CN102690419B - Silicon-containing prepolymer and silicone hydrogel biomaterial containing same - Google Patents

Silicon-containing prepolymer and silicone hydrogel biomaterial containing same Download PDF

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CN102690419B
CN102690419B CN201210044457.3A CN201210044457A CN102690419B CN 102690419 B CN102690419 B CN 102690419B CN 201210044457 A CN201210044457 A CN 201210044457A CN 102690419 B CN102690419 B CN 102690419B
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詹前庆
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Abstract

The invention provides a silicon-containing prepolymer and a silicone hydrogel biomaterial containing the same, wherein the structure of the silicon-containing prepolymer is as follows:wherein n1 is an integer from 1 to 20; a represents a divalent aliphatic group or an aromatic group; y represents H orAll Y's are the same or different, or some Y's are the same and some Y's are different; ryRepresents a fluorine-containing aromatic group, an ether-containing group, a fluorine-containing ether group or an amine-containing group; x represents O or-NRx-，RxRepresents H, or a monovalent alkyl group having 1 to 5 carbon atoms, orWherein R isyIs as defined above; all of RxAre identical or completely different, or are part of RxIdentical and the moiety RxThe difference is that; and Z represents an alkene-containing group.

Description

Siliceous prepolymer and the silicone hydrogel biological material that contains this siliceous prepolymer
Technical field
The invention relates to a kind of prepolymer and hydrogel, and particularly relevant for a kind of siliceous prepolymer and silicone hydrogel.
Background technology
Hydrogel is a kind of hydrated cross-linked polymer, and character is soft, can keep certain shape, and can absorb a large amount of water.Hydrogel has oxygen-permeable and biological fitness conventionally, therefore, is applicable to very much for manufacturing biomaterial for medical purpose, and for example contact lens, ophthalmology apply material or general surgery applies material.
Traditional hydrogel is mainly prepared by the mixture that contains hydrophilic monomer, for example 2-HEMA (HEMA) or NVP (NVP).But the oxygen-permeable of the hydrogel that these are traditional is still not enough, made doctor's material is not suitable for wearing for a long time with hydrogel.
Advanced hydrogel is to make silicone hydrogel with silicone monomer, and the hydrogel that its oxygen-permeable is more traditional is high, yet silicone hydrogel but exists elasticity not enough, and made hydrogel cannot meet the comfortable demand of user.
Summary of the invention
The invention provides a kind of siliceous prepolymer, it can be as the reactant of silicone hydrogel.
The invention provides a kind of silicone hydrogel biological material, it has high oxygen permeability and snappiness.
The present invention proposes a kind of siliceous prepolymer, and its structure is as shown in the formula shown in one:
Figure BDA0000138216730000011
Wherein n1 is 1 to 20 integer; A represents aliphatic group or aromatic group; Y represent H or
Figure BDA0000138216730000012
Whole Y can be identical or completely different, or part Y is identical and part Y is different; R yrepresent fluorine-containing aromatic group, ether-containing group, fluorine-containing ether group or the group of amino-contained; X represent O or-NR x-, R xrepresent H, or carbon number is 1 to 5 univalent alkyl, or
Figure BDA0000138216730000021
R wherein ydefinition as above; Whole R xfor identical or completely different, or part R xidentical and part R xdifferent; And Z represents containing thiazolinyl group.
Described in one embodiment of the invention, the two valency aliphatic groups that above-mentioned A is represented or the carbon number of aromatic group are 1 to 20; The represented divalence siloxanes of E, its structure is as shown in the formula shown in two:
Figure BDA0000138216730000022
R wherein e1with R e2represent respectively that separately hydrogen, carbon number are 1 to 5 univalent alkyl, fluorine-containing substituent alkyl or ether; R e1with R e2can be identical or different; M is 0 to 40 integer; Q represents that carbon number is the divalent alkyl of 1 to 10 straight or branched; L represents singly-bound, ether or silane alcohol base; The structure of Z is as shown in the formula shown in three:
Figure BDA0000138216730000023
R wherein zrepresent that hydrogen or carbon number are 1 to 5 univalent alkyl; And n3 represents 0 to 5 integer.
Described in one embodiment of the invention, the structure of above-mentioned L is as follows
Figure BDA0000138216730000024
Wherein O and Q bond; N is 1 to 10 integer; And n2 is 0 to 20 integer.
The present invention also proposes a kind of silicone hydrogel biological material, it is to be made by the reaction mixture of above-mentioned siliceous prepolymer, wherein reaction mixture also comprises initiator, and selectivity further comprises containing silicone monomer, hydrophilic monomer, thinner or its combination.
Described in one embodiment of the invention, above-mentioned siliceous prepolymer and the above-mentioned weight ratio that contains silicone monomer are 1: 0 to 1: 99.
Described in one embodiment of the invention, above-mentioned siliceous prepolymer and above-mentioned content containing silicone monomer and be that the content of 5 to 99 % by weight, above-mentioned hydrophilic monomer is that the content of 5 to 90 % by weight, above-mentioned thinner is that the content of 0 to 80 % by weight and above-mentioned initiator is 0.05 to 5 % by weight, the above-mentioned reaction mixture of take calculates as 100 % by weight.
Described in one embodiment of the invention, the above-mentioned silicone monomer that contains comprises 3-methacryloyl oxygen propyl group three (trimethylsiloxane group) silane (TRIS), acrylyl oxy-ethyl phenyl tetramethyl disiloxane (phenyltetramethyldisiloxanylethyl acrylate), methacryloxypropyl methyl pentamethyl disiloxane (pentamethyldisiloxanylmethyl methacrylate), methacryloxypropyl methyl n-pentyl hexam ethylcyclotrisiloxane (n-pentylhexamethyltri siloxanylmethyl methacrylate), seven methylacryoyloxyethyl trisiloxanes (heptamethyltrisiloxanylethy acrylate), acrylyl oxy-ethyl triisopropyl tetramethyl-trisiloxanes (tri-i-propyltetramethyltrisiloxanylethyl acrylate), methylacryoyloxyethyl n-propyl octamethylcyclotetrasiloxane (n-propyloctamethyltetrasiloxanylpropyl methacrylate), methacryloxypropyl methyl two (trimethylsiloxy group) methyl-monosilane (methyldi (trimethylsiloxy)-methacryloxymethylsilane), acryloyl-oxy methyl triphenyl dimethyl sily oxide (triphenyldimethyldisiloxanylmethyl acrylate), acrylyl oxy-ethyl phenyl tetraethyl-sily oxide (phenyltetraethyldisiloxanylethyl methacrylate), acryloyl-oxy methyl-isobutyl hexam ethylcyclotrisiloxane (isobutylhexamethyltrisiloxanylmethyl methacrylate) or acrylyl oxy-ethyl isobutyl-tetramethyl disiloxane (t-butyltetramethyldisiloxanylethyl acrylate).
Described in one embodiment of the invention, above-mentioned hydrophilic monomer comprises N,N-DMAA (DMA), 2-HEMA (HEMA), glyceral methacrylate, 2-hydroxyethyl first acrylamide, NVP (NVP), poly-monomethyl vinylformic acid glycol ester, methacrylic acid, vinylformic acid or its combination.
Described in one embodiment of the invention, above-mentioned thinner comprises ethanol, 1-propyl alcohol, Virahol, n-butyl alcohol, isopropylcarbinol, 2-butanols, 2-methyl-2-propanol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 3-methyl butanol, 3-methyl-2-butanols, 2-methyl-2-butanols, 2-methyl butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 3-methyl-2-amylalcohol, 4-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-3-amylalcohol, 3, 3-dimethyl-1-butanol, 2-ethyl-n-butyl alcohol, 1-heptanol, 2-enanthol, 3-enanthol, 4-enanthol, 1-octanol, 1 nonyl alcohol or its combination.
Described in one embodiment of the invention; above-mentioned initiator comprises 2-hydroxy-2-methyl-1-phenyl-1-acetone, two (2; 4; 6-trimethylbenzoyl)-phenyl phosphine oxide, 1-hydroxy-cyclohexyl phenyl-acetone, 2-(2; 4; 6-trimethylbenzoyl) diphenyl phosphine oxide, 2,2-dimethoxy-Phenyl ethyl ketone, Diisopropyl azodicarboxylate (AIBN), benzoyl peroxide, tert-Butyl peroxypivalate, azo two different heptan fine, dilauroyl peroxide or peroxidation (2 ethyl hexanoic acid) tert-butyl ester.
Described in one embodiment of the invention, above-mentioned silicone hydrogel biological material is by above-mentioned reaction mixture irradiation or heated polymerizable forms or its combination.
Described in one embodiment of the invention, above-mentioned silicone hydrogel biological material is that contact lens, ophthalmology apply material, general surgery applies material or intelligent medicine applies material.
The siliceous prepolymer of the embodiment of the present invention, it can be as the reactant of silicone hydrogel.
The silicone hydrogel of the embodiment of the present invention, it has high oxygen permeability and snappiness.
For above-mentioned feature and advantage of the present invention can be become apparent, special embodiment below is described in detail below.
Embodiment
The present invention proposes a kind of siliceous prepolymer, and its structure is as shown in the formula shown in one:
A represents that carbon number is 1 to 20 two valency aliphatic group or aromatic groups.Aliphatic group can be straight-chain alkyl-sub-, branched alkylidene, cycloalkyl or two valency ketone groups, for example, be propylidene, butylidene, pentylidene, hexylidene, sub-heptyl, octylene or isophorone base (isophoronyl group).Aromatic group is two valency aralkyl for example, for example diphenylmethane group or tolyl.
In arbitrary embodiment, whole Y can be identical or completely different, or part Y is identical and part Y is different.In one embodiment, Y represents hydrogen (H).In another embodiment, Y can following chemical formulation
Figure BDA0000138216730000042
R wherein yrepresent fluorine-containing aromatic group, ether-containing group, fluorine-containing ether group or the group of amino-contained.R yin fluorine-containing, can reduce the ester matter of formed siliceous prepolymer and be stained with stickiness.Fluorine-containing aromatic group is the fluoro-5-of 2-(trifluoromethyl) phenyl or the fluoro-5-of 2-(methyl) phenyl for example.R yfor the group of ether-containing group or amino-contained, can improve the wetting ability of formed siliceous prepolymer.Ether-containing group is the co-polymer (PEG/PPG copolymer) of polyethylene glycol groups (PEG), polypropylene glycol base (PPG) or polyethylene/polypropylene glycol base for example.The group of amino-contained is polyvinylpyrrolidone--based (PVP) or poly-N,N-DMAA base (poly-DMA) for example.R yfor fluorine-containing ether group, can improve the wetting ability of formed siliceous prepolymer, also can reduce the ester matter of formed siliceous prepolymer and be stained with stickiness, N for example, N-dimethyl-(2-isophorone) Propylamino 2,2,3,3-tetrafluoro propyl ether base or N, N-dimethyl-(2-isophorone) Propylamino 2,2,3,3,4,4,5,5-octafluoro amyl ether base, its structure is as follows:
Figure BDA0000138216730000051
X represent O or-NR x-, in arbitrary embodiment, whole R xcan be identical or completely different, or part R xidentical and part R xdifferent.Its for example, R xrepresent H, or carbon number is 1 to 5 univalent alkyl, for example methyl or ethyl, or
R wherein ydefinition as above, in this, repeat no more.
E is the divalence siloxanes with lower array structure, and its structure is as shown in the formula shown in two:
Figure BDA0000138216730000053
R e1with R e2represent respectively separately hydrogen, or carbon number is 1 to 5 univalent alkyl, fluorine-containing substituent alkyl or ether.R e1with R e2can be identical or different.M is 0 to 40 integer, preferably 3 to 35 integer, more preferably 5 to 30 integer.Q represents that carbon number is the divalent alkyl of 1 to 10 straight or branched.L represents singly-bound (direct bond), ether or silane alcohol base.In one embodiment, ether can be alkane glycol-based (alkylene glycol group), and it can be expressed as
Figure BDA0000138216730000061
Wherein oxygen and Q bond.N is 1 to 10 integer, preferably 2 to 8 integer.N2 is 0 to 20 integer, preferably 0 to 18 integer, more preferably 0 to 15 integer.
N1 is 1 to 20 integer, preferably 1 to 12 integer, more preferably 1 to 6 integer.
Z be expressed as have following chemical formula containing thiazolinyl group, as the reaction end points of the raw doctor of the follow-up preparation of aforementioned silicon prepolymer material, its structure is as shown in the formula shown in three:
Figure BDA0000138216730000062
R wherein zrepresent hydrogen, or carbon number is 1 to 5 univalent alkyl, for example methyl or ethyl.N3 represents 0 to 5 integer.
In order to make the reactant of above-mentioned siliceous prepolymer, comprise:
O＝C＝N-A-N＝C＝O
HO-E-OH or NH 2-E-NH 2and
Figure BDA0000138216730000063
Wherein A, E and R zdefinition as mentioned above.
The aliphatic example of O=C=N-A-N=C=O comprises isophorone diisocyanate, 1,3-the third vulcabond (1,3-diisocyanatopropane), 1, the pungent vulcabond (1 of 8-, 8-diisocyanatooctane), 1,5-penta vulcabond (1,5-diisocyanatopentane), 1, hexamethylene-diisocyanate (1,6-diisocyanatohexane), 1,4-fourth vulcabond (Isosorbide-5-Nitrae-diisocyanatobutane) or isocycloheximide.Preferably Isosorbide-5-Nitrae-Ding vulcabond or isocycloheximide.The aromatic example of O=C=N-A-N=C=O comprises diphenylmethane diisocyanate or toluene di-isocyanate (TD.I).
The example of HO-E-OH comprises that two ends are the polydimethylsiloxane (Poly (dimethylsiloxane), bis (hydroxyalkyl) terminated) of hydroxyalkyl, for example:
Or polyethersiloxanediol (polyethyleneoxide-b-dimethylsiloxane-polyethylenoxide), for example:
Figure BDA0000138216730000072
NH 2-E-NH 2example comprise that two ends are the polydimethylsiloxane (Poly (dimethylsiloxane), bis (3-aminoalkyl) terminated) of amido alkyl, for example:
Figure BDA0000138216730000073
Example comprise methacrylic acid isocyanato ethyl ester, vinylformic acid isocyanato ethyl ester, methacrylic chloride or acrylate chloride.Preferably methacrylic acid isocyanato ethyl ester or methacrylic chloride.
When the Y of above-mentioned siliceous prepolymer represents H, in one embodiment, the synthetic method of above-mentioned siliceous prepolymer is for example, by above-mentioned three kinds of compositions of suitable proportion,
O＝C＝N-A-N＝C＝O：
HO-E-OH or NH 2-E-NH 2:
After equaling to dilute with thinner respectively for 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 with mole ratio, add in reaction vessel, thinner is tetrahydrofuran (THF), toluene, N,N-dimethylacetamide or its combination for example.Afterwards, add catalyzer, organotin for example, as 2 ethyl hexanoic acid tin, dibutyl tin laurate, oleic acid tin or dibutyl tin two-2-ethylhexoate; Or tertiary amine, as triethylamine, dimethylethanolamine, tetramethyl butane diamine, dimethylcyclohexylamine or Isosorbide-5-Nitrae-diazonium two ring (2,2,2) octanes, in for example 45 ℃～150 ℃ reactions of suitable temperature, make.In another embodiment, it can also be first first react O=C=N-A-N=C=O and HO-E-OH (or NH2-E-NH2) with the mole ratio of 2: 3 after, then add appropriate ratio
Figure BDA0000138216730000082
React.
When the Y of above-mentioned siliceous prepolymer represents
Figure BDA0000138216730000083
(R ydefinition as above) time, can be by the prepared siliceous prepolymer of aforesaid method (Y represents H) and R y-N=C=O reaction, to carry out upgrading.R ythe example of-N=C=O comprises methoxypolyethylene glycol isocyanate, the fluoro-5-of 2-(trifluoromethyl) phenyl isocyanate, the fluoro-5-of 2-(methyl) phenyl isocyanate, polyethylene/polypropylene glycol co-polymer isocyanate, polypropylene glycol isocyanate, polyvinylpyrrolidone isocyanate, poly-N, N-DMAA isocyanate, N, N-dimethyl-(2-isophorone diisocyanate base) Propylamino 2,2,3,3-tetrafluoro propyl ether or N, N-dimethyl-(2-isophorone diisocyanate base) Propylamino 2,2,3,3,4,4,5,5-octafluoro amyl ether.N, N-dimethyl-(2-isophorone diisocyanate base) Propylamino 2,2,3,3-tetrafluoro propyl ether and N, N-dimethyl-(2-isophorone diisocyanate base) Propylamino 2,2,3,3,4,4,5, the structure of 5-octafluoro amyl ether is as follows:
Figure BDA0000138216730000091
Preferably methoxypolyethylene glycol isocyanate or polyvinylpyrrolidone isocyanate.
Above-mentioned siliceous prepolymer can react with other composition makes various silicone hydrogels.The manufacture method of aforesaid silicone hydrogel can see through initiator and carry out polyreaction by above-mentioned siliceous prepolymer as reactant, is cured afterwards again.Interpolation appropriate in the reaction mixture that contains above-mentioned siliceous prepolymer, containing silicone monomer, effectively to adjust flexibility and the ventilation property of hydrogel, and improves the compatibility between each monomer.In addition, in reaction mixture, can also selectivity further comprise hydrophilic monomer, linking agent, thinner or its combination.In reaction mixture, siliceous prepolymer with containing the content of silicone monomer be 5 to 99 % by weight of reaction mixture gross weight, preferably 10 to 90 % by weight, more preferably 15 to 80 % by weight.Siliceous prepolymer can be 1: 0 to 1: 99 with the weight ratio containing silicone monomer.The content of hydrophilic monomer is 5 to 90 % by weight of reaction mixture gross weight, preferably 15 to 70 % by weight, more preferably 20 to 50 % by weight.The content of linking agent is 0 to 5 % by weight of reaction mixture gross weight, preferably 0 to 3 % by weight, more preferably 0 to 2 % by weight.The content of thinner is 0 to 80 % by weight of reaction mixture gross weight, preferably 0 to 50 % by weight, more preferably 0 to 35 % by weight.In one embodiment, the content that siliceous prepolymer and the content that containing the content of silicone monomer is 30 to 40 % by weight, hydrophilic monomer are 30 to 40 % by weight, thinner is that the content of 20 to 35 % by weight and initiator is 0.05 to 5 % by weight, and the reaction mixture of take calculates as 100 % by weight.
Above-mentioned different from above-mentioned siliceous prepolymer containing silicone monomer, it comprises 3-methacryloyl oxygen propyl group three (trimethylsiloxane group) silane (TRIS), acrylyl oxy-ethyl phenyl tetramethyl disiloxane, methacryloxypropyl methyl pentamethyl disiloxane, methacryloxypropyl methyl n-pentyl hexam ethylcyclotrisiloxane, seven methylacryoyloxyethyl trisiloxanes, acrylyl oxy-ethyl triisopropyl tetramethyl-trisiloxanes, methylacryoyloxyethyl n-propyl octamethylcyclotetrasiloxane, methacryloxypropyl methyl two (trimethylsiloxy group) methyl-monosilane, acryloyl-oxy methyl triphenyl dimethyl sily oxide, acrylyl oxy-ethyl phenyl tetraethyl-sily oxide, acryloyl-oxy methyl-isobutyl hexam ethylcyclotrisiloxane or acrylyl oxy-ethyl isobutyl-tetramethyl disiloxane.
Above-mentioned hydrophilic monomer can be the open hydrophilic monomer for the manufacture of aquogel polymer in any prior art.Hydrophilic monomer for the manufacture of silicone hydrogel biological material of the present invention can be containing vinyl or propylene.Hydrophilic monomer comprises N,N-DMAA (DMA), 2-HEMA (HEMA), glyceral methacrylate, 2-hydroxyethyl first acrylamide, NVP (NVP), poly-monomethyl vinylformic acid glycol ester, methacrylic acid, vinylformic acid or its combination.
Reaction mixture can be selected to heat or UV-light or its combination or other method are brought out polyreaction according to the initiator of polyreaction.Catalyzer for example can be under middle high temperature; for example 45 ℃ to 150 ℃ Celsius; produce radical person, for example Diisopropyl azodicarboxylate (AIBN), benzoyl peroxide, tert-Butyl peroxypivalate, azo two different heptan is fine, dilauroyl peroxide or peroxidation (2 ethyl hexanoic acid) tert-butyl ester.When reaction mixture is while bringing out polyreaction with UV-light; initiator can be photo-induced initiator; comprise 2-hydroxy-2-methyl-1-phenyl-1-acetone, two (2; 4; 6-trimethylbenzoyl)-phenyl phosphine oxide, 1-hydroxy-cyclohexyl phenyl-acetone, 2-(2; 4,6-trimethylbenzoyl) diphenyl phosphine oxide or 2,2-dimethoxy-Phenyl ethyl ketone.
Thinner comprises ethanol, 1-propyl alcohol, Virahol, n-butyl alcohol, isopropylcarbinol, 2-butanols, 2-methyl-2-propanol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 3-methyl butanol, 3-methyl-2-butanols, 2-methyl-2-butanols, 2-methyl butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 3-methyl-2-amylalcohol, 4-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-3-amylalcohol, 3, 3-dimethyl-1-butanol, 2-ethyl-n-butyl alcohol, 1-heptanol, 2-enanthol, 3-enanthol, 4-enanthol, 1-octanol, 1 nonyl alcohol or its combination.
Except above-mentioned siliceous prepolymer, containing silicone monomer, initiator, hydrophilic monomer and thinner, in order to manufacture in the reaction mixture of silicone hydrogel biological material of the present invention, can also comprise other monomer (as ultraviolet radiation absorption monomer), reactive colors, non-reacted pigment or its combination.In addition, in reaction mixture, also can comprise processing auxiliary agent, for example releasing agent or wetting agent.
After reacting formation polymkeric substance, with removal of solvents thinner and responseless various composition, then by formed polymer hydration, to form hydrogel.The solvent that manufacture hydrogel is used can be water or normal saline solution, or the dissolubility property of thinner and the dissolubility property of responseless various compositions that when first foundation is manufactured polymkeric substance, use are selected suitable organic solvent, the mixture of ethanol, methyl alcohol, Virahol or aforementioned solvents and water for example, again with pure water or normal saline solution extraction, to manufacture the silicone hydrogel of water swelling.Water content in silicone hydrogel is 20 to 70 % by weight of silicone hydrogel gross weight, preferably 25 to 65 % by weight, more preferably 30 to 50 % by weight.
Above-mentioned silicone hydrogel can be made various biomaterials, and for example contact lens, ophthalmology apply material, general surgery applies material (surgery beyond ophthalmology applies material) or intelligent medicine applies material.Silicone hydrogel can see through various known methods and form required shape, for example rotary die filling method or mould note method.
Example 1: siliceous prepolymer synthetic
Getting the two hydroxy polydimethylsiloxanes (PDMS-diol) of 0.5 mole dewaters 24 hours with 4A molecular sieve.Afterwards, the two hydroxy polydimethylsiloxanes after dewatering are placed in to four hole reaction flasks, and with 10 times of tetrahydrofuran (THF) dilutions.Then, add 0.4 mole toluene di-isocyanate (TD.I) and 0.2 mole methacrylic acid isocyano-ethyl ester, logical nitrogen gas stirring 30 minutes.Then the 2 ethyl hexanoic acid tin that, adds 0.5 % by weight of gross weight.With 60 ℃ of oil baths, stir 48 hours, then remove solvent with rotation thickner, obtain micro-yellow transparent liquid.Remove low volatility materials afterwards, then with 50 ℃ of vacuum drying ovens.
Example 2: siliceous prepolymer synthetic
Getting the two hydroxy polydimethylsiloxanes (PDMS-diol) of 0.3 mole dewaters 24 hours with 4A molecular sieve.Two hydroxy polydimethylsiloxanes after dewatering are placed in to four hole reaction flasks, and with 10 times of tetrahydrofuran (THF) dilutions.Afterwards, add 0.2 mole Isosorbide-5-Nitrae-Ding vulcabond and 0.2 mole methacrylic acid isocyano-ethyl ester, logical nitrogen gas stirring 30 minutes.Then the 0.5 % by weight 2 ethyl hexanoic acid tin that, adds gross weight.With 60 ℃ of oil baths, stir 48 hours, more concentrated with rotation thickner, obtain micro-yellow transparent liquid.Remove low volatility materials afterwards, then with 50 ℃ of vacuum drying ovens.
Example 3: the upgrading of siliceous prepolymer
Siliceous prepolymer 0.1 mole of getting above-mentioned example 2 is placed in four hole reaction flasks, and with 10 times of tetrahydrofuran (THF) dilutions.Afterwards, add the fluoro-5-of 0.01 mole 2-(trifluoromethyl) phenyl isocyanate, logical nitrogen gas stirring 30 minutes.Then the 0.5 % by weight dibutyl tin laurate that, adds gross weight.60 ℃ of oil baths, stirred after 48 hours, concentrated to rotate thickner, then removed low volatility materials with 50 ℃ of vacuum drying ovens.
Example 4: the upgrading of siliceous prepolymer
Siliceous prepolymer 0.005 mole of getting above-mentioned example 1 is placed in four hole reaction flasks, and with 10 times of tetrahydrofuran (THF) dilutions.Afterwards, add 0.005 mole methoxypolyethylene glycol isocyanate (MW :～750), lead to nitrogen gas stirring 30 minutes.Then the 0.5 % by weight dibutyl tin laurate that, adds gross weight.60 ℃ of oil baths, stirred after 48 hours, concentrated to rotate thickner, then removed low volatility materials with 50 ℃ of vacuum drying ovens.
Example 5: ophthalmology applies material or contact lens are made
By siliceous prepolymer 16.0 % by weight of example 3 and methacryloyl oxygen propyl group three (trimethylsiloxane group) silane (TRIS) 18.0 % by weight, N, N-DMAA (DMA) 22.0 % by weight, NVP (NVP) 17.5 % by weight, 1 nonyl alcohol 25.0 % by weight, ethylene glycol dimethacrylate 0.5 % by weight and 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173) 1.0 % by weight mix, with about 5mW/cm2 UVA, carry out polyreaction 90 minutes, after unreacted monomer and solvent being cleaned with alcohol again, be placed in normal saline solution standing 2 hours, again with 121 ℃ of sterilizings 30 minutes.
Example 6: general surgery applies material
By siliceous prepolymer 15.0 % by weight of the upgrading of example 4 and methacryloxypropyl three (trimethylsiloxane group) silane 19.0 % by weight, N, N-DMAA 18.0 % by weight, NVP 20.0 % by weight, 3-methyl-1-pentene alcohol 27.0 % by weight and Diisopropyl azodicarboxylate (AIBN) 1.0 % by weight mix, at 100 ℃, carry out polyreaction 180 minutes, after unreacted monomer and solvent being cleaned with Virahol again, be placed in normal saline solution standing 2 hours, then with 121 ℃ of sterilizings 30 minutes.
The prepared ophthalmology of the inventive example 5 applies material or its oxygen value of contact lens (DK) > 50, visible ray penetration > 90%, water content (%) > 40; The prepared general surgery of the inventive example 6 applies its oxygen value of material (DK) > 30, water content (%) > 30.
In sum, siliceous prepolymer of the present invention, it can be as the reactant of silicone hydrogel, and prepared silicone hydrogel has high oxygen permeability, high-penetration degree, snappiness and humectant, can be as various biomaterials, for example contact lens, ophthalmology apply material, general surgery applies material (surgery beyond ophthalmology applies material) or intelligent medicine applies material etc.
Finally it should be noted that: each embodiment, only in order to technical scheme of the present invention to be described, is not intended to limit above; Although the present invention is had been described in detail with reference to aforementioned each embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or some or all of technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.

Claims (11)

1. a siliceous prepolymer, its structure is as shown in the formula shown in one:
Figure FDA0000393536120000011
Wherein:
N1 is 1 to 20 integer;
A represents that carbon number is 1 to 20 aliphatic divalent group or aromatic group;
Y represent H or
Figure FDA0000393536120000012
Whole Y is identical or completely different, or part Y is identical and part Y is different; R ythe group that represents fluorine-containing aromatic group, fluorine-containing ether group, ether-containing group or amino-contained;
X represent O or-NR x-, R xrepresent H, or carbon number is 1 to 5 univalent alkyl, or
R wherein ydefinition as above;
Whole R xfor identical or completely different, or part R xidentical and part R xdifferent;
The represented divalence siloxanes of E, its structure is as shown in the formula shown in two:
[formula two]
Figure FDA0000393536120000014
R wherein e1with R e2represent respectively that separately hydrogen, carbon number are 1 to 5 univalent alkyl, fluorine-containing substituent alkyl or ether;
R e1with R e2can be identical or different;
M is 0 to 40 integer;
Q represents that carbon number is the divalent alkyl of 1 to 10 straight or branched;
L represents singly-bound, ether or silane alcohol base; And
Z represents that its structure is as shown in the formula shown in three containing thiazolinyl group:
[formula three]
R wherein zrepresent that hydrogen or carbon number are 1 to 5 univalent alkyl; And
N3 represents 0 to 5 integer.
2. siliceous prepolymer according to claim 1, wherein:
The structure of L is as follows
Figure FDA0000393536120000022
Wherein O and Q bond; N is 1 to 10 integer; And n2 is 0 to 20 integer.
3. a silicone hydrogel biological material, it is to make as claim 1 to the reaction mixture of the siliceous prepolymer as described in arbitrary in claim 2 by comprising, wherein this reaction mixture also comprises initiator, and selectivity further comprises containing silicone monomer, hydrophilic monomer, thinner or its combination.
4. silicone hydrogel biological material according to claim 3, wherein this siliceous prepolymer with should be 1:0 to 1:99 containing weight ratio of silicone monomer.
5. silicone hydrogel biological material according to claim 3, wherein this siliceous prepolymer with should and be that the content of 5 to 99 % by weight, this hydrophilic monomer is that the content of 5 to 90 % by weight, this thinner is that the content of 0 to 80 % by weight and this initiator is 0.05 to 5 % by weight containing the content of silicone monomer, take this reaction mixture to calculate as 100 % by weight.
6. silicone hydrogel biological material according to claim 3, wherein should comprise 3-methacryloyl oxygen propyl group three (trimethylsiloxane group) silane containing silicone monomer, acrylyl oxy-ethyl phenyl tetramethyl disiloxane, methacryloxypropyl methyl pentamethyl disiloxane, methacryloxypropyl methyl n-pentyl hexam ethylcyclotrisiloxane, seven methylacryoyloxyethyl trisiloxanes, acrylyl oxy-ethyl triisopropyl tetramethyl-trisiloxanes, methylacryoyloxyethyl n-propyl octamethylcyclotetrasiloxane, methacryloxypropyl methyl two (trimethylsiloxy group) methyl-monosilane, acryloyl-oxy methyl triphenyl dimethyl sily oxide, acrylyl oxy-ethyl phenyl tetraethyl-sily oxide, acryloyl-oxy methyl-isobutyl hexam ethylcyclotrisiloxane or acrylyl oxy-ethyl isobutyl-tetramethyl disiloxane.
7. silicone hydrogel biological material according to claim 3, wherein this hydrophilic monomer comprises N,N-DMAA (DMA), 2-HEMA (HEMA), glyceral methacrylate, 2-hydroxyethyl first acrylamide, NVP (NVP), poly-monomethyl vinylformic acid glycol ester, methacrylic acid, vinylformic acid or its combination.
8. silicone hydrogel biological material according to claim 3, wherein this thinner comprises ethanol, 1-propyl alcohol, Virahol, n-butyl alcohol, isopropylcarbinol, 2-butanols, 2-methyl-2-propanol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 3-methyl butanol, 3-methyl-2-butanols, 2-methyl-2-butanols, 2-methyl butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 4-methyl-1-pentene alcohol, 2-methyl-2-amylalcohol, 3-methyl-2-amylalcohol, 4-methyl-2-amylalcohol, 2-methyl-3-amylalcohol, 3-methyl-3-amylalcohol, 3, 3-dimethyl-1-butanol, 2-ethyl-n-butyl alcohol, 1-heptanol, 2-enanthol, 3-enanthol, 4-enanthol, 1-octanol, 1 nonyl alcohol or its combination.
9. silicone hydrogel biological material according to claim 3; wherein this initiator comprises 2-hydroxy-2-methyl-1-phenyl-1-acetone, two (2; 4; 6-trimethylbenzoyl)-phenyl phosphine oxide, 1-hydroxy-cyclohexyl phenyl-acetone, 2-(2; 4; 6-trimethylbenzoyl) diphenyl phosphine oxide, 2,2-dimethoxy-Phenyl ethyl ketone, Diisopropyl azodicarboxylate, benzoyl peroxide, tert-Butyl peroxypivalate, azo two different heptan fine, dilauroyl peroxide or peroxidation (2 ethyl hexanoic acid) tert-butyl ester.
10. silicone hydrogel biological material according to claim 3, is by this reaction mixture irradiation or heated polymerizable forms or its combination.
11. silicone hydrogel biological materials according to claim 3, described material is that contact lens, ophthalmology apply material, general surgery applies material or intelligent medicine applies material.
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