CN1323102C - Silicone rubber with permanent hydrophilic property on surface, preparing method and use thereof - Google Patents
Silicone rubber with permanent hydrophilic property on surface, preparing method and use thereof Download PDFInfo
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- CN1323102C CN1323102C CNB2004100149811A CN200410014981A CN1323102C CN 1323102 C CN1323102 C CN 1323102C CN B2004100149811 A CNB2004100149811 A CN B2004100149811A CN 200410014981 A CN200410014981 A CN 200410014981A CN 1323102 C CN1323102 C CN 1323102C
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- 238000000034 method Methods 0.000 title claims abstract description 27
- 229920002379 silicone rubber Polymers 0.000 title abstract description 66
- 239000004945 silicone rubber Substances 0.000 title abstract description 8
- -1 polyethylene Polymers 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229920000151 polyglycol Polymers 0.000 claims abstract description 13
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- 238000002360 preparation method Methods 0.000 claims description 16
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- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
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- 229910052697 platinum Inorganic materials 0.000 claims description 2
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- 238000004987 plasma desorption mass spectroscopy Methods 0.000 abstract description 9
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Abstract
The present invention relates to silicon rubber with permanent surface hydrophilicity, which is polyglycol modified silicone rubber with Si-C covalent bonds of polyethylene which is generated by the reaction of a hydro-silicon bond on the surface of the silicon rubber, and polyethylene glycol monoallyl ether, alpha-allyl-omega-methyl-polyethylene glycol or polyethylene glycol diallyl ether. The average molecular weight of the surface modified polyethylene glycol is from 1, 000 to 8, 000. After a polyethylene glycol derivative modifies the PDMS surface, the polyethylene glycol derivative and a silicon rubber material are connected. The silicon rubber greatly improves the compactness, the uniformity and the stability of a hydrophilic layer. The surface of the silicon rubber does not absorb protein basically and keeps hydrophilicity permanently. Simultaneously, the biologic compatibility of the surface of the silicon rubber is more perfect. As a result, necessary and sufficient conditions are provided for the application of the silicon rubber with permanent surface hydrophilicity in biomedicine. Therefore, the silicon rubber with permanent surface hydrophilicity can be used for manufacturing lenses of contact lens. The present invention discloses a manufacture method of the silicon rubber.
Description
Technical field
The present invention relates to a kind of silicon rubber of polyoxyethylene glycol finishing, relate in particular to silicon rubber and method for making thereof, the invention still further relates to the contact lens of making of the silicon rubber of polyoxyethylene glycol finishing of the present invention with the allyl polyglycol finishing.
Background technology
Silicon rubber (silicone) is made up of the Si-O chain backbone, and its side-chain radical R, R ' can select according to the material physical properties desired.According to the size of macromolecular chain skeleton and the difference of side-chain radical, silicon rubber can present gel, liquid and rubber-like, and side-chain radical comprises methyl, hydrogen, phenyl, vinyl or hydroxyl.Thereby si-h bond, vinyl or hydroxyl can be used for modifying with other molecular reaction the physico-chemical property of silicon rubber.
Silicon rubber has very wide temperature working range (50～300 ℃), good oxytolerant and light fastness aging, mildew resistance and chemical stability, excellent electric insulating, better physical and mechanical property, easily machine-shaping, to characteristics such as the reaction of tissue are minimum.Owing to had these excellent performances, make that silicon rubber has obtained very widely, important purposes in modern biomedical.
Polyoxyethylene glycol (Polyethylene Glycol) and derivative thereof are the polymers that the unique approval of united States food and drug administration (FDA) can be used in human body, why important it except it has fabulous biocompatibility, also because the avidity of this compound and water is high, the avidity that is much higher than it and biomacromolecule such as protein etc., therefore biomacromolecule, bacterium, virus (as SARS virus) etc. can not be adsorbed on the surface of polyoxyethylene glycol material, thereby reach from clean effect.This also is why we select for use polyoxyethylene glycol to modify the reason of silicon rubber.
In recent years, with polydimethylsiloxane (Polydimethyl Siloxane, be called for short: PDMS) be the silicon rubber of major ingredient, owing to contain the Si-O key on the chemical constitution, therefore has air permeability and good, handle the back and be used as soft silicon rubber contact lens (Silicone rubber contactlens, abbreviation: SRCL) material through special surface hydrophilic.Because extremely low to the absorptivity of water, can exempt the shortcoming that general soft contact lens is subjected to bacterial contamination, be difficult for fragmentation and high oxygen permeability advantage such as Dai Yong for a long time because of having elasticity.But still have some gordian techniquies not overcome fully as yet, particularly wetting ability has the phenomenon that goes down along with the prolongation of duration of service.
At present, the general method of surface modification has: thermooxidizing, gas and microwave plasma processing, physics and chemical vapour deposition, evaporation, sputter, uv irradiating combine processing etc. with ozonize.Recently, Cha study group has proposed again the molecule crosslinking technology of multi-polyamide covalence graft to the PDMS surface, the poly-propionic acid amide chemical modification that Xiao study group adopts free radical to cause, make the PDMS wetting ability after the modification can remain on about 1 month, and the absorption than primary PDMS significantly reduces to the irreversible adsorption of enzyme, but wetting ability still can not forever keep.
The material of contact lens should be considered following important factor:
Biocompatibility: this is the primary condition that all biomaterials must satisfy, biocompatibility is defined as: a kind of desirable material, in specific time, can induce the physiological reaction of its surrounding tissue such as osseous tissue, reticular tissue and epithelium, induce the biological tissue useful reaction of generation and unhelpful reaction does not take place.
Permeability: contact lens prerequisite capable of being worn for long period is the function that cornea still can be kept abundant absorption oxygen, and { perviousness of PHEMA (polymethyl acrylic acid hydroxyethanoic acid) about 38%} and oxygen has confidential relation for thickness, the water ratio of this and eyeglass.Therefore will be towards the lens materials development of high oxygen permeating amount.
Good in optical property: the material of contact lens must be transparent.
Surface hydrophilic: if the surface is hydrophobic, it will produce a big tear film, and this has destroyed flowing naturally of tear, and protein can deposit to the film surface.It has reduced effective contact and has caused infection.The surface of the material static that do not have, electric charge also causes proteinic deposition easily.
Density is low: what the size that contact lens can be reached should be enough is little, and its weight should be very light, and it just can be worn and produce stress for a long time and not like this.
Young's modulus is big: its intensity height has suitable Young's modulus to make and also is not easy to sample operation and processing easily damage.
Ratio of performance to price height: contact lens must be cheap.
Two main directions of contact lens material development at present are: the finishing of silicone hydrogel material and existing material.The silicone hydrogel material has possessed some advantage of silicon rubber: as oxygen flow, permeable gas, higher intensity, the water-wet behavior of hydrogel is arranged again, therefore, the research of silicone hydrogel and the commercial impetus are very powerful.But it is its weakness that optical clarity weakens with high price.Our invention focuses on the finishing of existing material.
Summary of the invention
The solid state si rubber that the purpose of this invention is to provide a kind of surperficial permanent hydrophilic, its method for making, and the application in the preparation contact lens.
Technical scheme of the present invention is as follows:
A kind of solid state si rubber of surperficial permanent hydrophilic, it is the si-h bond and allyl polyglycol (the Polyethylene Glycol Monoallyl Ether of solid state si rubber surface, be called for short: PEG-MAE), ω-methyl-α-allyl polyglycol (α-Allyl-ω-Methyl-Polyethylene Glycol, be called for short: PEG-AM) or the diallyl polyoxyethylene glycol (Polyethylene Glycol Diallyl Ether, be called for short: PEG-DAE) reaction generates Si-C solid state si rubber covalent linkage, the polyoxyethylene glycol finishing.
The solid state si rubber of above-mentioned surperficial permanent hydrophilic, the molecular-weight average of the polyoxyethylene glycol of finishing are 1000～3000 for PEG-MAE and PEG-AM preferred range between 1000～8000, are 2000～4000 for the PEG-DAE scope.
Above-mentioned surperficial permanent hydrophilic solid state si rubber can be by liquid and solid phase reaction or gas-solid phase reaction preparation.
A kind of method for making of above-mentioned surperficial permanent hydrophilic solid state si rubber, it is in the presence of catalyzer, PEG-MAE, PEG-AM or PEG-DAE are coated in the surface of the solid state si rubber that contains the Si-H key, the solid state si rubber that perhaps will contain the Si-H key is positioned in the alcoholic solution of PEG-MAE, PEG-AM or PEG-DAE, promptly gets surperficial permanent hydrophilic solid state si rubber of the present invention in 5～480 minutes 60～120 ℃ of reactions.
Alcoholic solution described in the above-mentioned method for making can be ethanol, propyl alcohol, Virahol, butanols or low molecular poly solution.
Catalyzer described in the above-mentioned method for making can be Speier catalyzer (Platinic chloride, H
2PtCl
6), Karstedt catalyzer (complex compound of platinum/vinyl silica, Pt{ (CH
2=CHMe
2Si)
2O} (P-t-Bu
3)) and Pt (CH
2=CH
2)
2Cl
2
A kind of method for making of above-mentioned surperficial permanent hydrophilic solid state si rubber, it is that the solid state si rubber that will contain the Si-H key places in the withstand voltage encloses container, is evacuated to pressure 1-100Pa, with CATALYST Co
2(CO)
8Or Fe (CO)
5And allyl polyglycol, ω=methyl-α-allyl polyglycol or diallyl polyoxyethylene glycol inject in the reaction vessel, in 80～200 ℃ of reactions 2～120 minutes, promptly get surperficial permanent hydrophilic solid state si rubber of the present invention.
The solid state si rubber that contains the Si-H key described in two kinds of above-mentioned method for makings can be the two-pack solid state si rubber that contains the single component solid state si rubber of Si-H key or contain the add-on type of Si-H key.
There is appropriate Si-H key active group in the above-mentioned solid state si rubber surface of the present invention that satisfies, and the Si-H/Si-Me peak area ratio is in 1.0-17.5% among the ATR.Infrared absorption peak (the 2160cm of Si-H key stretching vibration
-1) and Si-Me symmetrical deformation vibration absorption peak (～1255cm
-1) area can be used for weighing the surface density of Si-H and Si-Me group.
The two-pack solid state si rubber of the above-mentioned add-on type that contains the Si-H key can be by containing CH
2The first composition of=C-Si group and mixing cured the forming of second composition of containing the Si-H group.So that the two-component silicone rubber Dow Corning Sylgard 184 and the GE RTV 615 of two kinds of main brands are the example explanation in the market.Their two kinds of components are that containing with the first composition is the A component of main component and to contain with the second composition be the B component of main component.Studies show that: the ratio A of the A in the silicon rubber, B two components: B=10: 1 o'clock, two active group CH in the silicon rubber in A component and the B component
2=C-Si and Si-H almost completely react.Work as A: B＞10: 1, there is not active Si-H key residue basically, be not suitable for requirement of the present invention.Work as A: B＜2: 1, too many active Si-H residue is then arranged, and the silicon rubber stability is relatively poor, oxidation easily is not suitable for requirement of the present invention yet.When the ratio of the quality of the material of A component and B component at 2: 1 between 9: 1 the time, surperficial Si-H/Si-Me peak area ratio is between the 1.0-17.5%, is the optimum range that contact lenses is made material among the present invention with 2: 1～7: 1.Therefore, the ratio of two parts in the two-component silicone rubber is selected most important, and it directly influences the reaction with the PEG derivative.
In two kinds of above-mentioned method for makings, the amount ranges of monoene propyl group polyoxyethylene glycol, ω-methyl-α-allyl polyglycol or diallyl polyoxyethylene glycol can be that every square centimeter solid state si rubber surface is with 10
-8～10
-4Mole.
In two kinds of above-mentioned method for makings, catalyst consumption be polyethyleneglycol derivative quality 0.1～0.001.
The inventor adopts the hydrosilation grafting of unsaturated double-bond, has realized the surface modification to PDMS, has obtained surperficial permanent hydrophilic solid state si rubber.After the modification of polyethyleneglycol derivative to the PDMS surface, polyethyleneglycol derivative and silicon rubber body material fuse, compactness, homogeneity and the stability of hydrophilic layer have greatly been improved, its surface is adsorbed proteins not basically, and forever keep wetting ability, simultaneously, its surperficial bio-compatibility is perfect more, and this just provides necessary and sufficient condition for the application of surperficial permanent hydrophilic solid state si rubber of the present invention on biomedicine.Surperficial permanent hydrophilic solid state si rubber permeability of the present invention and good in optical property, Young's modulus is big, and density is low, is well suited for being used to make contact lens.Surperficial permanent hydrophilic solid state si rubber of the present invention prepares simple and easy, and cost is low, is convenient to promote, utilize.Therefore, surperficial permanent hydrophilic solid state si rubber of the present invention can be used in making contact lens.
Use surperficial permanent hydrophilic solid state si rubber manufacturing contact lens of the present invention following advantage arranged:
1 can make the various high oxygen permeability contact lenss of software to hardware;
2 good toughness, dimensionally stable is difficult for having cut and breach, is easy to processing;
3 printing opacities are good, the first-class light effect of looking;
4 do not need water to keep its shape, do not need to consume a lot of tears, can not be adsorbed with harmful substances;
5 surfaces are hydrophilic polyoxyethylene glycol, be difficult for to produce static charge, so the protein in the tear and outside bacterium can not be deposited to lens surface, and it is healthy and allow eyes feel more comfortable that this will more be of value to eye;
6 are suitable for the damp and hot sterilization of high temperature;
7 maintenances do not need a large amount of costs easily;
8 life-spans are long, can be used for the production of week or month throwing type eyeglass;
9 easily add color;
10 low prices, large-scale production can reach every only needs several units of Renminbi;
11 easily maintenances.
Description of drawings
Fig. 1 is the ATR spectrum of the silicon rubber of different ratios;
Fig. 2 is the content of the silastic surface Si-H of different ratios with respect to Si-Me;
Fig. 3 is PEG-MAE, PEG-AM, the transmitted infrared light spectrum of PEG-DAE;
Fig. 4 is PEG-MAE's
1H-NMR (CDCl
3, ppm) spectrum;
Fig. 5 is PEG-AM's
1H-NMR (CDCl
3, ppm) spectrum;
Fig. 6 is PEG-DAE's
1H-NMR (CDCl
3, ppm) spectrum;
Fig. 7 is for modifying the ATR spectrum of forward and backward solid state si rubber, and a is for before modifying, and b is that PEG-AM modifies, and c is that PEG-DAE modifies, and d is that PEG-MAE modifies;
Fig. 8 modifies the SIMS mass spectrum of PDMS for PEG-MAE;
Fig. 9 is that the contact lens made of common solid state si rubber and surperficial permanent hydrophilic solid state si rubber of the present invention is to the absorption of proteins curve, its middle and upper part is the adsorption curve of unmodified silicon rubber to IgG or Albumin, and the bottom is that PEG-MAE modifies the adsorption curve of silicon rubber to IgG or Albumin;
The fluoroscopic image of Figure 10 for before and after the PEG-MAE modification Albumin being adsorbed, a are for before modifying, and b is after modifying.
Embodiment
With Dow Corning Sylgard 184 silicon rubber is example, with A component (main component is the polydimethylsiloxane that contains vinyl) and two kinds of components of B component (main component is the polymethyl siloxane of siliceous hydrogen base) respectively according to mass ratio 10: 1: 7: 1; 4: 1; 3: 1; 2: 1 ratio is taken out 30g, mixes and stirs, and makes two portions thorough mixing.Be poured over the container interior (as glass culture dish) of surface level, vacuumize and remove bubble, till transparent no bubble.100 ℃ of reactions 0.5 hour, promptly obtain water white solid state si rubber.Carefully peel off silicon rubber, be divided into fritter, standby.ATR-FTIR spectral investigation (seeing Fig. 1,2): at 1110-1030cm
-1Between the vibration peak of Si-O-Si key has appearred, 1255 and 800cm
-1The vibration peak of Si-C key, 2160cm have appearred in the place
-1More or less Si-H key chattering peak has appearred in the place.Show that the surface has as yet the not Si-H key of complete reaction, calculate their surperficial Si-H/Si-Me peak area ratios and be in 1.0-17.5% (with 2160cm
-1The place the stretching vibration of Si-H key and～1255cm
-1The area of the Si-Me symmetrical deformation vibration absorption peak at place is a benchmark).
With the mixed of two kinds of components of A, B according to 3: 1, press embodiment 1 operation steps, 150 ℃ following 0.2 hour, transparent cure silicone rubber.Take out small amount of solid state silicon rubber, do ATR-FTIR spectrum.The ATR-FTIR infrared spectra is at 1110-1000cm
-1Between the vibration peak of Si-O-Si key has appearred, 1255 and 800cm
-1The vibration peak of Si-C key has appearred in the place, at 2160cm
-1Si-H key chattering peak has appearred in the place, and showing still has the Si-H key to have neither part nor lot in reaction.
With the mixed of two kinds of components of A, B according to 2: 1, press embodiment 1 operation steps, 80 ℃ of reactions 0.5 hour, get transparent solid state si rubber.Do ATR-FTIR spectrum.The ATR-FTIR infrared spectra is at 1110-1000cm
-1Between the vibration peak of Si-O-Si key has appearred.1255 and 800cm
-1The vibration peak of Si-C key has appearred in the place.2160cm
-1Strong Si-H key chattering peak has appearred in the place.Show to remain at the Si-H key at this moment and have neither part nor lot in reaction.
With the mixed of two kinds of components of A, B according to 9: 1, press embodiment 1 operation steps, 40 ℃ of reactions 24 hours, get water white solid state si rubber.Do ATR-FTIR spectrum.The ATR-FTIR infrared spectra is at 1110-1000cm
-1Between the vibration peak of Si-O-Si key has appearred.1255 and 800cm
-1The vibration peak of Si-C key has appearred in the place.2160cm
-1Weak Si-H key chattering peak has appearred in the place.Show that exist a small amount of Si-H key to have neither part nor lot in reaction this moment.
The mixed solid state si rubber that contains the Si-H key that gets of embodiment 5. different ratioss relatively
With ratio is 2: 1, and 3: 1,4: 1, the ATR-FTIR infrared spectra of the solid state si rubber of 7: 1 and 10: 1 relatively.The Si-H key is at 2160cm
-1The vibration peak power at place is different, and 2: 1 o'clock the strongest, and 9: 1 o'clock the most weak, gets involved therebetween in 4: 1 o'clock.Their physical strength also there are differences, and from 10: 1 to 2: 1, hardness reduced gradually, and the solid state si rubber intensity between 7: 1～2: 1 is moderate, is fit to make biomedical articles.
The preparation of embodiment 6. polyethyleneglycol derivatives
The preparation of PEG-MAE
A. under nitrogen atmosphere, NaH (0.75g) is suspended in the anhydrous THF of 100mL (uses CaH earlier
2Handle with Na) in the solution, controlled temperature is 0 ℃, (M=1000 10.0g) adds, and stirs after 2 hours, with the adding of 0.87mL 3-bromopropylene, stirs 40 hours, and centrifugal, solution is washed with 50mL, continuous 3 times, uses the 30g anhydrous Na with polyoxyethylene glycol
2SO
4Drying is filtered.Reduction vaporization, drying gets the about 5.5g of product P EG-MAE, productive rate about 50%.The FTIR spectral results; (cm
-1) 530,824,963,1116,1243,1280,1345,1467,1668,1968,2884,3422.
B. under nitrogen atmosphere, NaH (0.75g) is suspended in the 100mL anhydrous THF solution, controlled temperature is 0 ℃, (M=2000 20g) adds, and stirs after 2 hours with polyoxyethylene glycol, 0.87mL 3-bromopropylene is added, stirred 40 hours, centrifugal, abandon liquid, solid is with the dissolving of 100mL chloroform, and is centrifugal, discard solid, solution is washed with 50mL, continuous 3 times, uses the 30g anhydrous Na
2SO
4Drying is filtered.Reduction vaporization, drying gets the about 11.5g of product P EG-MAE, productive rate about 55%.FTIR spectral results (see figure 3): (cm
-1) 529,842,962,1112,1241,1281,1343,1413,1468,1696,2884,2965,3449.Nuclear-magnetism is studied following (see figure 4):
1H-NMR δ (CDCl
3, ppm): 2.809 (H,
HO-), 3.56 (2H, HOC
H 2-) 3.60 (2H, HOC
H 2C
H 2O-), 3.65[4 (n-1) H, (C
H 2C
H 2O-) n], 3.93 (2H, C
H 2CH=C
H 2), 5.08 (1H, CH
2CH=C
H 2), 5.18 (1H, CH
2CH=C
H 2), 5.92 (1H, CH
2C
H=CH
2).
C. press the PEG-MAE product of the polyoxyethylene glycol of above-mentioned b prepared in reaction M=3000, standby.
The preparation of PEG-AM
A. under argon gas atmosphere, NaH (2.0g) is suspended in the 200mL anhydrous THF solution 0 ℃, with methyl polyoxyethylene glycol (M=1000,20g) add, stir after 2 hours, 3.1mL 3-bromopropylene is added, stirred 40 hours, centrifugal, solution is washed with 50mL, continuous 3 times, with 30g anhydrous Na 2SO4 drying, filter.Reduction vaporization, drying gets the about 19g of product P EG-AM, productive rate about 90%.FTIR spectral results: (cm
-1) 842,963,1050,1130,1184,1242,1280,1343,1360,1467,1650,2694,2740,2888.
B. under argon gas atmosphere, NaH (2.0g) is suspended in the 200 mL anhydrous THF solutions, controlled temperature is 0 ℃, (M=1900 40g) adds, and stirs after 2 hours with the methyl polyoxyethylene glycol, add 3.1mL 3-bromopropylene, stirred 20 hours, centrifugal, abandon liquid, solid is with the dissolving of 200mL chloroform, and is centrifugal, discard solid, solution is washed with 50mL, continuous 3 times, uses 30gNa
2SO
4Drying is filtered.Reduction vaporization, drying gets the about 38g of product P EG-AM, productive rate 90%.FT-IR spectral results (see figure 3): (cm
-1) 847,967,1040,1130,1242,1343,1360,1463,2694,2746,2889.Nuclear-magnetism research (see figure 5) is as follows:
1H-NMR δ (CDCl
3, ppm): 3.38 (3H, C
H 3O-), 3.56 (2H, CH
3OC
H 2-) 3.59 (2H, CH
3OCH
2C
H 2O-), 3.64[4 (n-1) H, (C
H 2C
H 2O-)
n], 4.03 (2H, C
H 2CH=CH
2), 5.19 (1H, CH
2CH=C
H 2), 5.29 (1H, CH
2CH=C
H 2), 5.93 (1H, CH
2C
H=CH
2).
C. be that 3000 and 5000 PEG prepares PEG-AM with above-mentioned similar methods and obtains analog result with molecular-weight average.
The preparation of PEG-DAE
A. under nitrogen atmosphere, a little excessive N aH is suspended in the 150mL anhydrous THF solution of 20gPEG (M=2000), 0 ℃ was stirred 1.5 hours down, be added dropwise to the 50mL anhydrous THF solution of 2.4mL 3-bromopropylene, stirred 48 hours, centrifugal, abandon liquid, solid dissolves with the 200mL chloroform, centrifugal, discard solid, solution is washed with 50mL, continuous 3 times, use 30gNa
2SO
4Drying is filtered.Reduction vaporization, drying gets product P EG-DAE 18g, productive rate 85%.FTIR spectral results (see figure 3): (cm
-1) 842,962,1060,1112,1241,1281,1343,1468,1637,1728,2695,2887,3445.Nuclear-magnetism research (see figure 6) is as follows:
1H-NMR δ (CDCl
3, ppm): 3.65[4nH, (C
H 2C
H 2O-)
n], 3.95 (2H, C
H 2CH=CH
2), 5.16 (1H, CH
2CH=C
H 2), 5.25 (1H, CH
2CH=C
H 2), 5.91 (1H, CH
2C
H=CH
2).
B. be that 4000 and 8000 PEG prepares PEG-DAE with above-mentioned similar methods and obtains analog result with molecular-weight average.
The preparation of embodiment 7. surperficial permanent hydrophilic solid state si rubber of the present invention
Get the solid state si rubber fritter of embodiment 3 preparations.With catalyzer and PEG derivative (PEG-MAE, PEG-AM, PEG-DAE) mix, be coated on the surface of solid state si rubber fritter, perhaps the silicon rubber fritter is put into the alcoholic solution that contains the PEG derivative, add catalyzer, reacting by heating makes surperficial permanent hydrophilic solid state si rubber of the present invention.Sample thief with methyl alcohol and washed with de-ionized water, carries out ATR-FTIR spectral measurement (see figure 7).Reaction conditions and infrared data see Table 1.
The preparation of embodiment 8. surperficial permanent hydrophilic solid state si rubber of the present invention
Get embodiment 3 preparation solid state si rubber fritters and put into encloses container, vacuumize, catalyzer [Co
2(CO)
8Or Fe (CO)
5] and the PEG derivative (PEG-MAE, PEG-AM, PEG-DAE) injection, reacting by heating makes surperficial permanent hydrophilic solid state si rubber of the present invention.Sample thief with methyl alcohol and washed with de-ionized water, carries out the ATR-FTIR spectral investigation.Reaction conditions and infrared data see Table 1.
In above-mentioned experiment, 2160 and 910cm
-1The Si-H key chattering peak at place disappears substantially, and simultaneously, the charateristic avsorption band of PEG has appearred respectively in infrared spectra at 2880-2900 and 1340-1370 two places, among their corresponding respectively PEG-and CH
2The flexible and rocking vibration peak of symmetry.Show on the surface of silicon rubber the allyl polyglycol modification has taken place.
Embodiment 9.
The SIMS mass spectra peak of the of the present invention surperficial permanent hydrophilic solid state si rubber sample that PEG-MAE (M=2000) modifies as shown in Figure 8.The mass spectrum result: in m/z=0～50 scopes, occurred the single aggressiveness among the PEG-MAE the peak (45 ,-CH
2CH
2O-); Dimer and trimerical peak (119 (CH that PDMS in the scope of m/z=100-240, occurred
3Si
2O
3), 133 (C
2H
5Si
2O
3), 149 (C
3H
9Si
2O
3), 223 (C
5H
15Si
3O
4)).Show on the surface of silicon rubber the PEG-MAE modification has taken place.
The research of embodiment 10. contact angles
Deionized water is dropped in the surface of the solid state si rubber before and after the modification, repeatedly measure its contact angle respectively with the contact angle goniometer and ask its mean value (seeing Table 2).The contact angle of the water droplet of ordinary silicon rubber is between 100～110 °, and the contact angle that PEG-MAE of the present invention modifies the silicon rubber of (experiment 2) is 15 °; The contact angle that PEG-AM of the present invention modifies the silicon rubber of (experiment 5) is 35 °; The contact angle that PEG-DAE of the present invention modifies the silicon rubber of (experiment 9) is 40 °.Place air after 30 days on their surfaces, measure its contact angle, contact angle still remains between 15～40 °, and the wetting ability on the surface of the silicon rubber of the present invention that this explanation allyl group ethylene glycol is modified is extremely stable, is very suitable for the application on the biomedicine.
The detected result of reaction conditions that table 1 is different and products thereof
| Reaction type | Experiment number | Silastic surface amasss (cm 2) | The PEG derivative a | Catalyzer b | Temperature of reaction (℃) | Reaction solvent c | Air pressure (Pa) | Reaction times (min) | Characteristic infrared data (cm -1) | |||
| Title | Molecular-weight average M | Consumption (mg) | Title | Consumption (μ g) | ||||||||
| Liquid and solid phase reaction | 1 | 5×1 | 1 | 1000 | 500 | A | 5000 | 110 | PEG /M＝200 | - | 480 | 3402，2961， 2901，2874， 2153，1352， 1254，1040， |
| 2 | 5×1 | 1 | 2000 | 50 | B | 500 | 80 | PEG /M＝200 | - | 5 | The same | |
| 3 | 5×1 | 3000 | 10 | B | 1000 | 80 | PEG /M＝200 | - | 10 | The same | ||
| 4 | 5×1 | 2 | 1000 | 50 | C | 100 | 80 | PEG /M＝200 | - | 60 | 2967，2906， 2161，1420， 1346，1257， 1040，800 | |
| 5 | 5×1 | 2 | 2000 | 500 | B | 500 | 80 | Do not have | - | 10 | The same | |
| 6 | 5×1 | 2 | 3000 | 300 | A | 1000 | 110 | Do not have | - | 120 | The same | |
| 7 | 5×1 | 2 | 5000 | 20 | A | 50 | 80 | Virahol | - | 10 | The same | |
| 8 | 5×1 | 3 | 2000 | 100 | B | 20 | 78 | Ethanol | - | 10 | 2962，2904， 2877，2161， 1433，1368， 1257，1040 | |
| 9 | 5×1 | 3 | 4000 | 200 | B | 10 | 80 | Propyl alcohol | - | 5 | The same | |
| 10 | 5×1 | 3 | 8000 | 0.5 | A | 0.5 | 100 | Butanols | - | 480 | The same | |
| Gas-solid phase reaction | 11 | 5×1 | 1 | 1000 | 500 | D | 500 | 80 | - | 1 | 120 | 3414，2961， 2901，2875， 2160，1352 1254，1040 |
| 12 | 5×1 | 1 | 2000 | 50 | E | 5000 | 200 | - | 10 | 2 | The same | |
| 13 | 5×1 | 2 | 2000 | 100 | D | 200 | 120 | - | 10 | 30 | 2967，2907， 2888，2158， 1451，1374， 1040，800 | |
| 14 | 5×1 | 2 | 5000 | 200 | D | 50 | 150 | - | 100 | 15 | The same | |
| 15 | 5×1 | 3 | 2000 | 100 | D | 500 | 150 | - | 10 | 10 | 2962，2907， 2877，2165， 1440，1356， 1250，1040 | |
| 16 | 5×1 | 3 | 8000 | 20 | D | 150 | 120 | - | 10 | 10 | The same | |
APEG derivative 1:PEG-MAE, 2:PEG-MA, 3:PEG-DAE
B catalyst A: H
2PtCl
6B:Pt{ (CH
2=CH
2Me
2Si)
2O} (P-t-Bu
3), C:.Pt (CH
2=CH
2)
2Cl
2, D:Co
2(CO)
8, E:Fe (CO)
5.
The water contact angle (degree) of the silicon rubber after table 2 is modified
| The Speier catalyzer | The Karstedt catalyzer | |
| PEG-DAE(M＝4000) | 65 | 40 |
| PEG-AM(M＝2000) | 55 | 35 |
| PEG-MAE(M＝1000) | 40 | 30 |
| PEG-MAE(M＝2000) | 25 | 15 |
Embodiment 11. specific refractory poweres
Under the same terms, the specific refractory power of ordinary silicon rubber is between 1.44-1.47, and PEG-MAE of the present invention modifies the specific refractory power of silicon rubber between 1.42-1.48; PEG-AM of the present invention repaiies the specific refractory power of silicon rubber between 1.42-1.47; PEG-DAE of the present invention modifies the specific refractory power of silicon rubber between 1.40-1.50.
The preparation of embodiment 12. contact lens
The general turning method of using of the shape processing of contact lens, centrifugal pouring method, compression molding and hybrid technique method are produced.With turning method and centrifugal pouring method is the shape course of processing of example explanation contact lens.
Turning method: at first, embodiment 1,2 or 3 silicon rubber that prepare are cut into appropriate size, utilize computer control lathe that firm silicone rubber is cut and form desired contact lens shape.The also available semi-automatic cutting of turning method is finished, and is the contact lens workprint after cutting is finished.Workprint is placed in the ultrasonic unit washes respectively one time, 80 ℃ of vacuum-dryings 4 hours with ethanol and high purity deionized water.Then, make contact lens of the present invention with the method for embodiment 7 or 8 again.
Centrifugal pouring method: two-component silicone rubber GE RTV615 takes out A and B two components in proportion at 3: 1, mixes, and stirs, and vacuumizes the bubble of removing formation, until transparent no bubble.Be poured in the mould of a rotation, when mixture was configured as eyeglass according to the shape of mould and rotating speed, the dioptry of eyeglass was by the speed of rotation decision of mould.Separate the contact lens workprint from substrate carefully.Be placed in the ultrasonic unit and wash respectively one time, 80 ℃ of vacuum-dryings 4 hours with methyl alcohol and high purity deionized water.Then, make contact lens of the present invention with the method for embodiment 7 or 8 again.
Embodiment 13. ventilation properties
The ventilation property of contact lens sees Table 3.
The permeability of the various material contact lens of table 3
| Form | Material | Ventilation property ml.Cm/cm 2.sec.mmHg |
| Rigid | Polymethylmethacrylate | 0.01±0.00 |
| Acetic acid/cellulose butyrate | 0.23±0.02 | |
| The copolymer of methyl methacrylate and silyl acrylate methyl esters | 0.58±0.03 | |
| Soft | 28% water-absorbent hydrogel | 0.42±0.07 |
| 35% water-absorbent hydrogel | 0.62±0.05 | |
| 72% water-absorbent hydrogel | 0.66±0.12 | |
| The silicon rubber of unmodified | 12.0±0.32 | |
| After PEG-MAE modifies | 12.0±0.50 |
| After PEG-AM modifies | 11.0±0.50 | |
| After PEG-DAE modifies | 11.0±0.80 |
As shown in Table 2: ordinary silicon rubber and silicon rubber of the present invention have good ventilation property.Studies show that: it is relevant that the ventilation property of silicon rubber and its inside have the Si-O-Si key, and we have kept the Si-O-Si key by the silicon rubber after with the grafting of allyl group ethylene glycol.Therefore, silicon rubber of the present invention still has air permeability and good.
Embodiment 14. absorption of proteins characteristics
Under the room temperature, ordinary silicon rubber and silicon rubber of the present invention is taken up in order of priority be positioned over immunoglobulin (Ig) (IgG, 0.02mg/mL) (Albumin 0.015mg/mL) soaks 24 hours (immunoglobulin (Ig) and albumin fluorescent mark) in the solution for solution and albumin.After taking out sample, use washed with de-ionized water.Fluorescence detector is measured its fluorescence intensity.The result as shown in Figure 9.Ordinary silicon rubber reaches 2 to 3 * 10 to the absorption of IgG and Albumin
-10Mol/cm
2, silicon rubber of the present invention [PEG-MAE (M=2000)] surface proteicly is adsorbed as 0.3 to 0.5 * 10 to two kinds
-10mol/cm
2Contrasted the fluoroscopic image of the absorption of the Albumin that modifies forward and backward silicon rubber among Figure 10.The silicon rubber that the result all shows finishing of the present invention is adsorbed proteins not, and this is the needed characteristic of contact lens material just.
Claims (7)
1. the solid state si rubber of a surperficial permanent hydrophilic is characterized in that: it is the si-h bond of solid state si rubber surface and the solid state si rubber that monoene propyl group polyoxyethylene glycol, ω-methyl-α-allyl polyglycol or the reaction of diallyl polyoxyethylene glycol generate the polyoxyethylene glycol finishing of Si-C covalent linkage.
2. the solid state si rubber of surperficial permanent hydrophilic according to claim 1, it is characterized in that: the molecular-weight average of the polyoxyethylene glycol of finishing is between 1000～8000.
3. the solid state si rubber of surperficial permanent hydrophilic according to claim 2, it is characterized in that: for monoene propyl group polyoxyethylene glycol and ω-methyl-α-allyl polyglycol, the scope of the molecular-weight average of the polyoxyethylene glycol of finishing is 1000～3000, is 2000～4000 for its average molecular weight range of diallyl polyoxyethylene glycol.
4. the method for making of the solid state si rubber of the described surperficial permanent hydrophilic of claim 1 is characterized in that: at the complex compound or the Pt (CH of catalyzer Platinic chloride, platinum/vinyl silica
2=CH
2) Cl
2Exist down, monoene propyl group polyoxyethylene glycol, ω-methyl-α-allyl polyglycol or diallyl polyoxyethylene glycol are coated in the surface of the solid state si rubber that contains the Si-H key, the solid state si rubber that perhaps will contain the Si-H key is positioned in the alcoholic solution of monoene propyl group polyoxyethylene glycol, ω-methyl-α-allyl polyglycol or diallyl polyoxyethylene glycol, 60～120 ℃ of reactions, promptly got the solid state si rubber of surperficial permanent hydrophilic in 5～480 minutes.
5. the method for making of the solid state si rubber of the described surperficial permanent hydrophilic of claim 1, it is characterized in that: the solid state si rubber that will contain the Si-H key places in the withstand voltage encloses container, and being evacuated to pressure is 1～100Pa, with CATALYST Co
2(CO)
8Or Fe (CO)
5Inject in the reaction vessel with monoene propyl group polyoxyethylene glycol, ω-methyl-α-allyl polyglycol or diallyl polyoxyethylene glycol,, promptly get the solid state si rubber of surperficial permanent hydrophilic in 80～200 ℃ of reactions 2～120 minutes.
6. according to claim 4 or 5 described method for makings, it is characterized in that: the solid state si rubber of the described Si-H of containing key is the two-pack solid state si rubber that contains the single component solid state si rubber of Si-H key or contain the add-on type of Si-H key.
7. the application of the solid state si rubber of surperficial permanent hydrophilic according to claim 1 in the preparation contact lens.
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| EP1911791A1 (en) | 2006-10-03 | 2008-04-16 | Institut Curie | Method for treating surfaces containing Si-H groups |
| CN101265329B (en) | 2007-03-16 | 2011-06-22 | 马雄明 | Polydimethylsiloxane with initiator on surface and its preparation method and use |
| CN101987887B (en) * | 2009-08-06 | 2012-12-26 | 张义浜 | Modified silicon rubber and modification method and application thereof |
| CN102417602B (en) * | 2011-09-22 | 2012-10-31 | 天津大学 | Medical silicon rubber with modified hydrophilic structure on surface, and preparation and application of medical silicon rubber |
| US10723842B2 (en) * | 2015-03-11 | 2020-07-28 | University Of Florida Research Foundation, Inc. | Mesh size control of lubrication in gemini hydrogels |
| CN107519542A (en) * | 2017-08-23 | 2017-12-29 | 上海交通大学医学院附属第九人民医院 | Silicon rubber expander that a kind of surface permanent hydrophilic is modified and its preparation method and application |
| CN109575610A (en) * | 2018-12-20 | 2019-04-05 | 海昌隐形眼镜有限公司 | Surface silicon hydrogen functionalized silicon rubber material and preparation, hydrophilic treated and methods for using them |
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| CN111110430A (en) * | 2019-12-31 | 2020-05-08 | 帝斯博（常州）医疗用品股份有限公司 | Self-adhesive type male urethral catheterization sleeve and manufacturing method thereof |
| US11344526B2 (en) * | 2020-03-20 | 2022-05-31 | The Regents Of The University Of California | Implantable drug delivery devices for localized drug delivery |
| US11338119B2 (en) | 2020-03-20 | 2022-05-24 | The Regents Of The University Of California | Implantable drug delivery devices for localized drug delivery |
| US11173291B2 (en) | 2020-03-20 | 2021-11-16 | The Regents Of The University Of California | Implantable drug delivery devices for localized drug delivery |
| CN112892443A (en) * | 2021-01-14 | 2021-06-04 | 江西欧普特实业有限公司 | Modified silica gel reation kettle of upper and lower circulation material |
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Assignee: Nanjing Jinsanli Rubber & Plastic Co., Ltd. Assignor: Nanjing University Contract fulfillment period: 2009.2.10 to 2014.2.9 contract change Contract record no.: 2009320000521 Denomination of invention: Silicone rubber with permanent hydrophilic property on surface, preparing method and use thereof Granted publication date: 20070627 License type: Exclusive license Record date: 2009.3.27 |
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