CN109641832A - Azo-compound, polymer and Preparation method and use - Google Patents

Azo-compound, polymer and Preparation method and use Download PDF

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CN109641832A
CN109641832A CN201780052242.7A CN201780052242A CN109641832A CN 109641832 A CN109641832 A CN 109641832A CN 201780052242 A CN201780052242 A CN 201780052242A CN 109641832 A CN109641832 A CN 109641832A
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separately
azo
alkyl
compound
polymer
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CN109641832B (en
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康小林
李德珊
曹立
罗敏
黄芳芳
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Dongguan Dongguan Sunshine Medical Intelligent Device Research and Development Co., Ltd.
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Sunshine Lake Pharma Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
    • C07C245/12—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention proposes azo-compound, polymer and Preparation method and uses.The azo-compound has preferable interception blue light performance, and above compound is polymerizable azo-compound, is not easy that diffusion mobility occurs in the polymer.

Description

Azo-compound, polymer and Preparation method and use Technical field
The present invention relates to eye medical device fields, and in particular, to azo-compound, polymer and Preparation method and use.
Background technique
In recent years, have that researches show that the blue light components in visible light to damage to human eye, especially retina, visual impairment is caused even to be blinded.Therefore occur in the eyes medical device such as eyeglass, addition can intercept the pad pasting of blue light or can intercept the ingredient of blue light, prevent blue light from damaging to human eye.
However, the polymer for intercepting the eye medical device of function with blue light at present and preparing eye medical device still has much room for improvement.
Summary of the invention
The application is to be made based on inventor to the discovery of following facts and problem and understanding:
Although the eyeglass at present with blue light interception function is more universal, in the eye medical device that artificial lens etc. is directly contacted with human eye, it is more rare that blue light intercepts function.Inventor is generally to be realized and adding the weld with absorption blue light function in eye medical device this is mainly due to the interception function of blue light by furtheing investigate discovery.And the above-mentioned eye medical device directly contacted with human eye, it is required that the weld of addition can not occur to spread and be migrated in eye medical device, in other words, need to guarantee that the weld of addition is stabilized in above-mentioned eye medical device, human eye will not be entered, to guarantee the security performance of above-mentioned eye medical device.And the weld that can satisfy above-mentioned requirements is extremely limited, therefore limits the development that the eye medical device of function is intercepted with blue light.
The present invention is directed to solve at least to a certain extent it is above in the related technology the technical issues of one of.Thus, the present invention proposes a kind of azo-compound, which has preferable interception blue light performance, and above compound is polymerizable azo-compound, it is not easy diffusion mobility to occur in the polymer, therefore can be used as artificial lens etc. the blue-light absorbers in eyes medical device to use.
The present invention also proposes a kind of polymer, which contains above-mentioned azo-compound, therefore has the function of intercepting blue light.And above-mentioned azo-compound is polymerizable compound, therefore above-mentioned azo-compound is not easy that diffusive migration occurs in polymer proposed by the present invention.
The present invention also proposes that polymer of the present invention is preparing the purposes in eye medical device.It is prepared using above-mentioned polymer Eye medical device can realize the interception function of blue light, and have preferable safety under the premise of not influencing the use function of the eye medical device.
In addition, the present invention also proposes the method for preparing polymer of the present invention.
Detailed description of the invention
Fig. 1 shows the spectral transmittance test chart of polymer A-0 according to the present invention；
Fig. 2 shows the spectral transmittance test chart of polymer A-1 according to the present invention；
Fig. 3 shows the spectral transmittance test chart of polymer A-2 according to the present invention；
Fig. 4 shows the spectral transmittance test chart of polymer A-3 according to the present invention；
Fig. 5 shows the spectral transmittance test chart of polymer B -0 according to the present invention；
Fig. 6 shows the spectral transmittance test chart of polymer B -1 according to the present invention；
Fig. 7 shows the spectral transmittance test chart of polymer B -2 according to the present invention.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings.The embodiments described below with reference to the accompanying drawings are exemplary, it is intended to be used to explain the present invention, and be not considered as limiting the invention.
Unless otherwise stated, all scientific and technical terminologies used in the present invention, which have, is generally understood identical meaning with those skilled in the art of the invention.All patents of the present invention and public publication are integrally incorporated the present invention by reference.Term "comprising" or " comprising " are open language, that is, include content specified by the present invention, but otherwise content is not precluded.In the present invention, wordings such as " about " or " about " whether or not using, all numbers being disclosed are approximation.The numerical value of each number is possible to the reasonable difference that will appear 10% difference below or those skilled in the art think, such as 1%, 2%, 3%, 4% or 5% difference.
In the present invention, azo-compound proposed by the invention has general formula shown in Formulas I a, also includes the stereoisomer or tautomer of general formula compound shown in meeting formula Ia." stereoisomer " refers to identical chemical constitution, but atom or the group spatially different compound of arrangement mode.Stereoisomer includes enantiomter, diastereoisomer, conformer (rotational isomer), geometric isomer (cis/trans) isomers and atropisomer etc..
Stereochemical definitions used in the present invention and rule generally follow S.P.Parker, Ed., McGraw-Hill Dictionary of Chemical Terms (1984) McGraw-Hill Book Company, New York；And Eliel, E.and Wilen, S., " Stereochemistry of Organic Compounds ", John Wiley&Sons, Inc., New York, Stereochemical definitions described in 1994 and rule.
Many organic compounds exist with optical active forms, i.e., they have the energy for rotating the plane of linearly polarized light Power.When describing optically active compound, absolute configuration of the molecule about one or more chiral centre is indicated using prefix D and L or R and S.Prefix d and l or (+) and (-) are the symbols for the rotation of linearly polarized light caused by appointed compound, wherein (-) or l indicate that compound is left-handed.Prefix is (+) or the compound of d is dextrorotation.A kind of specific stereoisomer is enantiomter, and the mixture of this isomers is referred to as enantiomeric mixture.The 50:50 mixture of enantiomter is known as racemic mixture or racemic modification, when chemical reaction or in the process without stereoselectivity or stereospecificity when, may occur in which such case.
Any asymmetric atom (for example, carbon etc.) of disclosed compound of present invention can exist in the form that racemic or enantiomer are enriched with, such as (R)-, (S)-or (R, S)-configuration exist.In certain embodiments, each asymmetric atom has at least 50% enantiomeric excess in terms of (R)-or (S)-configuration, at least 60% enantiomeric excess, at least 70% enantiomeric excess, at least 80% enantiomeric excess, at least 90% enantiomeric excess, at least 95% enantiomeric excess, or at least 99% enantiomeric excess.
According to the selection of starting material and method, the compounds of this invention can be with one or their mixture in possible isomers, such as the form presence of racemic modification and non-corresponding isomer mixture (this depends on the quantity of asymmetric carbon atom).Chiral synthon or chiral reagent preparation can be used in optically active (R)-or (S)-isomers, or is split using routine techniques.If compound contains a double bond, substituent group may be E or Z configuration；If containing disubstituted naphthenic base in compound, the substituent group of naphthenic base may have cis or trans configuration.
The mixture of resulting any stereoisomer can be separated into pure or substantially pure geometric isomer, enantiomter, diastereoisomer according to the difference in component physicochemical properties, for example, passing through chromatography and/or Steppecd crystallization.
The racemic modification of any gained final product or intermediate can be split into optical antipode by method familiar to those skilled in the art by known method, e.g., be separated by its diastereoisomeric salt to acquisition.Racemic product can also be separated by chiral chromatogram, e.g., use the high performance liquid chromatography (HPLC) of chiral sorbent.Particularly, enantiomter can be prepared by asymmetric syntheses, for example, can refer to Jacques, et al., Enantiomers, Racemates and Resolutions (Wiley Interscience, New York, 1981)；Principles of Asymmetric Synthesis(2nd Ed.Robert E.Gawley,Jeffrey Aubé,Elsevier,Oxford,UK,2012)；Eliel,E.L.Stereochemistry of Carbon Compounds(McGraw-Hill,NY,1962)；Wilen,S.H.Tables of Resolving Agents and Optical Resolutions p.268(E.L.Eliel,Ed.,Univ.of Notre Dame Press,Notre Dame,IN 1972)；Chiral Separation Techniques:A Practical Approach(Subramanian,G.Ed.,Wiley-VCH Verlag GmbH&Co.KGaA,Weinheim,Germany,2007).
Term " tautomer " or " tautomeric form " refer to that with different energy can be by the constitutional isomer of the mutual inversion of phases of low energy barrier (low energy barrier).If tautomerism is possible (as in the solution), the chemical balance of tautomer can achieve.For example, proton tautomer (protontautomer) (also referred to as Prototropic tautomers (prototropic tautomer)) it include the mutual inversion of phases carried out by proton transfer, such as keto-enol isomerization and imine-enamine isomerizations.Valence tautomerism body (valence tautomer) includes the mutual inversion of phases carried out by the recombination of some bonding electrons.The specific example of ketoenol tautomerization is the interconversion of pentane -2,4- diketone and the amyl- 3- alkene -2- keto tautomer of 4- hydroxyl.Another tautomeric example is phenol-keto tautomerism.One specific example of phenol-keto tautomerism is the interconversion of pure and mild pyridine -4 (1H) the -one tautomer of pyridine -4-.Unless otherwise noted, all tautomeric forms of the compounds of this invention are within the scope of the present invention.
In the present invention, wordings such as " about " or " about " whether or not using, all numbers being disclosed are approximation.The numerical value of each number is possible to the reasonable difference that will appear 10% difference below or those skilled in the art think, such as 1%, 2%, 3%, 4% or 5% difference.Term " blue light " refers to wave-length coverage in the visible light of 400~550nm, the terms such as " intercepting blue light ", " absorbing blue light " refer to when the visible light containing blue light, the material surface side that is made of substances such as azo-compound proposed by the present invention or polymer is incident and when passing through the material, the light intensity of blue light, which is compared to have in apparent reduction or even emergent light compared with the light intensity of blue light in incident light, in the emergent light of another side surface of material does not include blue light." room temperature " refers to temperature by about 10 degrees Celsius to about 40 degrees Celsius in the present invention.In some embodiments, " room temperature " refers to temperature by about 20 degrees Celsius to about 30 degrees Celsius；In other embodiments, " room temperature " refers to 20 degrees Celsius, 22.5 degrees Celsius, 25 degrees Celsius, 27.5 degrees Celsius etc..
It is disclosed in the substituent group of each section of this specification, disclosed compound of present invention according to radical species or range.It particularly points out, the present invention includes each independent sub-combinations thereof of each member of these radical species and range.For example, term " C1-6Alkyl " refers in particular to the methyl being individually disclosed, ethyl, C3Alkyl, C4Alkyl, C5Alkyl and C6Alkyl.
Term " alkyl " or " alkyl group " indicate the linear chain or branched chain hydrocarbyl group of saturation, which can be monovalence, divalent or trivalent hydrocarbon radical group.In one embodiment, alkyl group contains 1-12 carbon atom；In another embodiment, alkyl group contains 1-6 carbon atom；Again in one embodiment, alkyl group contains 1-4 carbon atom；Also in one embodiment, alkyl group contains 1-2 carbon atom.
Unless otherwise detailed instructions, term " C1-12Alkyl " group contains 1-12 carbon atom.Term " C1-6Alkyl " has and " C1-12The similar meaning of alkyl ", the difference is that C1-66 carbon atoms are contained up in alkyl, details are not described herein.
The example of alkyl group includes, but is not limited to, methyl (Me ,-CH3), ethyl (Et ,-CH2CH3), n-propyl (n-Pr ,-CH2CH2CH3), isopropyl (i-Pr ,-CH (CH3)2), normal-butyl (n-Bu ,-CH2CH2CH2CH3), isobutyl group (i-Bu ,-CH2CH(CH3)2), sec-butyl (s-Bu ,-CH (CH3)CH2CH3), tert-butyl (t-Bu ,-C (CH3)3), n-pentyl (- CH2CH2CH2CH2CH3), 2- amyl (- CH (CH3)CH2CH2CH3), 3- amyl (- CH (CH2CH3)2), 2- methyl -2- butyl (- C (CH3)2CH2CH3), 3- methyl -2- butyl (- CH (CH3)CH(CH3)2), 3- methyl-1-butyl (- CH2CH2CH(CH3)2), 2-methyl-1-butene base (- CH2CH(CH3)CH2CH3), n-hexyl (- CH2CH2CH2CH2CH2CH3), 2- hexyl (- CH (CH3)CH2CH2CH2CH3), 3- hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2- methyl -2- amyl (- C (CH3)2CH2CH2CH3), 3- methyl -2- amyl (- CH (CH3)CH(CH3)CH2CH3), 4- methyl -2- amyl (- CH (CH3)CH2CH(CH3)2), 3- methyl -3- amyl (- C (CH3)(CH2CH3)2), 2- methyl -3- amyl (- CH (CH2CH3)CH(CH3)2), 2,3- dimethyl -2- butyl (- C (CH3)2CH(CH3)2), 3,3- dimethyl -2- butyl (- CH (CH3)C(CH3)3), n-heptyl, n-octyl, undecyl, etc..
Term " alkoxy " indicates that alkyl group is connected by oxygen atom with molecule rest part, and wherein alkyl group has meaning as described in the present invention.In one embodiment, alkoxy base contains 1-12 carbon atom；In another embodiment, alkoxy base contains 1-6 carbon atom；Again in one embodiment, alkoxy base contains 1-4 carbon atom；Also in one embodiment, alkoxy base contains 1-2 carbon atom.
Unless otherwise detailed instructions, term " C1-12Alkoxy " group contains 1-12 carbon atom.Term " C1-6Alkoxy " has and " C1-12The similar meaning of alkoxy ", the difference is that C1-66 carbon atoms are contained up in alkoxy, details are not described herein.
The example of alkoxy base includes, but is not limited to, methoxyl group (MeO ,-OCH3), ethyoxyl (EtO ,-OCH2CH3), 1- propoxyl group (n-PrO, n- propoxyl group ,-OCH2CH2CH3), 2- propoxyl group (i-PrO, i- propoxyl group ,-OCH (CH3)2), 1- butoxy (n-BuO, n- butoxy ,-OCH2CH2CH2CH3), 2- methyl-l- propoxyl group (i-BuO, i- butoxy ,-OCH2CH(CH3)2), 2- butoxy (s-BuO, s- butoxy ,-OCH (CH3)CH2CH3), 2- methyl -2- propoxyl group (t-BuO, t- butoxy,-OC (CH3)3), 1- amoxy (n- amoxy ,-OCH2CH2CH2CH2CH3), 2- amoxy (- OCH (CH3)CH2CH2CH3), 3- amoxy (- OCH (CH2CH3)2), 2- methyl -2- butoxy (- OC (CH3)2CH2CH3), 3- methyl -2- butoxy (- OCH (CH3)CH(CH3)2), 3- methyl-l- butoxy (- OCH2CH2CH(CH3)2), 2- methyl-l- butoxy (- OCH2CH(CH3)CH2CH3), etc..
Bivalent hydrocarbon chain that term " alkylidene " and " alkylidene chain " refer to linear chain or branched chain, being only made of carbon and hydrogen atom is free of unsaturated bond, has 1 to 12 carbon atoms, for example, methylene, ethylidene, propylidene, positive butylidene etc..Alkylidene chain can be connected on the remainder of molecule by any two carbon atom in chain.
Term " sub- miscellaneous alkyl " and " sub- miscellaneous alkyl chain ", which refer to, can be inserted the hetero atoms such as one or more O, N, S, NR in alkylidene and alkylidene chain, and/or, wherein optionally one or more-CH2By-C (=O) ,-S (=O) ,-S (=O)2Equal groups substitution, wherein alkylidene and alkylidene chain have meaning as described in the present invention.Unless otherwise detailed instructions, sub- miscellaneous alkyl or sub- miscellaneous alkyl chain contain 1-12 carbon atom, some embodiments are, sub- miscellaneous alkyl group contains 1-10 carbon atom, other embodiment is, sub- miscellaneous alkyl group contains 1-5 carbon atom, and other embodiment is that sub- miscellaneous alkyl group contains 1-4 carbon atom.Such example includes, but is not limited to ,-CH2OCH2,-CH2CH2OCH2,-CH2SCH2,-CH2NHCH2,-CH2O- ,-CH2CH2O- ,-CH2CH2CH2O- ,-CH2CH2CH2CH2O- ,-CH2CH2CH2CH2CH2O- ,-CH2CH2CH2CH2CH2CH2O- ,-CH2OCH2CH2,-CH2CH2OCH2CH2, -CH2C (=O) CH2,-CH2C (=O) OCH2,-CH2S (=O)2OCH2Etc..
Term " bivalent organic group " refers to tool, and there are two the groups of unpaired electron, there is no particular limitation for bivalent organic group of the present invention, can enumerate the aromatic hydrocarbyl of divalent, the saturation of divalent or unsaturated fatty hydrocarbons base, the heterocycle of divalent, the miscellaneous alkyl of divalent etc..
Term " naphthenic base " indicates to be made of using carbon atom as annular atom 3-12 carbon atom, the saturation monocycle of unit price or multivalence, bicyclic or three-ring system.In one embodiment, naphthenic base is made of 3-10 carbon atom；In another embodiment, naphthenic base is made of 3-8 carbon atom；In yet another embodiment, naphthenic base is made of 3-6 carbon atom.The group of naphthene base can be independently unsubstituted or replaced one or more substituent group described in the invention.Such example includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, cyclooctyl, cyclononyl, cyclodecyl, ring undecyl, cyclo-dodecyl, etc..
Term " heterocycle " and " heterocycle " are used interchangeably here, all refer to the unsaturated monocyclic, bicyclic or tricyclic of saturation or part comprising 3-12 annular atom, and wherein at least one annular atom is selected from nitrogen, sulphur and oxygen atom.Unless otherwise stated, heterocycle can be carbon-based or nitrogen base, and-CH2- group can be substituted optionally by-C (=O)-, and the sulphur atom of ring can optionally be oxidized to S- oxide, and the nitrogen-atoms of ring can optionally be oxidized to N- oxygen compound.The example of heterocycle includes, but it is not limited to: Oxyranyle, azelidinyl, oxetanylmethoxy, thietanyl, pyrrolidinyl, 2- pyrrolinyl, 3- pyrrolinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, tetrahydrofuran base, dihydrofuryl, tetrahydro-thienyl, dihydrothiophene, 1, 3- dioxy cyclopenta, two sulphur cyclopenta, THP trtrahydropyranyl, dihydro pyranyl, 2H- pyranose, 4H- pyranose, tetrahydro thiapyran base, piperidyl, morpholinyl, thio-morpholinyl, 1- oxo-thiomorpholin base, 1, 1- dioxo-thiomorpholinyl, piperazinyl, dioxanes base, dithianyl, thiophene oxane base, high piperazine base, homopiperidinyl, high morpholinyl, oxepane alkyl, thia cycloheptyl alkyl, oxygen azepineBase, diazaBase, sulphur azepineBase, indoline base, 1, 2, 3, 4- tetrahydric quinoline group, 1, 2, 3, 4- tetrahydro isoquinolyl, 1, 3- benzo two dislikes cyclopentadienyl, 2- oxa- -5- azabicyclo [2.2.1] hept- 5- base, benzopyrrolodinyl, dihydro benzo furyl, benzo morpholinyl, 3, 4- dihydro-pyrido [3, 2-b] [1, 4] oxazines base, 1, 3- benzo dioxolane base, tetrahydro pyridyl, 1, 4- benzdioxan base, pyridine -2 (1H) -one -3- base, pyridine -2 (1H) -one -4- base, pyridine -2 (1H) -one -5- base, pyridine -2 (1H) -one -6- base, pyrazine -2 (1H) -one -3- base, pyrazine -2 (1H) -one -5- base, pyrazine -2 (1H) -one -6- base.- CH2- group is included, but are not limited to by-C (=O)-example replaced in heterocycle: 2- oxo-pyrrolidine base, oxo -1,3-thiazoles alkyl, 2- piperidone base, 3,5- dioxy piperazine piperidinyls and hybar X base.The example that sulphur atom is oxidized in heterocycle includes, but are not limited to: sulfolane base, 1,1- dioxothiomorpholinyl.The heterocyclyl groups can be optionally replaced one or more substituent groups described in the invention.
In one embodiment, heterocycle is 4-7 former molecular heterocycle；In another embodiment, heterocycle is 4 molecular heterocycles of original；In another embodiment, heterocycle is 5 molecular heterocycles of original；In another embodiment, heterocycle is 6 molecular heterocycles of original；Also in one embodiment, heterocycle is 7-12 atom composition Heterocycle；Also in one embodiment, heterocycle refers to Heterocyclylalkyl.
Term " aryl " indicates to contain 6-14 annular atom, or 6-12 annular atom, or monocycle, bicyclic and tricyclic the carbocyclic ring system of 6-10 annular atom, wherein, at least one ring system is aromatic, wherein each ring system includes 3-7 former molecular ring, and has one or more attachment points to be connected with the rest part of molecule.Term " aryl " can be used interchangeably with term " aromatic rings ".The example of aryl group may include phenyl, indenyl, naphthalene and anthracene.The aryl group can be individually optionally replaced one or more substituent groups described in the invention.
Term " heteroaryl " indicates to contain 5-12 annular atom, or 5-10 annular atom, or monocycle, the bicyclic and three-ring system of 5-6 annular atom, wherein at least one ring system is aromatic, and at least one ring system includes one or more hetero atoms, wherein each ring system includes 5-7 former molecular ring, and has one or more attachment points to be connected with molecule rest part.Term " heteroaryl " can be used interchangeably with term " hetero-aromatic ring " or " heteroaromatics ".The heteroaryl groups are optionally replaced one or more substituent groups described in the invention.In one embodiment, 5-10 former molecular heteroaryl includes 1,2,3 or 4 hetero atom for being independently selected from O, S and N.
The example of heteroaryl groups includes, but it is not limited to, 2- furyl, 3- furyl, TMSIM N imidazole base, 2- imidazole radicals, 4- imidazole radicals, 5- imidazole radicals, 3- isoxazolyl, 4- isoxazolyl, 5- isoxazolyl, 2- oxazolyl, 4- oxazolyl, 5- oxazolyl, N- pyrrole radicals, 2- pyrrole radicals, 3- pyrrole radicals, 2- pyridyl group, 3- pyridyl group, 4- pyridyl group, 2- pyrimidine radicals, 4- pyrimidine radicals, 5- pyrimidine radicals, pyridazinyl (such as 3- pyridazinyl), 2- thiazolyl, 4- thiazolyl, 5- thiazolyl, tetrazole radical (such as 5- tetrazole radical), triazolyl (such as 2- triazolyl and 5- triazolyl), 2- thienyl, 3- thienyl, pyrazolyl (such as 2- pyrazolyl), isothiazolyl, 1, 2, 3- oxadiazoles base, 1, 2, 5- oxadiazoles base , 1,2,4- oxadiazoles base, 1,2,3-triazoles base, 1,2,3- thio biphosphole base, 1,3,4- thio biphosphole base, 1,2,5- thio biphosphole base, pyrazinyl, 1,3,5-triazines base；It also include below bicyclic, but it is bicyclic to be not limited to these: benzimidazolyl, benzofuranyl, benzothienyl, indyl (such as 2- indyl), purine radicals, quinolyl (such as 2- quinolyl, 3- quinolyl, 4- quinolyl), isoquinolyl (such as 1- isoquinolyl, 3- isoquinolyl or 4- isoquinolyl), imidazo [1, 2-a] pyridyl group, pyrazolo [1, 5-a] pyridyl group, pyrazolo [1, 5-a] pyrimidine radicals, imidazo [1, 2-b] pyridazinyl, [1, 2, 4] triazol [4, 3-b] pyridazinyl, [1, 2, 4] triazol [1, 5-a] pyrimidine radicals, [1, 2, 4] triazol [1, 5-a] pyridyl group, etc..
The obtained divalent alkylene base group of two hydrogen atoms is removed in term " alkenylene " expression from linear chain or branched chain alkene.Unless otherwise detailed instructions, alkenylene group contains 1-12 carbon atom.In one embodiment, alkenylene group contains 1-8 carbon atom；In one embodiment, alkenylene group contains 1-6 carbon atom；In another embodiment, alkenylene group contains 1-4 carbon atom；In yet another embodiment, alkenylene group contains 1-3 carbon atom；Also in one embodiment, alkenylene group contains 1-2 carbon atom.Such example includes-CH=CH- ,-CH=CH-CH2,-CH=CH-CH (CH3)-,-CH=CH-C (CH3)2, etc..
The obtained divalent alkynes hydrocarbyl group of hydrogen atom is removed in term " alkynylene " expression from linear chain or branched chain alkynes.Unless In addition it is described in detail, alkynylene group contains 1-12 carbon atom.In one embodiment, alkynylene group contains 1-8 carbon atom；In one embodiment, alkynylene group contains 1-6 carbon atom；In another embodiment, alkynylene group contains 1-4 carbon atom；In yet another embodiment, alkynylene group contains 1-3 carbon atom；Also in one embodiment, alkynylene group contains 1-2 carbon atom.Such example includes-C ≡ C- ,-C ≡ C-CH2,-C ≡ C-CH (CH3)-,-C ≡ C-C (CH3)2, etc..
In one aspect of the invention, the invention proposes a kind of azo-compounds.The azo-compound has the compound of general formula shown in meeting formula Ia, or stereoisomer or tautomer for general formula compound shown in meeting formula Ia.
In formula (Ia),
R1For H or alkyl；
X is O, NH or NR6；
Y1、Y2It is separately O, S, NH or NR6；Wherein R6It is C1-10Alkyl；
W1、W2It is separately singly-bound or bivalent organic group；
R2、R3、R4And R5It is separately alkyl, alkoxy, F, Cl, Br, hydroxyl, phenoxy group, benzyloxy, sulfonic group, CN, NO2Or COOR7；Wherein each R7It independently is H or C1-4Alkyl；
M and n be separately 0,1,2,3 perhaps 4 p and q be separately 0,1,2,3,4 or 5.M is equal with n, can also be unequal；P and q can be equal, can also be unequal.Azo-compound with above structure is polymerizable weld, can play preferable blue light absorption/interception function, and can be with other materials (for example, being used for Form the monomer or additive of the eyes medical devices such as artificial lens) copolymer is formed, therefore the risk that above-mentioned azo-compound migrates in eye medical device is reduced, there is the eye medical device for intercepting blue light function so as to be used to prepare.
In an embodiment of the invention, R1For H or alkyl；In another embodiment, R1For H or C1-4Alkyl；Again in one embodiment, R1For H or methyl, ethyl, propyl, isopropyl, methylol or ethoxy.
In an embodiment of the invention, X is O, NH or NR6, R6It is C1-10Alkyl；In another embodiment, X is O, NH or NR6, R6It is C1-6Alkyl；Again in one embodiment, X is O or NH.
In an embodiment of the invention, Y1、Y2It is separately O, S, NH or NR6, R6It is C1-10Alkyl；In another embodiment, Y1、Y2It is separately O, S, NH or NR6, R6It is C1-6Alkyl；；Again in another embodiment, Y1、Y2It is separately O, S.
In an embodiment of the invention, W1、W2It is separately singly-bound or bivalent organic group；In another embodiment, W1、W2It is separately singly-bound or sub- miscellaneous alkyl or alkylidene；Again in another embodiment, W1、W2It is separately singly-bound, C1-12Sub- miscellaneous alkyl, C1-12Alkylidene；In some embodiments, W1、W2It is separately singly-bound, C1-10Sub- miscellaneous alkyl, C1-10Alkylidene；In some embodiments, W1、W2It is separately singly-bound, C1-8Sub- miscellaneous alkyl, C1-8Alkylidene；In some embodiments, W1、W2It is separately singly-bound, C1-6Sub- miscellaneous alkyl, C1-6Alkylidene；In some embodiments, W1、W2It is separately singly-bound, C1-4Sub- miscellaneous alkyl, C1-4Alkylidene.The example of the bivalent organic group includes but is not limited to alkylidene, halogeno alkylen, amino alkylidenyl, the alkylidene that hydroxyl replaces, the alkylidene that cyano replaces, the alkylidene that naphthenic base replaces, the alkylidene that heterocycle replaces, the alkylidene that aryl replaces, the alkylidene that heteroaryl replaces, alkylidene alkenylene, alkylidene alkynylene, sub- miscellaneous alkyl, halogenated Asia miscellaneous alkyl, amino Asia miscellaneous alkyl, the sub- miscellaneous alkyl that hydroxyl replaces, the sub- miscellaneous alkyl that cyano replaces, the sub- miscellaneous alkyl that naphthenic base replaces, the sub- miscellaneous alkyl that heterocycle replaces, the sub- miscellaneous alkyl that aryl replaces, the sub- miscellaneous alkyl that heteroaryl replaces, sub- miscellaneous alkyl alkenyl, sub- miscellaneous alkyl alkynyl；The alkylidene is the bivalent hydrocarbon chain being made of carbon and hydrogen atom, has 1~12 carbon atom, and the example of alkylidene includes being not limited to methylene, ethylidene, propylidene, positive butylidene, 2- methyl propylene etc..The Asia miscellaneous alkyl, which refers to, can be inserted the hetero atoms such as one or more O, N, S, NR in alkylidene or alkylidene chain, and/or, wherein one or more-CH2By-C (=O) ,-S (=O) ,-S (=O)2Equal groups substitution, wherein alkylidene and alkylidene chain have meaning as described in the present invention.The example of sub- miscellaneous alkyl includes but is not limited to alkylidene-O-, alkylidene-N-, alkylidene-S-, alkylene-O-alkylene, alkylidene-N- alkylidene, alkylidene-S- alkylidene, alkylidene-C (=O)-, alkylidene-S (=O)-, alkylidene-S (=O)2,-C (=O) alkylidene-,-S (=O) alkylidene-,-S (=O)2Alkylidene-, alkylidene-C (=O)-alkylidene, alkylidene-S (=O)-alkylidene, alkylidene-S (=O)2Alkylidene, alkylidene-C (=O)-NR- ,-C (=O) NR alkylidene-,-C (=O)-O- alkylidene-, alkylidene-C (=O)-O- ,-C (=O)-O- alkylidene-,-C (=O)-alkylidene-NR- ,-C (=O)-alkylidene-O- etc., wherein each R is alkyl；Specific example such as-CH2CH2O-、-CH2O-、-CH2CH2CH2O-、-CH2CH2CH2CH2O-、-CH2CH2CH2CH2CH2O- ,-CH2CH2CH2CH2CH2CH2O-、-CH2OCH2-、 -CH2CH2OCH2-、-CH2SCH2-、-CH2NHCH2-、-CH2- C (=O)-,-CH2- S (=O)-,-CH2- S (=O)2,-C (=O)-CH2,-S (=O)-CH2,-S (=O)2-CH2-、-CH2- C (=O)-CH2-、-CH2- S (=O)-CH2、-CH2- S (=O)2-CH2、-CH2- C (=O)-NR- ,-C (=O) NR-CH2,-C (=O)-O-CH2-、-CH2- C (=O)-O- ,-C (=O)-O-CH2,-C (=O)-CH2- NR- ,-C (=O)-CH2- O- etc., wherein each R is alkyl.
In an embodiment of the invention, m and n are separately 0,1,2,3 or 4, R2And R3It is separately alkyl, alkoxy, hydroxyl, F, Cl, Br, phenoxy group, benzyloxy, sulfonic group, CN, NO2、COOR7, wherein each R7For H or C1-4Alkyl；In another embodiment, R2And R3It is separately C1-12Alkyl, C1-12Alkoxy, hydroxyl, F, Cl, Br, phenoxy group, NO2；Again in one embodiment, R2And R3It is separately C1-6Alkyl, C1-6Alkoxy, hydroxyl, F, Cl, NO2At least one of；Also in one embodiment, R2And R3It is separately methyl, methoxyl group or hydroxyl.In the embodiment above of the invention, R2And R3Quantity and type be independent of each other, and multiple R when m or n is greater than 1, in the azo-compound2Can be identical or not identical, multiple R3It can also be identical or not identical.
In an embodiment of the invention, p and q are separately 0,1,2,3,4 or 5, R4And R5It can separately be alkyl, alkoxy, F, Cl, Br, hydroxyl, phenoxy group, benzyloxy, sulfonic group, CN, NO2Or COOR7, wherein each R7For H or C1-4Alkyl；In another embodiment, R4And R5It is separately C1-12Alkyl, hydroxyl, C1-12Alkoxy, F, Cl, Br, phenoxy group, NO2；Again in one embodiment, R4And R5It is separately C1-6Alkyl, hydroxyl, C1-6Alkoxy, F, Cl, NO2；Also in one embodiment, R4And R5It is separately methyl, hydroxyl, fluorine or methoxyl group.In the embodiment above of the invention, R4And R5Quantity and type be independent of each other, and multiple R when p or q is greater than 1, in the azo-compound4Can be identical or not identical, multiple R5It can also be identical or not identical.
In an embodiment of the invention, R1For H or methyl, m and n separately can be 0 or 1 or 2 for 0, p and q, in other words, R not included in the azo-compound2And R3, R can not included4Or R5, also may include one or two R4Or R5。R4、R5It is separately hydroxyl, methyl, fluorine or methoxyl group.In other words, R4And R5The quantity and type of substituent group can be identical or not identical, and when containing in the azo-compound, there are two R4And/or two R5When, two R4Can be identical or not identical, two R5It can also be identical or not identical.
In another embodiment of the present invention, R1For H or methyl, m and n are 1, only include a R in the azo-compound in other words2An and R3.Wherein, R2For hydroxyl, methyl or methoxyl group, R3With R2It is identical or different.R4、R5It is separately hydroxyl, methyl or methoxy, p and q are 0 or 1 or 2.In other words, can not have R in the azo-compound4Or R5, it is possible to have one or two R4And one or two R5。R4And R5The quantity and type of substituent group can be identical or not identical.
In another embodiment of the present invention, azo-compound of the present invention can be to meet following formula (1)~(19) Shown in general formula compound, or to meet the stereoisomer of the compound of general formula or tautomer:
Meet the compound of general formula shown in above formula (1)~(19), or meet the stereoisomer of the compound of above-mentioned general formula or the azo-compound of tautomer, with ideal interception blue light effect, it can be used as blue-light absorbers to be added in the raw material of synthesis eye medical device, and above compound will not optics (index of refraction and spectral transmittance etc.) to eye medical device, mechanical property (tensile strength, elongation at break and elasticity modulus etc.) it adversely affects, therefore can be used for preparing the flexible eye medical device such as foldable artificial lens.
In another aspect of this invention, the invention proposes a kind of polymer.The monomer for constituting the polymer includes bulk monomer and blue-light absorbers, and blue-light absorbers are the mentioned-above azo-compound of the present invention.In other words, the monomer for constituting the polymer includes the monomer (bulk monomer) and azo-compound set forth above of the invention to form polymer body.The polymer has the effect of intercepting blue light as a result,.And, during synthesizing the polymer, blue-light absorbers can be with bulk monomer or other additives for synthesizing in the raw material of the polymer are copolymerized, so as to which the risk that blue-light absorbers are migrated in polymeric inner is greatly reduced, and then the security performance of the device of the direct and human contact prepared using the polymer can be improved.For example, such as artificial lens eye medical device can be prepared using the polymer, so as to which and then injury of the blue light for organs such as human eyes in visible light can be reduced so that the eye medical device also has the function of interception blue light.
In the present invention, the ratio of blue-light absorbers and bulk monomer can be adjusted according to the actual situation in above-mentioned polymer.Term " bulk monomer " refers in particular to the principal monomer material for being used to form the polymer body.Bulk monomer is can to constitute the main component of above-mentioned polymer proposed by the present invention by polymerization, can be copolymerized in the course of the polymerization process with blue-light absorbers.Due to containing polymerizable groups in blue-light absorbers, therefore forming monomer commonly used by polymer can be copolymerized with blue-light absorbers proposed by the invention, so in the present invention, the concrete type of bulk monomer is not particularly limited, and may include at least one of (methyl) acrylic ester monomer, vinyl monomer, allylic monomers.In an embodiment of the invention, bulk monomer is (methyl) acrylic ester monomer, can include but is not limited at least one of following monomer: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Butyl methacrylate, Tert-butyl Methacrylate, Isobutyl methacrylate, pentylmethacrylate, t-amyl methacrylate, hexyl methacrylate, metering system heptyl heptylate, 2-Propenoic acid, 2-methyl-, octyl ester, methacrylic acid 2- ethylhexyl ester, nonyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, stearyl methacrylate, methacrylic acid ring pentyl ester, cyclohexyl methacrylate, methacrylic acid phenoxy group ester；Methoxyethyl methacrylate, ethoxyethyl methacrylates, ethoxyethyl acrylate, methacrylic acid methoxyl group diethylene glycol (DEG) ester, methacrylic acid -2- ethyl phenoxy group ester, acrylic acid-2-ethyl phenoxy group ester, methacrylic acid -2 acetyl thiophene ester, acrylic acid-2-ethyl thiophene ester, methacrylic acid -2- ethylamino phenyl ester, acrylic acid-2-ethyl amino phenyl ester, phenyl methacrylate, benzyl methacrylate, methacrylic acid -2- phenyl chlorocarbonate, acrylic acid -2- phenyl chlorocarbonate, methacrylic acid -3- phenylpropyl acrylate, methacrylic acid -4- butyloxy phenyl, methacrylic acid -4- methyl phenyl ester, methacrylic acid -4- methyl benzyl ester, methacrylic acid -2, 2- aminomethyl phenyl ethyl ester, methacrylic acid -2, 3- aminomethyl phenyl ethyl ester, metering system Acid -2, 4- aminomethyl phenyl ethyl ester, methacrylic acid -2- (4- propyl phenyl) ethyl ester, methacrylic acid -2- (4- (1- Methylethyl) phenyl) ethyl ester, methacrylic acid -2- (4- methoxyphenyl) ethyl ester, methacrylic acid -2- (4- cyclohexyl phenyl) ethyl ester, methacrylic acid -2- (2- chlorphenyl) ethyl ester, methacrylic acid -2- (3- chlorphenyl) ethyl ester, methacrylic acid -2- (4- chlorphenyl) ethyl ester, methacrylic acid -2- (4- bromophenyl) ethyl ester, methacrylic acid -2- (3- phenyl) ethyl ester, methacrylic acid -2- (4- phenyl) ethyl ester, methacrylic acid -2- (4- benzyl phenyl) ethyl ester.In another embodiment of the present invention, bulk monomer may include at least one of acrylic acid -2- phenyl chlorocarbonate, methacrylic acid -2- phenyl chlorocarbonate and ethoxyethyl methacrylates.In another embodiment of the present invention, bulk monomer is vinyl monomer, it can include but is not limited at least one of following monomer: styrene, 4- butylstyrene, propenyl benzene, vinylacetate, 4- ethoxyl methyl styrene, 4- hexoxymethyl styrene, 4- hexyloxyehtyl styrene, vinyl ethers, n- butyl vinyl ether, isobutyl vinyl ether, tert-Butyl vinyl ether, cyclohexene vinyl ethers, butanediol divinyl ether, N- caprolactam, dodecyl vinyl, octadecyl vinyl ether, divinyl glycol divinyl ether, trivinyl divinyl ether.In another embodiment of the invention, bulk monomer is allylic monomers, can include but is not limited at least one of following monomer: M Cr, butenoic acid ethyl, butenoic acid phenethyl ester, propylene acetate, propylene carbonate, butyric acid acrylic ester, valeric acid acrylic ester, allyl bexanoate, butyric acid 3- phenyl -2- acrylic ester.Above-mentioned bulk monomer has preferable optics and mechanical property, can be further improved the service performance of the polymer.
In polymer proposed by the invention, at least one of crosslinking agent, ultraviolet absorber and initiator can further include.Above-mentioned crosslinking agent, ultraviolet absorber and initiator can be mixed with bulk monomer and blue-light absorbers, form polymer proposed by the invention by polymerization.In an embodiment of the invention, crosslinking agent can include but is not limited to ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1, 3-propanediol dimethylacrylate, 1, 6- hexanediol dimethacrylate, 1, 3- butanediol dimethylacrylate, 1, 4- butanediol dimethylacrylate, 1, 4- butanediol diacrylate, trimethylol-propane trimethacrylate, 1, 5- bis- (methacryloxy) -2, 2, 3, 3, 4, 4- hexafluoro hexane, 1, 6- bis- (acryloxy) -2, 2, 3, 3, 4, 4, 5, 5- octafluoro hexane and pentaerythrite 4 third Olefin(e) acid ester.Ultraviolet absorber can include but is not limited to 2- (2'- hydroxyl -3'- methylallyl -5'- aminomethyl phenyl) benzotriazole, 2- [3- (2H- benzotriazole -2- base) -4- hydroxy phenyl] ethyl 2- methacrylate, 2- (2H- benzotriazole -2- base) -4- methyl -6- (2- acrylic) phenol, 2- (the chloro- 2H- benzo [d] [1 of 5-, 2, 3] triazole) -4- methyl -6- (2- allyl) phenol, 4- allyl -2- (the chloro- 2H- benzo [d] [1 of 5-, 2, 3] triazole) -6- metoxyphenol, 2- (the chloro- 2H-1 of 5-, 2, 3- benzo [d] [1, 2, 3] triazole) -4- methyl -6- chavicol, 2- hydroxyl -4- (methacryloxypropyl Base) benzophenone and 2- acrylic acid 2- (4- benzoyl -3- hydroxyphenoxy) ethyl ester.It is bis- (2,4- methyl pentane nitrile) that initiator can include but is not limited to benzoyl peroxide, tert-butyl hydroperoxide, cumyl hydroperoxide, bis- (4- tert-butylcyclohexyl) peroxy dicarbonates, azodiisobutyronitrile and azo.Thus, it is possible to further increase the performance of the polymer.
In another aspect of this invention, the invention proposes a kind of eye medical devices.The eye medical device includes present invention polymer set forth above.As a result, the eye medical device have the advantages that whole features of polymer noted earlier and, details are not described herein.Specifically, the eye medical device has ideal mechanics, optical property, while the blue light ingredient in visible light can be intercepted, so as to reduce damage of the blue light for organs such as human eyes.The eye medical device has preferable security performance, because the blue-light absorbers in polymer proposed by the invention are not easy that diffusion mobility occurs in the polymer, so as to prevent from being formed azo-compound and the direct body contact of blue-light absorbers.
In an embodiment of the invention, above-mentioned eye medical device can correct object, intracorneal lens, cornea insert, corneal ring or glaucoma filtering apparatus for artificial lens, intraocular lens, contact lens, cornea.
In still another aspect of the invention, the invention proposes a kind of methods for preparing mentioned-above polymer.This method comprises: gradient type heat treatment is carried out to raw mixture, to obtain polymer.Wherein, raw mixture contains mentioned-above bulk monomer and blue-light absorbers.About the concrete type of bulk monomer and blue-light absorbers, before detailed description has been carried out, details are not described herein.In method proposed by the invention, the ratio of bulk monomer and blue-light absorbers is also not particularly limited.Those skilled in the art can make adjusting for aforementioned proportion according to bulk monomer, the specific type of blue-light absorbers of the requirement of the specific physico-chemical property of the specific polymer for preparation, and selection.In order to further increase the performance for the polymer for utilizing this method preparation, in raw mixture, acceptable further at least one of packet crosslinking agent, initiator and ultraviolet absorber.This method step operating procedure is easy, the production cycle is shorter, and the polymer obtained has the function of ideal physical and chemical performance (such as optics, mechanical property and interception blue light).
In one embodiment, above-mentioned gradient type, which heats, may include:
First stage of reaction:
In first stage of reaction, raw mixture is heated to 40~70 degrees Celsius and is reacted, the reaction time can be 1~24 hour.Reaction can prevent reaction rate too fast at a lower temperature, the sample of appearance uniform be advantageously formed, to mention The performance of high polymer.
Second stage of reaction:
In second stage of reaction, the raw mixture Jing Guo first stage of reaction is heated to 80~120 degrees Celsius and is reacted, the reaction time can be 1~24 hour.It may advantageously facilitate surplus stock as a result, further to react, promote feed stock conversion, can be further improved the performance of the polymer using this method preparation.
The solution of the present invention is explained below in conjunction with embodiment.It will be understood to those of skill in the art that the following examples are merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Particular technique or condition are not specified in embodiment, described technology or conditions or is carried out according to the literature in the art according to product description.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.
The embodiments described below, unless otherwise indicated, all temperature are set to degree Celsius.Used reagent is available on the market or described method can be prepared through the invention.
The use of logogram word below is through the present invention
G grams
ML milliliters
Mmol mMs
H hours
Min minutes
S seconds
Boc tertbutyloxycarbonyl
EtOAc ethyl acetate
N-Hex n-hexane
The preparation of 1 azo-compound of embodiment
Below as synthetic route, azo-compound: the preparation of the preparation (chemical formula is as follows) of 1,3- bis- (4- (4'- hydroxyazobenzene) oxygroup) -2- propyl methacrylate is described:
(1) 1,3- bis- (4-nitrophenoxy) -2- propyl alcohol is prepared:
4- nitrophenol (11.2g is sequentially added into three-necked flask, 81.2m mol), potassium carbonate (11.2g, 81.2mmol) and dehydrated alcohol (200mL), after mixed liquor return stirring 1h, 1 is slowly added dropwise thereto, the bromo- 2- propyl alcohol (4.4g, 20.2mmol) of 3- bis-, and continue stirring for 24 hours.Reaction solution is poured into water (500mL), it is filtered after stirring 0.5h, filter cake sodium hydrate aqueous solution (10%wt, 200mL), water (300mL) rinses, the solid being collected into is dried in vacuo 5h at 50 DEG C, obtain pale solid 1,3- bis- (4'- nitro-phenoxy) total 4.8g of -2- propyl alcohol, yield 68%.Mass spectrum and nuclear magnetic resonance H modal data are as follows:
LC-MS (ESI, pos.ion) m/z:357 [M+Na]+；
1H NMR(400MHz,CDCl3) δ (ppm): 8.26 (t, 2H), 8.23 (t, 2H), 7.06 (t, 2H), 7.03 (t, 2H), 4.52-4.50 (m, 1H), 4.26-4.34 (m, 4H), 2.61-2.60 (d, 1H).
(2) 1,3- bis- (4'- amino-benzene oxygen) -2- propyl alcohol is prepared:
1 obtained in step (1) is sequentially added into single-necked flask, 3- bis- (4-nitrophenoxy) -2- propyl alcohol (4.8g, 14.4mmol), 5% palladium carbon (3.05g, 1.4mmol), ammonium formate (18.1g, 287.3mmol) with tetrahydrofuran (50mL), mixed liquor is in 45 DEG C of stirring 1h.Reaction is filtered, filter cake is rinsed with methylene chloride (100mL), the filtrate being collected into is diluted to 250mL with methylene chloride, and with saturated common salt water washing (80ml × 4), solvent is evaporated off in the organic phase dry 2h of anhydrous sodium sulfate, filtering back spin after liquid separation, obtain pink solid 1,3- bis- (4- amino-benzene oxygen) -2- propyl alcohol 3.3g, yield 96%, mass spectrum and nuclear magnetic resonance H modal data are as follows:
LC-MS (ESI, pos.ion) m/z:275 [M+H]+；
1H NMR(400MHz,CDCl3) δ (ppm): 6.80-6.78 (m, 4H), 6.67-6.66 (m, 4H), 4.35-4.31 (m, 1H), 4.11-4.05 (m, 4H), 3.47 (s, 4H), 2.66 (s, 1H).
(3) 1,3- bis- (4- ((tertbutyloxycarbonyl) amino) phenoxy group) -2- propyl alcohol is prepared:
The 1 of step (2) preparation is sequentially added into single-necked flask, (4- the amino-benzene oxygen) -2- propyl alcohol of 3- bis- (3.3g, 12mmol), Boc acid anhydrides (6.3g, 28.9mmol) and methanol (50mL), mixed liquor stirs 1h at normal temperature.Reaction is filtered, filter cake is rinsed with n-hexane (300mL), and the solid being collected into is dried in vacuo 2h at 40 DEG C and obtains white solid 5.6g, yield 98%.Mass spectrum and nuclear magnetic resonance H modal data are as follows:
LC-MS (ESI, pos.ion) m/z:497 [M+Na]+；
1H NMR(400MHz,CDCl3) δ (ppm): 7.29-7.27 (m, 4H), 6.89-6.87 (m, 4H), 6.40 (s, 2H), 4.40-4.33 (m, 1H), 4.16-4.08 (m, 4H), 2.65-2.64 (d, 1H), 1.53 (s, 18H).
(4) 1,3- bis- (4- ((tertbutyloxycarbonyl) amino) phenoxy group) -2- propyl methacrylate is prepared:
The 1 of step (3) preparation is sequentially added into single-necked flask, 3- bis- (4- ((tertbutyloxycarbonyl) amino) phenoxy group) -2- propyl alcohol (5.6g, 11.8mmol), diisopropylethylamine (6.3g, 60.6mmol), 4-dimethylaminopyridine (0.76g, 6.2mmol) and tetrahydrofuran (70mL), after completely dissolution, methacrylic chloride (10.4g is slowly added dropwise thereto, 100mmol), and continue stirring for 24 hours.Reaction solution is filtered, revolving removes tetrahydrofuran, and product chromatographs (n-Hex/EtOAc (v/v)=5:1) by column, obtains yellow thick liquid 5.7g, yield 64%.Mass spectrum and nuclear magnetic resonance H modal data are as follows:
LC-MS (ESI, pos.ion) m/z:565 [M+Na]+；
1H NMR(400MHz,CDCl3) δ (ppm): 7.29-7.26 (m, 4H), 6.89-6.87 (m, 4H), 6.40 (s, 2H), 6.16 (s, 1H), 5.61 (s, 1H), 5.53-5.48 (m, 1H), 4.27-4.26 (m, 4H), 1.97 (s, 3H), 1.53 (s, 18H).
(5) 1,3- bis- (4- amino-benzene oxygen) -2- propyl methacrylate is prepared:
The 1 of step (4) acquisition is sequentially added into single-necked flask, 3- bis- (4- ((tertbutyloxycarbonyl) amino) phenoxy group) -2- propyl methacrylate (5.1g, 9mmol), trifluoroacetic acid/dichloromethane mixed solution (volume ratio 3:4,35mL), stirring at normal temperature 15min after completely dissolution.Reaction solution is diluted to 200mL with methylene chloride, and it is neutralized with saturated sodium bicarbonate, liquid separation, the organic phase dry 2h of anhydrous sodium sulfate, filtering, revolving remove solvent, and product chromatographs (n-Hex/EtOAc (v/v)=1:1) by column, obtain yellow thick liquid 2.6g, yield 80%.Mass spectrum and nuclear magnetic resonance H modal data are as follows:
LC-MS (ESI, pos.ion) m/z:343 [M+H]+；
1H NMR(400MHz,CDCl3) δ (ppm): 6.80-6.78 (m, 4H), 6.66-6.64 (m, 4H), 6.16 (s, 1H), 5.61-5.60 (s, 1H), 5.50-5.46 (m, 1H), 4.25-4.21 (m, 4H), 3.48 (s, 4H), 1.97 (s, 3H).
(6) 1,3- bis- (4- (4'- hydroxyazobenzene) oxygroup) -2- propyl methacrylate is prepared:
The 1 of step (5) acquisition is sequentially added into three-necked flask, (4- the amino-benzene oxygen) -2- propyl methacrylate of 3- bis- (0.8g, 2.34mmol), potassium bromide (0.614g, 5.16mmol) concentrated hydrochloric acid (1.7g, 16.77mmol) and the mixed solution of acetone/water (volume ratio 1:1) (20mL), mixed liquor stirs in -5 DEG C of low temperature baths, when interior temperature reaches 0 DEG C or less, by sodium nitrite (0.32g, 4.75mmol) it is dissolved in water (10mL), it is slowly dropped in above-mentioned reaction solution, and continues to stir 0.5h.Phenol (0.49g, 5.21mmol), sodium hydroxide (0.21g, 5.25mmol) are dissolved in water (15mL), and are added drop-wise to above-mentioned diazonium salt solution, process is added dropwise, solution temperature is kept to be not higher than 5 DEG C.Continue to filter reaction after stirring 0.5h, and rinse filter cake with water (100mL), the solid being collected into is chromatographed by column, obtains azo-compound orange solids 0.6g, yield 47%.Mass spectrum and nuclear magnetic resonance H modal data are as follows:
LC-MS (ESI, pos.ion) m/z:554 [M+H]+；
1H NMR(400MHz,CDCl3) δ (ppm): 7.90-7.84 (m, 8H), 7.11-6.94 (m, 4H), 6.96-6.94 (m, 4H), 6.21 (s, 1H), 5.66 (s, 1H), 5.64-5.61 (m, 1H), 5.41 (s, 2H), 4.43-4.42 (m, 4H), 2.00 (s, 3H).
The preparation of 2 azo-compound of embodiment
Below as synthetic route, azo-compound: the preparation of 1,3- bis- (4- (2', 4'- dihydroxy azobenzene) oxygroup) -2- propyl methacrylate (chemical formula is as follows) is described:
Remaining step is the same as embodiment 1, except that, in step (6), 1 is sequentially added into three-necked flask, (4- the amino-benzene oxygen) -2- propyl methacrylate of 3- bis- (1.2g, 3.5mmol), potassium bromide (2.99g, 25.6mmol) concentrated hydrochloric acid (2.55g, 25.6mmol) and the mixed solution of acetone/water (volume ratio 1:1) (20mL), mixed liquor stirs in -5 DEG C of low temperature baths, when interior temperature reaches 0 DEG C or less, by sodium nitrite (0.485g, 7.0mmol) it is dissolved in water (10mL), it is slowly dropped in above-mentioned reaction solution, and continue to stir 0.5h.Resorcinol (0.88g, 8.0mmol), sodium hydroxide (0.63g, 15.8mmol) are dissolved in water (20mL), and are added drop-wise to above-mentioned diazonium salt solution, process is added dropwise, solution temperature is kept to be not higher than 5 DEG C.Continue to filter reaction after stirring 0.5h, and filter cake is rinsed with water (100mL), the solid being collected into chromatographs (n-Hex/EtOAc (v/v)=3:1) by column, and obtains azo-compound dark red solid 0.3g after recrystallizing in methyl alcohol Yield is 15%.Mass spectrum and nuclear magnetic resonance H modal data are as follows:
LC-MS (ESI, pos.ion) m/z:585 [M+H]+；
1H NMR (400MHz, DMSO-d6) δ (ppm): 12.28 (s, 2H), 10.42 (s, 2H), 7.86-7.84 (d, 4H), 7.66-7.64 (d, 2H), 7.18-7.15 (d, 4H), 6.50-6.47 (d, 2H), 6.35-6.34 (d, 2H), 6.06 (s, 1H), 5.72 (s, 1H), 5.57-5.55 (m, 1H), 4.49-4.41 (m, 4H), 1.98 (s, 3H).
The preparation of 3 azo-compound of embodiment
Below as synthetic route, azo-compound 1 is described, the preparation of 3- bis- (4- (2'- methyl -4'- hydroxyazobenzene) oxygroup) -2- propyl methacrylate (chemical formula is as follows):
Remaining step is the same as embodiment 1, except that, in step (6), 1 is sequentially added into three-necked flask, (4- the amino-benzene oxygen) -2- propyl methacrylate of 3- bis- (2.0g, 5.83mmol), potassium bromide (1.2g, 10.1mmol) concentrated hydrochloric acid (4.0g, 39.5mmol) and the mixed solution (20mL) of acetone/water (v/v=1:1), mixed liquor stirs in -5 DEG C of low temperature baths, when interior temperature reaches 0 DEG C or less, by sodium nitrite (0.97g, 14.0mmol) it is dissolved in water (10mL), it is slowly dropped in above-mentioned reaction solution, and continue to stir 0.5h.By m-methyl phenol (1.26g, 9.20mmol), sodium hydroxide (0.93g, 23.3mmol), sodium carbonate (1.23g, 11.6mmol) are dissolved in water (20mL), and it is added drop-wise to above-mentioned diazonium salt solution, process is added dropwise, solution temperature is kept to be not higher than 5 DEG C.Continue to filter reaction after stirring 0.5h, and filter cake is rinsed with water (100mL), the solid being collected into chromatographs (n-Hex/EtOAc (v/v)=3:1) by column, and it is dark red solid (0.3g, 15%) that title compound is obtained after recrystallizing in methyl alcohol.
LC-MS (ESI, pos.ion) m/z:581 [M+H]+；
1H NMR (400MHz, CDCl3)) δ (ppm): 7.89-7.87 (d, 4H), 7.66-7.64 (d, 2H), 7.07-7.05 (d, 4H), 6.79-6.79 (d, 2H), 6.73-6.71 (t, 2H), 6.21 (s, 1H), 5.66 (s, 1H), 5.64-5.62 (m, 1H), 5.55 (s, 2H), 4.43-4.42 (d, 4H), 2.69 (s, 6H), 2.00 (s, 3H).
The preparation of 4 azo-compound of embodiment
Below as synthetic route, azo-compound 1 is described, the preparation of 3- bis- (4- (2'- methoxyl group -4'- hydroxyazobenzene) oxygroup) -2- propyl methacrylate (chemical formula is as follows):
Remaining step is the same as embodiment 1, except that, in step (6), 1 is sequentially added into three-necked flask, (4- the amino-benzene oxygen) -2- propyl methacrylate of 3- bis- (1.0g, 2.97mmol), potassium bromide (0.61g, 5.1mmol) concentrated hydrochloric acid (2.10g, 19.8mmol) and the mixed solution (20mL) of acetone/water (v/v=1:1), mixed liquor stirs in -5 DEG C of low temperature baths, when interior temperature reaches 0 DEG C or less, by sodium nitrite (0.50g, 7.2mmol) it is dissolved in water (10mL), it is slowly dropped in above-mentioned reaction solution, and continue to stir 0.5h.By meta-methoxy phenol (0.8g, 6.4mmol), sodium hydroxide (0.51g, 12.8mmol), sodium carbonate (0.61g, 5.8mmol) are dissolved in water (20mL), and it is added drop-wise to above-mentioned diazonium salt solution, process is added dropwise, solution temperature is kept to be not higher than 5 DEG C.Continue to filter reaction after stirring 0.5h, and filter cake is rinsed with water (100mL), the solid being collected into chromatographs (n-Hex/EtOAc (v/v)=2:1) by column, and it is dark red solid (0.5g, 28%) that title compound is obtained after recrystallizing in methyl alcohol.
LC-MS (ESI, pos.ion) m/z:613 [M+H]+；
1H NMR (400MHz, CDCl3)) δ (ppm): 7.87-7.85 (d, 4H), 7.68-7.66 (d, 2H), 7.03-7.01 (d, 2H), 6.57 (s, 2H), 6.49-6.46 (t, 4H), 6.20 (s, 1H), 5.65 (s, 1H), 5.60-5.59 (m, 1H), 4.39-4.38 (d, 4H), 3.97 (s, 6H), 1.98 (s, 3H).
The preparation of 5 azo-compound of embodiment
Below as synthetic route, azo-compound 1 is described, the preparation of 3- bis- (4- (2', 4'- dihydroxy azobenzene) oxygroup) -2- propyl acrylate (chemical formula is as follows):
(1) 1,3- bis- (4- amino-benzene oxygen) -2- propyl acrylate is prepared
1 is sequentially added into single-necked flask, 3- bis- (4- ((tertbutyloxycarbonyl) amino) phenoxy group) -2- propyl alcohol (5.0g, 10.4mmol), triethylamine (4.5g, 44.6mmol), 4-dimethylaminopyridine (0.26g, 2.1mmol) and acryloyl chloride (4.2g is slowly added dropwise after completely dissolution in tetrahydrofuran (70mL) thereto, 46.6mmol), and continue to be stirred to react.After for 24 hours, revolving removes tetrahydrofuran, and methylene chloride (50mL) dissolution is added in mixture, adds trifluoroacetic acid (30mL), reacts at room temperature 1hour.After reaction, with methylene chloride (200mL) dilute reaction solution, and it is neutralized with sodium bicarbonate aqueous solution, after liquid separation, the organic phase dry 2h of anhydrous sodium sulfate, filtering, revolving removes solvent, product chromatographs (n-Hex/EtOAc1:1) by column, obtains light yellow thick liquid 2.0g, yield 60%.Mass spectrum and nuclear magnetic resonance H modal data are as follows:
LC-MS (ESI, pos.ion) m/z:329 [M+H]+；
1H NMR(400MHz,CDCl3) δ (ppm): 6.80-6.78 (d, 4H), 6.66-6.64 (d, 4H), 6.50-6.45 (t, 1H), 6.23-6.20 (t, 1H), 5.90-5.87 (t, 1H), 5.54-5.49 (m, 1H), 4.23-4.21 (m, 4H), 3.46 (s, 4H).
(2) 1,3- bis- (4- (2', 4'- dihydroxy azobenzene) oxygroup) -2- propyl acrylate is prepared
1 obtained in step (1) is sequentially added into three-necked flask, (4- the amino-benzene oxygen) -2- propyl acrylate of 3- bis- (2.0g, 6.1mmol), potassium bromide (6.2g, 52.1mmol) concentrated hydrochloric acid (5.1g, 50.3mmol) and the mixed solution of acetone/water (volume ratio 1:1) (20mL), mixed liquor stirs in -5 DEG C of low temperature baths, when interior temperature reaches 0 DEG C or less, by sodium nitrite (0.98g, 14.2mmol) it is dissolved in water (10mL), it is slowly dropped in above-mentioned reaction solution, and continues to stir 0.5h.Resorcinol (1.7g, 15.5mmol), sodium hydroxide (1.3g, 32.5mmol) are dissolved in water (20mL), and are added drop-wise to above-mentioned diazonium salt solution, process is added dropwise, solution temperature is kept to be not higher than 5 DEG C.Continue to filter reaction after stirring 0.5h, and Filter cake is rinsed with water (100mL), the solid being collected into chromatographs (n-Hex/EtOAc (v/v)=3:1) by column, and obtains azo-compound dark red solid 0.3g, yield 8.6% after recrystallizing in methyl alcohol.Mass spectrum and nuclear magnetic resonance H modal data are as follows:
LC-MS (ESI, pos.ion) m/z:571 [M+H]+；
1H NMR (400MHz, DMSO-d6) δ (ppm): 12.29 (s, 2H), 10.44 (s, 2H), 7.86-7.84 (d, 4H), 7.66-7.63 (d, 2H), 7.17-7.15 (d, 4H), 6.50-6.47 (t, 2H), 6.42-6.38 (d, 1H), 6.35-6.34 (d, 2H), 6.28-6.22 (m, 1H), 6.02-6.00 (d, 1H), 5.63-5.58 (m, 1H), 4.48-4.42 (m, 4H).
Embodiment 6 prepares polymer A-1
By acrylic acid -2- phenyl chlorocarbonate 0.3500g, methacrylic acid -2- phenyl chlorocarbonate 0.2500g, ethoxyethyl methacrylates 0.3500g, 1, 4- butanediol diacrylate 0.0350g, 2- (2 '-hydroxyls -3 '-methylallyl -5 '-aminomethyl phenyl) benzotriazole 0.0100g, azo-compound 0.0100g prepared by bis- (4- tert-butylcyclohexyl) peroxy dicarbonate 0.0200g and embodiment 1 is uniformly mixed, it is then transferred into the mold that one is made of the teflon plate of layer glass and a 0.4mm thickness, mold is put into again in 60 DEG C of baking oven and is reacted 3 hours, baking oven increases temperature to 100 DEG C and continues to be kept for 3 hours afterwards, obtain transparent flexible polymer , resulting materials, which flow back to clean by dehydrated alcohol, removes remaining raw material, and 60 DEG C are dried in vacuo 24 hours.
Embodiment 7 prepares polymer A-2
By acrylic acid -2- phenyl chlorocarbonate 0.3500g, methacrylic acid -2- phenyl chlorocarbonate 0.2500g, ethoxyethyl methacrylates 0.3500g, 1, 4- butanediol diacrylate 0.0350g, 2- (2 '-hydroxyls -3 '-methylallyl -5 '-aminomethyl phenyl) benzotriazole 0.0100g, azo-compound 0.0015g prepared by bis- (4- tert-butylcyclohexyl) peroxy dicarbonate 0.0200g and embodiment 2 is uniformly mixed, it is then transferred into the mold that one is made of the teflon plate of layer glass and a 0.4mm thickness, mold is put into again in 60 DEG C of baking oven and is reacted 3 hours, baking oven increases temperature to 100 DEG C and continues to be kept for 3 hours afterwards, obtain transparent flexible polymer , resulting materials, which flow back to clean by dehydrated alcohol, removes remaining raw material, and 60 DEG C are dried in vacuo 24 hours.
Embodiment 8 prepares polymer A-3
By acrylic acid -2- phenyl chlorocarbonate 0.3500g, methacrylic acid -2- phenyl chlorocarbonate 0.2500g, ethoxyethyl methacrylates 0.3500g, 1, azo-compound 0.0015g prepared by 4- butanediol diacrylate 0.0350g, 2- (2 '-hydroxyls -3 '-methylallyl -5 '-aminomethyl phenyl) benzotriazole 0.0100g, bis- (4- tert-butylcyclohexyl) peroxy dicarbonate 0.0200g and embodiment 5 is uniformly mixed, and is then transferred into one by layer glass and the polytetrafluoroethylene (PTFE) of a 0.4mm thickness In the mold of piece composition, mold is put into again in 60 DEG C of baking oven and is reacted 3 hours, rear baking oven increases temperature to 100 DEG C and continues to be kept for 3 hours, obtains transparent flexible polymer, resulting materials, which flow back to clean by dehydrated alcohol, removes remaining raw material, and 60 DEG C are dried in vacuo 24 hours.
Comparative example 1: polymer A-0 is prepared
By acrylic acid -2- phenyl chlorocarbonate 0.3500g, methacrylic acid -2- phenyl chlorocarbonate 0.2500g, ethoxyethyl methacrylates 0.3500g, 1, 4- butanediol diacrylate 0.0350g, 2- (2 '-hydroxyls -3 '-methylallyl -5 '-aminomethyl phenyl) benzotriazole 0.0100g and bis- (4- tert-butylcyclohexyl) peroxy dicarbonate 0.0200g (not adding azo-compound) are uniformly mixed, it is then transferred into the mold that one is made of the teflon plate of layer glass and a 0.4mm thickness, mold is put into again in 60 DEG C of baking oven and is reacted 3 hours, baking oven increases temperature to 100 DEG C and continues to be kept for 3 hours afterwards, obtain transparent flexible polymer, resulting materials pass through anhydrous second Alcohol reflux cleaning removes remaining raw material, and 60 DEG C are dried in vacuo 24 hours.
Embodiment 9 prepares polymer B -1
By acrylic acid -2- phenyl chlorocarbonate 0.6500g, methacrylic acid -2- phenyl chlorocarbonate 0.3000g, 1, 4- butanediol diacrylate 0.0500g, azo-compound 0.0015g prepared by 2- (2 '-hydroxyls -3 '-methylallyl -5 '-aminomethyl phenyl) benzotriazole 0.0180g and bis- (4- tert-butylcyclohexyl) peroxy dicarbonate 0.0180g and embodiment 3 is uniformly mixed, it is then transferred into the mold that one is made of the teflon plate of layer glass and a 0.4mm thickness, mold is put into again in 60 DEG C of baking oven and is reacted 3 hours, baking oven increases temperature to 100 DEG C and continues to be kept for 3 hours afterwards, obtain transparent flexible polymer, resulting materials are flowed back to clean by dehydrated alcohol and be removed Remaining raw material, 60 DEG C are dried in vacuo 24 hours.
Embodiment 10 prepares polymer B -2
By acrylic acid -2- phenyl chlorocarbonate 0.6500g, methacrylic acid -2- phenyl chlorocarbonate 0.3000g, 1, 4- butanediol diacrylate 0.0500g, azo-compound 0.0015g prepared by 2- (2 '-hydroxyls -3 '-methylallyl -5 '-aminomethyl phenyl) benzotriazole 0.0180g and bis- (4- tert-butylcyclohexyl) peroxy dicarbonate 0.0180g and embodiment 4 is uniformly mixed, it is then transferred into the mold that one is made of the teflon plate of layer glass and a 0.4mm thickness, mold is put into again in 60 DEG C of baking oven and is reacted 3 hours, baking oven increases temperature to 100 DEG C and continues to be kept for 3 hours afterwards, obtain transparent flexible polymer, resulting materials are flowed back to clean by dehydrated alcohol and be removed Remaining raw material, 60 DEG C are dried in vacuo 24 hours.
Comparative example 2: preparation polymer B -0
By acrylic acid -2- phenyl chlorocarbonate 0.6500g, methacrylic acid -2- phenyl chlorocarbonate 0.3000g, 1,4- butanediol diacrylate Ester 0.0500g, 2- (2 '-hydroxyls -3 '-methylallyl -5 '-aminomethyl phenyl) benzotriazole 0.0180g and bis- (4- tert-butylcyclohexyl) peroxy dicarbonate 0.0180g (not adding azo-compound) are uniformly mixed, it is then transferred into the mold that one is made of the teflon plate of layer glass and a 0.4mm thickness, mold is put into again in 60 DEG C of baking oven and is reacted 3 hours, baking oven increases temperature to 100 DEG C and continues to be kept for 3 hours afterwards, obtain transparent flexible polymer, resulting materials, which flow back to clean by dehydrated alcohol, removes remaining raw material, 60 DEG C are dried in vacuo 24 hours.
Spectral transmittance measurement
(1) test method: at room temperature, pass through spectral transmittance of the Agilent Cary60 ultraviolet-uisible spectrophotometer test material within the scope of 200nm-800nm light wave.
(2) test result: attached drawing 1-7 illustrates the polymer and comparative example 1, the spectral transmittance result of comparative example 2 of the preparation of embodiment 6~10.The comparative example materials A -0 and B-0 of weld of the present invention (azo-compound) is not added it can be seen from attached drawing, spectrum has begun to stronger percent of pass in 400nm, to blue light almost without absorption.And the polymer A-1 to A-3, B-1, B-2 of weld is added, wavelength can be substantially reduced in the spectral transmission of 400-550nm.
In the description of this specification, the description of reference term " embodiment ", " another embodiment ", " example " etc. means that particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are included at least one embodiment or example of the invention.In the present specification, the schematic representation of the above terms does not necessarily have to refer to the same embodiment or example.Moreover, particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more of the embodiments or examples.In addition, without conflicting with each other, the feature of different embodiments or examples described in this specification and different embodiments or examples can be combined by those skilled in the art.
Although embodiment of the present invention and embodiment have been shown and described above, it can be understood that, the embodiment above, embodiment are exemplary, it is not considered as limiting the invention, those skilled in the art can be changed the embodiment above, embodiment within the scope of the invention, modify, replacement and variant.

Claims (18)

  1. A kind of azo-compound, which is characterized in that the azo-compound be formula (Ia) compound represented or be compound shown in formula (Ia) stereoisomer or tautomer:
    Wherein,
    R1For H or alkyl；
    X is O, NH or NR6；
    Y1、Y2It is separately O, S, NH or NR6；Wherein R6It is C1-10Alkyl；
    W1、W2It is separately singly-bound or bivalent organic group；
    R2、R3、R4And R5It is separately alkyl, alkoxy, F, Cl, Br, hydroxyl, phenoxy group, benzyloxy, sulfonic group, CN, NO2Or COOR7, wherein each R7It independently is H or C1-4Alkyl；
    M and n is separately 0,1,2,3 or 4；
    P and q is separately 0,1,2,3,4 or 5.
  2. Azo-compound according to claim 1, which is characterized in that in azo-compound shown in the formula (Ia):
    R1For H or C1-4Alkyl；
    X is O, NH or NR6；
    Y1、Y2It is separately O, S, NH or NR6；Wherein R6It is C1-6Alkyl；
    W1、W2It is separately singly-bound, sub- miscellaneous alkyl or alkylidene；
    R2、R3、R4And R5It is separately C1-10Alkyl, C1-10Alkoxy, F, Cl, Br, hydroxyl, phenoxy group, benzyloxy, sulfonic group, CN, NO2Or COOR7；Wherein each R7It independently is H or C1-4Alkyl；
    M and n is separately 0,1,2,3 or 4；
    P and q is separately 0,1,2,3,4 or 5.
  3. Azo-compound according to claim 1 or 2, which is characterized in that in azo-compound shown in the formula (Ia):
    R1For H or C1-4Alkyl；
    X is O or NH；Y1、Y2It is separately O or S；
    W1、W2It is separately singly-bound, C1-12Sub- miscellaneous alkyl or C1-12Alkylidene；
    R2、R3、R4And R5It is separately C1-8Alkyl, C1-8Alkoxy, hydroxyl, CN, NO2, F, Cl, Br, phenoxy group, benzyloxy, sulfonic group or COOR7；Wherein each R7It independently is H or C1-4Alkyl；
    M and n is separately 0,1,2,3 or 4；
    P and q is separately 0,1,2,3,4 or 5.
  4. Azo-compound according to claim 1, which is characterized in that the azo-compound be formula (I) compound represented or be compound shown in formula (I) stereoisomer or tautomer:
    Wherein,
    R1For H or alkyl；
    R2、R3、R4And R5It is separately alkyl, alkoxy, F, Cl, Br, hydroxyl, phenoxy group, benzyloxy, sulfonic group, CN, NO2Or COOR7；Wherein each R7It independently is H or C1-4Alkyl；
    M and n is separately 0,1,2,3 or 4；
    P and q is separately 0,1,2,3,4 or 5.
  5. Azo-compound according to claim 1 or 4, which is characterized in that the R1For H or methyl.
  6. Azo-compound according to claim 1 or 4, which is characterized in that the R2、R3、R4And R5It is separately C1-6Alkyl, C1-6Alkoxy, hydroxyl, CN, NO2, F, Cl or Br.
  7. Azo-compound according to claim 6, which is characterized in that the R2、R3、R4And R5It is separately C1-4Alkyl, C1-4Alkoxy, hydroxyl, NO2, F or Cl.
  8. Azo-compound according to claim 1 or 2, which is characterized in that W1、W2It is separately singly-bound, C1-8Sub- miscellaneous alkyl or C1-8Alkylidene.
  9. Azo-compound according to claim 7, which is characterized in that the R2、R3、R4And R5It is separately methyl, hydroxyl, fluorine atom or methoxyl group.
  10. Azo-compound according to claim 4, which is characterized in that the R1For H or methyl, the m and n are 0, and the p and q are separately 0 or 1 or 2, the R4And R5It is separately hydroxyl, methyl, fluorine atom or methoxyl group；
    Alternatively, the R1For H or methyl, the m and n are 1, the R2For methyl, methoxyl group or hydroxyl, the R3With R2Identical, the p and q are separately 0 or 1, the R4And R5It is separately hydroxyl, methyl, fluorine atom or methoxyl group.
  11. Azo-compound according to claim 1, which is characterized in that the azo-compound is formula (1)~(19) compound represented, or stereoisomer or tautomer for the compound:
  12. A kind of polymer, which is characterized in that the monomer for constituting the polymer includes bulk monomer and blue-light absorbers, and the blue-light absorbers are the described in any item azo-compounds of claim 1~11.
  13. Polymer according to claim 12, which is characterized in that the bulk monomer includes at least one of (methyl) acrylic ester monomer, vinyl monomer and allylic monomers.
  14. Polymer according to claim 12, which is characterized in that the polymer further comprises at least one of crosslinking agent, ultraviolet absorber and initiator.
  15. A kind of eye medical device, which is characterized in that including polymer described in any one of claim 12-14.
  16. Eye medical device according to claim 15, feature exist, and the eye medical device is artificial lens, intraocular lens, contact lens, cornea amendment object, intracorneal lens, cornea insert, corneal ring or glaucoma filtering apparatus.
  17. A method of preparing the described in any item polymer of claim 12-14 characterized by comprising
    Gradient type heat treatment is carried out to raw mixture, to obtain the polymer,
    Wherein, the raw mixture at least one of contains bulk monomer, blue-light absorbers and is optionally selected from crosslinking agent, initiator and ultraviolet absorber.
  18. According to the method for claim 17, which is characterized in that the gradient type, which heats, includes:
    First stage of reaction, the temperature of first stage of reaction are 40~70 degrees Celsius, the reaction time 1~24 hour；And
    Second stage of reaction, the temperature of second stage of reaction are 80~120 degrees Celsius, and the reaction time is 1~24 hour.
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