CA1045296A - Method for producing new biologically tolerated polymers - Google Patents
Method for producing new biologically tolerated polymersInfo
- Publication number
- CA1045296A CA1045296A CA174,171A CA174171A CA1045296A CA 1045296 A CA1045296 A CA 1045296A CA 174171 A CA174171 A CA 174171A CA 1045296 A CA1045296 A CA 1045296A
- Authority
- CA
- Canada
- Prior art keywords
- polymerization
- carried out
- dienols
- group
- groups
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Medical Uses (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Eyeglasses (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The invention is concerned with a method for producing polymers which are biologically acceptable, because of their elastic properties due to a system of conjugated double bonds in their molecule, and their hydrophilic properties due to the presence of -OH groups in their molecule. This method comprises polymerizing monomers containing at least 60 mole % of dienols having 5 - 10 carbon atoms and at least one -OH group, preferably in the presence of a solvent, according to a radical mechanism or an ionic coordination mechanism, by using an azo initiator, or in the presence of a catalyst consisting of a mixture of an polyalkyl aluminium with Rh acetylacetonate, Co acetylacetonate or TiCl3, respectively, with the proviso that when the polymeri-zation is carried out according to an ionic coordination mecha-nism, the -OH groups of the dienols are previously blocked in a reversible manner by reaction with Cl-Si(CH3)3. Soluble polymers can be prepared by polymerization to a low conversion degree or by polymerization at high dilution, or in the presence of chain transfer agents such as CBr4, mercaptans, etc... Three-dimensional, cross linked polymers can be prepared by polymerization in the presence of a cross linking agen or by cross linking of the soluble polymers, especially if the polymer contains both -OH
groups and double bonds.
The invention is concerned with a method for producing polymers which are biologically acceptable, because of their elastic properties due to a system of conjugated double bonds in their molecule, and their hydrophilic properties due to the presence of -OH groups in their molecule. This method comprises polymerizing monomers containing at least 60 mole % of dienols having 5 - 10 carbon atoms and at least one -OH group, preferably in the presence of a solvent, according to a radical mechanism or an ionic coordination mechanism, by using an azo initiator, or in the presence of a catalyst consisting of a mixture of an polyalkyl aluminium with Rh acetylacetonate, Co acetylacetonate or TiCl3, respectively, with the proviso that when the polymeri-zation is carried out according to an ionic coordination mecha-nism, the -OH groups of the dienols are previously blocked in a reversible manner by reaction with Cl-Si(CH3)3. Soluble polymers can be prepared by polymerization to a low conversion degree or by polymerization at high dilution, or in the presence of chain transfer agents such as CBr4, mercaptans, etc... Three-dimensional, cross linked polymers can be prepared by polymerization in the presence of a cross linking agen or by cross linking of the soluble polymers, especially if the polymer contains both -OH
groups and double bonds.
Description
lO~S296 The invention relates to a method for producingbiologically acceptable polymers.
Methods are known for preparing various hydrophilic polymers from hydrophilic esters of methacrylic or acrylic acid or hydrophic esters of acrylamide, methacrylamide or their N-substituted derivatives, and also copolymers thereof with various other comonomers. The so prepared hydrophilic polymers cannot be used for many applications, in particular bio medical application, essentially because of their mechanical properties. Up to now, attemps to prepare hydrophilic elastomers meeting the bio medical requirements have been unsuccessful.
-The subject invention proposes a method for producing ; polymers which are biologically acceptable, elastic due to a ~ system of conjugated double bonds in their molecules, and .~, hydrophilic because they contain one or two -OH groups in their molecule.
; -.~: :
The method for producing such polymers according to the present invention comprises the step of polymerizing monomers : containing at least 60 mole % of dienols having 5 - 10 carbon .. . ..
atoms in a straight chain and at least one -OH group prefera~ly in the presence of a solvent such as for example, alcohols having 1 to 5 carbon atoms, dimethylformamide, dimethylsulfoxide, glycol monoethylether, pyridine, benzene, and the like. The polymeriza-tion is carried out according to a radical mechanism or an ionic coordination mechanism, by using an azo initiator or in the presence of a catalyst consisting of a mixture of a polyalkyl aluminium with Rh acetylacetonate, Co acetylacetonate or TiC13, respectively, with the proviso that when the polymerization is carried out according to an ionic coordination mechanism, the --OH groups of the dienols are previously blocked in a reversible manny by reaction with Cl-Si(CH3)3 and subsequently released by hydrolisis.
C ' ~
:.
,., - ;
,,".,,~,;, , . ' ' .
5;~6 ; In accordance wlth the present invention, the polymerization can be carried out without solvent.
Soluble polymers can be prepared by polymerization to a low conversion degree or by polymerization at high dilution, or in the presence of chain transfer agents such as CBr4, mer-captans, etc...
Three-dimensional, cross-linked polymers can be prepared by polymerization in the presence of a cross-linking agent, such as glycol dimethacrylate, 1,6-heptadiene-4-ol, divinyl carbinol, methylene bis-acrylamide, l,l,l-trimethyl-propane triacrylate, bis phenol A dimethacrylate, 1,5-hexadiene-~:.:
l-ol, etc., in the amount of 0.1 - 30% by weight. Three-dimensional polymers can be also prepared by cross-linking the soluble polymers, especially if the polymer contains both -OH groups and double bonds. Thls cross-linking can be carried out by means of diisocynates, ammonium bichromate, dialdehydes, dicarboxylic acids and other bifunctional compounds capable of reacting with the -OH groups or the -C~C- bonds which are present in the polymer.
In accordance with the present invention, polymerization or copolymerization of the monomers can be carried out according to radical mechanism by using an azo initiator. If the free -OH
group in the dienols are blocked by reaction with Cl-Si(CH3)3, the polymerization or copolymerization can be carried out according to an ionic coordination mechanism in the presenceof a catalyst such as diethylaluminium chloride ~Rh acetylacetonate, diethyla-luminium chloride ~Co acetylacetonate, triisobutylaluminium tTiC13 and the like. The so formed polymer is hydrolyzed after the polymerization has been completed, to release the -OH groups and thus to obtain the stereoregular hydrophilic elastomer.
The biological compatibility of the polymer was esta-blished by proceeding to a subcutaneous implantationof the polymer to 50 rats and 5 pigs. Samples were examined at the end ~J .
, ~
: 1~45;~96 of 1st, 2nd, 3rd, and 4th weeks, and 2nd, 3rd, 4th, 5th, 6th and 12th months from the implantation. The polymers are healed by encapsulation with a capsule formed by positively stained colla-gen fibers and few fibrocytes, which were located in the ` fundamental substance; they were positively stained by Alciane blue and gave a positive reaction on glycoproteins. The collagen fibers are oriented parallel with the implant surface. Giant multinucle cells were not found in the surrounding of the implant.
The aforesaid tests have therefore positively established that the polymer according to the invention is biologically compatible.
- In accordance with the present invention, the dienols can be copolymerized with numerous monomers, such as glycol methacrylates, either alone or even in admixtures (glycol is meant to include not only simple ethylene glycol, but also -dimethylene glycol, triethylene glycol and other homolegous ", polyglycols, i.e. all hydrophilic diols of this type), N-substituted amides of methacrylic and acrylic acid, methacryloni-trile, acrylonitrile, monomers containing ionogenic groups, e.g.
methacrylic and acrylic acids, ~-vinyl-acrylic acid, vinyl pyridine, diethylaminoethyl methacrylate, and a number of other compounds which contain a polymerizable double bond.
The polymers according to the invention are especially ` suitable for the preparation of bio medical materials, such as tubular implants, heart valves, contact lenses, cosmetic implants, membranes haemodialysis and reverse osmosis. Because of the ~; excellent elastic properties of the film formed, the soluble -polymer can be used for the formation of elastic coats. These coats may be used in a non-cross linked form or they can also be cross-linked. They find various applications, form coats for ~ catheters or foods, to protection of roads and building materials.
The invention will be understood with reference to the following non-restricting examples.
. . . . . : . .
lV45;~96 A mixture, consisting of 98 parts of 2,4-pentadiene-l-ol, 1,9 parts of ethylene dimethacrylate and 0.1 part of azobisisobutyronitrile, was charged into a Teflon (trademark~
mold, through which nitrogen which was bubbed and was polymerized in an inert atmosphere for 20 hours at 70C. The obtained polymer has the shape of the old and, after swelling in a physiological saline solution and sterilization (eAg. 30 minutes in an autocla-ve at 120C or by irradiation), may be used as an artificial heart valve.
A mixture, consisting of 85 parts of 1,3-decadiene-8, 9-diol, 10 parts of ~-vinylacrylic acid, 10 parts of diethylamino-ethyl methacrylate, 10 parts of triethylene glycol dimethacrylate and 5 parts of azobisisobutyronitrile, is polymerized for 10 hours at 80 C in an inert atmosphere in a glass mold. The polymer can be used for implants after equilibrium swelling in a physiological saline solution and sterilization.
Methods are known for preparing various hydrophilic polymers from hydrophilic esters of methacrylic or acrylic acid or hydrophic esters of acrylamide, methacrylamide or their N-substituted derivatives, and also copolymers thereof with various other comonomers. The so prepared hydrophilic polymers cannot be used for many applications, in particular bio medical application, essentially because of their mechanical properties. Up to now, attemps to prepare hydrophilic elastomers meeting the bio medical requirements have been unsuccessful.
-The subject invention proposes a method for producing ; polymers which are biologically acceptable, elastic due to a ~ system of conjugated double bonds in their molecules, and .~, hydrophilic because they contain one or two -OH groups in their molecule.
; -.~: :
The method for producing such polymers according to the present invention comprises the step of polymerizing monomers : containing at least 60 mole % of dienols having 5 - 10 carbon .. . ..
atoms in a straight chain and at least one -OH group prefera~ly in the presence of a solvent such as for example, alcohols having 1 to 5 carbon atoms, dimethylformamide, dimethylsulfoxide, glycol monoethylether, pyridine, benzene, and the like. The polymeriza-tion is carried out according to a radical mechanism or an ionic coordination mechanism, by using an azo initiator or in the presence of a catalyst consisting of a mixture of a polyalkyl aluminium with Rh acetylacetonate, Co acetylacetonate or TiC13, respectively, with the proviso that when the polymerization is carried out according to an ionic coordination mechanism, the --OH groups of the dienols are previously blocked in a reversible manny by reaction with Cl-Si(CH3)3 and subsequently released by hydrolisis.
C ' ~
:.
,., - ;
,,".,,~,;, , . ' ' .
5;~6 ; In accordance wlth the present invention, the polymerization can be carried out without solvent.
Soluble polymers can be prepared by polymerization to a low conversion degree or by polymerization at high dilution, or in the presence of chain transfer agents such as CBr4, mer-captans, etc...
Three-dimensional, cross-linked polymers can be prepared by polymerization in the presence of a cross-linking agent, such as glycol dimethacrylate, 1,6-heptadiene-4-ol, divinyl carbinol, methylene bis-acrylamide, l,l,l-trimethyl-propane triacrylate, bis phenol A dimethacrylate, 1,5-hexadiene-~:.:
l-ol, etc., in the amount of 0.1 - 30% by weight. Three-dimensional polymers can be also prepared by cross-linking the soluble polymers, especially if the polymer contains both -OH groups and double bonds. Thls cross-linking can be carried out by means of diisocynates, ammonium bichromate, dialdehydes, dicarboxylic acids and other bifunctional compounds capable of reacting with the -OH groups or the -C~C- bonds which are present in the polymer.
In accordance with the present invention, polymerization or copolymerization of the monomers can be carried out according to radical mechanism by using an azo initiator. If the free -OH
group in the dienols are blocked by reaction with Cl-Si(CH3)3, the polymerization or copolymerization can be carried out according to an ionic coordination mechanism in the presenceof a catalyst such as diethylaluminium chloride ~Rh acetylacetonate, diethyla-luminium chloride ~Co acetylacetonate, triisobutylaluminium tTiC13 and the like. The so formed polymer is hydrolyzed after the polymerization has been completed, to release the -OH groups and thus to obtain the stereoregular hydrophilic elastomer.
The biological compatibility of the polymer was esta-blished by proceeding to a subcutaneous implantationof the polymer to 50 rats and 5 pigs. Samples were examined at the end ~J .
, ~
: 1~45;~96 of 1st, 2nd, 3rd, and 4th weeks, and 2nd, 3rd, 4th, 5th, 6th and 12th months from the implantation. The polymers are healed by encapsulation with a capsule formed by positively stained colla-gen fibers and few fibrocytes, which were located in the ` fundamental substance; they were positively stained by Alciane blue and gave a positive reaction on glycoproteins. The collagen fibers are oriented parallel with the implant surface. Giant multinucle cells were not found in the surrounding of the implant.
The aforesaid tests have therefore positively established that the polymer according to the invention is biologically compatible.
- In accordance with the present invention, the dienols can be copolymerized with numerous monomers, such as glycol methacrylates, either alone or even in admixtures (glycol is meant to include not only simple ethylene glycol, but also -dimethylene glycol, triethylene glycol and other homolegous ", polyglycols, i.e. all hydrophilic diols of this type), N-substituted amides of methacrylic and acrylic acid, methacryloni-trile, acrylonitrile, monomers containing ionogenic groups, e.g.
methacrylic and acrylic acids, ~-vinyl-acrylic acid, vinyl pyridine, diethylaminoethyl methacrylate, and a number of other compounds which contain a polymerizable double bond.
The polymers according to the invention are especially ` suitable for the preparation of bio medical materials, such as tubular implants, heart valves, contact lenses, cosmetic implants, membranes haemodialysis and reverse osmosis. Because of the ~; excellent elastic properties of the film formed, the soluble -polymer can be used for the formation of elastic coats. These coats may be used in a non-cross linked form or they can also be cross-linked. They find various applications, form coats for ~ catheters or foods, to protection of roads and building materials.
The invention will be understood with reference to the following non-restricting examples.
. . . . . : . .
lV45;~96 A mixture, consisting of 98 parts of 2,4-pentadiene-l-ol, 1,9 parts of ethylene dimethacrylate and 0.1 part of azobisisobutyronitrile, was charged into a Teflon (trademark~
mold, through which nitrogen which was bubbed and was polymerized in an inert atmosphere for 20 hours at 70C. The obtained polymer has the shape of the old and, after swelling in a physiological saline solution and sterilization (eAg. 30 minutes in an autocla-ve at 120C or by irradiation), may be used as an artificial heart valve.
A mixture, consisting of 85 parts of 1,3-decadiene-8, 9-diol, 10 parts of ~-vinylacrylic acid, 10 parts of diethylamino-ethyl methacrylate, 10 parts of triethylene glycol dimethacrylate and 5 parts of azobisisobutyronitrile, is polymerized for 10 hours at 80 C in an inert atmosphere in a glass mold. The polymer can be used for implants after equilibrium swelling in a physiological saline solution and sterilization.
2,4-pentadiene-1-oxytrimethylsilane (10 parts), prepa-red by reaction of 2,4-pentadiene-1-ol with chlorotrimethylsilane in a benzene solution, is mixed with 90 parts of benzene in a glass ampoule sealed with a rubber closure. Into the mixture, 5xlO 3 mol/l of diethylaluminium chloride is added. Traces of oxygen are removed in vacuo and, in an inert atmosphere, 10 mol/l rhodium acetylacetonate is added. The polymerization is ~ -carried out and for 10 hours at 20 C. The polymer formed is precipitated into ether, dissolved in ethanol and hydrolyzed by addition of a small amount of alcoholic hydroxide solution.
By neutralization and reprecipitation, there is obtained a stereoregular poly(2,4-pentadiene-1-ol).
2,4-pentadiene-1-oxytrimethylsilane (60 parts) and 1~)45Z96 divinyl-methoxysilane (10 parts) are mixed with 30 parts of ben-zene, containing 10 mol/l of diethylaluminium chloride, 10 mol/l of cobalt acetylacetonate and 10 mol/l of water (all three concentrations calculated on the total volume of the mixture).
The polymerization is carried out for 10 hours at ambient temperature. The three-dimensional polymer formed is swollen first in ethanol and then in alcoholic hydroxide. Then it is washed ~- with an alcohol - water (1 : 1) mixture and which water and finally is placed into a physiological saline solution.
EXAMPLE S
- A macroporous gel is prepared by copolymerization of a mixture consisting of 10 parts of acetone, 17 parts of 2,4-pentadiene-l-ol, 2 parts of ethylene dimethacrylate and 1 part of 2,2'-azobis-2,4-dimethyl-4-methoxyvaleronitrile. The aforesaid mixture is charged into a thick-walled glass vessel, through ;
nitrogen was bubbed, it was thereafter sealed and polymerized for ....
25 hours of 45C.
An ethanolic solution containing 10% of 2,4-pentadiene-l-ol and 1 wt.% of methyl azobisisobutyrate is charged into a glass vessel and polymerized for 15 hours at 65 C in an inert atmosphere. An insoluble film is prepared from the obtained solution by addition of 1 wt.% of diisocyanate (e.g. 2,4-toluene-diisocyanate), casting onto a glass plate and heating to 120C
for 30 minutes. The prepared film may be used e.g. for separations of salt solutions by reverse osmosis or for surface treatment of roads and building materials (concrete etc).
A mixture of 2,4-pentadiene-1-ol and glycerol metha-crylate t4 : 1~ was dissolved in pyridine form a 5~ solution, 1 wt.~ of methyl azobislsobutyrate and 0.1% of CBr4 were added and the polymerization was carried out in a glass kettle in an 1~4SZ96 inert atmosphere for 10 hours at 60 C. The polymer formed is precipitated into an excess of diethylether, dried in vacuo, and ` dissolved in ethanol to form a 7% solution. This solution can be used for the preparation of highly elastic foils by evaporation of the solvent from the cast film and, if needed, the film can be additionally cross-linked to become insoluble. Thus, for example 0.8 wt.% of (NH4)2Cr2O7 based on the weight of the polymer) was added to 100 wt.% of the solution having the above composi- -~
tion as a 20% aqueous solution. The cross-linked film was obtained after 16 hours-at ambient temperature. This procedure can be used for coating catheters and other medical tools.
. ~ .
'' - :
''' , ' :' ' ~ ' .'' . . .
:, .
' . .
,~
.. : . . .
By neutralization and reprecipitation, there is obtained a stereoregular poly(2,4-pentadiene-1-ol).
2,4-pentadiene-1-oxytrimethylsilane (60 parts) and 1~)45Z96 divinyl-methoxysilane (10 parts) are mixed with 30 parts of ben-zene, containing 10 mol/l of diethylaluminium chloride, 10 mol/l of cobalt acetylacetonate and 10 mol/l of water (all three concentrations calculated on the total volume of the mixture).
The polymerization is carried out for 10 hours at ambient temperature. The three-dimensional polymer formed is swollen first in ethanol and then in alcoholic hydroxide. Then it is washed ~- with an alcohol - water (1 : 1) mixture and which water and finally is placed into a physiological saline solution.
EXAMPLE S
- A macroporous gel is prepared by copolymerization of a mixture consisting of 10 parts of acetone, 17 parts of 2,4-pentadiene-l-ol, 2 parts of ethylene dimethacrylate and 1 part of 2,2'-azobis-2,4-dimethyl-4-methoxyvaleronitrile. The aforesaid mixture is charged into a thick-walled glass vessel, through ;
nitrogen was bubbed, it was thereafter sealed and polymerized for ....
25 hours of 45C.
An ethanolic solution containing 10% of 2,4-pentadiene-l-ol and 1 wt.% of methyl azobisisobutyrate is charged into a glass vessel and polymerized for 15 hours at 65 C in an inert atmosphere. An insoluble film is prepared from the obtained solution by addition of 1 wt.% of diisocyanate (e.g. 2,4-toluene-diisocyanate), casting onto a glass plate and heating to 120C
for 30 minutes. The prepared film may be used e.g. for separations of salt solutions by reverse osmosis or for surface treatment of roads and building materials (concrete etc).
A mixture of 2,4-pentadiene-1-ol and glycerol metha-crylate t4 : 1~ was dissolved in pyridine form a 5~ solution, 1 wt.~ of methyl azobislsobutyrate and 0.1% of CBr4 were added and the polymerization was carried out in a glass kettle in an 1~4SZ96 inert atmosphere for 10 hours at 60 C. The polymer formed is precipitated into an excess of diethylether, dried in vacuo, and ` dissolved in ethanol to form a 7% solution. This solution can be used for the preparation of highly elastic foils by evaporation of the solvent from the cast film and, if needed, the film can be additionally cross-linked to become insoluble. Thus, for example 0.8 wt.% of (NH4)2Cr2O7 based on the weight of the polymer) was added to 100 wt.% of the solution having the above composi- -~
tion as a 20% aqueous solution. The cross-linked film was obtained after 16 hours-at ambient temperature. This procedure can be used for coating catheters and other medical tools.
. ~ .
'' - :
''' , ' :' ' ~ ' .'' . . .
:, .
' . .
,~
.. : . . .
Claims (12)
1. A method for producing biologically acceptable polymers, comprising polymerizing monomers containing at least 60 mole % of dienols having from 5 to 10 carbon atoms in straight chain and at least one -OH group according to a radical mechanism or an ionic coordination mechanism, by using an azo initiator or in the presence of a catalyst consisting of a mixture of polyalkyl aluminium with Rh acetylacetonate, Co acetylacetonate or TiC13, respectively, with the proviso that when the polymerization is carried out according to an ionic coor-dination mechanism, the -OH groups of the dienols are previously blocked in a reversible manner by reaction with Cl-Si(CH3)3 and subsequently released by hydrolysis.
2. A method according to claim 1, comprising polymerizing monomers containing at least 60 mole % of dienols having from 5 to 10 carbon atoms in straight chain and at least one -OH group previously blocked in a reversible manner by reaction with Cl-Si(CH3)3, in the presence of a catalyst consisting of a mixture of a polyalkyl aluminium with Rh acetyl-acetonate or Co acetylacetonate, and subsequently hydrolyzing the obtained polymer to release the -OH group.
3. A method according to claim 1, comprising polymerizing monomers containing at least 60 mole % of dienols having from 5 to 10 carbon atoms in straight chain and at least one -OH group by using an azo initiator.
4. A method according to claim 1, 2 or 3, wherein the polymerization is carried out in a solvent.
5. A method according to claim 1, 2 or 3, wherein the polymerization is carried out in a solvent from the group consisting of alcohols having 1 to 5 carbon atoms, dimethylfor-mamide, dimethylsulfoxide, glycol monoethylether, pyridine and benzene.
6. A method according to claim 1, 2 or 3, wherein the polymerization is carried out in the presence of a chain transfer agent.
7. A method according to claim 1, 2 or 3, wherein the polymerization is carried out in the presence of a chain transfer agent selected from the group consisting of tetrabromomethane and mercaptans.
8. A method according to claim 1, 2 or 3, wherein the polymerization is carried out in the presence of a cross-linked agent.
9. A method according to claim 1, 2 or 3, wherein the polymerization is carried out in the presence of a cross-linking agent selected from the group consisting of glycol dimethacrylate, 1,6-heptadiene-4-ol, divinylcarbinol, methylenebisacrylamide, 1,1,1-triethylpropane triacrylate, bis-phenol A dimethacrylate, and 1,5-hexadiene-1-ol.
10. A method according to claim 1, 2 or 3, wherein after the polymerization is completed the polymer is additionally cross-linked by bifunctional compounds capable of reacting with -OH groups or -C=C- bonds present in the polymer.
11. A method according to claim 1, 2 or 3, wherein after the polymerization is completed, the polymer is additionally cross-linked by bifunctional compounds selected from the groups consisting of isocyanates, ammonium dichromate, dialdehydes and dicarboxylic acids.
12. A method according to claim 1, 2 or 3, wherein the polymerization is carried out with monomers consisting of a mixture of vinyl unsaturated compounds and dienols, the concentration of dienols in the monomer mixture being of at least 60 mole %.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS422172A CS161327B1 (en) | 1972-06-16 | 1972-06-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1045296A true CA1045296A (en) | 1978-12-26 |
Family
ID=5384460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA174,171A Expired CA1045296A (en) | 1972-06-16 | 1973-06-15 | Method for producing new biologically tolerated polymers |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS4952281A (en) |
| AU (1) | AU477290B2 (en) |
| CA (1) | CA1045296A (en) |
| CH (1) | CH583756A5 (en) |
| CS (1) | CS161327B1 (en) |
| DE (1) | DE2325169A1 (en) |
| FR (1) | FR2189431B1 (en) |
| GB (1) | GB1428436A (en) |
| IT (1) | IT987928B (en) |
| NL (1) | NL7307697A (en) |
| SE (1) | SE396953B (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2125685A (en) * | 1935-03-16 | 1938-08-02 | Ig Farbenindustrie Ag | Polymerization products and process of preparing them |
| US3041320A (en) * | 1961-05-01 | 1962-06-26 | Monsanto Chemicals | Copolymers of 2-hydroxymethyl butadienes and 1, 3-dienes |
-
1972
- 1972-06-16 CS CS422172A patent/CS161327B1/cs unknown
-
1973
- 1973-05-18 DE DE19732325169 patent/DE2325169A1/en active Pending
- 1973-05-18 GB GB2393873A patent/GB1428436A/en not_active Expired
- 1973-05-25 IT IT2463873A patent/IT987928B/en active
- 1973-06-01 NL NL7307697A patent/NL7307697A/xx not_active Application Discontinuation
- 1973-06-04 SE SE7308401A patent/SE396953B/en unknown
- 1973-06-04 JP JP48062065A patent/JPS4952281A/ja active Pending
- 1973-06-04 CH CH810673A patent/CH583756A5/xx not_active IP Right Cessation
- 1973-06-15 CA CA174,171A patent/CA1045296A/en not_active Expired
- 1973-06-15 FR FR7321819A patent/FR2189431B1/fr not_active Expired
- 1973-06-18 AU AU57024/73A patent/AU477290B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1428436A (en) | 1976-03-17 |
| CS161327B1 (en) | 1975-06-10 |
| FR2189431B1 (en) | 1977-09-09 |
| IT987928B (en) | 1975-03-20 |
| NL7307697A (en) | 1973-12-18 |
| CH583756A5 (en) | 1977-01-14 |
| AU5702473A (en) | 1974-12-19 |
| AU477290B2 (en) | 1976-10-21 |
| JPS4952281A (en) | 1974-05-21 |
| FR2189431A1 (en) | 1974-01-25 |
| DE2325169A1 (en) | 1974-01-03 |
| SE396953B (en) | 1977-10-10 |
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