneously converted into interior amount) process, its unfavorable light stabilization.
Summary of the invention
The technical issues of to solve described in technical background, the present invention be the shortcomings that overcoming the above-mentioned prior art with it is insufficient,
The purpose of the present invention is to provide a kind of ultraviolet absorbers of active structure, can be by simply reacting to obtain.With it is other non-
Active ultraviolet absorber is compared, and the active ultraviolet absorber resistance to migration of invention and safety are more preferable, the activity with other reports
Ultraviolet absorber is compared, and has wider array of applicability, more easily Adding Way, can be directly in (coating, adhesive) formula
It is added.
The present invention can be achieved through the following technical solutions:
The invention discloses a kind of active ultraviolet absorbing agents, including 2-(2 '-hydroxyl -4 '-(2 ", 3 "-the third oxygen of epoxy
Base) phenyl) -5- chlorobenzotriazole and/or 2-(2 '-hydroxyl -5 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzene and three
Azoles, chemical structure are as follows:
Ⅰ Ⅱ
In structural formula, structural formula I corresponds to 2-(2 '-hydroxyl -4 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzene and three
Azoles；Structural formula II corresponds to 2-(2 '-hydroxyl -5 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzotriazole.
In the above structural formula, chemical structure can be formed altogether with uv absorption property with multiple material
The crosslinking of valence link, UV absorbing wavelength are 270 ~ 380 nm.
Further, 2-(2 '-hydroxyl -4 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzotriazole (I) preparation
Method are as follows: with 2,4- dihydroxy -5- chlorobenzotriazole and epoxychloropropane for raw material, sodium hydroxide is catalyst, according to mole
It than 1:1.1-5:1.1, is reacted under solvents tetrahydrofurane, basic catalyst is added, reaction temperature is 60-80 DEG C, the reaction time
It for 2-8 h, washes after reaction, is dry, solvent and unreacted epoxychloropropane is removed under reduced pressure, can be chromatographed by column or again
Further separating-purifying is crystallized, solid product I is obtained.
Further, 2-(2 '-hydroxyl -5 '-(2 ", the 3 "-glycidoxy) phenyl) -5- chlorobenzotriazole (II)
The preparation method comprises the following steps: with 2- (2 ', 5 '-dihydroxy phenyl) -5- chlorobenzotriazole and epoxychloropropane for raw material, sodium hydroxide is
Catalyst reacts under solvents tetrahydrofurane according to molar ratio 1:1.1-5:1.1, and basic catalyst is added, and reaction temperature is
60-80 oC, reaction time are 2-8 h, wash after reaction, is dry, solvent and unreacted epoxy chloropropionate is removed under reduced pressure
Alkane can be chromatographed by column or recrystallize further separating-purifying, obtain solid product II.
A kind of application method of above-mentioned active ultraviolet absorbing agent, addition use in coating or adhesive, in coating or
Additional amount is 0.1-6wt% in adhesive formulation.
Further, sulfydryl, amido or active ring oxygroup are contained in the coating, the activity ultraviolet absorbing agent is direct
It is added with formula.
Further, hydroxyl, carboxyl in the coating, while suitable Lewis Acid metal catalysis being added in coating
Agent, and heated baking paint film.
Further, the hydroxyl is the hydroxyl except phenolic hydroxyl group, and the amido is brothers amido.
Activity ultraviolet absorbing agent of the invention has following beneficial technical effect: (1) it is ultraviolet to be prepared for a kind of response type
Absorbent can be reacted with various kinds of resin material, can be directly added into formula；(2) preparation method is simple；(3) work invented
Property ultraviolet absorber resistance to migration and safety it is more preferable, compared with the active ultraviolet absorber of other reports, have wider array of suitable
With property, can be directly added in (coating, adhesive) formula
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, below with reference to embodiment and to this
Invention product is described in further detail.
Embodiment 1
The invention discloses a kind of active ultraviolet absorbing agent, 2-(2 '-hydroxyl -4 '-(2 ", 3 "-glycidoxy) benzene
Base) -5- chlorobenzotriazole, chemical structure is as follows:
Ⅰ
In structural formula, structural formula I corresponds to 2-(2 '-hydroxyl -4 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzene and three
Azoles.
2, the 4- dihydroxy -5- chlorobenzotriazole of 10.00 g is added in round-bottomed flask, 5 g of epoxychloropropane is added,
The tetrahydrofuran solvent of 150 ml is added, the catalyst sodium hydroxide of 1.67 g, reaction temperature 80 is addedoC, reaction time
For 2-8 h, washes after reaction, is dry, solvent and unreacted epoxychloropropane being removed under reduced pressure, end product can pass through column
Chromatography purification, obtains solid product I, yield 78%.
Embodiment 2
The invention discloses a kind of active ultraviolet absorbing agent, 2-(2 '-hydroxyl -5 '-(2 ", 3 "-glycidoxy) benzene
Base) -5- chlorobenzotriazole, chemical structure is as follows:
Ⅱ
Structural formula II corresponds to 2-(2 '-hydroxyl -5 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzotriazole.
2, the 5- dihydroxy -5- chlorobenzotriazole of 10.00 g is added in round-bottomed flask, 10 g of epoxychloropropane is added,
The tetrahydrofuran solvent of 150 ml is added, the catalyst sodium hydroxide of 2 g, reaction temperature 80 is addedoC, reaction time 2-
8 h wash after reaction, are dry, solvent and unreacted epoxychloropropane being removed under reduced pressure, end product can be chromatographed by column
Separating-purifying obtains solid product II, yield 75%.
Embodiment 3
The invention discloses a kind of active ultraviolet absorbing agent, 2-(2 '-hydroxyl -4 '-(2 ", 3 "-glycidoxy) benzene
Base) its chemical structure of -5- chlorobenzotriazole is as follows:
Ⅰ
In structural formula, structural formula I corresponds to 2-(2 '-hydroxyl -4 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzene and three
Azoles.
The application method of above-mentioned activity ultraviolet absorbing agent, addition are used in coating, and additional amount is in formulation for coating material
0.5wt%.The coating is bi-component epoxy coating, and active ultraviolet absorbing agent is directly added into epoxy component.
Embodiment 4
The invention discloses a kind of active ultraviolet absorbing agent 2-(2 '-hydroxyl -5 '-(2 ", 3 "-glycidoxy) benzene
Base) -5- chlorobenzotriazole, chemical structure is as follows:
Ⅱ
Structural formula II corresponds to 2-(2 '-hydroxyl -5 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzotriazole.
The application method of above-mentioned activity ultraviolet absorbing agent, addition use in coating, match in hydroxy acryl acid coating
Additional amount is 0.5wt% in side.Lewis Acid metal catalyst, and heated baking paint film is added in coating simultaneously.
Embodiment 5
The invention discloses a kind of active ultraviolet absorbing agents, including 2-(2 '-hydroxyl -4 '-(2 ", 3 "-the third oxygen of epoxy
Base) phenyl) its chemical structure of -5- chlorobenzotriazole is as follows:
Ⅰ
In structural formula, structural formula I corresponds to 2-(2 '-hydroxyl -4 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzene and three
Azoles.
The application method of above-mentioned activity ultraviolet absorbing agent, addition are used in adhesive, are added in adhesive formulation
Amount is 0.2wt%.The adhesive is epoxy AB glue, and epoxy component is added in active ultraviolet absorbing agent.
Embodiment 6
The invention discloses a kind of active ultraviolet absorbing agent, 2-(2 '-hydroxyl -5 '-(2 ", 3 "-glycidoxy) benzene
Base) -5- chlorobenzotriazole, chemical structure is as follows:
Ⅱ
In structural formula, corresponding 2-(2 '-hydroxyl -5 '-(2 ", the 3 "-glycidoxy) phenyl of structural formula II) -5- chlorobenzene is simultaneously
Triazole.
The application method of above-mentioned activity ultraviolet absorbing agent, addition use in adhesive, the additional amount in viscose glue formula
It is 0.1%, the adhesive is polyurethane adhesive.
Embodiment 7
Take 0.3 g above-mentioned product I and 0.3 g II, with formula be added 100 g one pack systems polyurethane paint, make to stir
It mixes uniformly, the not transportable coating of ultraviolet absorber is obtained after dried coating film.
At the same time, in order to assess technical effect of the invention, correlated performance test, tool are carried out to embodiment 3~7 respectively
Body test result difference is as shown in table 1:
1 test result of table
| Performance indicator | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Rate of absorbing UV | >95% | >92% | >85% | >82% | >95% |
| Frosting | It is no | It is no | It is no | It is no | It is no |
Absorptivity measures absorbing state at 320 nm, rate of absorbing UV with fiber spectrometer at purple is defined as:
ABlankFor the value of each embodiment film or adhesive film blank sample in fiber spectrum at 320 nm, ASampleFor different implementations
Value of the example sample in fiber spectrum at 320 nm.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the present invention in any form；It is all
The those of ordinary skill of the industry can be shown in by specification and described above and swimmingly implement the present invention；But it is all familiar
Professional and technical personnel without departing from the scope of the present invention, makes using disclosed above technology contents
A little variation, modification and evolution equivalent variations, be equivalent embodiment of the invention；Meanwhile all realities according to the present invention
The variation, modification and evolution etc. of matter technology any equivalent variations to the above embodiments, still fall within technology of the invention
Within the protection scope of scheme.
Claims (6)
1. a kind of activity ultraviolet absorbing agent, it is characterised in that including 2-(2 '-hydroxyl -4 '-(2 ", 3 "-glycidoxy) benzene
Base) -5- chlorobenzotriazole and/or 2-(2 '-hydroxyl -5 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzotriazole, change
It is as follows to learn structure:
Ⅰ Ⅱ
In structural formula, structural formula I corresponds to 2-(2 '-hydroxyl -4 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzotriazole；
Structural formula II corresponds to 2-(2 '-hydroxyl -5 '-(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzotriazole.
2. activity ultraviolet absorbing agent according to claim 1, it is characterised in that: 2-(2 '-hydroxyl -4 '-(2 ", 3 "-rings
Oxygen propoxyl group) phenyl) -5- chlorobenzotriazole (I) the preparation method comprises the following steps: with 2- (2 ', 4 '-dihydroxy phenyl) -5- chlorobenzene and three
Azoles and epoxychloropropane are raw material, and sodium hydroxide is catalyst, according to molar ratio 1:1.1-5:1.1, under solvents tetrahydrofurane
Basic catalyst is added in reaction, and reaction temperature is 60-80 DEG C, and the reaction time is 2-8 h, washes after reaction, is dry, subtracting
Pressure removes solvent and unreacted epoxychloropropane, can be chromatographed by column or recrystallize further separating-purifying, obtains solid production
Object I.
3. activity ultraviolet absorbing agent according to claim 1 or 2, it is characterised in that: the 2-(2 '-hydroxyl -5 ' -
(2 ", 3 "-glycidoxy) phenyl) -5- chlorobenzotriazole (II) the preparation method comprises the following steps: with 2- (2 ', 5 '-dihydroxy phenyl) -
5- chlorobenzotriazole and epoxychloropropane are raw material, and sodium hydroxide is catalyst, according to molar ratio 1:1.1-5:1.1, in solvent
It is reacted under tetrahydrofuran, basic catalyst, reaction temperature 60-80 is addedoC, reaction time are 2-8 h, after reaction water
It washes, dry, solvent and unreacted epoxychloropropane is removed under reduced pressure, can chromatograph or recrystallize further separating-purifying by column,
Obtain solid product II.
4. a kind of application method of the described in any item active ultraviolet absorbing agents of claim 1-3, it is characterised in that: addition exists
It is used in coating or adhesive, additional amount is 0.1-6wt% in coating or adhesive formulation.
5. the application method of activity ultraviolet absorbing agent according to claim 4, it is characterised in that: the coating or gluing
Contain amido, active ring oxygroup or sulfydryl in agent, the activity ultraviolet absorbing agent is directly added with formula.
6. the application method of activity ultraviolet absorbing agent according to claim 4, it is characterised in that: contain hydroxyl in the coating
Base, carboxyl, while suitable Lewis Acid metal catalyst being added in coating, and heated baking paint film.
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| CN201710478509.0A CN107383980B (en) | 2017-06-22 | 2017-06-22 | A kind of activity ultraviolet absorbing agent and its application method |
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| CN201710478509.0A CN107383980B (en) | 2017-06-22 | 2017-06-22 | A kind of activity ultraviolet absorbing agent and its application method |
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| CN112552250B (en) * | 2020-12-14 | 2022-04-29 | 天津利安隆新材料股份有限公司 | Reactive benzotriazole compound, application thereof and high polymer material comprising reactive benzotriazole compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717372A (en) * | 2009-11-20 | 2010-06-02 | 大连化工研究设计院 | Method for synthesizing substituted benzotriazole compound |
| CN102675823A (en) * | 2011-03-18 | 2012-09-19 | 唐来江 | Preparation process of transparent epoxy nanocomposite material for encapsulating high-power LED (light-emitting diode) |
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2017
- 2017-06-22 CN CN201710478509.0A patent/CN107383980B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717372A (en) * | 2009-11-20 | 2010-06-02 | 大连化工研究设计院 | Method for synthesizing substituted benzotriazole compound |
| CN102675823A (en) * | 2011-03-18 | 2012-09-19 | 唐来江 | Preparation process of transparent epoxy nanocomposite material for encapsulating high-power LED (light-emitting diode) |
Non-Patent Citations (1)
| Title |
|---|
| 高分子材料稳定剂的研究进展;丁著明等;《化工文摘》;20051231(第5期);第49-53页 * |
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