GB2086400A - Water-absorptive vinyl lactam polymer compositions - Google Patents
Water-absorptive vinyl lactam polymer compositions Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/58—Adhesives
- A61L15/585—Mixtures of macromolecular compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/14—Post-treatment to improve physical properties
- A61L17/145—Coating
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/08—Materials for coatings
- A61L29/085—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
- A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
- A61L29/145—Hydrogels or hydrocolloids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/24—Nitric oxide (NO)
- C01B21/26—Preparation by catalytic or non-catalytic oxidation of ammonia
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J139/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
- C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09J139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
Abstract
The composition is capable of absorbing more than 45 % of its weight of water without dissolving at room temperature to form an optically clear hydrogel. The composition is employed especially for the preparation of catheters or sutures or antimist glass sheets.
Description
SPECIFICATION
Water-absorptive compositions
This invention relates to a composition capable of absorbing more than 45% of its weight of water without dissolution at room temperature to form a hydrogel and pertains more specifically to an optically clear blend of a water-soluble poly(vinyl lactam) or of a water-soluble copolymer of a vinyl lactam with 1 to 90 mole percent of copolymerizable monomer containing a polymerizable ethylenic unsaturation, with a water-insoluble copolymer derived from 50% to 90% by weight, based on the total weight of the copolymer, of a hydrophobic water-insoluble ethylenically unsaturated monomer, 2% to 12% by weight of an ethylenically unsaturated monomer containing an acid group, and 1 5 to 45% by weight of a hydrophilic ethylenically unsaturated monomer free from acidic groups.
It has previously been proposed to insolbilize polymeric N-vinyl lactams such as poly(vinyl pyrrolidone) by reaction with water-soluble polymers containing carboxyl groups, the reaction product precipitating from solution when the two are mixed, as described in Stoner U.S. Patent 2,901,457. As pointed out by Stoner et al. at column 4, lines 56-73, the reaction product there described always has substantially the same properties and contains the two polymeric components in the same proportions regardless of the proportions of the two used to make the product. The compositions of the present invention, on the other hand, vary in properties and in proportions of components depending upon proportions of starting materials. It has also been proposed in O'Driscoll et al. U.S. Patent 3,700,761, in
Grucza U.S.Patent 3,807,398, and in Le Boeuf et al. U.S. Patent 4,018,853 to make covalently crosslinked hydrogels by polymerizing hydrophilic methacrylate monomers in the presence of poly(vinyl pyrrolidone). Moreover, it has been reported in Boyer-Kawnoki, Compt. Rend., Ser. C, Vol. 263, p. 278 (Chem. Abs. Vol. 65, 20283d) 1966 that an I.R. spectrum of the addition product of polyvinyl
Pyrrolidone) and poly(acrylic acid) indicated hydrogen bonding between the pyrrolidone carbonyl groups and the carboxyl groups of the poly(acrylic acid). In Ono et al. U.S.Patent 3,975,570, it has been proposed to improve the moisture permeability of conventional pressure-sensitive adhesives which are copolymers of alkyl acrylates with acrylic or methacrylic acid by blending with them hydroxyethyl cellulose, and it was stated that blends of such adhesives with poly(vinyl pyrrolidone) did not exhibit improved moisture permeability. Other blends of a poly(vinyl lactam) with various copolymers are described and claimed in copending applications of Shah Serial No. 137,297 filed April 4, 1 980 and of
Shah and Temin Serial No. 142,986 filed April 23, 1980.
The compositions of the present invention are capable of absorbing more than 45% of their own weight of water when immersed in water at room temperature and may absorb even more than ten times their weight of water. Despite the absorption of such large amounts of water, the compositions retain their coherence and dimensional integrity and do not dissolve; these characteristics make them particularly useful for several bio-medical purposes which require that the hydrogel come into intimate contact with body tissue or cavities.
The mechanism of interaction between the water-soluble vinyl lactam polymer or copolymer and the water-insoluble copolymer in the blend is not fully understood, but the blend does behave like a physical mixture rather than a chemical reaction product in that it can be separated into the two polymeric components by gel permeation chromatography. The blends are optically clear and substantially free from haziness, indicating that the blend is homogeneous despite the fact that the vinyl lactam polymer or copolymer is water-soluble and the copolymer is water-insoluble. Examination at high magnification under an electron microscope shows the presence of microphase domains (4000 A or less in diameter) of water-insoluble material dispersed in the continuous phase of water-soluble vinyl lactam polymer or copolymer.The presence of these microphase domains of the water-insoluble copolymer prevents dissolution of the continuous phase polymer in water, but unlike covalent cross-linking of polymers does not render the blend non-thermoplastic. Instead, the blend possesses the ability to be repeatedly shaped or formed under moderate pressure at a temperature as low as 1 500C., or in some cases even lower.
The shaped or formed composition retains its shape at room temperature subject to distortion when swollen with water. The compositions of the present invention in which the dispersed submicroscopic particles (micro-phase domains) act as multiple cross-links to prevent dissolution of the hydrophilic continuous phase (which by itself is water-soluble), form a new class of hydrogels, distinct from those in which the cross-linking is provided by weak cohesive forces, hydrogen bonds, ionic bonds, or covalent bonds.
The vinyl lactams, polymers and copolymers of which can be used in the present invention, are
preferably N-vinyl lactams including those having the structure
in which X represents an alkylene bridge having three to five carbon atoms, such as 1-vinyl-2- pyrrolidone, 1-vinyl-5-methyl-2-pyrrolidone, 1 -vinyl-2-piperidone, and N-vinyl-E-caprolactam,
homopolymers of 1 -vinyl-2-pyrrolidone being excluded. The polymers and copolymers may also be formed from various N-vinyl oxazolidinones including N-vinyl oxazolidinone itself and various 4- and/or
5-alkyl substituted N-vinyl oxazolidinones.The copolymerizable monomers with which the N-vinyl
lactams can be copolymerized to form copolymers containing 10 to 99, preferably 25 to 99, mole
percent N-vinyl lactam and correspondingly 1 to 90, preferably 1 to 75, mole percent of comonomer,
include N,N-dimethyl acrylamide, glyceryl methacrylate, diethylene or triethylene glycol
monomethacrylate or other hydrophilic monomers, as well as vinyl acetate, alkyl acrylate or
methacrylate, vinyl alkyl ethers, acrylonitrile, vinyl chloride, or other hydrophobic monomers. In the case
of monomers such as vinyl acetate which themselves form water-insoluble homopolymers, the upper
limit of the amount of such monomer which can be employed to form the desired water-soluble
copolymer is much lower than in the case of monomers such as N,N-dimethyl acrylamide which form
water-soluble homopolymers.These polymers and copolymers may have molecular weights from
10,000 to 1,000,000 or more, but those having molecular weights to 1,000,000 are preferred.
Copolymers of 1 -vinyl-2-pyrrolidone are preferred.
The water-insoluble copolymers which can be employed as blends with the vinyl lactam polymer or
copolymer in the compositions of the present invention include water-insoluble copolymers of a
hydrophobic water-insoluble ethylenically unsaturated monomer such as alkyl esters of acrylic or
methacrylic acid in which the alkyl group has from 1 to 1 6 carbon atoms, styrene, acrylonitrile, vinyl
acetate, vinyl butyrate, vinyl chloride, vinylidene chloride, ethylene, propylene, butylene butadiene and
other polymerizabie alkadienes, vinyl alkyl ethers and vinyl alkyl ketones in which the alkyl group has 3 or more carbon atoms.The copolymers also include as another essential monomer an ethylenically unsaturated monomer containing an acid group such as a carboxylic, sulfonic, or phosphonic acid group;
among suitable acidic monomers are acrylic acid, methacrylic acid, crotonic acid, maleic acid, 2
sulfoethyl methacrylate and 1-phenyl vinyl phosphonic acid. The third monomer is selected from a
group of hydrophilic ethylenically unsaturated monomers possessing a solubility parameter in excess of
11 [calories/cm3]2, free from acidic groups, such as methacrylamide, acrylamide, p-styrene
sulfonamide, hydroxyethyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol
monomethacrylate and glyceryl methacrylate.
In the case of each of the three types of monomers a mixture of two or more individual monomers
of the same type can be used.
Compatability or incompatability of the water-insoluble copolymer with the water-soluble vinyl
lactam polymer or copolymer in the hydrated form of the blend, that is, its suitability for use in the
present invention, can in each case be readily determined by visual examination of a blend of the two
polymers after equilibration in water at room temperature. If the blend is transparent and optically clear
and remains so after immersion in water at 200C. without dissolution in the water, it forms a
satisfactory hydrogel. If the blend is cloudy or opaque after equilibration in water, or if it dissolves in
water at 200 C., the blend made from that copolymer is not satisfactory and possesses poor mechanical
properties.For a blend composition to possess satisfactory mechanical properties in the hydrated form,
the size of the microphase domains of the terpolymer in the hydrogel should not be greater than
4,000 , and preferably should be below about 1000 A.
The relative proportions of the different monomers in the water-insoluble copolymer may vary
widely; the hydrophobic water-insoluble ethylenically unsaturated monomer may amount to 50% to
90% by weight, based on the total weight of the copolymer, while the ethylenically unsaturated
monomer containing an acidic group may amount to 2% to 12% by weight; the hydrophilic ethylenically.
unsaturated monomer may amount to 1 5 to 45% by weight. The exact proportions of the three types of
monomers are determined by the hydrophobic-hydrophilic balance required in each case.
Thus, in the case of one preferred class of water-insoluble copolymers the amount of methyl
methacrylate (or styrene or 2-ethylhexyl acrylate) is from 55 to 70% by weight based on the total
copolymer weight, the amount of acrylic acid is from 2 to 12% by weight, and the amount of
methacrylamide is from 2543% by weight.
In the case of another preferred water-insoluble copolymer, the amount of n-butyi methacrylate is from 55 to 80% by weight based on the total copolymer weight, the amount of acrylic acid is from 2 to
12% by weight, and the amount of methacrylamide is from 1 5 to 35% by weight.
In the case of still another preferred water-insoluble copolymer, the amount of n-butyl methacrylate is from 50 to 78% by weight of the total copolymer, the amount of acrylic acid is from 2 to 12% by weight, and the amount of hydrophilic p-styrene sulfonamide is from 20 to 35% by weight. In another preferred water-insoluble copolymer, the amount of n-butyl methacrylate is from 55 to 70% of the total copolymer weight, acrylic acid is from 2 to 12%, and hydroxyethyl methacrylate is from 25 to 43%.
The relative proportions of water-soluble vinyl lactam polymer or copolymer and of waterinsoluble copolymer in the blend vary over a wide range, from 40 to 98% by weight, preferably from 50 to 98%, based on the total weight of the blend, of the former and from 2 to 60% by weight, preferably from 2 to 50%, of the water-insoluble copolymer; optimum proportions of each within the range vary depending upon the particular properties desired in the blend as well as upon the identity of the particular polymer or copolymer present in the blend. The greater the proportion of the water-insoluble copolymer in the blend, the lower is the equilibrium water content of the resultant hydrogel.The water content of the blend hydrogels of this invention can be varied from approximately 30% to 95% or higher by judicious selection of the water-soluble and water-insoluble polymer and copolymer and its proportion in the blend. In general, the higher the water content of the hydrogel, the poorer becomes its mechanical properties.
The blend can be made by mixing together solutions or dipersions of the water-soluble polymer or copolymer and of the water-insoluble copolymer in any desired vehicles or solvents which are miscible with each other, then removing the vehicle or solvent, as by evaporation. It may also be possible to blend the two components on a hot roll mill or in an extruder or in other conventional mixing equipment.
Shaped articles of the blend can be prepared by casting from a suitable solvent or by a molding process under the influence of heat and pressure.
The thermoplasticity of these hydrogel-forming blends confers on them a special processing advantage over covalently cross-linked synthetic hydrogels. Tailoring of mechanical and physical properties (e.g., water content, solute and water permeability, softness, flexibility and tensile strength) of the hydrogel is readily accomplished by control of the physico-chemical characteristics and the proportion in the blend of the water-insoluble copolymer. In addition, the physical properties of the blend can be modified by the inclusion of a compatible, water-soluble suitable solvent. The coating has a good adhesion to glass, is colorless, optically clear, and non-fogging upon exposure to hot, moist air.
The following specific examples are intended to illustrate more fully the nature of the present invention without acting as limitations upon its scope.
EXAMPLES 1-8
A series of water-soluble 1 -vinyl-2-pyrrolidone copolymers containing varying proportions of vinyl acetate, N,N-dimethylacrylamide, and mixtures of both of the latter two was prepared by dissolving the desired proportions of monomers in equal volumes of methanol and by employing as initiator approximately 0.15% by weight (based on monomers) of a free radical generator such as 2,2'azobisisobutyronitrile. Polymerization was carried out under solvent reflux conditions to a degree of conversion of about 9095%, and the copolymer was obtained as a residual brittle transparent and colorless solid after evaporation of solvent and residual monomers by heating the reaction mix at 1000C. under vacuum.
A water-insoluble copolymer of a mixture of 62 parts by weight of n-butyl methacrylate, 30 parts of methacrylamide, and 8 parts of acrylic acid was prepared by a conventional solution polymerization procedure by dissolving the desired proportions of monomers in a 1 1 by weight mixture of ethyl alcohol and dioxane and by employing as an initiator of polymerization a small amount (0.20.4% by weight of monomers) of a free radical generator such as azobisisobutyronitrile or 2-t-butylazo-2cyanopropane. Polymerization was carried out at 80--950C. to a high degree of conversion. The colpolymer was isolated from the reaction mixture by precipitation into methanol, collected by filtration, and dried at 1000C. under a vacuum.
Blends of the water-soluble and water-insoluble copolymers were prepared by dissolving the copolymers in the desired proportions in N,N-dimethylformamide to obtain a solution containing 10-1 5% by weight of the polymeric blend and subsequently evaporating the solvent at 1 000C in vacuo, leaving a mass of optically transparent blended solid material. Approximately 8-12 mil thick sheets of the blends were compression molded, after which they were equilibrated in deionized water at room temperature for 72 hours.
The compositions of the vinyl pyrrolidone copolymers, the amounts of the copolymers in blends with the water-insoluble copolymer, and the equilibrium water content of each hydrogel blend in deionized water at room temperature after 72 hours are set forth in-the following Table I. in each case the blends were optically transparent solids, forming optically transparent hydrogels when equilibrated in water.
TABLE I
Water-Soluble Blend Copolymer Parts by Weight Mole Ratio of Water-Soluble Equilibrium Example Copolymer per Water Content No. - DMA VP VA 100 Parts of Blend Weight % 1 - 50 50 90 70 2 - 50 50 70 59 3 90 10 - 90 77 4 90 10 - 70 65 5 70 30 - 90 79 6 70 30 - 70 67 7 50 25 25 90 76 8 50 25 25 70 65 DMA - N,N-Dimethylacly lamide VP -N-Vinyl Pyrrolidone
VA - Vinyl Acetate EXAMPLE 9
Poly-E-caprolactam (Peak M.W. 36,000) was prepared as follows:
200 mg. of azobisisobutyronitrile (AIBN) were dissolved in 1009. of N-vinyl-E-caprolactam which had been previously heated to 450C in a beaker. The solution was kept in an oven at 750C for 4 hours, by which time the composition had polymerized to a solid mass.The solid was dissolved in one liter of chlorform and the solution added dropwise to ten liters of petroleum ether (B.P. range 300C-600C) with agitation to obtain a granular precipitate of polymer; the polymer was isolated by filtration and dried in a vacuum over (500C--3 hours at 100 mm Hg). The yield was 75 g. of polymer whose gel permeation chromatographic peak M.W. was 36,000. The infra-red spectrum showed absorption at
1640 cm~1, characteristic of lactam carbonyl.
EXAMPLES 10-13
Each of the copolymers of these Examples was prepared by conventional solution polymerization
procedure by dissolving the desired proportions of monomers in a suitable solvent, the compositions of
the polymerization mixtures being shown in Table II, and by employing as an initiator of polymerization a
small amount (0.20.4% by weight of monomers) ofa free radical generator such as
azobisisobutyronitrile or 2-t-butylazo-2-cyanopropane. Polymerization was carried out at 80--950C to
a high degree of conversion. Copolymers of the Examples 10 to 12 were isolated from the reaction
mixture by precipitation into methanol, collected by filtration, and dried at 1000C under vacuum,
whereas the colymer of Example 13 was isolated by removal of the volatiles by heating in vacuum at 1000C.
TABLE II
Example No.
Reaction Ingredients 10 11 12 13 Comonomers - Grams Methyl methacrylate 65 - - Methacrylamide 30 30 15 30 Styrene - 55 - - Acrylic acid 5 5 5 5 n-Butyl methacrylate - - 80 2-Acrylamido-2-methyl- propane sulfonic acid - - - - 2-Ethylhexyl acrylate - - - 65 Solvents - Milliliters Ethanol 100 100 100 100 Dioxane 100 100 100 N,N-Dimethylformamide - - - 100
EXAMPLES 14-20 Each of the blend compositions of these Examples was prepared by dissolving in N,Ndimethylformamide the desired proportions of the water-insoluble copolymer and the poly-Ecaprolactam as prepared in Example 9 to obtain a solution containing 10-15% by weight of the polymeric blend. The solution of the blend was then heated at 1000C under a vacuum to evaporate the solvent, leaving a mass of optically transparent blended solid material.The blend, which was thermoplastic, was pressed into a disc in a mold heated at 1 500C. The molded disc was placed in deionized water for 72 hours, during which time it absorbed water and swelled to form a hydrogel. The compositions of the blends, their physical appearance, and the equilibrium water content of their hydrogels are described in Table Ill.
TABLE lil
BLEND OF COMPOSITION PHYSICAL APPEARANCE Parts by Weight of Copolymer poly-E-caprolactam Equilibrium Example of Example per 100 parts of Dry Hydrated Water Content No. No. the Blend Form Forum Weight % 14 10 70 Transparent, Transparent, 68 solid strong 15 10 90 , . , . 91 16 11 70 ,. .. 58 17 11 90 ,, ,, 80 18 12 90 ,, Translucent, 70 coherent 19 13 70 ., Transparent, 77 strong 20 13 90 ,, ,, 90 EXAMPLE 21
Examples 14 to 20 were repeated using a higher molecular weight polyvinyl caprolactam (Peak M.W. 8,000,000). This polyactam was prepared by solution polymerization in methanol. Thus a solution of 1009. of N-vinyl-E-caprolactam in 550 ml of methanol was dissolved 100 mg. of azobisisobutyronitrile as initiator.The solution was stirred for 20 hours at 500C while under nitrogen in a resin kettle equipped with a reflux condenser. The polymer solution was dried in a vacuum oven at 50OC and 10 mm pressure. The peak M.W. was 500,000.
The results were similiar to Examples 14 to 20.
EXAMPLE 22
Examples 14 to 20 were again repeated using a poly-N-vinyl-E-caprolactam prepared in water similiarly to the polymer preparation of Example 22, but using water in place of methanol and 1 .2g of potassium persulfate and 0.6g of solution metabisulfate in place of AIBN. The temperature-time sequence was 500C for 3 hours and then 600C for 17 hours (rather than 50"C for 20 hours). The peak molecular weight was 600,000.
EXAMPLE 23
Examples 14 to 20 were again repeated using in lieu of the polyvinyl caprolactam, the following polymers:
(a) polyvinyl 2-piperidone (H.W.-250.000)
(b) polyvinyl -5-methyl-pyrrolidone (H.W. -360,000) (c) polyvinyl oxazolidinone (H.W. -- 40,000) (d) polyvinyl oxazolidinone (H.W. - 350,000).
(e) polyvinyl-5-ethyl-oxazolidinone (H.W. - 340,000)
The results were similiar to those of Examples 14 to 20.
EXAMPLE 24
Hydroxyethyl methacrylate (HEMA) was purified by extracting (4 to 6 times) a 1:1 solution of the polymer in water with petroleum ether, then saturating the aqueous monomer solution with sodium chloride, and extracting the monomer with chloroform. The combined chloroform extracts were dried over anhydrous magnesium suifate and the solution distilled in vacuo (0.1 mm on Hg) using cuprous chloride as inhibitor. The monomer fraction distilled over at 70-820C.
A copolymer of 52% butyl methacrylate, 40% HEMA and 8% acrylic acid was prepared in the usual way, as described in Examples 1 0-1 3, employing 25% concentration of the monomers in a mixture of ethyl alcohol and dioxane.
Optically clear blends of the copolymer in varying proportions with each of the polymers of
Examples 9,21,22 and 23(a) to (e) were prepared as described in Examples 14-20 by dissolving the copolymer and the polymer in dimethylformamide and subsequently evaporating the solvent at 1 OO"C in vacuo. Approximately 8-12 mil thick sheets of the blends were compression molded, after which they were equilibrated in deionized water at room temperature for 72 hours. It was found that blends containing 70, 80 and 90% by weight of the polymer formed hydrogels containing 75.8%, 82.3% and 88.9% by weight of water, respectively.
EXAMPLE 25
A copolymer of 62% butyl methacrylate, 8% acrylic acid, and 30% methacrylamide was prepared by the same general method as described in Examples 10-13, and optically clear blends of the resultant copolymer with amounts of each of the polymers of Examples 9, 21, 22 and 23(a) to (e) of from 60 to 90% by 5% increments were prepared as described in Examples 1-8.
It was found that a linear relationship existed between the proportion (10 to 40%) of the copolymer in the blend and equilibrium water content of the resultant hydrogels.
EXAMPLE 26
Examples 1 to 8 were repeated except that in place of 1 -vinyl-2-pyrrolidone used as a component of the copolymer (Examples 1-6) orterpolymer (Examples 7 and 8) there were used:
(a) N-vinyl-2-piperidone
(b) N-vinyl-5-methyl-pyrrolidone
(c) N-vinyl-4-methyl-5-butyl:oxazolidone (d) N-vinyl oxalidinone
The results are similiar to those of the other Examples.
The blends of the present invention possess the properties of thermoplasticity, fusibility, and solubility in organic solvents as well as hydratability. But while they retain the thermoplasticity, fusibility, and solubility in organic solvents of the vinyl lactam polymer or copolymer portion of the blend, they exhibit varying hydration characteristics of that portion depending upon the amount of copolymer present.
Claims (14)
1. A composition capable of absorbing more than 45% of its weight of water without dissolution at room temperature to form an optically clear hydrogel consisting essentially of an optically clear blend of (1) 40 to 98% by weight, based on the total weight of the blend, of a water-soluble polymer of a vinyl lactam or a water-soluble copolymer thereof with 1 to 90 mole percent of copolymerizable monomer containing a polymerizable ethylenic unsaturation but excluding homopolymers of 1-vinyl-2- pyrrolidone, said polymer or copolymer having a molecular weight of at least 10,000 and (2) 2 to 60% by weight of a water-insoluble copolymer consisting essentially of 50 to 90% by weight, based on the total weight of the copolymer, of a hydrophobic water-insoluble ethylenically unsaturated monomer, 2 to
12% by weight of an ethylenically unsaturated monomer containing an acid group, and from 1 5 to 45% by weight of a hydrophilic ethylenically unsaturated monomer free from acidic groups.
2. A composition as claimed in Claim 1, in which component (1) is a water-soluble polymer or copolymer of a vinyl lactam having the structure
in which X represents an alkylene bridge having three to five carbon atoms.
3. A composition as claimed in Claim 2, in which component (1) is a water-soluble copolymer of
N-vinyl-2-pyrrolidone.
4. A composition as claimed in Claim 1, in which component (1) is a water-soluble polymer of an
N-vinyl oxazolidinone.
5. A composition as claimed in any preceding claim, in which said water-insoluble copolymer is derived from 55 to 70% by weight, based on the total weight of the copolymer, of a monomer selected from methyl methacrylate, styrene, and 2-ethylhexyl acrylate, 2 to 12% by weight of acrylic acid, and 25 to 43% by weight of methacrylamide.
6. A composition as claimed in any one of Claims 1 to 4, in which said water-insoluble copolymer is derived from 55 to 80% by weight of n-butyl methacrylate, based on the total weight of the copolymer, 2 to 12% by weight of acrylic acid, and 1 5 to 35% by weight of methacrylamide.
7. A composition as claimed in any one of Claims 1 to 4, in which said water-insoluble copolymer is derived from 50 to 78% by weight, based on the total weight of the copolymer, of n-butyl methacrylate, 2 to 12% by weight of acrylic acid, and from 20 to 35% by weight of p-styrene sulfonamide.
8. A composition as claimed in any one of Claims 1 to 4, in which said water-insoluble copolymer
is derived from 55 to 70% by weight, based on the total weight of the copolymer, of n-butyl methacrylate, 2 to 12% by weight of acrylic acid, and from 25 to 43% by weight of hydroxyethyl methacrylate.
9. A composition as claimed in any one of Claims 1 to 8, in which polymer or copolymer (1) has a molecular weight of from 10,000 to 1,000,000.
10. A water-absorptive composition as claimed in Claim 1 and substantially as herein described
with reference to any one of Examples 1-8 and 14-26.
11. A catheter or suture coated with a composition as claimed in any preceding claim.
12. A composition as claimed in any one of Claims 1 to 10 having a drug incorporated therein.
13. A glass sheet coated with a composition as claimed in any one of Claims 1 to 10.
14. The features as herein disclosed, or their equivalents, in any novel selection.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/201,349 US4300820A (en) | 1978-11-06 | 1980-10-27 | Water absorptive composition |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2086400A true GB2086400A (en) | 1982-05-12 |
GB2086400B GB2086400B (en) | 1984-04-18 |
Family
ID=22745483
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8114811A Expired GB2086400B (en) | 1980-10-27 | 1981-05-14 | Water-absorptive vinyl lactam polymer compositions |
Country Status (5)
Country | Link |
---|---|
JP (1) | JPS5776046A (en) |
CH (1) | CH650009A5 (en) |
GB (1) | GB2086400B (en) |
IE (1) | IE51292B1 (en) |
ZA (1) | ZA813679B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0121331A2 (en) * | 1983-03-02 | 1984-10-10 | National Research Development Corporation | Hydrogel-containing envelopes |
GB2147002A (en) * | 1983-09-15 | 1985-05-01 | Kendall & Co | Microphase separated hydrogels for controlled release of bioactive materials |
US5342624A (en) * | 1989-02-16 | 1994-08-30 | British Technology Group Ltd. | Dispensing device |
NL1001746C2 (en) * | 1995-11-27 | 1997-05-30 | Belden Wire & Cable Bv | Guide wire for medical application. |
WO2002071106A1 (en) * | 2001-03-07 | 2002-09-12 | Novartis Ag | Process for the manufacture of moldings |
US9623614B2 (en) | 2010-11-10 | 2017-04-18 | Novartis Ag | Method for making contact lenses |
-
1980
- 1980-12-05 JP JP55171045A patent/JPS5776046A/en active Granted
-
1981
- 1981-05-14 GB GB8114811A patent/GB2086400B/en not_active Expired
- 1981-05-22 IE IE1149/81A patent/IE51292B1/en unknown
- 1981-06-02 ZA ZA00813679A patent/ZA813679B/en unknown
- 1981-10-15 CH CH9020/80A patent/CH650009A5/en not_active IP Right Cessation
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0121331A2 (en) * | 1983-03-02 | 1984-10-10 | National Research Development Corporation | Hydrogel-containing envelopes |
EP0121331A3 (en) * | 1983-03-02 | 1986-08-13 | National Research Development Corporation | Hydrogel-containing envelopes |
US5147646A (en) * | 1983-03-02 | 1992-09-15 | National Research Development Corporation | Hydrogel containing envelopes |
GB2147002A (en) * | 1983-09-15 | 1985-05-01 | Kendall & Co | Microphase separated hydrogels for controlled release of bioactive materials |
GB2177708A (en) * | 1983-09-15 | 1987-01-28 | Kendall & Co | Microphase separated hydrogels for controlled release of bioactive materials |
AU577056B2 (en) * | 1983-09-15 | 1988-09-15 | Kendall Company, The | Microphase separated hydrogels for controlled release of bioactive materials |
US5342624A (en) * | 1989-02-16 | 1994-08-30 | British Technology Group Ltd. | Dispensing device |
NL1001746C2 (en) * | 1995-11-27 | 1997-05-30 | Belden Wire & Cable Bv | Guide wire for medical application. |
WO1997019712A1 (en) * | 1995-11-27 | 1997-06-05 | Belden Wire And Cable B.V. | Wire for medical use |
US6086547A (en) * | 1995-11-27 | 2000-07-11 | Belden Wire And Cable B.V. | Wire for medical use coated with polyether sulphone and a copolymer |
WO2002071106A1 (en) * | 2001-03-07 | 2002-09-12 | Novartis Ag | Process for the manufacture of moldings |
US6849210B2 (en) | 2001-03-07 | 2005-02-01 | Novartis Ag | Process for the manufacture of moldings |
US9623614B2 (en) | 2010-11-10 | 2017-04-18 | Novartis Ag | Method for making contact lenses |
Also Published As
Publication number | Publication date |
---|---|
JPH0312104B2 (en) | 1991-02-19 |
JPS5776046A (en) | 1982-05-12 |
IE51292B1 (en) | 1986-11-26 |
ZA813679B (en) | 1982-06-30 |
IE811149L (en) | 1982-04-27 |
GB2086400B (en) | 1984-04-18 |
CH650009A5 (en) | 1985-06-28 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19920514 |