Method of producing polymers for contact lenses

专利摘要:
Ophthalmic devices, such as contact lenses, of polymers of telechelic perfluorinated polyether monomers, and compositions for making such devices are disclosed. The devices possess improved oxygen permeability.
公开号:SU1614766A3
申请号:SU833573325
申请日:1983-01-17
公开日:1990-12-15
发明作者:Эльмер Райс Дэвид；Вайнинг Иленфельд Джэй
申请人:Миннесота Майнинг Энд Мануфакчуринг Компани (Фирма)；
IPC主号:

专利说明:

The invention relates to the preparation of polymers for contact lenses.
A pell of the invention is the emergence of a projectile lens performance;
The term telechelate perfluoropolyether compound denotes a material containing peruteroxynalkylene units in the main chain and reactive groups, mainly known terminal
CM
i-pyiniM, i; rn.Mui; i.4i.)) (i in the direction of the basics
well 10 CSCP).
11Molime1)) telehepatnogo c.oej, i, n- and is carried out, using initiators that give free radicals when active energy is activated, as well as using polymers of ethylene monosomes. Their O-radic; 1Ln initiators include well-known thermally activated ionisation agents, such as organic peryses and organic hydroperoxides. Examples of such i11Il catalysts are benzoyl ireoxide, tertiary butyl peroxide benzoate, dIi isopropylpereoxidicarbonate, cumene hydroperoxide, azobis (isobutyronitrile), and others. Usually, about 0.1 to 5% by weight of thermal initiator is used,
Photoinitiators can also be used to initiate polymerization. Preferred initiators in photoinitiators that accelerate polymerization when the composition is irradiated. Examples of such initiators are acyloin and its derivatives, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl BbB-i, ether and alpha methyl benzoin; dicentons such as benzyl and diacetyl, etc .; ketones, such as acetophenone, C (0 b Trichloroacetophenone, S, 0, CC-tribric acetosphere, s, o6-diethoxyacetophenone, (1ZHAR), 2-hydroxy-2-methyl-1-phenyl-1-pro-papone, 0-nitro-about {, Cx, (- tribromoacetophore
R
, (
non, oenzophenone and p, p-tetramethyl-; dia # 1nobenzo (renon; Ob-adyloxime esters, such as 6eii3HJ- (0--ethoxycarbonyl) -a-monoxime; ketone-new combinations, such as benzofonon (N -methyl diethanolamine) J, benzofenonon / tributylamine and benzophenone / ketone, Michler; and benzyl ketals, such as benzyl dimethyl ketal, benzyl dimethyl tal, and 2,5-dichlorobenzyl dimethyl ketal, 7 Typically, photoinitiators are used in amounts from about 0.01 to 5% by weight,% by weight, by weight, by weight, by weight, by wt. Oligomeric Composition. When co: the amount is less than 0, () 1 wt.%, the degree of photopolymerization becomes zvychaY1yu low totoinitsiator If used in excess of 5% by weight, corresponding improvement is not observed esrfekt;.. 1 aets, preferably about 0.25-1.0% used
(ttoi) un; iat (1p, zitsii.
1 shmmerizable component
iO
15
20
25
thirty
35
40
45
0
five
The polymerization can be carried out mass by known methods.
When the activating energy; lll is ultrario light, the irradiation is usually carried out at a temperature of about 0.5 min to 5 h more than. Following ultraviolet radiation, the composition can be heated at 50-100 ° C to complete the polymerization.
When the activating energy is only heat, the polymerizable is usually carried out at a temperature of from about 40 to 140 ° C for about 3 to 50 hours, the polymerization can also be carried out in stages. Thus, in the first stage, the composition can be heated at 40 to within about 5 to 25 hours and in the second stage it can be heated at 50-100 ° C for 5-25 hours.
However, the polymerization conditions are not limited to such temperatures and time, as well as the use of ultraviolet or heating as the initiating energy.
Suitable catalysts or thermal polymerization initiators include acidic vulcanizing agents such as Brønsted and Lewis acids, for example, aluminum chloride, chlorine, mercury pentasulforide, bis (trihydrogen methanesulfonyl) methane, etc .; Lewis acid adducts such as trifluoride diethyl etherate. boron, boron trifluoride / amine adducts, mercury pentachloride / aniline adduct, tin alkyl carboxy compounds such as dibutyl tin diacetate, etc .; inorganic acids, such as phosphoric acid, and Lewis bases, such as diethanolamine, benzyldimethylamine and triethyl amine. Usually use from 1 to 5 wt.% By weight of the catalyst. Many catalysts give exothermic reactions and crosslink completely for several hours without applying external heat. Many other catalysts, in particular amine adducts, give COMPOSITES that are stable when stored for a long time; -; months, and then can be polymerized by applying heat for several minutes to several hours at temperatures up to 250 s.
When optional radiation is used for polymerization; YuIomerov, where the q group of the i.e. is the -toxy group
It is advantageous to use a photoinitiator, which releases a Lewis acid during radiation. An approach for 1 of these photoinitiators are arylonium salts of halogen-containing complex anions, including, for example, aryl diazonium salts, arylhalonium salts, such as aromatic halonium salts and aromatic halo salt groups, such as aromatic sulfonium salts. Examples of suitable arylonone salts are; p-tcn , 4,4 -biphenyl iodonium-tetrafluoroborate, triphenylsulfonium hexafluorine-free, non-pyrfnexphenyl, triphenyltetramethylenesulfonium tetrafluorohydrate, triphenylselenenium hexachlorophosphate, triphenylsulphonium hexafluoroanthimonate, 4 -phenylphenyl, hexachlorophosphate, triphenylsulphonium hexafluoroanthimonate, 4 -phenylphenyl, and hexahlorophosphate, triphenylsulphonium hexafluoroanthimonate, 4 -phenylphenyl, and hexahlorophosphate, triphenylsulphonium hexafluoroanthimonate, 4 -phenylphenyl, and hexahlorophosphate;
The polymers for lenses in accordance with the invention can be obtained by loading the material to be polymerized into the shape of the desired configuration and polymerization in the form. In this way, you can get devices of the desired final form. The resulting device can be processed and / or sanded, if desired, using technology known in the art.
In addition, the MorjT devices of the invention can be obtained by polymerizing a telechelic perfluoropolyether monomer in the form of a rod, block or sheet, followed by cutting out the device from them. This technology is used when the polymerization product contains at least about 30% by weight of compatible comonomer co-polymerized with perfluoropolyether
0
5 0 5
five
0
five
0
monomer. Where the function D (onalis) of the monomers is resolved, a thermoplastic polymer is obtained, from which the device is molded by injection molding - NLP by means of molding methods
The invention is illustrated by examples. All temperature values are in degrees Celsius and all parts are given in parts by weight, unless indicated otherwise.
Example 1. Preparation of a telechelic perfluoropolyether compound.
In accordance with the procedures described in c- {, a telecholate perfluoropolyether (ether) monomer with terminal hydroxy- was prepared. scrap, having the formula, 0 (C.)) CF.2.CH2-OH and an equivalent weight of hydroxyl of about 1050. In a 250 ml vessel, 222 g of this material with terminal hydroxyl, 3-2.0 g of 2-isocyanatoethyl methacrylate and 0.14 g of dilaurate dibutyl tin. The vessel was closed with a lid and shaken on a mechanical shaker for 20 hours, while a soft exotherm was observed during the first hour. After shaking, the infrared spectrum, removing from the cloudy reaction product, showed the disappearance of the isocyanate. The mixture was dissolved in 400 ml of 1,1,2-trichloro-2, 2,1-trifluoroethane (Freon-113) and sequentially washed with three 100 ml portions of water each. The freon was distilled from the washed material, the residue was shaken in a separating funnel with 500 ml of FC-75 (perfluorinated cyclic ether, supplied by the company ZM Company), and the bottom layer was periodically removed over two days. until there was any more sharing. Remove solvent from. the top layer gave 214 g of light oil (p 1.337), identified by NMR as a substantially pure telechelate perfluoropolysing compound, had the following formula:
Have
about
H2CC-CO-fCH2 NHCO-CH2-CF 04CF2CF20yCF O) ttCF-2-CH -OCNH4CH -bOC-C-C
CH,
where ra / n-ok, 0.6 and m ok, 8.0,
Removal of the solvent from the bottom layer gave 37 g of a cloudy oil.
about
sn.
(p 1.3230), indented with .NMR as
  16147668
S 0
H, (CH,) 2 NHCO-CH CH, 0 (CF, CF, OV (CF, 0), CF, CH, -OCNH (CH,) ,,
SNS
unreacted () (CF, 2 ()) and iefuncture is a basic material that has a perfluoroxyalkyl skeleton,
II g. 2. A round-bottom flask with a capacity of 25 cm, equipped with a magnetic stirrer and a freeze-stop valve, was charged with 9.8 g of a telechelic perfluoropoly-ester-dimethacrylate monomer of example 1, 0.2 g of methyl methacrylate and 0.05 g of O jOd-LIethoxyacetophenone. The mixture was stirred to effect dissolution and then frozen by immersion of KOJi6bi in liquid nitrogen. The flask was evacuated for 5 min under a pressure of 1 Torr. Then the stop-valve closes
from the bag, hung in a vertical position and irradiated from a solar lamp
10 located at a distance of
18 cm. After 5 minutes the form was turned 180 and the irradiation was continued eh; e for an additional 55 minutes. The forms were opened, the polymer lens was removed,
15 It was flexible, transparent, had a refractive index of 1.355 and oxygen permeability of 115 bar peres, measured as described 7. Paragraph 13 and measure 3, carried out similarly to Example 2; using 10 g of telechelate perfluoropolyether monomer in the absence of methyl methacrylate. The resulting contact lens was flexible, transparent and had
the flask and the flask were given the possibility of under-
warm to room temperature. Pro-25 „1, and permeability for freezing / thawing procedure was performed a total of three times.
To dissolve dissolved oxygen from telechelate perfluoro-:
polyester monomer. Flask then 30
125 barrers.
And Example 4. A telehelate perfluoro polyether monomer with a terminal hydroxyl, having the same formula as in Example 1, and having a hydroxyl equivalent weight of 400, was prepared in accordance with the procedures described in ClJ. This material was used to prepare 35 telechelate perfluoropolyether monomer, its formula is /
transferred into a mitten-type bag filled with nitrogen, and part of the contents were loaded into a mold for contact lenses permeable to ultraviolet light using a syringe. After loading the lens form, it is removed.
 ABOUT
 co CH2CF20 () (
CH.
in which the ratio was type 0.6 and in which m was about 3 and n was about 5, the Monomer was prepared by reacting a perfluoropolyether (simple) with terminal hydroxyl with methacryl chloride in accordance with the procedures described first in P1
The contact lens, obtained in accordance with the procedure of Example 2, was transparent, somewhat rigid, had n. 1.360 and an oxygen permeability of 47 barrels.
Example 5. A series of mixtures were prepared from a tele-acetate perfluoropoly-ethylene monomer of Example 1 and methyl-methacrylate (MML) with a content of 0.5% by weight of midrange X of diethoxyacetophenone.
P I
With SNZ
I.
and deoxygenated (oxygen) as described
5 Deoxygenated bag and bag, syringe with syringe leaf forms. Does it consist of two glasses
P (each 15x15 in size on the inner side of 100 microns of glycol terephthalate), was matched as free. Plates are placed i: oM between them with the help of black vinyl electr (total THICKNESS 375 microns la nebolaye tubule n
(CF, 0), CF, CH, -OCNH (CH,) ,,
SNS
from the bag, hung in a vertical position and irradiated from a solar lamp
located at a distance
18 cm. After 5 minutes the form was turned 180 and the irradiation was continued eh; e for an additional 55 minutes. The forms were opened, the polymer lens was removed,
It was flexible, transparent, had a refractive index of 1.355 and oxygen permeability of 115 barrels, measured as described 7. P 13 and measure 3, Carried out as in Example 2; using 10 g of telechelate perfluoropolyether monomer in the absence of methyl methacrylate. The resulting contact lens was flexible, transparent and had
„..
"1, and permeability for sis"; 1, and permeability for sis
125 barrers.
And Example 4: A hydrohexyl terminal perfluoro-polyester monomer having the same formula as in Example 1 and having a hydroxyl equivalent weight of 400 was prepared according to the procedures described in ClJ. This material was used to prepare the telechelic perfluoropolyether monomer, which has its formula /
Ov
P I
With SNZ
I.
and deoxygenated (with oxygen absorption), as described in example 2.
5 Deoxygenated mixtures were transferred in a glove bag filled with nitrogen using a syringe into individual leaf forms. Sheet forms consisted of two glass plates.
P (each 15x15 cm in size), coated on the inside with a 100 micrometer thick film of poly (ethylene glycol terephthalate), which was provided as a release surface. Plates were placed with spaced-i: oM between them using two layers, black vinyl tape of electrical tape (total 375 µM THICK; which had a small channel on one side, allowing the syringe to be loaded and allowing the bubbles to exit. fastened together, hung upright and irradiated from an RS solar lamp located Measured according to ASTM D-542 method. Measured according to ASTM D-882 method. Measured according to Refojo et al. Shae.
PRI me R 6. A mixture of 7.0 g of the telehexaceous perfluoropolyether monomer of example 1, 3.0 g of meta-methacrylate and 0.02 g of diisopropyl peroxycarbonate were mixed and deoxygenated according to the procedure of example 2, the mixture was transferred in a sleeve bag filled with nitrogen , in glass nanometer vessel (inner diameter 14 mm, length 50 mm), the vessel was closed with a lid and heated in an oven for 24 hours, followed by heating for an additional 24 hours, - Bypo found that the resulting light polymer plug had a hardness of Shore D 50, and its Mechanical processing doors using conventional means to obtain contact lenses.
II p and m e. P 7, Carried out analogously to example 6 using a mixture of 5.0 g of the telechelic perfluoropolyether monomer of Example 1, 5.0 g of methyl methacrylate and 0.02 g of diisopropyl peroxycarbonate. The resulting light plug was easily transformed by mechanical processing into conventional contact lenses,
EXAMPLE 8 The wettability of the molded polymers of Example 5, obtained from mixtures of the telechelic perfluoropolyether monomer of Example 1 and methyl methacrylate (MMA), was improved by confirming the molding surfaces to the effect of a glowing plasma.
18 cm. across; The form was turned on for 3 minutes and irradiation continued for another 55 minutes. It was found that the obtained crystalline molded polymers had the properties given in table. one.
Table 1
AC 60 Hz in medium gels at low pressure (400 mtorr). Before and after surface treatment, contact angles with a Sessile water droplet were measured (using an NRL contact angular goniometer, model A-100, manufactured by Rame-Hart, Inc.).
The results are shown in Table. 2,
table 2
0
These data demonstrate the usefulness of glow-glow treatment for improving the surface wettability of products (devices) containing a tele-chelating perfluoropolyether polymer.
EXAMPLE 9 A mixture of 7.0 g of the telechelic perfluoropolyether monomer of Example 1, 3.0 g of methyl methacrylate, 0.8 g of hydroxyethyl methacrylate and 0.06 g, 0b-diethoxyacetophenone was polymerized according to the procedure of example 5. Improved The wettability of this polymer was demonstrated by measuring the contact angle with water after soaking the polymer in water. for 5 days. Received 45. It was found that a similar polymer, not containing hydroxyethyl methacrylate, had 78 °.
II p im 10, A polymer was prepared from a mixture of 5.0 g of the telechelic perfluoropolyether monomer of Example 1, 5.0 g of a compound of formula
About II
BUT
14., - J
| and 0.05 g o (,, o (, - diethoxyacetophenone in accordance with the procedure of Example 5.; It was found that the resulting transparent polymer had a permeability to oxygen of 53 barrera and an index of 1.566 and was suitable for use as a contact lens,
PRI me R 11, A mixture of 7.0 g of telechelate. Perfluoropolyether monomer of Example 1, 2.0 g of N-vinylpyrrolidone, 1.0 g of methyl methacrylate and 0.05 g of 0, o, -diztoxyacetophenone polymerization | in accordance with the method of example 5, the resulting optical and
ABOUT
ABOUT
H2C-C-CO-CH2CH2NHCO-CH2-CF O () () ttClY-CH2-OCNHCH CHrOC-C CH2 i:
sh
in which the ratio m / n is approximately
0.7, that is about 15, n is about. 40 Dow-Corning) 21, and the perfluoropolyether pfm molecules are 4000, 3.0 g of methyl methacrylate and 0.05 g of 2,2-diethoxyacetophenone are polymerized according to the procedure of example 5. Optically pure or light a film having a pp of 1.394, a tensile strength of 150 kg / cm, an elongation of 78%, a modulus of 340 kg / cm, and an oxygen permeability of 95 barrels.
PRI me R 15. A mixture of 4.8 g of telechelic perfluoropolyether monomer of example 1, 1.2 g of methyl methacrylate CH3
(Silkem 21, trademark of the company
and 0.04 g of od, o-diethoxyacetophenone was polymerized according to the procedure of Example 4, an optically pure sheet was obtained, the polymer of which had a tensile strength of 150 kg / cm, an elongation of 78% and oxygen permeability of 96 barreres, and n 1,404,
50 Example 1.6, A mixture of 7.27 g of telechelic perfluoropolyether monomer of Example 1, 2.19 g of methyl methacrylate, 0.54 g of hydroxyethyl methacrylate and 0.05 g of S, 1x1-diethoxyacetophenone is prepared, 1.2 g of a compound of the formula
sns snz about
CHo-Si-0-Si-CHnOCC CH M i I
SNS SNZ
CH:
The cleaner, flexible polymer, as it was found, had the following properties: tensile strength at stretching 105 kg / cm, modulus 1060 kg / cm, elongation 41%, Pr 1.403, contact angle with water 24 ° and oxygen permeability 36 barreres,
EXAMPLE 12 A lens was made according to the procedure of Example 2 from a mixture of 8.0 g of the telechelic perfluoropolyether monomer of Example 1, 2.0 g of vinylidene chloride and 0.05 g of {(1) -diethoxyacetophenone in accordance with the method of example. 2. The resulting contact lens was flexible and transparent and had an oxygen permeability of 140 barrels and 1.385.
Example 13. A mixture of 8.0 g of telechelate perfluoropolyether monomer of Example 1, 2jO g of methacrylic acid and 0.05 g of vol., In α-diethoxyacetophenone, was polymerized according to the procedure of Example 5. The resulting transparent polymer had a tensile strength. Upon stretching 235 kg / cm, elongation
46%
73
oxygen permeability
7 h
barrera and nj, 1.389 and was suitable for use as a contact lens. I
Example 14. A mixture of 7.0 g of telechelic perfluoropolyether monomer having the structure
ABOUT
) ttClY- CH2-OCNHCH CHrOC-C C
ay-corning)
SNS
(Silkem 21, trademark of the company
Dow-Corning)
and 0.04 g of od, o-diethoxyacetophenone was polymerized according to the procedure of Example 4, an optically pure sheet was obtained, the polymer of which had a tensile strength of 150 kg / cm, an elongation of 78% and oxygen permeability of 96 barreres, and 1.404,
Example 1.6, A mixture of 7.27 g of the telechelic perfluoropolyether monomer of Example 1, 2.19 g of methyl methacrylate, 0.54 g of hydroxyethyl methacrylate and 0.05 g of S, 1x1-diethoxyacetophenone were prepared for polymerization using freezing techniques and described in example. 2. The flask was transferred to a mitten bag filled with nitrogen, and some of the contents were loaded from to - 1614766
using a syringe into a contact lens mold. The molded material was a suitable specimen transparent to ultraviolet radiation, so the mixture was left to polymerize for 1 hour under ultraviolet irradiation of low intensity. The resulting lens was transparent, flexible, free of air and had an oxygen permeability of 48 barreres and
14
P
§ 1,395.
II p and me R 17. Polymer film
70/30 of example 5 was evaluated for the adsorption of 15 discharged (shredded) protein as follows .. A solution was created imitating harmonization, which contained the following components for each liter of water 20 solution, g:
Sodium Chloride 8 Calcium Chloride 0.08 Sodium Phosphate (pH 7.4) 1.38 Glutamic Acid 0.075 Lizozim1.7
Albumin; 3.9 J-Globulin1.05
Radioactive proteins were prepared by displacing 5 mg of each protein with 100 MKCJ H-N-succinimidyl propionate and storing the reaction mixture at 0 ° C for 1 hour. N-. succinimidyl propionate, which was not covalently attached to the protein, was separated from the protein by gel permeation chromatography.
Prepared three solutions. Each solution had only one protein component that was radioactive; the other two protein components were non-radioactive.
Samples polyoxyethylmethacrylate pHEMA) in the form of sheets and 70/30 copolyTripalmitin0, 4
Cetyl alcohol 0.03 Oleic acid O, 1 Lecithin 0.16
Vessels into a shaking apparatus in a water bath, which was maintained at. Polymer samples were soaked for 1 day. At the end of this time period, the polymer samples were removed from the vessels and rinsed with brine. The polymer material was placed in a scintillation vial and examined for tritium content. Using this procedure, it was determined that the amount of protein deposited on. polymer material was as follows (see tab. 3).
Table 3
These data show that the amount of protein absorbed by: 70/30 copolymer is much less than the amount of protein adsorbed by HEMA ...
EXAMPLE 18 A mixture of 7.27 g of perfluoropolyethylene monomer of Example 1.2, 19 g of methyl methacrylate, 0.54 g of 2-hydroxyethyl methacrylate and 0.05 g of 2-hydroxy-2-methyl-1 -phenyl-1-pro40
The measure was cut into 0.4 cm pieces prepared for polymerization using the methods of freezing of example 2. The composition was then polymerized into a film, as described in Example 5. Its
and equilibrated in saline (8.3 g sodium chloride / 1.0 l water).
Polymeric samples were individually placed in separate vessels, each of which contained 0.4 ml of the spent solution. A 20 μl lipid mixture was layered on top of the aqueous layer.
The lipid mixture had the following oxygen permeability for 45 barre 5Q tensile strength at stretching was 140 kg / cm, an elongation of 4t%, a modulus of elasticity of 4015 kg / cm, n 1.410. The film was optically clear and had a water contact angle of 47 and
tang, mcg:
Butyl stearate 0.23.
Cholesteryl oleate 0.16
Cholesteryl palminate 0.16
14
Tripalmitin0,4
Cetyl alcohol 0.03 Oleic acid O, 1 Lecithin 0.16
Vessels into a shaking apparatus in a water bath, which was maintained at. Polymer samples were soaked for 1 day. At the end of this time period, the polymer samples were removed from the vessels and rinsed with brine. The polymer material was placed in a scintillation vial and examined for tritium content. Using this procedure, it was determined that the amount of protein deposited on. polymer material was as follows (see tab. 3).
Table 3
These data show that the amount of protein absorbed by: 70/30 copolymer is much less than the amount of protein adsorbed by HEMA ...
EXAMPLE 18 A mixture of 7.27 g of perfluoropolyethylene monomer of Example 1.2, 19 g of methyl methacrylate, 0.54 g of 2-hydroxyethyl methacrylate and 0.05 g of 2-hydroxy-2-methyl-1 -phenyl-1-pro
5Q ultimate tensile strength was 140 kg / cm, an elongation of 4t%, a modulus of elasticity of 4015 kg / cm, p 1.410. The film was optically clear and had a water contact angle of 47 and
ditch
Example 19. A mixture of 4.8 g of a tele chelate perfluoropolyether monomer having the formula
15
sixteen
ABOUT
1614766 O
SGZO- (CF O) CF, CH OCNH-CH. OS - RZ
1 0.03 g o, b -diethoxyacetophenone, the field was impregnated according to the procedure described in Example 5. The resulting film was clean and clean.
permeability 117
and | chalk the oxygen npoi b | arrer, and 1, 365,
ten
SNS
CF30 (CF2-CFO) CF2CF3
 . The strength limit at a stretch of 23.5 kg / cm and an elongation of 657 was suitable for optical purposes.
Telechelate perfluoropolyether monomer prepared using re-2-isocyanateethyl methacrylate with
as described in the example
Cleaned up m
n 2
3J 1.3449. His identity was with the help of I) 5 P R i me R 20
a mixture with the content of (a) plate perfluoropolyether having the formula
  jo o
(CH2) 2 JHCO-CH, CI ,, 0) fn (CF, 0) CF, CH, -OCNH {m l2-OCC
About II
BUT
 ABOUT
where m / n is 0.6, m
about
SNS
8.3,, 25 a p 13.9; (c) 3.0 g of monomer having the formula
About p
H2C CHCH2-NHC-CF, 0-fCF2CF, oyCF, 0), CFrCNH-CH,
in which I m / n 0.6, m 8.3
and n 13.9; (c) 3.0 g methylmetacrillt; (d) 0.25 g oi 0 -diethoxyacetof (shona,
i The mixture was polymerized according to the procedure described in example.
four,
which had a tensile strength of 135 kg / cm and an oxygen permeability of 63 barrera.
The first of the above mentioned telefax perfluoropolymers monomers
Received optically clean film.
About II
about
H3COC-CF, OfCF, CF, 0) JCF, OVCF, - | loCH3,
S
the torment of which is also described in p. 1. The resulting liallsh, and ™ "had
50 formula
oo
HjC CH5-NHC-CF, 0 (CF, Cr, 0) (cr50) nCF2-CNH-CH,
55
in which m / n is 0.6; m 8.3 and p 13.9.
sixteen
NH-CH. OS -
ten
SNS
CF30 (CF2-CFO) CF2CH OH, CF3
as described in example 1.
Enhanced pure oil had
n 2
Oh oh
) fn (CF, 0) CF, CH, -OCNH {m l2-OCC
3J 1.3449. His identification was carried out using NMR. ) 5 P P and me 20 Prepared
a mixture with the content of (a) 6.0 g of teleheplate perfluoropolyether monomer having the formula
About II
35
40
were prepared using the procedure described in example 1, by reacting a perfluoropolyether with a terminal hydroxyl of the shown formula in which m is 8.3., with 2-isocyanatethyl methacrylate. The second of the two telechelic perfluoropolyether monomers was prepared by the reaction according to the procedure described in example 1, using the reaction of allylamine with perfluoropolyether-dicarboxylic acid methyl ester having the formula
about
, 0) JCF, OVCF, - | loCH3,
C R and mera 21. A mixture of 2.5 g of telochelny perft-orpolyester monomer having the formula
About II
about
about
HOC-CH CH CHRNHC-CF O-fCF CF O m Cf O CF -CNH-CH CHfH -COH
(having an equivalent weight of 1200 and obtained in p) and 2.5 g of epoxy-sintered resin (DEA-438, Dow Chemical. Company) were stirred by the cry until a clear clear liquid was obtained. The liquid was transferred into a sheet form from Teflon R and degassed at / 1 mm Hg. for 2 h. Then it was heated at 110 ° C for 48 h,
The resulting optically pure polymer film had a tensile strength of 18.3 kg / cm and an elongation at a cut of 110%.
The perfluoropolyether monomer segment is abbreviated PPE,
PRI me R 22. A mixture of 9.9 g of PRE SOYN-C Hz (CH3) MSO) obtained in accordance with 1 and 0.1 g of a trimerization catalyst (obtained by heating a mixture of trihexylene glycol borate borate (7 g) and sodium salts 2, b-di-tert-butyl-p-cresol (2 g) for 15 minutes at 120 ° C) were removed into a mold and heated for 16 hours. The resulting optically pure polymer had a tensile strength 24.6 kg / cm and an elongation of 180% and was suitable for optical purposes.
P 5 and measure 23, Mixture 24 g PPEiCK 02 CC tt NEz) j (obtained in. 1), 0.4 g cyclohexane triisocyanate; and 1.6 g hexamethylene diisocyanate: stirred in a beaker at room temperature until - ka she did not become homogeneous. The mixture was then transferred to a mold and bottled at 80 ° C for 3 days. The resulting optically pure polymer film had the following properties:. Tensile strength
when stretched
kg / cm 82.2
Elongation,% .280
Hardness PB Shore
A-270
Permeability for
oxygen barrera 190
about
0 5
0
five
0 5
about 5 0
five
PRI me R 24, a Mixture of 4.8 g. РГЕ СН20Н) 2., №1 2000, obtained in l, and 0.8 g of tetrafluorophenylene diisocyanate were stirred for 2 hours at 80 ° С, transferred to a mold and heated in for 16 hours at 80 ° C, followed by v heating for 24 hours at 125 ° C. The resulting optically pure flexible polymer had a tensile strength of 68.2 kg / cm and an elongation of 850% and was suitable for use as a flexible kontak
PRI me R 25 Liquid mixture of 5.0 g
 PPE-f CHoOCHoCHCHi).
V / MM 2000
(obtained in ij) and 0.10 g of the catalyst), CHCNHSCBg (CO., CH2CH3) g (placed in a form and heated for 90 seconds for 30 minutes. The resulting transparent polymer was suitable for use as a flexible contact lens and had permeability for oxygen 221 barrer.
Example 26,
Sample PPE- (CH OCgH40CN) 2., MM 2000,; prepared in accordance with 1, were placed in a mold and heated for 90 min with. followed by heating at 200 ° C for 135 min. The resulting optically pure film had a tensile strength of 42.3 kg / cm and an elongation of 150%,
Example 27 .PPE- {CH NH2.) 2, ™ equivalent weight of 1140 (prepared in accordance with L2 1), was polymerized into polyimide by reaction with a mixture of dicyclo- (2.2.2 - - Octane- (7) -2,3,5,6-tetracarboxylic acid and 4,4-methylenediphthalic an-, hydride according to the procedure described in. We obtained a flexible,; thermoplastic, transparent polyimide; that was easily molded,
P. 28, Illustrates an increase in the molecular weight of the telechelate perfluoropolyether monomer by lengthening the chain. A mixture of 108.0 g iPPE (). C4D having a molecular weight of 2160 (0.05 mol), and 1.85 g of 1,3-diaminopropane (0.025 mol) of fur 16 until
While the mixture was shaken until the pH value of the mixture showed no more presence of unreacted diamine (15–20 min), 3.05 g of ethanolamine (0.0500 mol) was added to Nath. After shaking for several hours, the pH value of the mixture no longer showed the presence of

ten
ethanolamine, Acrylate of this telehexyl perfluoropolyether monomer; With an extended chain and ethanolamine: A end cap was prepared as described in. using 20.00 g of an extended chain monomer, 1.01 g of acryloyl chloride and 2.24 g of trn-ethylamine. A mixture. of this long chain monomer, 0.49 g of methyl; methyl methacrylate, 0.36 g of N-vinylpyrro-IvDon, and 0.0200 g of 2-hydroxy-2-methyl-1-fer - 20 | Nilpropan-1-one were polymerized, as described in example 2, when irradiated with an RS solar lamp for 30 minutes, the resulting polymer had the following properties and was used at the preparation of a contact lens: tensile strength | 105 kg / cm, a modulus of 1680 kg / cm, an elongation of 28% and permeability to oxygen.
is obtained from the corresponding dimethyl ester in accordance with method 1-1 by ester exchange using a large excess of allyl alcohol instead of 1,1,5-trihydro-octafluoro pentyl. The resulting product is copolymerized with 20 wt.% methyl methacrylate in a mold for casting lenses using the method Example 5: Example 2, yielding flexible, transparent lenses with oxygen permeability of at least 20 barrers. In the monomer is contained as a Q-group.
ABOUT
ti C CtiCE - and as a group
| tsa 10S barrers, Example 29.
 ABOUT
i ,, II
PPE (CH2NHC-C CH2) 2 get
, .TS
| by adding 1 g (0.01 mol): vegan distilled methacryloyl chloride into an intensively stirred mixture of 5 ml 2N. sodium hydroxide, 20 ml of FC-75 and 10 g of PPEiCH NE -), (0.009 eq.), described in example 27. After stirring for 3 h, the aqueous phase is separated, FC-75 is removed by distillation to obtain the desired product . It is polymerized in a mold for pouring lenses as in Example 2, producing a polymer lens which is characterized by flexibility, transparency and
thirty
PRI me R 31. A mixture of 4.8 g of PPEiCE OE with M14 2000 prepared according to p, 5.0 g of dimethyl ester of Example 30 and 3 drops of trifluoromethanesulfonic anhydride are heated in a metal Wood bath in a continuous flow of nitrogen for 3 hours to hold this temperature for 6 hours. Upon cooling the reaction mixture, a transparent polymer is obtained which is machine-processed into contact 35 lenses with oxygen permeability of at least 20 barrels. In the monomer as Q- the group contains -COOH and -OH, and as a group nN W
About II
—COCH2e p 32.
40
Note o
45 HSCH CH2NHCCF2 (CF2Cr, 0) 23 (CF20) 5.2CFjCNHCHjCH2SH,
obtained according to the method described for compound 5 in (1), in coli. . . ≤ 0.005 mol, 5 g, heated with
permeability to oxygen is less than 50 1 dimethyl adipate and 3 drops of anhydrous, 20 barrers. As a group, trifluoromethanesulfonic acid
Py W in the monomer contains -CH, -, and
as a Q group
in a constant stream of nitrogen in Wood's metal bath at 200 ° C. for 6 hours. Upon cooling, a polymer is obtained, 55 of which contact lenses with oxygen permeability for n / m 20 barreres are obtained by machine. The polymer contains -SH as the Q group, and as the W group
Have
CH2 C CNHGNg
20
Example 30

OO
Iiii
H2C CH-CHjOC-CF, 0 (CF, CF, 0) e, 3 (Cr, 0), j, CFfOCH ,,
is obtained from the corresponding dimethyl ester in accordance with method 1-1 by an ester exchange using a large excess of allyl alcohol instead of 1,1,5-trihydrooctafluoro pentyl, the resulting product is copolymerized with 20 wt.% methyl methacrylate in a lens mold, using of Example 2, obtaining flexible, transparent lenses with oxygen permeability of at least 20 barrels. In the monomer is contained as a Q-group
ABOUT
ti C CtiCE - and as a group

PRI me R 31. A mixture of 4.8 g of PPEiCE OE) with M14 2000 prepared in accordance with p, 5.0 g of dimethyl ester of Example 30 and 3 drops of trifluoromethanesulfonic anhydride are heated in a Wood's metal bath a continuous stream of nitrogen for 3 hours before this temperature is maintained for 6 hours. Upon cooling the reaction mixture, a transparent polymer is obtained, which is machine-processed into contact lenses with oxygen permeability of at least 20 barrels. In the monomer as Q- groups contain -COOH and -OH, and as groups s W
About II
—COCH2e p 32.
Note o
45 HSCH CH2NHCCF2 (CF2Cr, 0) 23 (CF20) 5.2CFjCNHCHjCH2SH,
 trifluoromethanesulfonic acid
in a constant stream of nitrogen in Wood's metal bath at 200 ° C. for 6 hours. Upon cooling, a polymer is obtained, from which contact lenses with oxygen permeability for n / m 20 barreres are obtained by machine. The polymer contains -SH as the Q group, and as the W group
About II
-CH2CH2NHCn p m ime r 33.
(H3CCH20) 3Si (CH2) 3NHC-CF, 0 (Cr2CF20) t6 (CF20) 2sCF2-CNH (CH2) 3Si (OCHoCH
obtained by reacting dimethyl ether
H3COC-CF20 {CF2CF20), 6 (CF20) 28CF2-COCH3
3-aminopropyltriethoxysilane. A mixture of 12.0 g of this compound, 1.8 g of tetraethylsi-pikat and 0.24 g of dibutyltin di-acetate is heated in a flat-bottomed but-petrobe petri dish with a diameter of about 8 cm at about 90 ° C in a stream of nitrogen for about 30 minutes The product is polymerized to a flexible polymer with a thickness of about 2 mm, from which
It is possible to obtain contact lenses with a single bond as a group of oxygen for oxygen, at least 35.5 g CF SO OCEyCFiO, at least 20 barrels. As Q-rpyn- () (CF20: gCF2CH OSOj, CF3 (half-monomer contains -Si (OR), and rolled in accordance with the GP) heating of the group W.with 1 g of dimethyl adipate in continuous Q30 ° nitrogen flow at 150 ° C for
.111 h. Upon cooling, polyester is obtained,
from which oxygen permeability lenses are made n / m 20 barrers; As a Q group, the monomer co (CF, 0) 2g CFgCN is obtained in accordance with the group, and as a group
(CH21 SSCP im im 34. NcbvXCF CFj O),;
VII with the method described in 1.0 g polycyclotrimerized to poly-.
W-CH.;, -.
PRI me R 36.
Ooh
(CH2I20CNH CH3
oo
NII
NHCOCH2C O (CF2CF20) 9 (CF20) ioCF2CH30C
About II
nzs
from a hydroxyl-terminated telechelate perfluoropolyether (see Example 1) by loading a 250-mm flask with 222 g of a hydroxyl-terminated material, 36 g of 2,4-toluene diisocyanate and 0.14 g of dibutyltin dilaurate. The flask is closed and shaken for 20. h, then otkryshayut with the addition of 26 g of 2-hydroxyethyl methacrylate. Dimethacrylate monomer is copolymerized in a mold for casting lenses with 20 wt.% Methyl methacrylate.
Sym.-triazine by heating 10 g in a packed tube with 3 drops of trifluoromethanesulfonic acid for 36 hours at 90 ° C, then 3 hours at.
The polymer obtained is then used to obtain contact lenses with permeability of oxygen dd n / m 20 barrels. The monomer used contains as a Q-group -CNV. and covalentizes of which are manufactured for acids, as Q holds, and
W-CH.;, -.
PRI me R 36.
About II
nzs
(CH2) 20CNH CH3
0
Example 2, obtaining a polymer lens with oxygen permeability n / m 20 barreras. The monomer contains
. О: Н2С ССО СНз
as a Q-group and
ABOUT
P
- (CH,) 20CNH -L-MHCOSN, - as group W.
- - 16 II p and m r 37. By repeating Example 36 with the use of g (0.1%) - 0.5 g (5.0%) C) of C-diethoacetoacetophenone, similar lenses are obtained, except that in the case of formulations containing less than 0.25% of the photoinitiator, UV irradiation takes longer than about 2 hours. II p and measure 38, When repeated with if.epa 6 using 0.001 g (0.01%) Instead of 0.02 g of diisoproplperoxicar (onate, similar contact lenses are obtained. If 0.5 g (5.0%) of diisopropyl peroxydicarbonate is used as a thermal catalyst, | | the same1 results are obtained at ( occurrence of polymerization in a water - 1 | 1st bath at 30 C for 24 hours,
Example 39, Example 9 IJ repeated; using 6.3 g of telechelic orfluoropolyether monomer according to irimer 1 ji, 2.7 g of methyl methacrylate, I g of hydroxyethyl methacrylate and 1 g (x;, N-di-: | toxiadetofenone). suitable for use in contact lenses, I II p and me 40. Example 9 repetition using 6.86 g of telehelate ijioro perfluoropolyether monomer with example 2, 2.94 g of methyl methacrylate, 0, 2 g of hydroxyethyl methacrylate and 0.2 g of 0, () -diethoxyacetophenone. A semi-polymer has an improved (wettability and is suitable the manufacture of contact lenses, the effective fractions of fluorine used in the mixture of monomers according to the invention, and the oxygen permeability of the lenses obtained are given in Table 4,
Table 4

2 3 4 5
0
50
50
49,8
40
35
25
55.5
115,125
47 60
30 10 53
24 Continuation of table 4
20

权利要求:
Claims (3)
[1]
Invention Formula
 A method for producing dp contact lens polymers by polymerizing a fluorine-containing non-bonding compound, characterized in that, in order to increase the oxygen permeability of the lenses, the telechelate perfluoropolymer compound of the general formula is used as a fluorine-containing unsaturated compound.
thirty
20
35
QW
oh
where Q is H2C C-CO-, CHj
0OCN
 ,
45
sn
-NH, -ON, NAS SI, / оV-
OCN
OO
 Ii. P50 -; OC-05H5VCH2 C - CNH-vH2C cHCHj, CH3
-SH, -81 (,) з, -CN,,;
ABOUT . oo
- (, .. СОСН2- -CH CH NHCI / -
Bn OHN-CH NO, NHo-)
Have
Where
-CK, -CHgOCH-j -,, covalent-a bond,
OO
CHt) jOCNHRjNMCOCM2.,
 f - OCZ-WZ-W-Q or CFjO-; p - from 3 to 44; q - 1; k is from 1 to 2, and the process is carried out in the form.
[2]
2. The method according to claim 1, characterized in that the process is carried out in the presence of 2-50% by weight of the monomial t- and o
a moat of an ethylenically unsaturated compound selected from the group consisting of methyl methacrylate, N-vinyl pyrrolidone, viylidene chloride, methacrylic acid, a compound of the general formula
About II
S7N15en20ssn.
[3]
3. The method according to claim 2, distinguishes t5 y and n that the process is carried out in the presence of 2-10% by weight of hydroxyethyl methacrylate monomers.

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同族专利:

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公开号 | 公开日

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AU1051483A|1983-07-28|

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EP0084406A1|1983-07-27|

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US4440918A|1984-04-03|

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DE3364450D1|1986-08-21|

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JPH0342446B2|1991-06-27|

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AR242666A1|1993-04-30|

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ES518987A0|1984-08-16|

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IL67699D0|1983-05-15|

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IL67699A|1986-09-30|

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AU559669B2|1987-03-19|

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EP0084406B1|1986-07-16|

---

JPS58127914A|1983-07-30|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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US06/340,473|US4440918A|1982-01-18|1982-01-18|Contact lens containing a fluorinated telechelic polyether|

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