TW201239007A - Silicon containing prepolymer and silicon-hydrogel organic material including the same - Google Patents

Abstract

A silicon containing prepolymer represented by the following structure: wherein n1 is integer 1 to 20. A is a divalent aliphatic group or a divalent aromatic group. All Y's are identical or different. Alternatively, some Y's are identical and some Y's are different. Y is H atom or Ry is an aromatic alkyl group including fluorine atom, an ether group including fluorine atom, an ether group or an amino group. X is an oxygen atom or -NRx-, wherein Rx is a hydrogen atom or a monovalent alkyl group having 1 to 5 carbon atoms or. Ry is defined the same above. All Rx's are identical or different. Or, some Rx's are identical and some Rx's are different. Z represents a group containing C-C double bond.

Description

201239007 36950twf.doc/n VI. Description of the Invention: [Technical Field] The present invention relates to a prepolymer and a hydrogel, and more particularly to a cerium-containing prepolymer and a polyfluorene ketone hydrogel. . [Prior Art] A hydrogel is a hydrated crosslinked polymer which is soft in nature, can maintain a certain shape, and can absorb a large amount of water. Hydrogels are generally oxygen permeable and biocompatible and, therefore, are well suited for use in the manufacture of medical biomaterials such as contact lenses, ophthalmic dressings or general surgical dressings. Conventional hydrogels are mainly prepared from a mixture containing a hydrophilic monomer, such as 2-hydroxyethyl decyl acrylate (ΗΕΜΑμΐΝ_vinyl 11 to money i^I (NVP). Mosquito' a bit of money (10) Oxygen is still insufficient, and the hydrogel produced by the medical material is not suitable for long-term wear. ^Advanced hydrogel is made of polyfluorenone monomer to make polyfluorene ketone water condensate, and its oxygen permeability is better. The conventional hydrogel is high, however, the water hydrazine produced by the poly "smoke hydrogel has insufficient elasticity" cannot satisfy the demand for comfort. [Invention] The present invention provides a zephyr-containing prepolymer, which It can be used as a reactant of the polysulfone hydrogel. The present invention provides a high-permeability and high elasticity of the poly-stone. The present invention provides a cerium-containing prepolymer having the following structure: Show: [Formula 1]

Z—X—E—X—C—N—A—N—C—X—E—X—Z wherein nl is an integer from 1 to 20; Α represents an aliphatic group or an aromatic group; Y represents Η Or

—C=〇All Υ may be identical or completely different, or partially Υ identical and partially Υ different; Ry represents a fluorine-containing aromatic group, a mysterious group, a fluorine-containing ether group or a group of an amine group; X represents 0 or a hydrazine, or a valence alkyl group having a carbon number of 1 to 5, or

Wherein Ry is as defined above; all Rx are identical or completely different, or part of Rx is the same and part of Rx is different; and Z represents an alkenyl group. According to an embodiment of the present invention, the carbon number of the divalent aliphatic group or the aromatic group represented by the above A is from 1 to 20; wherein the E represents a divalent anthracene group, and the structure thereof is as shown in the following formula 2 : [Formula 2]

201239007 36950twf.doc/n wherein Rei and ReZ each represent hydrogen, a monovalent alkyl group having a carbon number of 1 to 5, a hospital group or an ether group of a fluorine-containing substituent; Rei and Re2 may be the same or different; m is An integer from 0 to 40; Q represents a linear or branched divalent alkyl group having a carbon number of 1 to 10; L represents a single bond, a benzyl group or an alkoxy group; and the structure of z is as shown in the following formula 3: 】 C— N—CH2CH2—

Wherein Rz represents hydrogen or a carbon number of 1 to 5; and n3 represents an integer of 0 to 5. According to an embodiment of the invention, the structure of the above L is as follows: +CnH2nO 七 2 wherein 0 and Q are bonded; n is an integer from i to 10; and n2 is an integer from 〇 to 2〇. The present invention also provides a biomaterial of a polyfluorene ketone hydrogel prepared from the above reaction mixture containing a ruthenium prepolymer, wherein the reaction mixture further comprises an initiator, and the selectivity further comprises polyfluorene. A ketone monomer, a hydrophilic monomer, a diluent, or a combination thereof. According to an embodiment of the invention, the weight ratio of the cerium-containing prepolymer to the poly-stone monomer is from 1:0 to 1:99. According to the embodiment-implementation, the content of the above-mentioned excision and the polyketone monomer is 5 to 99% by weight, the upper amount is 5 to 9% by weight, and the content of the above diluent is q to 7 = = 3 201239007 36950twf.doc/n and the above-mentioned initiator are contained in an amount of 5 to 5% by weight, based on 100% by weight of the above reaction mixture. According to an embodiment of the invention, the polyketone-containing monomer comprises 3-mercaptopropenyloxypropyltris(trimethylsulfonyloxyalkyl)decane (TRIS), propylene oxiranyl phenyl tetra Phenyltetramethyldisiloxanylethyl acrylate, pentamethyldisiloxanylmethyl methacrylate, methacryloyloxymethyl-n-pentyl hexamethylenetrioxane N-pentylhexamethyltrisiloxanylmethyl methacrylate), heptamethyltrisiloxanylethy acrylate, tri-i-propyltetramethyltrisiloxanylethyl acrylate, fluorenyl N-propyloctamethyltetrasiloxanylpropyl methacrylate, methyldi(trimethylsiloxy)_methacryloxymethylsilane, propylene Triphenyldimethyldisiloxanylmethyl acrylate, propylene oxyethyl phenyl tetraethyl lithium Phenyltetraethyldisiloxanylethyl methacrylate, isobutylhexamethyltrisiloxanylmethyl methacrylate or t-butyltetramethyldisiloxanylethyl acrylate ). According to an embodiment of the invention, the hydrophilic monomer comprises N, N-201239007 36950twf.doc/n dimethyl methacrylate (DMA), 2-hydroxyethyl methyl two (HEMA), glycerol methacrylate Ester, 2 夂曰r-』(NVP)' polystyrene methacrylic acid, acrylic acid or a combination thereof. 3, according to the invention - the examples, the above diluents include ethanol, propylene, isopropanol, butanol, isobutanol, 2-butanol, 2-methyl alcohol, 2-pentanol, 3 _Pentanol, 3-methylbutanol, 3-methyl-2, butanol: ~: soil _ _butanol, 2-methylbutanol, 丨-hexanol, 2-hexanol, 3·hexan Alcohol, 3-methyl pentanol, "yl+pentanol, 2·methyl_2: A:; 3: methylpentanol, 4-methylpentanol, 2-methyl·3'pentanol "", 3- soil y-pentanol, 3,3-dimethylbutanol, 2-ethyl butylbutanol's diterpene 2_heptanol '3-heptanol' 4_heptanol, l octanol , i• sterol or a combination thereof. /, according to the present invention - the examples, the above starting agent comprises 2 ° #_: gibberyl phenyl small acetone, bis (2,4,6-trimethylbenzylidene) benzene phosphine oxide , 1-hydroxycyclohexylphenylacetone, 2·(2 earth oxide = phosphine, 2,2-dimethoxy-benzene (ylethylene ==) peroxidation, peroxidic neodecanoic acid t-butyl vinegar, Even over-emulsified twelfth or peroxidized (2-ethylhexanoic acid) t-butyl vinegar. The above-mentioned polymunone hydrolyzed organisms as described in the example of the hexanyl sulphate material = illuminating or heating the above reaction mixture Or the material of the above-mentioned poly(tetra) hydrogel, γ y ^ 艮 敷, general surgical dressing or intelligent medicine

S 8 201239007 36950 twf.doc/n A cerium-containing prepolymer of the present invention, which can be used as a reactant for a polyfluorenone hydrogel. The polyfluorene ketone hydrogel of the embodiment of the invention has high oxygen permeability and high elasticity. The above described features and advantages of the present invention will become more apparent from the following description. [Embodiment] The present invention provides a stone-containing prepolymer having a structure as shown in the following formula 1: [Formula 1]

γ Y 2 X— E X- — C—N—A—N—C—X—E—X— -- ^ Ο Ο n1 A represents a divalent aliphatic group or an aromatic group having a carbon number of 1 to 20. The aliphatic group may be a linear alkylene group, a branched alkylene group, a cycloalkyl group or a divalent ketone group, for example, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group. Or isophoronyl group. The aromatic group is, for example, a divalent aralkyl group such as a diphenyl fluorenyl group or a fluorenyl phenyl group. In either embodiment, all of the gamma may be identical or completely different, or the portions Y may be the same and the portion Y may be different. In one embodiment, hydrazine represents hydrogen (H). In another embodiment, γ can be represented by the formula: r|i—η—c=o, wherein Ry represents a fluorine-containing aromatic group, an ether group, and a fluorine-containing ether 201239007 36950twf.doc/n group Or an amine group-containing group. Fluorine in Ry can reduce the ester viscosity of the formed human stone prepolymer. The fluorine-containing aromatic group is, for example, 2•fluoro/=fluoroindolyl or 2-fluoro-5-(indenyl)phenyl. Ry is a group containing a fluorenyl group or an amine group, and the hydrophilicity of the formed cerium-containing prepolymer can be improved. ^ Ether groups such as polyethylene glycol based (PEG), polypropylene glycol based (ppG) or polyethylene glycol / polypropylene glycol based copolymers (PEG / PPG copolymer). The amino group-containing group is, for example, polyvinylpyrrolidone (PVP) or poly N,N-dimercaptopropenylamine (poly-DMA). Ry is a fluorine-containing ether group, which can improve the hydrophilicity of the formed cerium-containing prepolymer, and can also lower the ester-based viscosity of the formed cerium-containing prepolymer, for example, ruthenium, ruthenium and decyl. -(2-Isophorone) propylamino 2,2,3,3-tetrafluoropropyl bond or oxime, Ν-dimethyl-(2-isophor g) propylamine 2,2,3, 3,4,4,5,5-octafluoropentyl ether group, the structure of which is as follows:

X represents Ο or -NRX-, and in any embodiment, all Rx may be identical or completely different' or partially identical and partially different. For example, Rx represents hydrazine or a monovalent alkyl group having a carbon number of 1 to 5, such as fluorenyl or ethyl' or 201239007 36950 twf.doc/n I|J-Η-C=0, wherein Ry The definition is as above, and will not be described here. E is a divalent oxiranyl group having the following structure, and its structure is as shown in the following formula 2: [Formula 2] fj^el Si——Q-Ir ^e1 —L·—Q-(-Si-Ο-

Re2 Re2

Rei and Re2 each represent hydrogen, respectively, or a monovalent alkyl group having a carbon number of 1 to 5, an alkyl group or an ether group having a fluorine-containing substituent. Rel and Re2 can be the same or different. m is an integer of 0 to 40, preferably an integer of 3 to 35, more preferably an integer of 5 to 30. Q represents a linear or branched divalent alkyl group having a carbon number of 1 to 1 Å. L represents a direct bond, an ether group or an alkoxy group. In one embodiment the 'ether group' may be an alkylene glycol group, which may be represented by χ2 wherein oxygen is bonded to Q. η is an integer of 1 to 10, preferably an integer of 2 to 8. Η2 is an integer from 〇 to 2〇, preferably an integer from 0 to 18, more preferably an integer from 〇 to 15. Nl is an integer of 1 to 20, preferably an integer of 1 to 12, more preferably an integer of 1 to 6. Z is represented by an alkenyl group having the following chemical formula, and is used as a reaction end point of the above-mentioned preparation of a biomedical material containing the shixi prepolymer, and its structure is as shown in the following formula 3: 200339007 36950 twf.doc/n: [Formula 3] Ο Η Ο —(-C—N—CH2CH2-〇-^CC^Rz η ch2 wherein Rz represents hydrogen' or a monovalent alkyl group having a carbon number of 1 to 5, such as methyl or ethyl. An integer of 5. The reactants used to prepare the above-described cerium-containing prepolymer include: 0=C=NAN = C=Ο HO-E-OH or NH2_E-NH2 and Ο Ο 〇=c=n-ch2ch2-〇-c —c/Rz or ci—έ—c/Rz ww ch2 ch2 wherein A, E and Rz are as defined above. 0 = C = NAN=C = 0 Examples of aliphatics include isophorone diisocyanate Self-acting, 1,3-propanediisocyanate g (l,3-diisocyanatopropane), 1,8-octane diisocyanate (1,8-diisocyanatooctane), 1,5-pentane diisocyanate (l,5-diisocyanatopentane , 1,6-diisocyanatohexane, 1,4-butane diisocyanate (1,4-diisocyanatobutane) or isocyclohexylimine. Preferred is i,4-butyl diisocyanate Or hetero ring (PEI) .0 = C = N-A-N = C = examples of aromatic incense square of aromatic diisocyanates include diphenylmethane diisocyanate Yue Yue alkyl or phenyl.

Examples of S 12 201239007 36950twf.doc/n HO-E-OH include poly(dimethylsiloxane), bis(hydroxyalkyl) terminated, for example: CH3 ch3 ch3

I [I 1 I

H〇-H2CH2CH2C-Si—〇一Si——〇——Si_CH2CH2CH2-〇H CH3 ch3 70 ch3 ch3 ch3 ch3

I [I 1 I

H〇-H2CH2CH2C-Si-〇-Si-〇-Si-CH2CH2CH2-〇H ch3 ch3 14ch3 or polyoxide oxide-b-dimethylsiloxane-polyethylenoxide, for example: CH, CH, ho -h2ch2co- 15 H2CH2CH2O-Si-0-S 卜CH2CH2CH2. och2ch2- -0H 15 ch3 ch3 Examples of NH2-E-NH2 include polydifluorenyl ruthenium V., · V ..., ·* .VV〆·,,.'vV..:.,,8....*V >.,,..·. . : . J ' . . w'., · ^ -*· V ., ->,,··,,, . - · 'V - 'Oxygen (Poly(dimethylsiloxane), bis(3-aminoalkyl)terminatec〇,Example 13 201239007 36950twf.doc/n ch3 ch3 H2N-H2CH2CH2C- Si-〇·

Si-0·CH3 ch3 20 ch3Si-CH2CH2CH2-NH2 ch3 CH' ch3 ch3 H2N-H2CH2CH2C-Si-〇-

Examples of Si—0— •Si—CH 2 CH 2 CH 2 —NH ^ CH, CH 3 ch 3 0=C=N—CH 2 CH 2 ——— I? /Rz ch 2 or Cl—c— ch 2 include isocyanatoethyl acrylate, acrylic acid Isocyanatoethyl ester, methyl propyl chloride or acrylonitrile chloride. Preferred are methacrylic acid isophthalic acid ethyl ester or mercapto acrylonitrile chloride. When Y of the above-mentioned cerium-containing prepolymer represents cerium, in one embodiment, the above-mentioned cerium-containing prepolymer is synthesized in such a manner that the above three components are in an appropriate ratio, for example, 0 = C = NAN = C = 0: HO -E-OH or NH2-E-NH2 : 〇 or a- CH2 Ο

II R

〇=C=N—CH2CH2—〇-C一.C〆Z ch2 with molar ratio equal to 1: 2 : 2, 2 : 3 : 2, 3 : 4 : 2, 2.5 : 3.5 : 2, 4 : 5 : 2, 3.5 : 4.5 : 2 or 5 : 6 : 2 are diluted with a diluent and added to the reaction vessel, for example, tetrahydrofuran, toluene, N,N-dimethylacetamide or a combination thereof. Thereafter, a catalyst such as an organotin such as tin 2-ethylhexanoate, dibutyltin dilaurate, tin oleate or dibutyltin 201239007 36950twf.doc/n di-2-ethylhexanoate; or tertiary An amine such as triethylamine, dimethylethanolamine, tetradecylbutanediamine, dinonylcyclohexylamine or 1,4-diazobicyclo(2,2,2) octyl" at a suitable temperature For example, the reaction is carried out at 45 ° C to 150 ° C. In another embodiment, it is also possible to first Ο = C = N_A-N = C = 〇 and ΗΟ-Ε-ΟΗ (or ΝΗ2-Ε-ΝΗ2) After reacting with a molar ratio of 2:3, an appropriate amount of 0=C=N-CH2CH2-〇 is added to carry out the reaction.

0 II ^ c—Q

Rz ch2 or Cl_^_c/Rz \\ ch2 When γ of the above ruthenium-containing prepolymer represents Ν-Η-c=〇 (Ry is as defined above), the content (γ) obtained by the above method can be used. Represents H) reacting with Ry-N=C=0 for upgrading. Examples of the prepolymerization include polyethylene glycol methyl ether isocyanate, 2-fluoro-5-(trisyl isocyanate, 2-fluoro-5-(methyl)phenyl isocyanate' polyethyl bromide Alcohol copolymer isocyanate, polypropylene glycol isocyanate, poly-2-olpropane ketone isocyanate, poly N,N-dimercapto acrylamide isocyanide salt, = bromo fluorenyl- (2-isophorol isocyanate) propylamino 2,2,3,3_tetraki'&-cis-dimercaptopurine oxime-isocyanate propylamine 2,2,3, 3 4 4 base shout or fluoropentyl ether. N,N-dimethyl-(2-isophorone isocyanate group j '5,=八2,2,3,3-tetrafluoropropyl ether and N,N-dimethyl-(2-isofoam) The structure of g-isocyside = aminoamine 2,2,3,3,4,4,5,5-octafluoropentyl ether is as follows: mercapto) C 15 201239007 36950twf.doc/n

Preferred are polyethylene glycol methyl ether isocyanate or polyvinyl pyrrolidone isocyanate. The above ruthenium-containing prepolymer can be reacted with other components to form various polyketone hydrogels. In the above method for producing a polyketone hydrogel, the above-mentioned ruthenium-containing prepolymer can be used as a reactant, and polymerization can be carried out by passing through an initiator, followed by curing. An appropriate amount of the poly-monomer-containing compound in the reaction mixture containing the above-mentioned cerium-containing prepolymer is used to effectively etch water, and the compatibility between the monomers is improved. In addition, optional further step-in-water monomer, cross-linking, diluent or combinations thereof may be optionally employed in the reaction mixture. The reaction mixture towel, the content of the (tetra) polymer and the polyaddition monomer is 5 to 99% by weight based on the total weight of the reaction, preferably 1 to 9 〇/6, more preferably 疋15 to 80% by weight. The weight ratio of the cerium-containing prepolymer to the polyorganism-containing monomer may be from 丨:G to 丨··99. The content of the hydrophilic monomer is from 5 to 9 % by weight based on the total weight of the mixture, preferably from 15 to 70% by weight, more preferably from 2 to 5 % by weight. The content of the cross-linking is 〇 to 5% by weight based on the total weight of the mixture, preferably (4) G to 3% by weight, and more preferably 0 to 2% by weight. The content of the diluent is 反应 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 The content of the ketone monomer is in an embodiment, and the content of the yttrium-containing prepolymer and the amount of the hydrophilic monomer is 30% by weight. The amount is calculated. Straight 罝, with a reaction mixture of 100 weights. The above-mentioned poly- _ _ 盘 ^ 基 基 _ _ _ 氧 oxypropyl 1 prepolymer, including 3- 醯 醯 ethoxyethyl phenyl tetra? 2;$夕^基)石夕烧闺)' propyl bismuth oxide, methyl =, methacryloyloxymethylpentamethyl methacrylate _ oxygen ^ 3 = yl-n-pentyl fluorenyl Wei Shao, methyl three-stone oxy-oxygen, hyperthyroidism, 酼t, two dilute oxime oxyethyl triisopropyl tetra^ ^ propylene oxiranyl oxyethyl n-propyl octamethyl tetra oxime & 'methyl propyl _ Oxymethyl group II (trimethyl 醯 醯 某 某 某 & & & & & 丙烯 丙烯 丙烯 丙烯 丙烯 丙烯 丙烯 丙烯 丙烯 丙烯 丙烯 丙烯 丙烯 丙烯 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The above hydrophilic monomer may be any hydrophilic monomer disclosed in the prior art for the manufacture of a hydrogel polymer. The hydrophilic monomer of the hydrogel biomaterial may be ethyl or propylene. The hydrophilic monomers include di-dimercaptopropylamine (DMA) and 2-ethylidene decyl acrylate (HEMA). ), glyceryl methacrylate, 2-hydroxyethyl decyl decylamine, N-vinyl pyrrolidone (NVP), polyethylene glycol methacrylate, methacrylic acid, acrylic acid or a combination thereof. According to the initiator of the polymerization reaction, the polymerization reaction can be induced by heating 17 201239007 36950twt.doc/n, or a combination thereof or other methods, for example, it can generate free radicals at medium and high temperatures, for example, Celsius to (9). For example, azobisisobutyronitrile (bronze), peroxidation, oxidized t-butyl pivalate, azobisisoheptyl, peroxidized twelfth or peroxidized (2-ethylhexanoic acid) Ding vinegar. #反应混合物 When the polymerization is carried out by ultraviolet light, the initiator can be a photoinducing initiator, including 2_ mercapto-2-methyl-1-phenyl-indole-acetone, double (2 , 4,6-trimethylbenzimidyl broad phenyl group, 1-hydroxycyclohexylphenylacetone, 2-(2,4,6-trimethylbenzylidene)diphenylphosphine oxide or 2,2-Dimethoxy-phenylacetamidine. Soil diluents include ethanol, 1-propanol, isopropanol, hydrazine-butanol, isobutanol, 2-butanol, 2-methyl-2. Propanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methylbutanol, 3-methyl-2-butanol '2-methyl-2-butanol, 2-methylbutyl Alcohol, = alcohol, 2-hexanol, 3-hexanol, 2-mercapto-1-pentanol, 3-mercapto-i-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-mercapto-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 3,3-dimercapto-i-butanol, 2-ethyl-1-butanol, i-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octyl alcohol, 1- Sterol or a combination thereof. In addition to the above-mentioned hair-containing prepolymer, a microparticle-containing monomer, a starter, a hydrophilic monomer, and a diluent, it is used to produce the polysulfide g-gel of the present invention. The reaction mixture of the biomaterial may also include other monomers (such as ultraviolet absorbing monomers), reactive pigments, non-reactive pigments, or a combination thereof. In addition, a processing aid such as a release agent or a wetting agent may also be included in the reaction mixture. After the reaction was carried out to form a polymer, the diluent and the various components which were not reacted at 201239007 36950 twf.doc/n were removed, and the formed polymer was hydrated to form a hydrogel. The solvent used in the manufacture of the hydrogel may be water or physiological saline' or may be selected according to the solubility characteristics of the (iv) diluent and the solubility characteristics of various components which are not reacted when the polymer is produced, for example, Ethanol, decyl alcohol, isopropanol or a mixture of the foregoing solvents and a mixture of water or physiological saline is used to prepare a water-soluble polyoxanthene hydrogel. The water content in the poly(tetra) hydrogel is from 20 to 70% by weight, preferably from 25 to 50% by weight, more preferably from 30 to 50% by weight, based on the total weight of the polyhydric hydrogel. The above polyglycol hydrogel can be made into various biological materials, such as contact lenses, ophthalmic dressings, and general surgical dressings (external ophthalmology materials or smart type materials). Polyporous hydrogels can be used. The desired shape is formed by various known methods, such as a rotary molding method or a molding method. Example 1: Synthesis of a ruthenium-containing prepolymer ' 〇 5 '5 Mo's dihydrooxy polydimethyl Shixi oxygen plant (PDMS di〇1) was dehydrated with 4A molecular sieve for 24 hours. After that, the dihydrogen-polydimethyl oxazepine after water removal was placed in a four-well reaction flask and bitten with tetrahydrogen. Dilute 10 times. After the addition, add 0.4 moles of diisocyanate toluene and 〇2 mol methacrylic acid isocyanoacetic acid, stir for 3 minutes with nitrogen. Then, add the total weight 〇 5 wt% tin 2-ethylhexanoate. In a 6〇t oil bath, then, by rotating the concentrated silk (4), a yellowish (four) liquid is obtained. Read, and then vacuum oven to remove low volatile substances Example 2: Synthesis of ruthenium-containing prepolymer 3.3 moles of dihydroxy oxypolydimethyl oxazepine (PDMS_di〇1) was placed in four holes with 19 201239007 36950twf.doc/n &^, when the water is removed, the dihydro oxidized dimethyl sulphur, in the w bottle, and diluted 10 times with tetrahydrofuran. Thereafter, M_T diisocyanate 3 and G.2 mol methacrylic acid Isocyanide = 曰 3 gas stirring for 30 minutes. Then, add a total weight of 05 weight tin. Stir in a 6 叱 oil bath, 48 hours, and then spin to obtain a yellowish transparent liquid. After that, then vacuum at 5G ° C The oven removes low volatile substances. Example 3: Modification of the ruthenium-containing prepolymer Take the above, 2 shixi prepolymer 〇1 molar is placed in a four-well reaction flask, and the corpse is diluted with tetrahydrofuran. () times. After that, add _ Mo Er 2 gas 5 · (trifluoromethyl) phenyl isocyanate, stir for 3 minutes with nitrogen. Then, add the total weight of G. 5 wt% dilauric acid After the thief oil bath was mixed for 48 hours, it was concentrated by a rotary concentrator, and then 5 〇 < 3 (: vacuum drying off low volatility. " Example 4: 矽-containing prepolymer modification The ruthenium-containing prepolymer of the above Example 1 was placed in a four-well reaction flask at 0.005 mol, and diluted 10-fold with tetrahydrofuran. Thereafter, 〇〇〇5 mol polyethylene glycol methyl ether isocyanate (MW: ~) was added. 750), nitrogen gas After stirring for 30 minutes, a total weight of 0.5% by weight of dibutyltin dilaurate was added. 6 (rc oil bath, stirred for 48 hours, concentrated by a rotary concentrator, and then removed in a vacuum oven to remove low volatility. Example 5 : Ophthalmic dressing or contact lens preparation 16.0% by weight of the cerium-containing prepolymer of Example 3 and methacryl oxime oxypropyl 201239007 36950 twf.doc/n bis (tridecyl decyl oxyalkyl) decane (TRIS) 18.0 % by weight, N, N• dimercapto acrylamide (DMA) 22.0% by weight, N-vinyl D ratio 嘻 _ (Ννρ) Π. 5 wt%, 1-nonanol 25. G wt%, Ethylene Alcohol dimercaptoacetic acid vinegar 0.5%|% and 2-n-yl-2-mercapto-1-phenyl-1·propionium with (m3) 1 〇% by weight mixed uniformly, with about 5mW/cm2 UVA The polymerization reaction was carried out for 9 minutes, and the unreacted monomer and the solvent were washed with alcohol, and then allowed to stand in physiological saline for 2 hours, and then sterilized at 31 °C for 30 minutes. < Example 6: General Surgical Dressing The modified yttrium-containing prepolymer of Example 4 was 5% by weight and thiol propylene oxypropyl bis(dimethyl oxalate) %, ν, Ν-dimercapto acrylamide 18.0% by weight, Ν-vinyl pyrrolidone 2 〇〇 weight 3_ decyl-1-pentanol 27.0% by weight, and azobisisobutyronitrile (ΑΙΒΝ) 1 〇% by weight The mixture was uniformly mixed, and polymerization was carried out at 100 ° C for 180 minutes, and then the unreacted monomer and the solvent were washed with isopropyl alcohol, and then placed in physiological chyme water for 2 hours, and then sterilized by (10) 3. minute. "Oxygen permeability material or contact lens obtained in Example 5 of the present invention has an oxygen permeability value (DK) > 50 'visible light transmittance> 90% 'water content (%)> The general surgical dressing prepared in Example 6 has an oxygen permeability value (DK) > 3 (), water content (%) > 30 °, and in summary, the cerium-containing prepolymer of the present invention can be used as Polyfluorene ketone water, a gel reactant, and the obtained poly phthalocyanine hydrogel has high oxygen permeability, tooth permeability, enthalpy elasticity and high moisture retention, and can be used as various biological materials, such as contact lenses. , ophthalmology, general surgical dressing (external ophthalmology outside the ophthalmology) or intelligent drug dressings and so on. 21 201239007 36950twf.doc/n Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any technical field of the present invention has a general knowledge, and the spirit and scope of the present invention may be changed. Retouching, the scope of protection of the invention shall be subject to the definition of the scope of the patent application. [Simple diagram description] None [Main component symbol description] None s 22

Claims (1)

201239007 36950twf.doc/n VII. Patent application scope: 1. A cerium-containing prepolymer whose structure is as follows: [Formula 1] γ Y Γ II 1 ZX— EX— C—N—A*—N —C—X— EX—Z Tll II ^ Ο 0 m where nl is an integer from 1 to 20; A represents a divalent aliphatic group or an aromatic group; Y represents Η or Η—Η—C=〇 Y is completely the same or completely different, or part Y is the same and partially Υ is different; Ry represents a fluorine-containing aromatic group, a fluorine-containing ether group, an ether group or an amine group-containing group; X represents Ο or -NRX-, Rx represents Η, or a carbon number of 1 to 5, or Η - C = 〇, where Ry is as defined above; all Rx are identical or completely Iso, or part of Rx is the same and part of Rx is different; and Z represents an alkenyl group. 2. The cerium-containing prepolymer according to claim 1, wherein: the monovalent aliphatic group or the aromatic group represented by A has a carbon number of i to 20; E represents a monovalent dream oxygen base, and its structure is as shown in the following formula 2: [Formula 2] - L - Q - Si - Ο - Si - Q - LI ml Re2 Re2 wherein Rel and Re2 each represent hydrogen, a monovalent alkyl group having a carbon number of 1 to 5, a flaming substituent or a group of a fluorine-containing substituent; Rel and Re2 may be the same or different; m is an integer from 0 to 40; Q represents a linear or branched divalent alkyl group having a carbon number of 1 to 10; and L represents a single bond, a fluorenyl group or an alkoxy group; The structure of Z is as shown in the following formula: [Formula 3] 丄-CH2CH2-〇4 /1 0 II /R2 -c-c 2 \ w ch2 wherein Rz represents hydrogen or a decyl group having a carbon number of 1 to 5; and n3 represents an integer of 〇 to 5. 3. The ruthenium-containing prepolymer as described in claim 1, wherein: the structure of L is as follows: f~fCnH2n〇^2 S 24 201239007 36950twf.doc/n where 〇 is bonded to Q; n is i An integer up to 10; and n2 is an integer from 〇 to 2〇. 4 a biomaterial of a polyfluorene ketone hydrogel, which comprises a reaction mixture and a substance I comprising a cut prepolymer as described in the patent application No. 1 to 3, wherein the reaction is The mixture also includes an initiator, and the selectivity further includes a polyfluorene containing monomer, a hydrophilic monomer, a diluent, or a combination thereof. 5. The biomaterial of the polyketone hydrogel of claim 4, wherein the weight ratio of the cerium-containing prepolymer to the polyfluorene-containing monomer is from 1:0 to 1:99. The biological material of the polyfluorene ketone hydrogel according to Item 4, wherein the content of the cerium-containing prepolymer and the poly-fluorene-containing monomer is 1. The content of the hydrophilic monomer is 5 to 9% by weight, the diluent contains 1 to 0 to 80% by weight, and the initial fine content is 〇〇5 to 5% by weight, calculated as 1% by weight of the reaction mixture. 7. The biomaterial of the poly-paste hydrogel according to the fourth aspect of the invention, wherein the poly-monomer comprises 3_f-based acryloyloxypropyl tris(di-decyl-Weiss) Wei, propylene Oxyethyl phenyl tetramethylene a certain hydrazine == propylene _ oxymethyl pentamethyl bismuth oxy-oxygen, methyl propyl oxymethyl ketone methyl celite oxy-oxygen, heptayl propylene oxy-oxyethyl three stone eve Oxygen, oxyethyltriisopropyltetramethyltricarb, thiopropyl propylene = ethyl n-propyl octamethyl tetraweix, methyl 醯 醯 甲基 甲基 ) ) ) Kidd, _ 醯 甲基 甲基 甲基 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Isobutyl, alkane. The earth material of the poly(tetra) hydrogel according to the fourth aspect of the invention, wherein the hydrophilic monomer comprises hydrazine, dimethyl dimethyl aryl amine 1 黯), 2-hydroxyethyl Methacrylic acid Μ Α 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 孓 孓 孓 孓 乙烯基 乙烯基 乙烯基 乙烯基 乙烯基 乙烯基 乙烯基 乙烯基 乙烯基 乙烯基 乙烯基. 9. The raw material for a poly-hydrogel according to claim 4, wherein the diluent comprises ethanol, i. propanol, isopropanol, diiso =, 2: butanol, 2-methyl _2_propanol, 1 rhyme, 2_pentanol, 3-pentanol, mercaptobutanol, 3_mercapto-2-butanol, 2-methyl-2-butanol, 2-methyl, hexyl Alcohol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl+pentanol, methylamine pentanol, 2-mercapto-2-pentanol, 3-methyl-2-pentyl Alcohol, 'methyl-2-alcohol di-2-mercapto-3-indolyl alcohol, 3-mercaptol pentanol, 3,3-dimethyl +butanol, ethyl·!·butanol, heptanol, 2_heptanol, 3 rhyme, 1-decyl alcohol or a combination thereof.千千子10. As stated in the scope of claim 4, == base)· stupyl phosphine oxide, h-cyclohexylphenyl propyl-, 2-(2,4 6_; methyl: methyl sulfhydryl) Diphenylphosphine oxide, 2,2-dimethoxy-phenyl ethyl ketone, iso-iso-nitrile, peroxygen, peroxidic neo-tert-butyl, azo, gamma, oxidized Or peroxidized (2•ethylhexanoic acid) tert-butyl vinegar. S material ten f special strip ^ item 4 敎 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 26 201239007 J6y3Utwt.doc/n 12. The biomaterial of the polyketone hydrogel as described in claim 4 is a contact lens, an ophthalmic dressing, a general surgical dressing or a smart drug dressing. 27 201239007 36950twf.doc/n y ijj—Η—O. Ry is defined the same above. All Rx's are identical or different. Or, some Rx,s are identical and some Rx's are different. Z represents a group containing CC double Bond. IV. Designated representative map: (1) Designated representative figure of the case: None (2) Simple description of the symbol of the representative figure: No. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: YY | | 1 ZxE—X--C—N—A—N—C—X—E—X—Z II || 0 0 n1