CN105566205B - A kind of piperidines for pigment antioxidant and preparation method thereof - Google Patents
A kind of piperidines for pigment antioxidant and preparation method thereof Download PDFInfo
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- CN105566205B CN105566205B CN201410555054.4A CN201410555054A CN105566205B CN 105566205 B CN105566205 B CN 105566205B CN 201410555054 A CN201410555054 A CN 201410555054A CN 105566205 B CN105566205 B CN 105566205B
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Abstract
The present invention provides a kind of piperidines for pigment antioxidant, and the compound meets below general formula (I)：The present invention also provides a kind of preparation method of above-claimed cpd, and formula (II) compound and formula (III) compound are chemically reacted.
Description
Technical field
The present invention relates to a kind of piperidines for pigment antioxidant and preparation method thereof.
Background technology
With the high speed development of information technology and digital technology, the application of printing class material penetrates into rapidly each field,
The high profit margin that the market capacity and high technical additional value expanded day by day is brought will necessarily attract trans-corporation to put into a large amount of technologies
The research and development and production of new printing class material are engaged in financial resources, the colour print material of some trans-corporations production has refreshed tradition
Printed material, bright in luster, the real printed material of reproducibility increasingly liked by huge numbers of families.With China's economic
High speed development, the living standard of our people improves constantly, and the thing followed is to print the increasingly sharp increase of class materials demand, state
The exploitation of input financial resource and material resource is not stinted with producing all kinds of new printing class materials by interior many producers, but due to by technology and raw material
Influence, domestic printed material, especially colour print material at present, show slightly inferior on color reducibility and color stability,
Reason is technological deficiency also be present to the pigment of all kinds of colors and the anti-oxidant aspect of dyestuff.
Benzophenone compound is that current output is maximum, the widest antioxidizing agent of use range.It is acted on
Mechanism is commonly considered as forming a chelating by the hydrogen bond action of intramolecular between the active hydrogen and ketonic oxygen in its structure
Hexatomic ring, when its absorb ultraviolet energy after, molecule occur thermal vibration be destroyed this hydrogen bond, chelate ring is opened,
Harmful ultraviolet energy is thus changed into harmless heat then to discharge again, so as to the macromolecule to pigment or dyestuff
Material plays a part of protection.Chinese patent CN103665677A discloses one kind and contains 2- hydroxyl -4- n-octyloxy hexichol first
Ketone is the synthetic resin high-pressure hose of antioxidant, and obtained synthetic resin high-pressure hose has excellent chemical-resistant resistance, resistance to
Organic solvent properties, ageing-resistant performance.But apply to benzophenone compound in printed material, for the stability of light
Aspect is still insufficient.
The content of the invention
What the present invention proposed to solve above mentioned problem of the prior art.
The invention provides a kind of compound of the piperidines antioxidant for good light stability.
Present invention also offers the preparation method of above-claimed cpd.
To achieve the above object, the present invention uses following technical scheme：
The first aspect of the invention is to provide a kind of piperidines for pigment antioxidant, compound symbol
Close below general formula (I)：
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10For H or C1-10Alkyl.
Preferably, the R1、R2、R3、R4、R9、R10For C1-10Alkyl, the R5、R6、R7、R8For H.It is it is highly preferred that described
R1、R2、R3、R4For methyl, the R9、R10For ethyl.
The second aspect of the invention is to provide the preparation method of above-mentioned piperidines, be by formula (II) compound with
Formula (III) compound is chemically reacted.
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10For H or C1-10Alkyl.
Preferably, the R1、R2、R3、R4、R9、R10For C1-10Alkyl, the R5、R6、R7、R8For H.It is it is highly preferred that described
R1、R2、R3、R4For methyl, the R9、R10For ethyl.
Preferably, formula (II) compound and formula (III) compound mix in the ethanol and ethyl acetate of volume ratio 1: 1
Reacted in solvent.
In a preferred embodiment of the present invention, it is described chemical reaction be in the presence of sodium hydroxide and KBr,
Carried out under inert gas shielding, reaction temperature is 50 DEG C -80 DEG C, and preferably 50 DEG C -60 DEG C, the reaction time is 3-8 hours, preferably
For 3-4 hours.
The chemical reaction cools to 0 DEG C -15 DEG C after terminating, and stands at least 2 hours, is filtrated to get sediment, will
The precipitate dried under reduced pressure, obtain above-mentioned formula (I) antioxidant.
As the R1、R2、R3、R4For methyl, R5、R6、R7、R8For H, R9、R10For ethyl when, i.e., formula (I) compound is 4- third
Diethyl adipate epoxide -2,2,6,6- tetramethyl piperidines, the weight proportion of sodium hydroxide and KBr is in the chemical reaction
(5-10)∶(1-3)。
Preferably, the weight content of each reacted constituent is in the chemical reaction：
Formula (II) compound 50-100 parts,
Formula (III) compound 50-100 parts,
Sodium hydroxide 5-10 parts,
KBr 1-3 parts,
Ethanol and ethyl acetate mixed solvent 200-400 parts.
A kind of piperidines provided by the invention, it is a kind of antioxidant in pigment or dyestuff, as anti-
Intermediate is answered, is mainly used in the paper pulp of printing paper, coating synthesis, the synthesis of synthesis of polymer material, all kinds of macromolecule membranes,
Due to directly participating in chemical reaction, the product of generation has superpower absorption and shielding ultraviolet rays function to pigment or dyestuff,
There is excellent effect in terms of inoxidizability, photostability.
Embodiment
The present invention is described in more detail below by specific embodiment, for a better understanding of the present invention,
But following embodiments are not intended to limit the scope of the invention.
Embodiment 1
The present embodiment provides a kind of antioxidant 4- diethyl malonate epoxide -2,2,6,6- tetramethyls being used in pigment
Piperidines, its preparation method comprise the following steps：50 parts by weight bromo diethyl malonates are added to the 1 of 200 parts by weight:1 ethanol
With ethyl acetate in the mixed solvent, the tetramethylpiperidinol of 100 parts by weight 2,2,6,6- and 200 parts by weight are added in four-hole boiling flask
1:1 ethanol and ethyl acetate mixed solvent, 5 parts by weight of sodium hydroxide and 3 parts by weight KBrs are added, are slowly introducing nitrogen
Gas, stir under 150 revs/min of mixing speed, under 60 DEG C of reaction temperatures, by the alcohol, acetic acid second containing bromo diethyl malonate
Ester mixed solvent is added drop-wise in four-hole boiling flask, is added dropwise in 30 minutes, then back flow reaction 4 hours, and reaction uses ice after terminating
Water cooling is cooled to 5 DEG C, stands 2 hours, is filtrated to get sediment, sediment is dried under reduced pressure again, obtain 4- malonic acid diethyls
Ester epoxide -2,2,6,6- tetramethyl piperidines.
Embodiment 2
The present embodiment provides a kind of antioxidant 4- diethyl malonate epoxide -2,2,6,6- tetramethyls being used in pigment
Piperidines, its preparation method comprise the following steps：100 parts by weight bromo diethyl malonates are added to the 1 of 200 parts by weight:1 ethanol
With ethyl acetate in the mixed solvent, the tetramethylpiperidinol of 50 parts by weight 2,2,6,6- and 200 parts by weight are added in four-hole boiling flask
1:1 ethanol and ethyl acetate mixed solvent, 10 parts by weight of sodium hydroxide and 1 parts by weight KBr are added, are slowly introducing nitrogen
Gas, stir under 170 revs/min of mixing speed, under 50 DEG C of reaction temperatures, by the alcohol, acetic acid second containing bromo diethyl malonate
Ester mixed solvent is added drop-wise in four-hole boiling flask, is added dropwise in 60 minutes, then back flow reaction 3 hours, and reaction uses ice after terminating
Water cooling is cooled to 10 DEG C, stands 2 hours, is filtrated to get sediment, sediment is dried under reduced pressure again, obtain 4- malonic acid diethyls
Ester epoxide -2,2,6,6- tetramethyl piperidines.
Embodiment 3
The present embodiment provides a kind of antioxidant 4- diethyl malonate epoxide -2,2,6,6- tetramethyls being used in pigment
Piperidines, its preparation method comprise the following steps：75 parts by weight bromo diethyl malonates are added to the 1 of 200 parts by weight:1 ethanol
With ethyl acetate in the mixed solvent, the tetramethylpiperidinol of 75 parts by weight 2,2,6,6- and 200 parts by weight are added in four-hole boiling flask
1:1 ethanol and ethyl acetate mixed solvent, 7.5 parts by weight of sodium hydroxide and 3 parts by weight KBrs are added, are slowly introducing nitrogen
Gas, stir under 160 revs/min of mixing speed, under 55 DEG C of reaction temperatures, by the alcohol, acetic acid second containing bromo diethyl malonate
Ester mixed solvent is added drop-wise in four-hole boiling flask, is added dropwise in 45 minutes, then back flow reaction 3.5 hours, and reaction is used after terminating
Frozen water cooling is cooled to 8 DEG C, stands 2 hours, is filtrated to get sediment, sediment is dried under reduced pressure again, obtains 4- malonic acid two
Ethyl ester epoxide -2,2,6,6- tetramethyl piperidines.
Application Example 4
1 ‰ 4- diethyl malonates epoxide -2,2,6,6- tetramethyl piperidines of the invention are added to life after printing paper paper pulp
The general level of printing paper bioassay standard of production, after 1 ‰ 2- hydroxyl -4- dodecyloxy benzophenones antioxidants are added with contrast groups
The printing paper of production does contrast test, and both measure is to the difference of the protective value of color, test structure such as table 1.
The contrast test of 1 antioxidant of the present invention of table and 2- hydroxyl -4- dodecyloxy benzophenones printing papers
In table, (1) xenon arc lamp xenon lamp power：1.8kw, wavelength：290nm~800nm, irradiation level：290nm~800nm, ripple
Average irradiance between length is 550W/m2, light source and 1 meter of measured object distance, irradiation time are 56 hours.
Above-mentioned printing test condition：
Printer：Epson Stylus Photo R2880, oil-soluble dyes printing；
Method of testing：According to standard GB/T/T17974-2000 method；
Level spectrum test equipment：Color reflection mode Density Measuring Instrument PRB03-36921.
4- diethyl malonate epoxides -2,2 of the present invention, 6,6- tetramethyl piperidines are can be seen that from the test result of table 1
There is extraordinary protective effect to dyestuff, get a desired effect.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, it is of the invention and unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of piperidines for pigment antioxidant, it is characterised in that the compound meets below general formula (I)：
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10For H or C1-10Alkyl.
2. compound according to claim 1, it is characterised in that the R1、R2、R3、R4、R9、R10For C1-10Alkyl, it is described
R5、R6、R7、R8For H.
3. compound according to claim 2, it is characterised in that the R1、R2、R3、R4For methyl, the R9、R10For second
Base.
4. the preparation method of compound described in a kind of claim 1, it is characterised in that change formula (II) compound and formula (III)
Compound is chemically reacted：
Wherein, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10For H or C1-10Alkyl.
5. preparation method according to claim 4, it is characterised in that formula (II) compound and formula (III) compound
Reacted in the ethanol and ethyl acetate in the mixed solvent of volume ratio 1: 1.
6. preparation method according to claim 4, it is characterised in that the chemical reaction is in sodium hydroxide and KBr
In the presence of react.
7. preparation method according to claim 4, it is characterised in that the chemical reaction is entered under inert gas shielding
OK.
8. preparation method according to claim 4, it is characterised in that the chemical reaction temperature is 50 DEG C -80 DEG C, reaction
Time is 3-8 hours.
9. preparation method according to claim 4, it is characterised in that it is described chemical reaction terminate after cool to 0 DEG C-
15 DEG C, at least 2 hours are stood, sediment is collected, obtains the compound described in claim 1.
10. preparation method according to claim 9, it is characterised in that sodium hydroxide and KBr in the chemical reaction
Weight proportion be (5-10): (1-3).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410555054.4A CN105566205B (en) | 2014-10-17 | 2014-10-17 | A kind of piperidines for pigment antioxidant and preparation method thereof |
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| CN201410555054.4A CN105566205B (en) | 2014-10-17 | 2014-10-17 | A kind of piperidines for pigment antioxidant and preparation method thereof |
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| CN105566205A CN105566205A (en) | 2016-05-11 |
| CN105566205B true CN105566205B (en) | 2017-12-01 |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100379724C (en) * | 1997-07-23 | 2008-04-09 | 西巴特殊化学品控股有限公司 | Inhibition of pulp and paper yellowing using nitroxides and other coadditives |
| US20060229393A1 (en) * | 2005-04-08 | 2006-10-12 | Prasad Duggirala | Compositions and methods for enhancing brightness and brightness stabilization in papermaking |
| CN103665677A (en) * | 2013-12-06 | 2014-03-26 | 苏州华东橡胶工业有限公司 | Synthetic resin high-pressure flexible pipe |
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Denomination of invention: A piperidine compound for pigment antioxidant and its preparation method Effective date of registration: 20210125 Granted publication date: 20171201 Pledgee: Bank of Hangzhou Limited by Share Ltd. Shanghai branch Pledgor: SHANGHAI DONGSHENG NEW MATERIALS Co.,Ltd. Registration number: Y2021310000003 |
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Date of cancellation: 20230308 Granted publication date: 20171201 Pledgee: Bank of Hangzhou Limited by Share Ltd. Shanghai branch Pledgor: SHANGHAI DONGSHENG NEW MATERIALS Co.,Ltd. Registration number: Y2021310000003 |