CN113321763A - Polymer, application thereof and ophthalmic medical equipment - Google Patents
Polymer, application thereof and ophthalmic medical equipment Download PDFInfo
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- CN113321763A CN113321763A CN202110878347.6A CN202110878347A CN113321763A CN 113321763 A CN113321763 A CN 113321763A CN 202110878347 A CN202110878347 A CN 202110878347A CN 113321763 A CN113321763 A CN 113321763A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 81
- 239000000178 monomer Substances 0.000 claims abstract description 119
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 37
- 239000000376 reactant Substances 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000004429 atom Chemical group 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- -1 acrylic compound Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical group C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 150000004292 cyclic ethers Chemical class 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- 239000004971 Cross linker Substances 0.000 claims description 2
- 150000003918 triazines Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 150000003384 small molecules Chemical class 0.000 abstract description 6
- 230000000379 polymerizing effect Effects 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007943 implant Substances 0.000 description 6
- 230000001678 irradiating effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical group CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 4
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 4
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical group C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical group C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 2
- IFQUPKAISSPFTE-UHFFFAOYSA-N 4-benzoylbenzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C1=CC=CC=C1 IFQUPKAISSPFTE-UHFFFAOYSA-N 0.000 description 2
- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QPQKUYVSJWQSDY-CCEZHUSRSA-N 4-(phenylazo)aniline Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=CC=C1 QPQKUYVSJWQSDY-CCEZHUSRSA-N 0.000 description 1
- 238000010546 Norrish type I reaction Methods 0.000 description 1
- 238000010547 Norrish type II reaction Methods 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical group C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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- 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
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to a polymer, application thereof and an ophthalmic medical device, wherein the ophthalmic medical device comprises the polymer, and the polymer is mainly obtained by polymerizing at least one first monomer, at least one cross-linking agent and at least one photoinitiator; the first monomer and the cross-linking agent are both acrylate compounds, and the first monomer further comprises aryl; the photoinitiator comprises at least one double bond. The photoinitiator can not only initiate polymerization reaction, but also be polymerized together with other reactants to form a component of the polymer due to the double bond structure of the photoinitiator, so that the photoinitiator is prevented from remaining in the polymer in the form of small molecules after the reaction is finished, the risk of migration and dissolution is avoided, and the biological safety of the polymer when being applied to ophthalmic medical devices is improved.
Description
Technical Field
The invention relates to a polymer, application thereof and an ophthalmic medical device.
Background
Intraocular lenses, as an ocular implant, not only have a high refractive index, good light transmittance, suitable softness, but also require high biosafety.
In the prior art, optical materials for preparing intraocular lenses are mostly obtained by initiating polymerization of polymer monomers through initiators such as photoinitiators, and some optical materials with harmful light prevention function also incorporate light absorbers. After the optical material is formed by the polymer monomer, the residual polymer monomer is removed by post-treatment, but the photoinitiator and the light absorber mostly exist in the optical material in the form of small molecules, and when the optical material is prepared into an ocular implant and implanted into eyes for a long time, the risk of migration and dissolution of the small molecules of the photoinitiator and the light absorber exists, so that the biological safety of the ocular implant is reduced.
Disclosure of Invention
The invention aims to provide a polymer, application thereof and an ophthalmic medical device, wherein the polymer is mainly obtained by initiating polymerization of a plurality of raw materials under a photoinitiator, the photoinitiator comprises photosensitive double bonds, the compatibility of the photoinitiator is improved, and the photoinitiator can be polymerized with other reactants, so that the structure of the photoinitiator finally becomes a part of the polymer, the risk of migration and dissolution from the polymer caused by the residue of the photoinitiator in the form of small molecules after reaction is effectively avoided, and the biological safety of the polymer is improved.
In order to achieve the above object, the present invention provides a polymer obtained by polymerizing at least one first monomer, at least one crosslinking agent, and at least one photoinitiator; the first monomer and the cross-linking agent are both acrylate compounds, and the first monomer further comprises aryl; the photoinitiator comprises at least one double bond.
Alternatively, the structure of the first monomer conforms to the general formula (I):
. Wherein Z is H or methyl; r2Is an alkyl or ether group; y is alkyl or aryl.
Alternatively, the structure of the cross-linking agent corresponds to general formula (II):
. In the formula, X1Any one of alkyl, ether, amino, aliphatic ureido and aryl; e1Is H or methyl; e2Is H or methyl; d1Is an acrylic or methacrylic group, or D1Has no atom; d2Is an acrylic or methacrylic group, or D2There is no atom.
Optionally, the photoinitiator is an acrylic compound.
Optionally, the reactants for synthesizing the polymer further comprise a second monomer, wherein the second monomer is an acrylate compound.
Alternatively, the structure of the second monomer conforms to general formula (III):
. In the formula, M1Is H or methyl; a. the1Is any one of S, a sulfur-containing group, a methylene group in which at least one hydrogen is substituted with an amino group, a methylene group in which at least one hydrogen is substituted with a hydroxyl group, a cycloalkyl group in which at least one hydrogen is substituted with an amino group, a cycloalkyl group in which at least one hydrogen is substituted with a hydroxyl group, or A1Has no atom; r1Is any one of alkyl, cyclic ether and siloxane groups.
Optionally, when the photoinitiator is a hydrogen abstraction photoinitiator, A in at least one of the second monomers1Comprising an amino group; and/or the presence of a gas in the gas,
the R is1Is straight chain alkylAnd the number of carbon atoms of the main chain is 1 to 10.
Alternatively, in percent by weight, A1The second monomer including an amino group accounts for 1% to 10% of all the first monomers.
Optionally, A in at least one of the second monomers1Including tertiary amino groups.
Optionally, the sum of the amounts of the first monomer, the second monomer and the cross-linking agent is 100%, wherein the amount of the first monomer is 50-99% and the amount of the second monomer is 0-20% by weight; the dosage of the photoinitiator is 0.1-5% of the sum of the dosages of the first monomer, the second monomer and the cross-linking agent.
Alternatively, the general formula of the photoinitiator corresponds to formula (IV):
. In the formula, R3Is any one of carbonyl, alkyl and ester amino; m2Is H or methyl.
Alternatively, the photoinitiator has the structural formula (V):
。
optionally, the raw material for polymerizing to obtain the polymer further includes a third monomer, the third monomer is an azobenzene derivative or a triazine derivative, and the third monomer further includes at least one terminal alkenyl group.
Alternatively, the third monomer is of formula (VI):
. In the formula, R4Is any one of alkoxy, amino and urethane.
Optionally, the refractive index of the polymer is 1.45-1.55.
In order to achieve the above object, the present invention also provides the use of said polymer for the preparation of an ophthalmic medical device.
To achieve the above object, the present invention also provides an ophthalmic medical device comprising the polymer according to any one of the preceding claims.
Compared with the prior art, the polymer, the application thereof and the ophthalmic medical device have the following advantages: firstly, the polymer is mainly obtained by polymerizing at least one first monomer, at least one cross-linking agent and at least one photoinitiator; the first monomer and the cross-linking agent are both acrylate compounds, and the first monomer comprises aryl; the photoinitiator comprises at least one double bond. In this way, the photoinitiator can not only initiate reaction, but also realize in-situ copolymerization with the cross-linking agent and the first monomer, and becomes a component of the polymer, so that the photoinitiator is prevented from remaining in the polymer in the form of small molecules and being migrated and dissolved out in the use process, and the polymer has high refractive index, good light transmittance and proper softness, and has good biological safety when being applied to an ocular implant such as an artificial lens.
Secondly, the raw materials for obtaining the polymer through polymerization also comprise a third monomer, and the third monomer can absorb blue light or medium wave ultraviolet light, or the structural formula of the photoinitiator comprises a light absorption structure, so that the polymer can also absorb the blue light or the medium wave ultraviolet light, and when the polymer is applied to an artificial lens, the eye protection effect is improved.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a first photoinitiator prepared according to a first embodiment of the present invention.
FIG. 2 is a nuclear magnetic hydrogen spectrum of a second photoinitiator prepared according to a second embodiment of the present invention.
FIG. 3 is a nuclear magnetic hydrogen spectrum of a third monomer prepared according to a third embodiment of the present invention.
Detailed Description
To further clarify the objects, advantages and features of the present invention, a more particular description of the invention will be rendered by reference to the appended drawings. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.
As used in this specification, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. As used in this specification, the term "or" is generally employed in its sense including "and/or" unless the content clearly dictates otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The embodiment of the invention provides a polymer, which is mainly obtained by polymerizing at least one first monomer, at least one cross-linking agent and at least one photoinitiator; the first monomer and the cross-linking agent are both acrylate compounds, and the first monomer further comprises aryl. The photoinitiator comprises at least one double bond. The photoinitiator generates free radicals under illumination, and initiates polymerization reaction of at least one first monomer and the cross-linking agent, and meanwhile, the free radicals can also initiate polymerization reaction of double bonds in the photoinitiator, the first monomer and the cross-linking agent, so that the molecular structure of the photoinitiator finally becomes a component of the polymer without being left in the form of small molecules, and further, the risk of migration and dissolution does not exist.
Further, in the embodiment of the present invention, the reactant for obtaining the polymer through polymerization may further include a second monomer, where the second monomer is an acrylate compound.
In the actual polymerization reaction, the sum of the amounts of the first monomer, the second monomer and the crosslinking agent is 100%, wherein the amount of the first monomer is 50-99%, the amount of the second monomer is 0-20%, and the balance is the crosslinking agent. The dosage of the photoinitiator is 0.1 to 5 percent of the dosage of the first monomer, the second monomer and the cross-linking agent. It is noted that the amount of the second monomer is 0 when the reactants for synthesizing the polymer do not include the second monomer, and is greater than 0 when the reactants for synthesizing the polymer include the second monomer.
The preparation method of the polymer comprises the following steps: and uniformly mixing all reactants according to a ratio, pouring the mixture into a reactor, and irradiating the reactants by adopting a light source matched with a photoinitiator and initiating a reaction. Preferably, the reactants are heated to a predetermined temperature and kept warm for a period of time while being irradiated with light, so that the polymerization activity of the monomers is improved, the reaction rate is further increased, the conversion efficiency is also improved, and the monomer residue is reduced. Optionally, the illumination time is 20min to 100min, the preset temperature is 70 ℃ to 120 ℃, and the heat preservation time is 20min to 60 min.
In the embodiment of the invention, monomers with different hardness can be selected, for example, the second monomer has higher hardness, the first monomer has lower hardness, and the two monomers are polymerized under the action of the cross-linking agent, so that the first monomer becomes the soft segment of the polymer, and the second monomer becomes the hard segment of the polymer, so that the polymer has proper softness, good light transmission and higher refractive index, and can be applied to an ocular implant such as an artificial lens. The refractive index of the polymer is 1.4-1.55.
In embodiments of the invention, the structural formula of the first monomer corresponds to formula (I):
wherein Z is H or methyl; r2Is an alkyl or ether group; y is alkyl or aryl. When R2 is alkyl, R2The number of carbon atoms in (a) is 1 to 6, preferably 2 to 4.
The structure of the cross-linking agent corresponds to the general formula (II):
in the formula, X1Any one of alkyl, ether, amino, aliphatic ureido and aryl; e1Is H or methyl; e2Is H or methyl; d1Is an acrylic or methacrylic group, or D1Is without atom；D2Is an acrylic or methacrylic group, or D2There is no atom. Wherein, when X1When it is an aliphatic ureido group, X1The number of carbon atoms of the main chain of (2) to (15), preferably 4 to 8. When D is present1And D2When the groups are present, they may be the same or different.
It will be understood that when D is used1Or D2In the absence of atoms, the structure of the crosslinking agent substantially corresponds to the general formula (II-I):
wherein D is an acrylic or methacrylic group.
And when D is1And D2When both are free of atoms, the structure of the crosslinker substantially conforms to the general formula (II-II):
。
the structure of the second monomer corresponds to formula (III):
in the formula, M1Is H or methyl. A. the1Is any one of S, a sulfur-containing group, a methylene group in which at least one hydrogen is substituted with an amino group, a methylene group in which at least one hydrogen is substituted with a hydroxyl group, a cycloalkyl group in which at least one hydrogen is substituted with an amino group, a cycloalkyl group in which at least one hydrogen is substituted with a hydroxyl group, or A1There is no atom. R1Is any one of alkyl, cyclic ether and siloxane groups.
When A is1In the case of a sulfur-containing group, the refractive index of the finally obtained polymer can be further increased. The sulfur-containing groups are, for example, -S-,
。
when R is1When alkyl, it may include straight chain alkyl or cycloalkyl groups, when R is1In the case of a straight-chain alkyl group, the number of carbon atoms in the main chain is 1 to 10, preferably 2 to 6.
When A is1And (b) when not atomic, the structural formula of the second monomer is actually general formula (III-I):
。
the photoinitiator includes, but is not limited to, a macrophotoinitiator or an acrylic group-containing photoinitiator. In terms of reaction type, the photoinitiator may be either a hydrogen abstraction type photoinitiator (Norrish type II) or a cleavage type photoinitiator (Norrish type I). In particular, when the photoinitiator used comprises at least one hydrogen abstraction type photoinitiator, it is preferable that A in at least one of the second monomers1Including amino groups, further preferably tertiary amino groups. The amino group can be used as a catalyst of a photoinitiated reaction to catalyze the polymerization reaction, so that the reaction rate and the conversion rate are improved. In percent by weight, A1The amount of the second monomer including an amino group is 1 to 10% of the total amount of all the second monomers.
In some embodiments, the structure of the photoinitiator corresponds to general formula (IV):
in the formula, R3Is any one of carbonyl, alkyl and ester amino; m2Is H or methyl. Alternatively, in other embodiments, the photoinitiator has a structure according to formula (V):
。
the inventors have in the course of their development hoped that the polymers are also capable of absorbing harmful light to improve the protection of the eye when applied to ocular implants such as intraocular lenses. Based on this, the raw materials for obtaining the polymer through polymerization further include a third monomer, where the third monomer includes a group capable of absorbing blue light or medium-wave ultraviolet light, and the third monomer further includes at least one terminal alkenyl group, so that the third monomer can be polymerized with other reactants (including the first monomer, the second monomer, the crosslinking agent, and the photoinitiator). The group capable of absorbing blue light is azophenyl, and the group capable of absorbing medium wave ultraviolet light is triazine ring.
Alternatively, the third monomer is an azobenzene-acrylic compound, the structure of which may correspond to general formula (VI):
in the formula, R4Is any one of alkoxy, amino and urethane.
The present invention will be described in further detail with reference to specific examples.
In the first embodiment of the present invention, a first photoinitiator is first prepared, the first photoinitiator is represented by formula (V), and the photoinitiator is a cleavage type photoinitiator.
The preparation method of the first photoinitiator comprises the following steps: 2.25g of 2-hydroxy-4 '(-2 hydroxyethoxy) -2-methyl propiophenone was weighed out, and then 2-hydroxy-4' (-2 hydroxyethoxy) -2-methyl propiophenone was dissolved in 40ml of tetrahydrofuran, and 1.5567g of isocyano ethyl methacrylate was added thereto, and the reaction was stirred at room temperature under nitrogen for 12 hours. After the reaction is finished, the solvent is removed by rotary evaporation, and the product is obtained by drying at room temperature, and a nuclear magnetic hydrogen spectrum of the product is shown in figure 1, the abscissa represents chemical shift, and the hydrogen proton peaks of propenyl double bond existing at 5.6 and 6.1 are shown in the figure. The structural formula of the product can be determined by the nuclear magnetic hydrogen spectrum diagram to be the formula (V).
The polymer is then prepared.
In this embodiment, the first monomer is 2-phenoxyethyl acrylate, the second monomer is isobutyl acrylate, the crosslinking agent is 1, 6-hexanediol dimethacrylate, the photoinitiator is represented by formula (V), and in percentage by weight, the amount of the first monomer is 94%, the amount of the second monomer is 5%, and the amount of the crosslinking agent is 1%. The dosage of the photoinitiator is 2% of the sum of the dosages of the first monomer, the second monomer and the cross-linking agent.
The synthesis method of the polymer comprises the following steps: mixing all the above reactants, injecting into a reactor, irradiating the reactants with 365nm ultraviolet light for 30min, heating the reactants to 80 deg.C, and maintaining the temperature for 50 min. After the reaction, a transparent and flexible polymer was obtained. The polymer had a glass transition temperature of 6.17 deg.C (as determined by DSC testing) and a refractive index of 1.55.
In the second embodiment of the present invention, a first photo-initiator is first prepared, where the first photo-initiator is a photo-initiator represented by formula (V), and the preparation method refers to the first embodiment, which is not repeated herein.
Next, a second photoinitiator is prepared, which is a hydrogen abstraction photoinitiator.
The preparation process of the second photoinitiator is as follows: 2.26g of 4-benzoylbenzoic acid was weighed into a flask, and 30ml of tetrahydrofuran was added to the flask, followed by stirring and dissolving of 4-benzoylbenzoic acid. Then 1.70g of isocyanoethyl methacrylate was slowly added to the flask while stirring at 60 ℃ under reflux for 24 h. After the reaction is finished, washing the product for 5 times, and then freeze-drying to obtain a product, wherein the structural formula of the product is shown as a formula (IV-I):
the nuclear magnetic hydrogen spectrum is shown in FIG. 2.
The polymer is then synthesized.
In this embodiment, the first monomer is benzyl acrylate, the second monomer includes isobutyl acrylate and 2- (dimethylamino) ethyl methacrylate, the cross-linking agent is 1, 6-ethylene glycol dimethacrylate, and the photoinitiator includes the first photoinitiator and the second photoinitiator. By weight percentage, the dosage of benzyl acrylate is 78%, the dosage of isobutyl acrylate is 5%, the dosage of 2- (dimethylamino) ethyl methacrylate is 15%, and the dosage of 1, 6-hexanediol dimethacrylate is 2%. The dosage of the first photoinitiator is 0.02 percent of the sum of the dosages of the first monomer, the second monomer and the cross-linking agent, and the dosage of the second photoinitiator is 0.08 percent of the sum of the dosages of the first monomer, the second monomer and the cross-linking agent.
The synthesis method of the polymer comprises the following steps: mixing all reactants uniformly, injecting into a reactor, irradiating the reactants for 30min by adopting an ultraviolet light source with the wavelength of 365nm, heating the reactants to 100 ℃, and preserving the heat for 60 min. After the reaction, a soft and transparent polymer was obtained. The glass transition temperature of the polymer was 10.18 ℃ (obtained by DSC test), and the refractive index of the polymer was 1.48.
In the embodiment, two photoinitiators are adopted to initiate polymerization reaction together, and a synergistic effect can be generated between the two photoinitiators, so that the reaction efficiency is improved.
In a third embodiment of the present invention, a second photoinitiator and a third monomer are first prepared. The second photoinitiator is represented by formula (IV-I), and the preparation method thereof is described in example two, which is not repeated herein.
In this embodiment, the third monomer is an azobenzene derivative, which can absorb blue light. The preparation method of the third monomer comprises the following steps: 3.0g of 4-aminoazobenzene was dissolved in 40ml of tetrahydrofuran, and then 2.40g of isocyanoethyl methacrylate was slowly added dropwise thereto, and the reaction was stirred for 12 hours. And after the reaction is finished, removing the solvent, and drying at room temperature for 12h to obtain a product, wherein the nuclear magnetic hydrogen spectrum of the product is shown in figure 3, and the structural formula of the product is shown as a formula (VI-I):
。
the polymer is then synthesized.
In this embodiment, the first monomer is 2-phenoxyethyl acrylate, the second monomer is isobutyl acrylate, the third monomer is a compound represented by formula (6-1), the crosslinking agent is trimethylolpropane triacrylate, and the photoinitiator is the second photoinitiator. The content of the first monomer is 93%, the content of the second monomer is 5%, the content of the third monomer is 2%, the content of the cross-linking agent is 1%, and the content of the photoinitiator is 1% of the sum of the content of the first monomer, the content of the second monomer and the content of the cross-linking agent.
The synthesis method of the polymer comprises the following steps: mixing all reactants uniformly, implanting into a reactor, irradiating the reactants for 60min by using an ultraviolet light source with the wavelength of 365nm, heating the reactants to 120 ℃, and preserving the heat for 60 min. After the reaction, a soft and transparent polymer was obtained. The glass transition temperature of the polymer was 15.00 ℃ and the refractive index was 1.53.
The reactants used to synthesize the polymer in the fourth embodiment of the present invention include only the first monomer, the crosslinking agent, and the photoinitiator. The first monomer comprises benzyl acrylate and benzyl methacrylate, the cross-linking agent is 1, 6-hexanediol dimethacrylate, and the photoinitiator is a commercially available photoinitiator 1173. In percentage by weight, the amount of benzyl acrylate is 78%, the amount of benzyl methacrylate is 20%, the amount of 1, 6-hexanediol dimethacrylate is 2%, and the amount of photoinitiator 1173 is 1% of the sum of the amounts of the first monomer, the second monomer, and the crosslinking agent.
The synthesis method of the polymer comprises the following steps: uniformly mixing all reactants, injecting the mixture into a reactor, irradiating the reactants for 30min by adopting an ultraviolet light source with the wavelength of 365nm, simultaneously heating the reactants to 100 ℃, preserving the heat for 60min, and obtaining a soft and transparent polymer after the reaction is finished. The polymer had a glass transition temperature of 19.68 deg.C (from DSC) and a refractive index of 1.55.
Further, the embodiment of the invention also provides an ophthalmic medical device, which comprises the polymer. Such as an intraocular lens or the like.
Although the present invention is disclosed above, it is not limited thereto. Various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (17)
1. A polymer, characterized by being polymerized primarily from at least one first monomer, at least one crosslinker, and at least one photoinitiator; the first monomer and the cross-linking agent are both acrylate compounds, and the first monomer further comprises aryl; the photoinitiator comprises at least one double bond.
2. The polymer of claim 1, wherein the first monomer has a structure according to formula I:
wherein Z is H or methyl; r2Is an alkyl or ether group; y is alkyl or aryl.
3. The polymer of claim 1, wherein the crosslinking agent has a structure according to formula II:
in the formula, X1Any one of alkyl, ether, amino, aliphatic ureido and aryl; e1Is H or methyl; e2Is H or methyl; d1Is an acrylic or methacrylic group, or D1Has no atom; d2Is an acrylic or methacrylic group, or D2There is no atom.
4. The polymer of claim 1, wherein the photoinitiator is an acrylic compound.
5. The polymer of any of claims 1-4, wherein the reactants for synthesizing the polymer further comprise a second monomer, the second monomer being an acrylate compound.
6. A polymer according to claim 5, wherein the second monomer has a structure according to formula III:
in the formula, M1Is H or methyl; a. the1Is any one of S, a sulfur-containing group, a methylene group in which at least one hydrogen is substituted with an amino group, a methylene group in which at least one hydrogen is substituted with a hydroxyl group, a cycloalkyl group in which at least one hydrogen is substituted with an amino group, a cycloalkyl group in which at least one hydrogen is substituted with a hydroxyl group, or A1Has no atom; r1Is any one of alkyl, cyclic ether and siloxane groups.
7. The polymer of claim 6 wherein when said photoinitiator is a hydrogen abstraction photoinitiator, at least one of A in said second monomer1Comprising an amino group; and/or the presence of a gas in the gas,
the R is1Is straight-chain alkyl, and the number of carbon atoms of the main chain is 1-10.
8. The polymer of claim 7, wherein A is present in weight percent1The second monomer including an amino group accounts for 1% to 10% of all the first monomers.
9. The polymer of claim 7, wherein A is in at least one of the second monomers1Including tertiary amino groups.
10. The polymer according to claim 5, wherein the sum of the amounts of the first monomer, the second monomer and the crosslinking agent is 100%, wherein the amount of the first monomer is 50 to 99% and the amount of the second monomer is 0 to 20% by weight; the dosage of the photoinitiator is 0.1-5% of the sum of the dosages of the first monomer, the second monomer and the cross-linking agent.
11. The polymer of claim 4, wherein the photoinitiator has a general formula corresponding to formula IV:
in the formula, R3Is any one of carbonyl, alkyl and ester amino; m2Is H or methyl.
12. The polymer of claim 4, wherein the photoinitiator has the formula V:
13. the polymer of claim 11 or 12, wherein the raw materials for polymerization to obtain the polymer further comprise a third monomer, the third monomer is an azobenzene derivative or a triazine derivative, and the third monomer further comprises at least one terminal alkenyl group.
14. The polymer of claim 13, wherein the third monomer has a formula corresponding to formula VI:
in the formula, R4Is any one of alkoxy, amino and urethane.
15. The polymer of claim 1, wherein the polymer has a refractive index of 1.45 to 1.55.
16. Use of a polymer according to any one of claims 1 to 15 in the manufacture of an ophthalmic medical device.
17. An ophthalmic medical device comprising the polymer of any one of claims 1-15.
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