CN105418858A - Silicon hydrogel material having high oxygen permeability, corneal contact lens, and preparation method thereof - Google Patents
Silicon hydrogel material having high oxygen permeability, corneal contact lens, and preparation method thereof Download PDFInfo
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- CN105418858A CN105418858A CN201510982242.XA CN201510982242A CN105418858A CN 105418858 A CN105418858 A CN 105418858A CN 201510982242 A CN201510982242 A CN 201510982242A CN 105418858 A CN105418858 A CN 105418858A
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/02—Lenses; Lens systems ; Methods of designing lenses
- G02C7/04—Contact lenses for the eyes
- G02C7/049—Contact lenses having special fitting or structural features achieved by special materials or material structures
Abstract
The invention discloses a silicon hydrogel material having high oxygen permeability. The silicon hydrogel material is prepared, through a polymerization reaction, from following components including, by mass, 10-40 parts of an amphipathic macro-molecular silicon monomer, 10-30 parts of a small-molecular silicon monomer, 40-80 parts of a hydrophobic monomer, 0-30 parts of an organic solvent, and an initiator and a crosslinking agent. The silicon hydrogel material and a corneal contact lens have the high oxygen permeability, are low in cost and are easy to prepare.
Description
Technical field
The present invention relates to silicone-hydrogel material, specifically, relate to a kind of the silicone-hydrogel material, contact lens and preparation method thereof with high oxygen permeability.
Background technology
From the fifties in last century, contact lens just engender in market, for correcting defects of vision, and the aesthetic feeling of protection eyeball or increase eyes.Along with the development of science and technology, contact lens also achieve by hard material to the development being more suitable for the flexible material that people's eyeball is worn.
Lens materials occur the earliest be hard corneal contact lens.Because its material is partially hard, the shortcomings such as wettability is poor, and oxygen flow is low, easily cause the sense of discomfort of eyeball, at present not as main commercially available eyeglass when wearing.Develop soft contact lens gradually subsequently, hydrophilic material and non-hydrophilic material can be divided into again.Hydrophilic contact lens mainly by hydrophilic monomer as the copolymerization such as hydroxyethyl methylacrylate (HEMA) form, such as Benz Research And Development Corp. (CN101855258A) describes a kind of by methacrylic acid 2,3-bis-hydroxypropyl acrylate is as hydrophilic segment, and methacrylic acid 2-methoxy acrylate is as the polymkeric substance of hydrophobic part.The advantage of this type of material is that wetting ability is strong, oxygen carrying content can be increased by improving water ratio, wear comfortable in short period, but the covering due to contact lens greatly reduces the contact of oxygen in eyeball and air, and along with the prolongation of wear-time, in High water cut eyeglass, moisture volatilizees gradually, and oxygen carrying content will be greatly affected, eyeglass can not permeate again the oxygen that the metabolism of eye cornea normal physiological needs for a long time simultaneously, thus easily causes ophthalmic diseases.The main raw of non-hydrophilic stealth is fluorosiloxane copolymer.The oxygen that the snappiness of siloxanes long-chain and loose structure directly can be transmitted in air arrives eyeball, make the oxygen permeability of higher than traditional hydrophilic material more than 8 times of this type of material, break traditional hydrophilic material takes oxygen limitation by water, but this type of material height hydrophobic, very easily adsorb the protein in tear, and quality is comparatively hard, and comfort is poor.
Between the deficiency of above material, scientists is devoted to find preferred lens materials.Silicone-hydrogel combines the advantage of silastic material height oxygen flow and hydrogel material strong hydrophilicity, is current most potential soft contact lens material.Siloxanes long-chain forms the external phase of " cellular " structure, for oxygen transmission provides good passage, becomes hydrogel after hydrophilic segment is swelling, for wearer provides good comfortableness.This material can meet the requirement of wearing continuously, and some silicone-hydrogel contact lenss can wear several weeks continuously, even one month, replaces traditional pure water swelling type gel lens gradually, and is expected to obtain larger market.
But still there is a lot of problem in current silicone-hydrogel material.The hydrophobic nature of material easily adsorbs the protein such as the lysozyme in tear, and easily sticks on eyeball and affect freely rotating of contact lens.For addressing this problem, directly become at the modifying surface of material the important directions improving lens performance.The comparatively widespread use of oxygen plasma treatment technology, its cardinal principle embeds the strong group of some wetting abilities by active centre to polydimethylsiloxane (PDMS) surface, as-OH ,-COOH.The low-temperature plasma coating that a kind of antibiont film of the Introduction To Cn Patent of publication number CN104204099A is formed, utilizes a kind of liquid contact apparatus at low temperatures by plasma technique, to form the microbial film of a kind of anti-bacteria attachment.But this kind for the treatment of process adds production line balance technique, and this surface hydrophilicity can not forever be kept due to the transporting action of chain.
In addition, surface grafting is also an important and surface modification for practicality.The Chinese patent of publication number CN1583834A discloses a kind of silicon rubber of surperficial permanent hydrophilic, main method is that the reaction of the diol monomer such as si-h bond and allyl polyglycol is generated Si-C covalent linkage, thus modification silastic surface, the polyoxyethylene glycol of macromolecular chain can form one deck tight zone on PDMS surface, not only maintains the wetting ability of height but also effectively can reduce the absorption of protein.But this type of technique is all comparatively complicated, needs secondary to produce, first generates preformed SiHy contact lens, and then hydrophilic monomer on secondary crosslinking.
In recent years, scientific workers are devoted to the hydrophilicity improving material body, main method is by the polydimethylsiloxane containing methacrylic ester end-blocking and the copolymerization of strongly hydrophilic biocompatibility group monomer, the network structure that formation silicon rubber phase and hydrogel run through mutually, but there is many problems equally.
First, the polysiloxane macromonomer chain of the methacrylic acid blocked that molecular weight several thousand is even up to ten thousand has very strong hydrophobic nature, mix mutually with various methacrylic ester or vinyl hydrophilic monomer, obtain the solution that consistency is good, thus the obtained eyeglass not a duck soup of transmittance more than 97%, being separated that incompatible between hydrophilic monomer and hydrophobic monomer causes is the difficult problem that this type of eyeglass makes.The people such as ShuahuaPeng (SOFTMATTER, 2012,40:10493-10501) list water, the polydimethylsiloxane of methacrylic acid blocked, the phasor of nonionic surfactant (TericG9A8) three through research, result shows only when oil water phase reaches suitable ratio, water-in-oil or oil-in-water single phase region could be formed, otherwise muddy phase-splitting.For this problem, scientists has to develop amphipathic increase-volume monomer to improve the consistency of mixing solutions, and then improves the light transmission of eyeglass.The exploitation of usual amphipathic increase-volume monomer is not easily and costliness.Suitable organic solvent is also added in formula as simple compatibilizing agent, and appropriate solvent can improve the consistency of eyeglass really preferably, but adding of solvent also destroys original network structure, reduces intensity and the toughness of final lens product.
Except above copolymerization process, it is also conventional method that macromole organosilane monomer and macromole hydrophilic monomer form inierpeneirating network structure.Hydrophilic macromolecule for the formation of network structure has molecular weight several ten thousand to the Polyvinylpyrolidone (PVP), polyvinyl alcohol, polymethyl acrylic acid-β hydroxyl ethyl ester etc. of hundreds of thousands of.Rely on and be mutually wound network structure between long molecular chain, in water or after soaking for some time in physiological saline, hydrogel mutually will slowly stripping, can not ensure lasting wetting ability, more can not ensure the stability of drug release.
Secondly, the performed polymer synthesis of part silicone-hydrogel is quite loaded down with trivial details, complex manufacturing technology.The people such as such as JohnChristopherPhelan (US20100120938A1) have developed a kind of silicon-containing hydrogel, macromole is the amphiphilic monomer with siloxanes long-chain, and containing hydrophilic monomer as methyl methacrylate provides good water content, provide good biocompatibility containing NVP.But monomer synthesize is comparatively complicated, needs the synthesis of substep catalyst and ultraviolet lighting, be not suitable for industrialization scale operation.
Therefore, still there is high oxygen flow to contact lens at present, wetting ability is strong, low elastic modulus, high-clarity, high-biocompatibility, and technique is simple, is easy to the difficult problems such as scale operation.
Summary of the invention
Technical problem: embodiment of the present invention technical problem to be solved is: provide a kind of silicone-hydrogel material, contact lens and preparation method thereof, this silicone-hydrogel material and contact lens have high oxygen permeability, and with low cost, and preparation is simple.
Technical problem: for solving the problems of the technologies described above, the technical scheme that the embodiment of the present invention adopts is:
First aspect, the present embodiment provides a kind of silicone-hydrogel material with high oxygen permeability, and this silicone-hydrogel material, according to mass fraction, comprises following component polyreaction and forms:
Initiator and linking agent;
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
In conjunction with first aspect, as the scheme that the first may be implemented, described amphiphilic macromolecular silicon monomer has the molecular formula of following structure:
or
Wherein, the structural formula of X is as follows:
Wherein, the span of a is the integer of 1 ~ 14, and the span of b is the integer of 1 ~ 6, and the span of c is the integer of 13 ~ 68.
In conjunction with first aspect, as the scheme that the second may be implemented, described small molecules silicon monomer comprises one in methacryloxypropyl three (trimethylsiloxane group) silane, methyl-two (trimethicone)-silylpropyl glyceral methacrylate (SIGMA), 3-(methacryloxypropyl) propyl trimethoxy silicane, methacryloxymethyl three (trimethylsiloxy group) silane or arbitrary combination.
In conjunction with first aspect, as the scheme that the third may be implemented, described hydrophilic monomer is NVP (NVP), two or more combinations of substances any in methacrylic acid (MMA), hydroxyethyl methylacrylate (HEMA), N-vinyl-N methylacetamide (VMA), N-vinyl acetamide (NVA) forms.
In conjunction with first aspect, as the 4th kind of scheme that may implement, described initiator is light trigger or thermal initiator; Described light trigger is 2-hydroxy-2-methyl Propiophenone (D1173), and thermal initiator is one in Diisopropyl azodicarboxylate (AIBN) and benzoyl peroxide (BPO) or combination.
In conjunction with first aspect, as the 5th kind of scheme that may implement, described linking agent is one in polyethyleneglycol diacrylate (PEGDA), Ethylene glycol dimethacrylate (EGDMA) or triallyl isocyanurate (TAIC) or arbitrary combination.
In conjunction with first aspect, as the 6th kind of scheme that may implement, described organic solvent is one in Virahol, ethanol, n-hexyl alcohol, propyl carbinol or arbitrary combination.
Second aspect, the present embodiment provides a kind of contact lens, and this contact lens is obtained by silicone-hydrogel material, and this silicone-hydrogel material, according to mass fraction, comprises following component polyreaction and forms:
Initiator and linking agent;
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
In conjunction with second aspect, as the 7th kind of scheme that may implement, described silicone-hydrogel material, according to mass fraction, comprises following component polyreaction and forms:
Initiator and linking agent;
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 2% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.5 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
The third aspect, the present embodiment provides a kind of preparation method of contact lens, this preparation method comprises following process: each component mixed, inject contact lens mould, light-initiated or thermal-initiated polymerization, the then demoulding, unconverted monomer and oligopolymer in deionized water extraction removing eyeglass, immerse in physiological saline and balance, obtained contact lens; Wherein, described each component comprises following component according to mass fraction:
Initiator and linking agent;
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
Beneficial effect: compared with prior art, the technical scheme of the embodiment of the present invention has following beneficial effect: the contact lense of the embodiment of the present invention has the oxygen permeability of higher than traditional soft contact lens more than 8 times, belong to high oxygen permeable type contact lens, there is excellent light transmission simultaneously, good elongation and good water content, meet the standard of wearing.Technique is simple in process of production, produces without the need to secondary, more cost-saving and labor force compared with the eyeglass of the good hydrophilic property simultaneously of high oxygen flow in the market.The contact lens made by above silicone-hydrogel has good oxygen-permeable and wetting ability, and eyeglass can be worn without the need to surface treatment simultaneously.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in detail.
Embodiment 1
A kind of silicone-hydrogel material with high oxygen permeability that the present embodiment provides, according to mass fraction, comprises following component polyreaction and forms:
Initiator and linking agent;
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
In above-described embodiment 1, macrosilicone monomer has the molecular formula of following structure:
Or
Wherein, the structural formula of X is as follows:
Wherein, the span of a is the integer of 1 ~ 14, and the span of b is the integer of 1 ~ 6, and the span of c is the integer of 13 ~ 68.
The silicone-hydrogel material of embodiment 1 has good oxygen permeability, has the oxygen value of at least 50barrer, even has the oxygen value higher than 150barrer.In the silicone-hydrogel material of embodiment 1, macrosilicone monomer has dimethyl siloxane long-chain.Because dimethyl siloxane long-chain has longer silica bond distance, higher silica bond energy, and the bond angle of Si-O-Si key can change within the scope of 104 °-180 °, simultaneously, due to the repulsive interaction between methyl and main chain, dimethyl siloxane long-chain is made to present loose soft characteristic.This structure provides excellent passage to oxygen transmission, and the oxygen that can directly transmit in air arrives eyeball.Linear dimethyl siloxane chain structure is loosened, and free volume is large, and when molecular weight is larger, organosilicon forms the continuous microfacies district of " cellular " structure, is conducive to the transmission of oxygen.Meanwhile, in macrosilicone monomer, embedded in PEG chain, improve the consistency of macrosilicone monomer and hydrophilic monomer.When PEG chain is longer, macrosilicone monomer and hydrophilic monomer consistency better, do not need to add organic solvent.When PEG chain is shorter, macrosilicone monomer and hydrophilic monomer compatibility poor, need to add organic solvent, to keep the light transmission of eyeglass.
As preference, described small molecules silicon monomer comprises one in methacryloxypropyl three (trimethylsiloxane group) silane (TRIS), methyl-two (trimethicone)-silylpropyl glyceral methacrylate (SIGMA), 3-(methacryloxypropyl) propyl trimethoxy silicane (KH570), methacryloxymethyl three (trimethylsiloxy group) silane (MTTS) or arbitrary combination.Described hydrophilic monomer is NVP (NVP), two or more combinations of substances any in methacrylic acid (MMA), hydroxyethyl methylacrylate (HEMA), N-vinyl-N methylacetamide (VMA), N-vinyl acetamide (NVA) forms.Described initiator is light trigger or thermal initiator.When initiator is light trigger, select 2-hydroxy-2-methyl Propiophenone (D1173) as light trigger.When initiator is thermal initiator, selects the one in Diisopropyl azodicarboxylate (AIBN) and benzoyl peroxide (BPO) or combine as thermal initiator.Described linking agent is one in polyethyleneglycol diacrylate (PEGDA), Ethylene glycol dimethacrylate (EGDMA) or triallyl isocyanurate (TAIC) or arbitrary combination.Described organic solvent is one in Virahol, ethanol, n-hexyl alcohol, propyl carbinol or arbitrary combination.
The method of the amphiphilic macromolecular silicon monomer in preparation embodiment 1 has multiple.Preferred following two kinds of methods in the present embodiment.First method: by hydroxy-end capped polydimethylsiloxane and the isocyanic ester (IEM) with methacrylic end group, under the effect of catalyzer, in 20 ~ 80 DEG C of temperature ranges, reaction generates siloxane oligomer.Concrete chemical equation is as follows:
Second method: by hydroxy-end capped polydimethylsiloxane and glycidyl ester (GMA), under the effect of catalyzer, in 20 ~ 80 DEG C of temperature ranges, reaction generates siloxane oligomer.Concrete chemical equation is as follows:
Wherein, the structural formula of X is as follows:
In above-mentioned two kinds of preparation methods, catalyzer is dibutyl tin laurate, trifluoromethanesulfonic acid, triethylamine or tetrabutylammonium chloride.
Exemplify six specific exampless below.
Example 1
Get 13g glycol (structural formula is as shown in the formula shown in W1), 20mL trichloromethane, 0.1g catalyst dibutyltin dilaurylate, 3.1g isocyanatoethyl (IEM), mixes, 50 DEG C of reflux 10h.Reaction terminates rear petroleum ether, stratification, takes off a layer liquid pressure-reducing distillation, obtains transparent amphiphilic macromolecular silicon monomer, be designated as M1-W1.
Example 2
Get 13g glycol (structural formula is as shown in above formula W1), 30mL tetrahydrofuran (THF), 2.8g glycidyl methacrylate (GMA), 0.5g trifluoromethanesulfonic acid, magnetic agitation, 60 DEG C of back flow reaction 30min, reaction terminates rear underpressure distillation, obtain transparent amphiphilic macromolecular silicon monomer, be designated as M2-W1.
Example 3
Get 65.2g glycol (structural formula is as shown in the formula shown in W2), 20mL chloroform, 0.3g triethylamine, 3.1g isocyanatoethyl (IEM) mixes, 65 DEG C of heating reflux reaction 3h.Reaction terminates rear petroleum ether gained liquid, stratification, takes off a layer liquid pressure-reducing distillation, obtains transparent amphiphilic macromolecular silicon monomer, be designated as M1-W2.
Example 4
Get 65.2g glycol (structural formula is as shown in above formula W2), 2.8g glycidyl methacrylate (GMA), 0.5g tetrabutylammonium chloride, magnetic agitation, room temperature back flow reaction 5h, underpressure distillation, obtain transparent amphiphilic macromolecular silicon monomer, be designated as M2-W2.
Example 5
Get 38.8g glycol (structural formula is as shown in the formula shown in W3), 20mL trichloromethane, 0.2g catalyst dibutyltin dilaurylate, 3.1g isocyanatoethyl (IEM), mixes, 50 DEG C of reflux 10h.Reaction terminates rear petroleum ether, stratification, takes off a layer liquid pressure-reducing distillation, obtains transparent amphiphilic macromolecular silicon monomer, be designated as M1-W3.
Example 6
Get 38.8g glycol (structural formula is as shown in above formula W3), 2.8g glycidyl methacrylate (GMA), 0.2g tetrabutylammonium chloride, magnetic agitation, room temperature back flow reaction 5h, underpressure distillation, obtain transparent amphiphilic macromolecular silicon monomer, be designated as M2-W3.
Embodiment 2
A kind of contact lens, this contact lens is obtained by silicone-hydrogel material, and this silicone-hydrogel material, according to mass fraction, comprises following component polyreaction and forms:
Initiator and linking agent;
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
The contact lens of embodiment 2 has front surface and rear surface, and front surface and rear surface are all not modified.In the present invention, organosilicon phase and hydrogel intersect and run through, and the wetting ability of hydrogel material makes the lipid in tears not easily adsorb, and have good lipotropism matter sedimentation function, therefore without the need to finishing.
Described eyeglass is obtained by the silicone-hydrogel material of embodiment 1.Because the silicone-hydrogel material of embodiment 1 has good oxygen-permeable, the contact lens therefore utilizing this material to prepare also has good oxygen-permeable.
The preparation method of above-mentioned contact lens, comprise following process: each component mixed, inject contact lens mould, light-initiated or thermal-initiated polymerization, then the demoulding, unconverted monomer and oligopolymer in deionized water extraction removing eyeglass, immerse in physiological saline and balance, obtained contact lens; Wherein, described each component, according to weight percent, comprises following component:
Initiator and linking agent;
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
Preferably, while maintenance eyeglass has certain water content and elongation at break, for obtaining better oxygen permeability, described contact lens, according to mass fraction, comprises following component polyreaction and forms:
Initiator and linking agent;
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 2% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.5 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
The oxygen permeability of the contact lens that said components obtains is greater than 130*10
-11.
Verify that the corneal contact lens of the embodiment of the present invention has the performance of excellent water content and high oxygen flow below by test.
Sample 1
By amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer, organic solvent, initiator and linking agent; Mix, inject contact lens mould, light-initiated or thermal-initiated polymerization, the then demoulding, unconverted monomer and oligopolymer in deionized water extraction removing eyeglass, immerse in physiological saline and balance, thus obtained silicone-hydrogel contact lens.
Wherein, the M2-w1 for preparing of the amphiphilic macromolecular silicon monomer amphiphilic macromolecular silicon monomer M1-w1 that adopts above-mentioned example 1 to prepare and example 2.Small molecules silicon monomer adopts methyl-two (trimethicone)-silylpropyl glyceral methacrylate (SIGMA), hydrophilic monomer adopts NVP (NVP), hydroxyethyl methylacrylate (HEMA), N-vinyl-N methylacetamide (VMA), initiator adopts 2-hydroxy-2-methyl Propiophenone (D1173), and linking agent adopts polyethyleneglycol diacrylate (PEGDA).
Each component is as shown in table 1 according to mass fraction.
Sample 2-11
The preparation process of sample 2-11 contact lens is identical with the process of sample 1, and difference is selection and the parts by weight thereof of each component materials, specifically as shown in table 1.
Comparative sample
Methyl-two (trimethicone)-silylpropyl glyceral methacrylate of 30 parts is added successively in glass beaker, the 2-hydroxyethyl methacrylate of 22 parts, the NVP of 33 parts, the methacrylic acid of 6 parts, account for the polyethyleneglycol diacrylate of monomer total mass 0.1 part, the Diisopropyl azodicarboxylate of 2 parts, mixes, solution is injected in polypropylene molds, thermal-initiated polymerization 10h.Then the demoulding.Dry plate is put into deionized water and is soaked, then puts into physiological saline and balance, obtained silicone-hydrogel contact lens.
Table 1 sample proportioning (mass fraction)
Use electronic tension tester XLW (PC) to test elongation, with clamping plate, contact lens specimen holder is lived in row and measure, record the long rate of break-draw of corneal contact lens sample.Test result is as shown in table 2.
Weighting method is adopted to survey water ratio, slide glass weight Q1, eyeglass and slide glass weight Q2, after 50 DEG C of baking oven inner drying 19h, gross weight G3.Water content=(Q2-G3)/(Q2-Q1).Test result is as shown in table 2.
GB (GBT11417.3-2012) coulomb method is adopted to survey the oxygen value of each sample.Test result is as shown in table 2.
Table 2
As can be seen from Table 2: the water content of the silicone hydrogel contact lenses of inventive samples is all higher than 20%, and elongation at break is all greater than 150%, and performance perameter meets commercial standard.Especially, the oxygen permeability of sample exceeds more than 4 times than ordinary lens, human eyeball is worn comfortable, especially and preparation technology is simple, without the need to later stage surface treatment.
Those skilled in the art should understand; the present invention is not by the restriction of above-mentioned specific embodiment; description in above-mentioned specific embodiment and specification sheets is just in order to further illustrate principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The scope of protection of present invention is defined by claims and equivalent thereof.
Claims (10)
1. have a silicone-hydrogel material for high oxygen permeability, it is characterized in that, this silicone-hydrogel material, according to mass fraction, comprises following component polyreaction and forms:
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
2. according to the silicone-hydrogel material with high oxygen permeability according to claim 1, it is characterized in that, described amphiphilic macromolecular silicon monomer has the molecular formula of following structure:
or
Wherein, the structural formula of X is as follows:
Wherein, the span of a is the integer of 1 ~ 14, and the span of b is the integer of 1 ~ 6, and the span of c is the integer of 13 ~ 68.
3. according to the silicone-hydrogel material with high oxygen permeability according to claim 1, it is characterized in that, described small molecules silicon monomer comprises one in methacryloxypropyl three (trimethylsiloxane group) silane, methyl-two (trimethicone)-silylpropyl glyceral methacrylate, 3-(methacryloxypropyl) propyl trimethoxy silicane, methacryloxymethyl three (trimethylsiloxane group) silane or arbitrary combination.
4. according to the silicone-hydrogel material with high oxygen permeability according to claim 1, it is characterized in that, described hydrophilic monomer is NVP, two or more combinations of substances any in methacrylic acid, hydroxyethyl methylacrylate, N-vinyl-N methylacetamide, N-vinyl acetamide forms.
5. according to the silicone-hydrogel material with high oxygen permeability according to claim 1, it is characterized in that, described initiator is light trigger or thermal initiator; Described light trigger is 2-hydroxy-2-methyl Propiophenone, and thermal initiator is one in Diisopropyl azodicarboxylate and benzoyl peroxide or combination.
6. according to the silicone-hydrogel material with high oxygen permeability according to claim 1, it is characterized in that, described linking agent is one in polyethyleneglycol diacrylate, Ethylene glycol dimethacrylate or triallyl isocyanurate or arbitrary combination.
7. according to the silicone-hydrogel material with high oxygen permeability according to claim 1, it is characterized in that, described organic solvent is one in Virahol, ethanol, n-hexyl alcohol, propyl carbinol or arbitrary combination.
8. a contact lens, is characterized in that, this contact lens is obtained by silicone-hydrogel material, and this silicone-hydrogel material, according to mass fraction, comprises following component polyreaction and forms:
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
9. according to contact lens according to claim 8, it is characterized in that, described silicone-hydrogel material, according to mass fraction, comprises following component polyreaction and forms:
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 2% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.5 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
10. the preparation method of a contact lens, it is characterized in that, this preparation method comprises following process: each component mixed, inject contact lens mould, light-initiated or thermal-initiated polymerization, the then demoulding, unconverted monomer and oligopolymer in deionized water extraction removing eyeglass, immerse in physiological saline and balance, obtained contact lens; Wherein, described each component comprises following component according to mass fraction:
Wherein, the mass fraction sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent is 100 parts; Initiator accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent; Linking agent accounts for 0.1 ~ 3% of the weight sum of amphiphilic macromolecular silicon monomer, small molecules silicon monomer, hydrophilic monomer and organic solvent.
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