CA1155591A - Polyurethane polymers characterized by lactone groups and hydroxyl groups in the polymer backbone - Google Patents
Polyurethane polymers characterized by lactone groups and hydroxyl groups in the polymer backboneInfo
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- CA1155591A CA1155591A CA000303879A CA303879A CA1155591A CA 1155591 A CA1155591 A CA 1155591A CA 000303879 A CA000303879 A CA 000303879A CA 303879 A CA303879 A CA 303879A CA 1155591 A CA1155591 A CA 1155591A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- 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
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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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
- A61L17/04—Non-resorbable materials
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/54—Polyureas; Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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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)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Dermatology (AREA)
- Transplantation (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Manufacturing & Machinery (AREA)
- Hematology (AREA)
- Surgery (AREA)
- Vascular Medicine (AREA)
- Polyurethanes Or Polyureas (AREA)
- Materials For Medical Uses (AREA)
Abstract
ABSTRACT
Polyurethane polymers characterized by a molecular weight above 6,000 and having lactone groups and hydroxyl groups in the polymer backbone are prepared by reacting a mixture of polyols, a polyfunctional lactone and a polyfunctional isocyanate proportioned so as to provide the desired polymer properties.
The product is soluble in alkaline solutions and may be used for light sensitive photographic layers on films, paper or glass; in drug delivery systems, as burn dressings, in body implants such as vascular prosthesis, in molding compositions, and in the manufacture of catheters. The novel polymers also find use in the manufacture of artificial finger nails, finger cots, adhesives, and in protective and hvdrostatic drag resistant coatings. The water absorptivity of the polyurethane lactone polymers is above 10%, preferably in the range of about 20%
to 60%, and these polymers may range in their physical properties from rigid solids to completely gel-like high water absorptive polymers. The polymers of the present invention can provide a leachable substrate wherein the leaching agent may be water, gases, alcohols, esters and body fluids, e.g., animal or human.
Polyurethane polymers characterized by a molecular weight above 6,000 and having lactone groups and hydroxyl groups in the polymer backbone are prepared by reacting a mixture of polyols, a polyfunctional lactone and a polyfunctional isocyanate proportioned so as to provide the desired polymer properties.
The product is soluble in alkaline solutions and may be used for light sensitive photographic layers on films, paper or glass; in drug delivery systems, as burn dressings, in body implants such as vascular prosthesis, in molding compositions, and in the manufacture of catheters. The novel polymers also find use in the manufacture of artificial finger nails, finger cots, adhesives, and in protective and hvdrostatic drag resistant coatings. The water absorptivity of the polyurethane lactone polymers is above 10%, preferably in the range of about 20%
to 60%, and these polymers may range in their physical properties from rigid solids to completely gel-like high water absorptive polymers. The polymers of the present invention can provide a leachable substrate wherein the leaching agent may be water, gases, alcohols, esters and body fluids, e.g., animal or human.
Description
~ ~S~59 1 This invention pertains to lactone modi~ied hydrophylic polyurethane resins that are insoluble in ~ater, but which swell in water and other solvents. More parti-cularly, the present invention rela-tes to ~.
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polyethPr urethane resins having ac-tive and available lactone groups in the polymer backbone that readily open and dissolve in alkaline solutions to produce carboxylates which can be converted to free carbonyl groups. Typically they are low-melting solids, qenerally having flow points in the range of 90 C. to 250 C. which can be Eabricated by typical polymer procedures.
. Numerous polymer systems that contain free carboxylic acid groups are known in the art. It is dificult, however, to prepare a polyurethane that has free carboxylic acid groups . for the reason that the isocyanate that is a necessary component . in any polyurethane system is quite reactive with carboxylic acid groups.
One approach to the introduction of carboxylic acid groups into a polyurethane resin chain is descri.bed in ~.S.
Patent No. 3,412,054. In accordance wi~h that method, a 2,2-; ¦ di(hydroxymethyl) alkanoic acid such as 2,2-di(hydroxymethyl) propionic acid is reacted with an organic diisocyanate to produce a polyurethane containing unreacted carboxylic acid groups.
; . The polyurethanes of the present invention may be made. by the reaction of~
,. (A) one or more diols having an equivalent weight in the range of from about 100 to 3,000, .selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation oE one or more diols with one , 30 .or more dibasic acids, and
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polyethPr urethane resins having ac-tive and available lactone groups in the polymer backbone that readily open and dissolve in alkaline solutions to produce carboxylates which can be converted to free carbonyl groups. Typically they are low-melting solids, qenerally having flow points in the range of 90 C. to 250 C. which can be Eabricated by typical polymer procedures.
. Numerous polymer systems that contain free carboxylic acid groups are known in the art. It is dificult, however, to prepare a polyurethane that has free carboxylic acid groups . for the reason that the isocyanate that is a necessary component . in any polyurethane system is quite reactive with carboxylic acid groups.
One approach to the introduction of carboxylic acid groups into a polyurethane resin chain is descri.bed in ~.S.
Patent No. 3,412,054. In accordance wi~h that method, a 2,2-; ¦ di(hydroxymethyl) alkanoic acid such as 2,2-di(hydroxymethyl) propionic acid is reacted with an organic diisocyanate to produce a polyurethane containing unreacted carboxylic acid groups.
; . The polyurethanes of the present invention may be made. by the reaction of~
,. (A) one or more diols having an equivalent weight in the range of from about 100 to 3,000, .selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation oE one or more diols with one , 30 .or more dibasic acids, and
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5~S~l (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
tB) a polyfunctional lactone having the formula Rl-CH ~ C=O
O
wherein Rl is a monovalent radical selacted rom the group consisting of -H, -CH2NH2, S02CH3, 10 I -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -~CHOH)m- ;
m being,an integer from 2 to 10, and ethers ¦ derived from said lactones; and (C) a urethane precursor selected from the group 15 ¦ consisting of organic polyisocyanates and nitrile ' carbonates.
The long-chain, water-soluble diols should have a molecular weight of at least about 200 and preferably 1450 to 6000 or more and may be derived from,ethers, esters and ether-esti r block-containing resins. Suitable diols consist predominantly of oxyethylene or oxypropylene groups, though a minor proportion ¦ of other oxyalkylane groups may be included. Block copolymer I polyols obtained by adding ethylene oxide to a polyoxypropylene ¦ chain are also useful as are the linear polyester diols derived I from ths condensation of one or more diols with one or more dihasic acids, and the reaction product of one or more alkylene ¦ diols with a diPunctional linear polyester derived from the I condensation of one or more diols with one or more dibasic acids. ' ; 30 Representative examples of the polyfunctional lactones are those derived from polysacharides and monosacharides such as mannolactone, delta gluconola'ctone, sorbolactone and D-glucur-onolactone.
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11~55~1 It is desirable tilat the lactones employed have at least 3 and preferably 4 or more hydroxyl groups in the molecule or at least l more than is required to form a linear polyurethane chain. These free ~unreacted) hydroxyl groups remain in the polymer backbone and are available for cross-linking the polymer.
The lactone ring is also reactive and may be opened, i.e., by hydrolysis, to form carboxylate groups or carboxyl groups in the polymer backbone.
The number of carboxylic groups that are present in the polymer chain will be determined by the amount of lactone that is present in the reaction mixture which may be v~ried from 0.1~ to 30~ of the weight of the total rea^tion mixture.
Preferably the weight of the lactone will be .5% to 15~ of the ~eight of the total reaction mixture.
The polyisocyanate used in the present invention may be represented by R(NCO)n wherein n is greater than 1, preferably 2-4, and R is an aliphatic, alicyclic, aliphatic-alicyclic, aromatic, or aliphatic-aromatic hydrocarbon compound of ~rom 4 to 26 carbon atoms, but more conventionally from 6 to 20 and generally rom 6 to 13 carbon atoms. Representati~e examples of the above isocyanates are: tetramethylene diisocyanate;
hexamethylene diisocyanate; trimethylhexamethylene diisocyanate;
dimer acid diisocyanate; isophorone diisocyanate; diethylbenzene diisocyanate; decamethylene 1, 10-diisocyanate; cyclohexylene 1,2-diisocyanate and cyclohexylene 1,4-diisocyanate; and the ~romatic isocyanates such as 2,4~and 2,6-tolylene diisocyanate;
4,4-diphenylmethane diisocyanate; 1,5-naphthalene diisocyanate;
dianisidine diisocyanate; tolidine diisocyanate; a polymeric polyisocyanate such as neopentyl tetra isocyanate; m-xylylene diisocyanate; -tetrahydronapthalene-1,5 diisooyanate; and bis _- .. ... ~
~ . 5 ~5'~ ~
~4-isocyanatophenyl) methane.
The preEerred isocyanate is methylene di(cyclohexyl isocyanate). Other but slightly less preferred diisocyanates are trime-thyl hexamethylene diisocyanate and isophorone diisocyanate.
Other compounds which are useful are the isocyanate equivalents which produce the urethane linkages such as the ¦ nitrile carbonates, i.e., the adiponitrile carbonate of the formula:
O O
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. /\ /~
r . N=C--CH2-CH2 -C~2--CH2--C=N
I In the manufacture of the polyurethane resins of the ¦ present invention, low molecular weight glycols such as ¦ diethylene glycol and dipropylene glycol or an aromatic glycol ¦ may be added to the reaction mixture. The preEerred low molecula ¦ weight aromatic polyols are bisphenol A and 4,4'-sulfonylcliphenol I ~he proportions in whiGh the long chain polyglycol and the low molecular weight glycol, i.e., diethylene glycol are used depends on the hydrophobic-hydrophilic balance present in each and desired in the final product. Increasing the molecu-lar weight of the long chain polyoxyalkylene glycol and~or the amount of this component contributes stron~ hydrophilic propertie to the final product. This effect may be counter-balanced by increasing the proportion of low molecular weight glycol, i.e., diethylene glycol or dipropylene glycol.
Reeping the above in mind (that it is the number of polyalkylene oxide groups in the polymer molecule that determines hydrophilic properties and the polyethylene oxide groups are more hydrophylic than a,re polypropylene oxide groups) it is a simple matter to choose mixtures of reactants such that the !
final product will have the desired propertiesO ~y choosing the molecular weight of the polyalkylene glycol or using two poly alkylene glycols of difEerent molecular weiyht one may "tailor make" products that satisfy a wide range of properties.
Amphoteric hydrophilic polyurethane polymers may be made by adding a dialkanol tertiary amine such as diethanol methyl amine to the reaction mixture.
In making the polyurethane resins of this invention the glycols are mixed with the lactone and the polyisocyanate is reacted with the mixture although other techniques may be used.
The reaction is catalyzed by known catalyst for such reaction, suitable ones being tin salts and organic tin esters such as dibutyl tin dilaurate, tertiary amines such as triethyl diamine (DABCD), N,N,N',N'-tetramethyl-1,3-butane diamine and other recognized catalysts for urethane reactions which are well known in the art. The reaction can be conduc-ted in the absence or presence of dilutent or solvent.
The polyurethane polyether resins of the present inven-tion because of their unique physical properties may advantageousl be used as burn dressings. The resin may ~e applied to the burn as a powder, film, or froln solution in a volatile non-toxi- solven and will form a barrier that is permeable to li~uids. Thus the physician has a choice of medicaments which may be applied to the burn prior to the resin coating or may be added to the resin for timed release. A particularly advantageous burn dressing is a powder obtained by the low -temperature grinding of from about 1 to about 80 parts by weight of polyvinylpyrolidone-iodine with about ~0 to about 99 parts by weight of polyether polyurethane resins having free hydroxyl and carboxylate groups in the polymer backbon, .
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~1555~1 The above described polyurethane polyether resins are also useful as coatings, molding compounds, absorbents, controlled release agents, ion exchange resins, in the repair of skin abrasions and in the manufacture of dialysis membranes, dentures, cannulae, contac-t lenses, solubilizing packaging components, hair sprays, cosmetics, burn dressings, contraceptive ¦devices, sutures, surgical implants, blood oxygenators, intra-uterine devices, vascular prostheses, oral delivery systems, battery seperator plates, eye bandages, dipilatory compositions, corneal prostheses, perfumes, deodorant compositions, antifog . coatings, surgical drapes, oxygen exchange membranes, artificial finger nails, finger cots, adhesives, gas permeable membranes, : and in protective and drag resistant coatings.
. . The practice of the invention is further illustrated : 15 by thè followin~ examples without being restricted thereto, ~the parts belng by we ht, unless o~herwise stated.
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1~S5591 A diethylene glycol solution of polyethylene glycol ¦ is prepared by heating 109.2 parts (0O075 mole) of polyethylene 1 glycol having a molecular weight of 1450 in 17.4 parts 50.l64 mol~
¦ of diethylene glycol with stirring. The solution is cooled to below 60 C~ and to it is added a solution of delta glucono-lactone prepared by dissolving llo6 parts (0.065 mole) of,delta I gluconolactone in 46.4 parts of dimethyl sulfoxide. Ei,~hty ! and eight tenths parts (0O316 mole~ of methylene bis cyclohexyl~
¦ 4,4'-isocyanate (a product identified as H~* W sold by E. Io DuPont de Nemours'& Co., Wilming-tonl Delaware~ is added to the ! mixture with stirringO One half part by weight of an organic ¦ tin catalyst solution; dibutyl tin dilaurate (a product identifie ~ as ~-12* manufactured by Metal and Thermite Company of Rahway, I New Jersey) is added to the reaction mixture with stirring at a 1l temperature below 45 C. to auoid undue temperature rise ,¦ caused by the heat of reaction.' After stirring for 20 minutes~
¦ the temperature increases to 80 CO The reaction mixture is I then trans~erred to a tray and placed in an oven at 90 C. for l hour to complete the reactionO This polymer~ in the wet state/ is soft~ compliant and flexibleO
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¦ A polymer -that is insoluble in wa-ter but soluble in a I mixture of a major portion of alcohol and a minor portion of ¦ aqueous base (1.0 N sodium hydroxide) is prepared by the method S ¦ described in Example 1 from:
Polyethylene Glycol (M. Wt. 1450) 3469 par-ts (2.37 mole) ¦ Diethylene254 parts (2.39 mole) ¦I Delta Gluconolactone (as a 20%
. ¦ solution in dimethyl sulfoxide) 116 parts (0.65 mole) HYLENE W ~trade mark)808 parts (3.16 mole) . . Dibutyl tin dilaurate 5 parts .A piece of this polymer, cast in the form of a cylinder .. ¦ having a volumn of 10 ml. is wei~hed, immersed in wate:r at room .
. I temperature for 12 hours, dried with a paper towel to remove ¦ surface moisture and again welghed~ rrhe increase in weight was 100%.
A pol~me.r containing lactone groups that is soIuble in ¦ a ma~or portion of al.cohol ha~ing a minor amount of base dissolve .
!¦ therein, or added with a minor amount of water or other carrier ¦l is prepared by the method described above in Example 1 from:
. I Polyethylene Glycol (M. Wt~ 1450) 2000 parts (1. 37 mole) Diethylene Glycol107.5 parts (1.64 mole) Delta Gluconolactone (as a 20%
solution in dimethyl sulfoxide) 116 parts (0.65 mole) . HYLENE W (trade markl808 parts (3.16 mole) : ¦ Stannous Octoate (Tg)*S parts ¦ *Tg is a trademark o~ the Metal and Thermite Company of Rahway, . I New Jersey.
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~XAMPLE 4 This example illustrates the preparation of a polymer soluble in alkaline solutions using a 5~ excess o cyanate ¦ groups. The me-thod of preparation is described in Example 1.
¦ Polyethylene Glycol (mol~ wto 1450) 1097 parts (0.7S mole) Diethylelle Glycol 174 parts (1.64 mole) Delta Gluconolactone (as a 20%
solution in dimethyl sulfoxid~ 116 parts (0.65 mole) 1~ HYLENE W (trade mark) 102.4 parts (0.4 mole) 10 ¦¦ Stannous Octoate (T~)* 5 parts Fifty grams of the polyurethane polyether resin described above in Example 1 is added to 500 ml of an aqueous solution containing 17.4 ml of 23% ammonium hydro~ide~ The ¦ solution is stirred at 90 CO until all of the polymer dissolves.
To the polymer solution is added 10 ml of an a~ueous 20% solution of ammonium dichromate 12.0 g (NH9)2Cr204]. The solution is applied to cellulose acetate film with a doctox knife and dried at room temperature in subdued light or darkness. A tough film of the photosensitive comple~ light yellow in color, is deposited that adheres well to the cellulose acetate substrate.
¦ A photographic image is proje~ted onto the film using a S-l sun lamp as the light source and an exposure time of 60 seconds.
The film is developed by washing in water at room temperature to dissolve ancl remove the unexposed and uncross-linked portion of the photographic image. Since the polymer that forms the photographic imaye is substantative to ink the developed film I may be used in lithography printing processes.
¦ *Tg is a trademark of the Metal and Thermite Company of I Rahway, New Jersey.
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E~AMPL~ 6 ~n anti-fouling marlne paint is formula-ted by grinding in a ball mill fo.r three hours:
I Polyurethane resin of Example 2 150 parts 5 I Five percent ammonium hydroxide . in ethanol 500 parts ¦ Potassium dichromate2 parts Titanium dioxide 50 parts Mercury:acetate 3 parts . The produc-t so ob-tained may be applied to wood and other surfaces ¦ to form a film that is cross-linked by sun light to an adherent ¦ insoluble protective coating. The product is particularly ¦ effective when applied to the hull of a boat as a hydrophylic ¦ nature of the urethane resins permits the slow release of the 1 mercury salts and prevents barnacle or algae formation on the ¦ painted surfaces.
EXAMPLE 7 .
¦~ A polyurethane polyether resin is prepared by the method described in Example 1 above substituting for the 1¦ polyethylene ylycol a block copolymer having a molecular we.ight of 4750 obtainecl by adding poly(oxyethylene) groups to a poly~oxypropylene~ chain having a molecular weight of ~50. .
.. Block copolymer ~M. Wt. 4750) . 3577 parts ll Diethylene glycol 174 parts .
25 I Delta gluconolactone (as.a 20%
solution in dimethyl sulfoxide) 116 parts ~YLENE W (.trade m~rk~ 808 parts Dibutyl tin dilaurate 5 parts I 1 ~ 5 5 ~ 1 EX~MPLE 8 A polyure-thane polyether resin is prepared by the method described in Example 1 above subs-tituting for the polyethylene ylycol a block copolymer having a molecular weight of 7500 obtained by adding poly(oxyethylene) groups to a poly(oxypropylene) chain having a molecular weight of 2250u Block copolymer (M. Wt. 7500) 1157.4 parts ; Diethylene Glycol 32O75 parts Delta gluconolactone (as a 20~
10 ~ solution in dimethyl sulfoxide) 116 parts HYLENE W ~trade markl 808 parts Dibutyl tin dilaurate 5 parts A polyurethane polyether resin is prepared by t,he lS method described in Example 1 above substituting for the polyethylene ylycol a block copolymer having a molecular weight of 6500 obtained by adding poly(oxyethylenel yroups to a .
poly(oxypropylenel chain having a molecular weight of 32500 " Block copolymer 325 parts Diethylene glycol 210 76 parts Delta gluconolactone (as a 20%
solution in dimethyl sulfoxide)41.41 parts HYLENE W (trade mark) 132 parts Dibutyl tin dilaurate 0.5 parts ~12-l i 5 ~ 5~ ~
I
¦ EXAMPLE 10 ¦ A polyurethane polyether resin is prepared by the method described in Example 1 above substituting for the polye-thylene glycol a block copolymer having a molecular weight j of 13,333 obtained by adding poly(oxyethylene) groups to a ¦ poly(oxypropylene) chain having a molecular weight of about 4000.
Block copolymer 1004 parts Diethylene glycol 170 4 parts Delta qluconolactone* llo 6 parts . Dimethyl sulfoxide 46.4 parts HYLENE W ~trade ma~k~ 80.8 parts Dibutyl~tin dilaurate 3 parts .
After stirring ~or one hour~ the reaction mixture is transferred to a tray and placed in an oven at 90 C. overnightO
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LS ~ ~ dissol ed in ~imethyl sulioxide "
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¦ A series of three polyurethane polyether resins is ¦ prepared by the procedure of Example 1 in which the amount of ¦ Delta glucono-lactone is varied.
S ¦ Polyethylene Diethylene Delta HYLENE* Dibutyl tin ¦ glycol glycol glucono- W dilaurate ¦ (~. Wt. 1450) lactone#
¦ Resin (a) 54.6 g8.7 g 2.9 g 40.4 g 0.5 g ¦ Resin (b) 54.6 y8.7 g 5.8 g 40.4 g 0.5 g 10 ! Resin (c) 54.6 g8.7 g 11.6 g 48.5 g 0.5 g ¦ After the initiai reaction, instead of curing the resin ¦ in an oven the three resin (3 g. of each) were mixed with 100 mg ¦ of norethandrolone (Nileva~), cast in the form of cylinders 1.3 c ¦ by 2.5 cm and polymerized at 80 C. for 30 hours. After removing lS ¦ from the mold, cylinders suitable for in vivo implantation to ¦ provide prolonged release of the norethandrolone (Nilevar*~ are - ¦ obtained for use in animal husbandry.
¦ EXAMPLE 12 Delta glucanolactone ~14.28 parts) is ground to a fine powder and thoroughly mixed with 29.15 parts of polyethylene glycol (M. Wt. 200). The mixture is heated to 60 C. and to it is added 56.57 parts of E~NE~ W and 0.5 parts of stannous octoat~
with stirring. After the exothermic reaction subsides, the resin is transferred into a tray and placed in an oven at 90 C. for one hour to complete the reaction.
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dissolved in dimethyl sulfoxide . . . .
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Polyethylene glycol of molecular weighit 1450 (218.4 ¦Iparts) is mixed with 34.8 parts of diethylene glycol and the llmixture is heated with stirrlng to the melting point. To this S ~Imelt is added 161~6 parts of HYL~ W.
A solution of delta gluconolactone is prepared by ¦Idissolving 23.2 parts of delta gluconolactone in 77 parts of dimethyl sulfoxide. The dleta gluconolactone solution is added to the mixture of glycols and ~IYLENE W with sti.rring and the reaction mixture is cooled ko 50 C. Eight tenths parts of dibutyl tin dilaurate catalyst is adde~ -to the reaction mixture, and stirring is continued until the exothermic reaction subsidesO
The resin is then cured in an oven at 90C. for one hourO
The cured resin (2.6 parts) is dissolved in alkaline methanol ~/.4 parts) and 2.5 parts o~ a 2% aqueous ammonium dichromate solution is addedO The dichromate catalyzed resin ~solution is poured through a S mm pyrex glass tube 4 feet in llen~th to form a uniform coating on the interior surface thereofO
¦The coating is air ~ried in ambient light for 5 minutesO
I One end of the coated tube is closed with a cork . pierced by a fine hypodermic needle~ The tube is filled with `
tap water and then in~erted to p~rmit the tap water to drain . out. The time required for all water to drain from the tube . iwas 24 seconds. The experiment was repeated ten timesO The 5 ¦Itime required for the tube ~o drain was always 24 ~ 1 secondsO
. In a control experiment an uncoated 5 mm pyrex -tube 4 feet in length is washed thoroughly with a detergent solution, ¦rinsed with distilled water and air driedO The tube is closed jwith the same cork pierced by a fine hypodermic needle referred * trade mark -15-,. ' .
:l~5559~
to above and filled with tap water. When this uncoated tubeis inverted (10 trials) it required 38 ~ 1 seconds for the water to drain from the tube.
¦ The dichromate catalyzed resin composition described ¦above in this example is applied to the hull and center-board of a Lightning Class sailboat and exposed to the sunlight for 6 minutes to cross-link the coating. In a light breeze the sailboat outperforms other boats in her class.
A diethylene glycol solution of polyethylene glycol is prepared by heating and stirring 249.3 parts tO.172 mole) of polyethylene glycol having a molecular weight of 1450 with 79.5 parts (O.g83 mole) o~ diethylene glycol. To this melt is added S2.9 parts (0.296 mole) of delta gluconolactone, 249.3 parts tO.86 mole) of diethylene glycol adipate and 520 parts (1.85 moles) of methylene bis cyclohexyl-4,4'-isocyanate. The mixture is stirred with heating to form a homogeneous melt and then cooled to 45 C. Two and one tenth parts of a solution of dibutyl tin dilaurate is added to the reaction mixture with rapid stirring to avoid undue temperature rise caused by the heat of reaction. After stirring for twenty minutes, the temperature is 85 C. The reaction mixture is then transferred to a tray and placed in an oven at 90 C. for one hour to complete the reaction. The resultinq polymer contains 21 weight percent adipic acid ester, is harder and more rigid than the polymer of Example 1 and is insoluble in water and aqueous alkaline solutioas. When immersed in water the increase in weight, due to the water take up, is less than 20 percent.
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¦l A polyurethane polymer derlved from a lincar polyester diol is prepared by reacting:
¦ polyethylene glycol (0.005 mole) 7.95 parts 5 ¦ delta glucanolactone (0.29 mole) 5.2 parts diethylene glycol adipate (0.172 mole) 49.86 parts ¦ HYLENE ~ (0.241 mole) 68q0 parts ¦The mixture of reactants is heated with stirring until homogeneous ¦and 0.2'1 parts of an organic tin catalyst solution; dibutyl tin Idilaurate (a product identified as T12* manufactured by Metal and IThermite Company of Rahway, New Jersey) is added to the reaction ¦with st~rring at a temperature below 45 C. to avoid undue temperature rise caused by the heat of reaction. After stirring for 20 minutes, the temperature increases to 80 CO The reaction mixture is then transerred to a tray and placed in an oven at 90 C. for l hour to complete the reaction. The resulting polymer contains 38 we.ight percent adipic acid ester and is ¦harder and more rigid than ~he pol~mer of Example 14. It is linsoluble in basic aqueous solutions and methanolO The water !take up of this polymer is less than lS weight percent.
E~AMPLE 16 Example 15 above is repeated but the amount of the diethylene glycol adipate present in the reaction mixture is Ireduced from 49.86 parts to 1.15 parts (1.4 weight percent of 2S Ithe reaction mixture). One gram of the polymer of this example rhen immersed in water swells and absorbs 0.48 g waterO One gram ~of this polymer may be dissolved in a mixture of 9 ml methanol iand 1 ml of 2 N aqueous sodium hydroxide.
trade mark Il .
11$5~1 EX~PLE 17 To 90 parts by volumn of a mixture of ethanol and ¦water (70:30) is added lO parts oE the polymer of Example l and !l part of sulfadia~ine. The polymer is dissolved by stirring !with the addition of l N sodium hydroxide to adjust the pH of ¦,the solution to 7Ø The polymer solution may be applied as a l! burn dressing directly to a burn area and upon evaporation of the I solvent forms a protective skin that does not interfere with ¦ healing because of its permeability to gases and fluids but ~prevents the growth of anerobic organisms under the dressing.
¦j EXAMPLE l8 A polymer having the composition set forth in Example 2 above is prepared by heating and stirring the polye-thylene ~lycol, diethylene glycol, delta glucanolactone and HYLENE W
1! to form a homogeneous mixture. The catalyst is added to the ¦' reaction mixture at 40 C. and stirring is continued until the ¦ exothermic reaction subsides (temperature starts to drop) at which time 232 parts (5 weight percent) of cortisone is added I with thorough stirring to assure uniform dispersion. The polymer ' is cast in the form of cylinders l.5 cm by 3 cm and is cured ~ at 70 C. After curing, the cylinders are removed from the ¦¦ mold and are suitable for implantation to provide prolonged jl release of cortisone.
I EXAMPLE l9 1 .
i Fifteen parts of the polymer described in Example 3 I above is placed in 70 parts by volumn of a mixture of isopropanol ¦ and water (50:50) and lO parts by volumn of l N sodium hydroxide solution is added. The mixture is refluxed to hydrolyse the ¦ lactone ring and dissolve the polymer. The solution is titrated to pH 5.0 with l N hydrochloric acid and the polymcr solids content adjusted to 15 percent with isopropanol. To this polymer * trade mark 1 i 5 5 ~ ~ 1 solution is added 15,000,000 units of phenoxyethyl penicillin.
The resulting solution may be applied to an abraided skin area to seal off the area from irritating physical and biological substances. The deposited film allows the free passage of gases and moisture from the area covered.
A twenty percent solution of the polymer described in Example 7 above is prepared by dissolving that polymer in a mixture of ethanol and water (50:50) with the addition of sufficient 1 N sodium hydroxide to effect solution. The pH of ¦the solution is adjusted to 6.0 with 1 N hydrochloric acid. The . solution so obtained may be applied topically to form a hypoallergenic base for cosme-tics. The polymer composition effectively covers skin blemishes and allows the skin to breathe.
A hair set composition is prepared by dissolving the polyurethane polyether resin of Example 8 above in 9S percent ethanol. Sufficient 1 N sodium hydroxide is added ~o effect solution and the pH of the final composition adjusted to 7Ø
The resulting solution may be applied to the hair in the form of a spray and provides superior holding with a soft feel.
Twenty parts of the unsaturated polyether resin of Example 1 is dissolved in 80 parts of ethanol-water (70:30) and sufficient 1 N sodium hydroxide to adjust the pH to 9.5. To the solution so obtained is added with stirring 5.6 parts of calcium thioglycolate. The resulting composition finds use as a dipillatory agent.
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¦ EXAMPLF ~3 I The polymer of Example 16 above is extruded to form ¦la tube 1.5 m in leng-th and 10 mm in diameter. Dry nitrogen ¦Igas is passed through this tube and into a dry ice trap. The ¦Itube is then immersed in a trough of water. Water vapor which ¦lis picked up by the nitrogen as it flows through the tube is ¦!deposited in the trap as ice.
il EXAMPLE 24 A series of three polyurethane polyether resins is prepared in which ~he amount of Delta glucano-lactone is varied.
Polyethylene Delta glycol Diethylene glucono- HYLENE* Dibutyl tin '~M. Wt. 1450) glycollactone W dilaurate ~ _ ¦Resin (a) 54.6 g 8.7 g 2.9 g 40.4 g ODO4 g IResin ~b) 54.6 g 8.7 g 5.8 g 40.4 g 0.04 g IResin (c) 54.6 g 8.7 g 11.6 g48.5 g 0.04 g IlThe polyethylene glycol and diethylene glycol are melted and ~jmixed together in the absence of a solvent at 70 C. The ~Delta glucanolactone and E~ * W are then added and stirring is ¦continued until the mixture is homogeneous~ The mixture is cooled to 45 C. and the dibutyl tin dilaurate is added rapidly ¦with stirringO Stirring is continued for about 15 minutes ¦during which time the exothermic heat of reaction causes the ¦¦temperature to rise to about 85 C. and the viscosity increases.
¦IThe polymer is poured while still viscous into a chilling pan and placed in an oven at 75 C. for ~0 minutes. The pan is then removed from the oven and cooled to room temperature. The polymer may be removed from the pan and stored indefinitely at -2~-¦',* trade mark 'l ' .
room temperature or used immediately as a molding resin. The resin will swell in me~hanol and may be dissolved in alkaline solutlons.
! EXAMPLE 25 I The resin (a~ of Example 24 above is molded in the ¦shape of a lens by placing in a water cooled mold sufficient resin to fill the cavity and applying 15,000 psi pressure at ~125 C~ The mold is cooled and the optically clear polymer llens is removed.
One part of norethandrolone (Nilevar*~s blended with 30 parts of resin (b~ of Example 25 on a Band mill at 40 CO
This composition is placed in the cavity of a cylindrical mold and molded at 15,000 psi and 125 C. to form a cylinder of the polyurethane polyester resin having uniformly distributed Ithrouyhout its mass a pharmacologically effective dosage of ¦,norethandrolone O
¦I EXAMPLE 27 1~ An esophageal prosthesis is prepared from a tube woven ¦of polyethylene terphthalate monofilament. The tube is slipped ¦over a cylindrical rod of slightly smaller diameter and the assembly is dipped in a 15% isopropanol solution of the polyure-thane polymer of Example 3 prepared as described in Example 19 jand air dried. The dipping and drying procedure is repeated until a coatiny 2 mm in thickness is built up on the external Isurface of the fabric tube.
¦ A polypropylene monofilament 1.5 mm in diameter is ¦spirally wound around the coated -tube with a pitch of 5 turns per I ., ~r~ trade ma k -21-~ 5 ~ ~ ~
Icentimeter and heat set by placing the assembly in an o~en for ¦15 minutes at 80 C. The supporting rod is then removed from ¦the tube and the tube is repeatedly dipped in the 15~ isopropanol ¦solution polyurethane polymer as described above in the preceding paragraph until the polypropylene monofilament is aovered with the polyurethana polymer and the coating of polyurethane polymer on the interior surface of the fabric tube is 2 mm in thickness.
10The polyurethane polymer of Example 3 is dissolved in alkaline ethanol to form a 10 weight percent solution and a pair of polycarbonate safety goggles are dipped in the solution and allowed to dry at room temperature. The coating deposited on the polycarbonate lenses of the safety goggles resulted in a marked improvement in fogging characteristics when compared with a slmilar pair of safety goggles not so treated.
i EXAMPLE 29 A surgical suture is prepared by extruding the resin ; (b) of Example 24 through an orifice at 110 C. and 15,000 psi.
The extruded monofilament is stretched four times, wound on a rack, annealed at 100 C. for one-half hour and cooled to room temperature. The resulting su'cure may be cut to length, packaged and sterilized by gamma irradiation. If an iodized suture is desired, the suture is immersed in a 10 weight percent solution of iodine in ethanol until the desired amount of iodine has been taken up by the suture. Multifilament sutures may be produced as described above in this example by extruding the polymer of ~ample Ib~ througù a spinnerette containing the ` -2~- _ ~_ .
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desired number of orifices and braiding the multifilament after it llas been annealed.
eX~MPLe 30 The polymer solution described above in Example 17 is cast on a flat glass surface to form a film that is air ! dried at room temperature. The dry film may be removed from ¦the glass surface and applied directly to the surface of a burn ~as a burn dressing or the film may be comminuted and applied to ¦the burn in the form o a powder.
¦ EXAMPLE 31 ¦ A surgical implant is prepared by blending one part of r . I neo-3-vitamin A with 30 parts of the polyurethane polyether resin of Example 24 ~a) on a band mill at 40 C. This composition is placed in the cavity of a cylindrical mold and molded at 15,000 psi and 125 C. to form a cylinder having uniformly ! distributed throughout its mass an effective dosage of neo-B-vitamin ~. In a similar manner surgical implants may be molded containing a pharmacologically effective dosage of a hormone, a drug protagonist, an anti-tubercular drug or a steroid.
One part of lactic acid is blended with 30 parts of the polyurethane polyether resin (c) of Example 24 on a band 1 mill at 45 CO The composition is placed in the cavity of , an annular mold and molded at 15,000 psi and 125 C. -to Eorm a polymer ring useful as an intrauterine device.
The resin ~c) of Example 24 is extruded through an annular orifice at 20,000 psi and 135 C. to form a cannula.
The cannula is immersed for 24 hours in a 10 weight percent solution of iodine in ethanol after which time the iodine is I
;' ~distributed throughou~ the resin mass. The cannula is then removec ¦from the iodine solution and air dried.
¦ EXAMPLE 3~
I A woven tube of textile fibers 3 mm in diameter is ¦ repeatediy dipped in the solution of polyurethane polyether Iresin described in Example 17 and air dried to fill the inter-¦stices between the strands with polyurethane polymer and produce a cannula useful in surgery.
I Larger diameter tubes of woven polyethylene terphthalate strands may be similarly treated to fill the interstices between the woven strands. The resulting product may be used by the ? ' surgeon as a vascular prosthesis.
A vascular prosthesis is prepared by coating an 8 mm - 15 tube of woven collagen strands with the solution of polyurethane polyether resin described in Example 17 and air drying at xoom temperature to fill the interstiCes between the 9trands and coat the interior and eXterior walls of the tube. The tube is then dipped in heparin which is absorbed by the polyurethane coating, dried, packaged and sterilized by gamma irradiation.
EXAMPLE_36 A compoSition effective in the control of dehydration in humans and animals is prepared by grinding together in a ball ; . mill with dry ice 75 parts by weight of the polyurethane polyether resin of Example 10, 5 parts by weight of paregoric, 10 parts by weight bismuth suboxide and 10 parts by weight of psyllium (p}antago) seeds. ~he composition may be administered orally to cattle afflicted With the scours.
~_' - ' . __ _ EX~MPLE 37 To 98 parts of the polymer solution of Example 20 is added 2 parts by weight of a Red Dye No. 2 and the mixture is ball milled for 2 hours. The resulting composition may be ¦ used as a cosmetic.
A black braided silk suture is passed through -the polymer solution of E~ample 20 wound on a rack and air dried.
The resulting suture has an improved hand and tie down properties when compared with black braided silk that has not been so treated . I The polymer solution described in Example 19 is adjusted to pH 7 and cast on a glass surface to Por~ a film that is air dried. The dry film may be applied directly to the lS eye as an eye bandage.
~XAMPLE 40 The resin (a) of Example 24 is placed in a press and molded at 15,000 psi and 115 C. to forrn a hattery separator plate.
To the hair set composition of Example 21 is added 2 weight percent of a perfume essence. When this composition is applied to the hair the solvent rapidly evaporates but the perfume is bound to the polyurethane polymer and is slowly ¦released over a period of 24 hours.
~XAMPLE 42 ' ................................ _ .
A household deodorant composition is prepared by mixing 10 parts of phenol with 50 parts of the polymer solution described . ' ., - _. .. ~ . ..
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1~5~91 ~! in :~ample 20 abovc, 5 par-ts of perfume alld 35 parts of water.
Il A surgical drape is prepared by coating one surface ¦lof a woven cottvn cloth wi-th the polyurethane polyether solu-tion l~described in E~ample 20 above.
ll EXAMPLE 44 I
The resin (b) of Exampie ~4 is pressed at 15,000 ¦psi and 110 C. in a hydraulic press to form a polyurethane ¦polyether film having utility as a dialysis membraneO The film Iso prepared may be advantageously used as the carbon dioxide -¦oxygen exchange membrane in a blood oxygenator with minimum .destruction of blood cells.
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. A diethylene glycol solution of polyethylene glycol is.prepared by heating 109.2 parts (0.075 mole) of polyethylene glycol having a molecular weight of 1450 in 17.4 parts ~0.164 mole) ¦lof diethylene glycol with stirring. The solution is cooled to i below 60 C. and to it is added a solution of delka glucono-I ~ lacto-ne prepared by dissolving 11.6 parts (0.065 mole) of delta 20. gluconolactone in 46.4 parts of dimethyl sulfoxide. Eighty ¦and eight tenths parts (0.316 mole) of methylene bis cyclohexyl-¦4,4'-isocyanate ~a product identified as E~ * W sold by E. Io DuPont de Nemours & Co., Wilmington, Delaware) and 0.4 parts of diethanol amine are added ~o the mixture with skirring. One half part by weight of an organic tin catalyst solution; dibutyl ~tin dilaurate (a product identified as T12* manufactured by Metal ¦ancl Thermite Cornpany of Rahway, New ~erseyj is added to the . Ireaction mixture with stirring at a temperature below 45 C. to i ~ ~* trade mark ~1 i~5.
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~avoid undue temperature rise caused by the heat of reaction.
,After stirring for 20 minutes, the temperature increases to ¦80 C. The reaction mixture is then transferred to a tray jand placed in an oven at 90 C. for 1 hour to complete the S reaction. This polymer is amphoteric and, in the wet state, is soft, compliant and Elexible.
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5~S~l (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
tB) a polyfunctional lactone having the formula Rl-CH ~ C=O
O
wherein Rl is a monovalent radical selacted rom the group consisting of -H, -CH2NH2, S02CH3, 10 I -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -~CHOH)m- ;
m being,an integer from 2 to 10, and ethers ¦ derived from said lactones; and (C) a urethane precursor selected from the group 15 ¦ consisting of organic polyisocyanates and nitrile ' carbonates.
The long-chain, water-soluble diols should have a molecular weight of at least about 200 and preferably 1450 to 6000 or more and may be derived from,ethers, esters and ether-esti r block-containing resins. Suitable diols consist predominantly of oxyethylene or oxypropylene groups, though a minor proportion ¦ of other oxyalkylane groups may be included. Block copolymer I polyols obtained by adding ethylene oxide to a polyoxypropylene ¦ chain are also useful as are the linear polyester diols derived I from ths condensation of one or more diols with one or more dihasic acids, and the reaction product of one or more alkylene ¦ diols with a diPunctional linear polyester derived from the I condensation of one or more diols with one or more dibasic acids. ' ; 30 Representative examples of the polyfunctional lactones are those derived from polysacharides and monosacharides such as mannolactone, delta gluconola'ctone, sorbolactone and D-glucur-onolactone.
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11~55~1 It is desirable tilat the lactones employed have at least 3 and preferably 4 or more hydroxyl groups in the molecule or at least l more than is required to form a linear polyurethane chain. These free ~unreacted) hydroxyl groups remain in the polymer backbone and are available for cross-linking the polymer.
The lactone ring is also reactive and may be opened, i.e., by hydrolysis, to form carboxylate groups or carboxyl groups in the polymer backbone.
The number of carboxylic groups that are present in the polymer chain will be determined by the amount of lactone that is present in the reaction mixture which may be v~ried from 0.1~ to 30~ of the weight of the total rea^tion mixture.
Preferably the weight of the lactone will be .5% to 15~ of the ~eight of the total reaction mixture.
The polyisocyanate used in the present invention may be represented by R(NCO)n wherein n is greater than 1, preferably 2-4, and R is an aliphatic, alicyclic, aliphatic-alicyclic, aromatic, or aliphatic-aromatic hydrocarbon compound of ~rom 4 to 26 carbon atoms, but more conventionally from 6 to 20 and generally rom 6 to 13 carbon atoms. Representati~e examples of the above isocyanates are: tetramethylene diisocyanate;
hexamethylene diisocyanate; trimethylhexamethylene diisocyanate;
dimer acid diisocyanate; isophorone diisocyanate; diethylbenzene diisocyanate; decamethylene 1, 10-diisocyanate; cyclohexylene 1,2-diisocyanate and cyclohexylene 1,4-diisocyanate; and the ~romatic isocyanates such as 2,4~and 2,6-tolylene diisocyanate;
4,4-diphenylmethane diisocyanate; 1,5-naphthalene diisocyanate;
dianisidine diisocyanate; tolidine diisocyanate; a polymeric polyisocyanate such as neopentyl tetra isocyanate; m-xylylene diisocyanate; -tetrahydronapthalene-1,5 diisooyanate; and bis _- .. ... ~
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~4-isocyanatophenyl) methane.
The preEerred isocyanate is methylene di(cyclohexyl isocyanate). Other but slightly less preferred diisocyanates are trime-thyl hexamethylene diisocyanate and isophorone diisocyanate.
Other compounds which are useful are the isocyanate equivalents which produce the urethane linkages such as the ¦ nitrile carbonates, i.e., the adiponitrile carbonate of the formula:
O O
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r . N=C--CH2-CH2 -C~2--CH2--C=N
I In the manufacture of the polyurethane resins of the ¦ present invention, low molecular weight glycols such as ¦ diethylene glycol and dipropylene glycol or an aromatic glycol ¦ may be added to the reaction mixture. The preEerred low molecula ¦ weight aromatic polyols are bisphenol A and 4,4'-sulfonylcliphenol I ~he proportions in whiGh the long chain polyglycol and the low molecular weight glycol, i.e., diethylene glycol are used depends on the hydrophobic-hydrophilic balance present in each and desired in the final product. Increasing the molecu-lar weight of the long chain polyoxyalkylene glycol and~or the amount of this component contributes stron~ hydrophilic propertie to the final product. This effect may be counter-balanced by increasing the proportion of low molecular weight glycol, i.e., diethylene glycol or dipropylene glycol.
Reeping the above in mind (that it is the number of polyalkylene oxide groups in the polymer molecule that determines hydrophilic properties and the polyethylene oxide groups are more hydrophylic than a,re polypropylene oxide groups) it is a simple matter to choose mixtures of reactants such that the !
final product will have the desired propertiesO ~y choosing the molecular weight of the polyalkylene glycol or using two poly alkylene glycols of difEerent molecular weiyht one may "tailor make" products that satisfy a wide range of properties.
Amphoteric hydrophilic polyurethane polymers may be made by adding a dialkanol tertiary amine such as diethanol methyl amine to the reaction mixture.
In making the polyurethane resins of this invention the glycols are mixed with the lactone and the polyisocyanate is reacted with the mixture although other techniques may be used.
The reaction is catalyzed by known catalyst for such reaction, suitable ones being tin salts and organic tin esters such as dibutyl tin dilaurate, tertiary amines such as triethyl diamine (DABCD), N,N,N',N'-tetramethyl-1,3-butane diamine and other recognized catalysts for urethane reactions which are well known in the art. The reaction can be conduc-ted in the absence or presence of dilutent or solvent.
The polyurethane polyether resins of the present inven-tion because of their unique physical properties may advantageousl be used as burn dressings. The resin may ~e applied to the burn as a powder, film, or froln solution in a volatile non-toxi- solven and will form a barrier that is permeable to li~uids. Thus the physician has a choice of medicaments which may be applied to the burn prior to the resin coating or may be added to the resin for timed release. A particularly advantageous burn dressing is a powder obtained by the low -temperature grinding of from about 1 to about 80 parts by weight of polyvinylpyrolidone-iodine with about ~0 to about 99 parts by weight of polyether polyurethane resins having free hydroxyl and carboxylate groups in the polymer backbon, .
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~1555~1 The above described polyurethane polyether resins are also useful as coatings, molding compounds, absorbents, controlled release agents, ion exchange resins, in the repair of skin abrasions and in the manufacture of dialysis membranes, dentures, cannulae, contac-t lenses, solubilizing packaging components, hair sprays, cosmetics, burn dressings, contraceptive ¦devices, sutures, surgical implants, blood oxygenators, intra-uterine devices, vascular prostheses, oral delivery systems, battery seperator plates, eye bandages, dipilatory compositions, corneal prostheses, perfumes, deodorant compositions, antifog . coatings, surgical drapes, oxygen exchange membranes, artificial finger nails, finger cots, adhesives, gas permeable membranes, : and in protective and drag resistant coatings.
. . The practice of the invention is further illustrated : 15 by thè followin~ examples without being restricted thereto, ~the parts belng by we ht, unless o~herwise stated.
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1~S5591 A diethylene glycol solution of polyethylene glycol ¦ is prepared by heating 109.2 parts (0O075 mole) of polyethylene 1 glycol having a molecular weight of 1450 in 17.4 parts 50.l64 mol~
¦ of diethylene glycol with stirring. The solution is cooled to below 60 C~ and to it is added a solution of delta glucono-lactone prepared by dissolving llo6 parts (0.065 mole) of,delta I gluconolactone in 46.4 parts of dimethyl sulfoxide. Ei,~hty ! and eight tenths parts (0O316 mole~ of methylene bis cyclohexyl~
¦ 4,4'-isocyanate (a product identified as H~* W sold by E. Io DuPont de Nemours'& Co., Wilming-tonl Delaware~ is added to the ! mixture with stirringO One half part by weight of an organic ¦ tin catalyst solution; dibutyl tin dilaurate (a product identifie ~ as ~-12* manufactured by Metal and Thermite Company of Rahway, I New Jersey) is added to the reaction mixture with stirring at a 1l temperature below 45 C. to auoid undue temperature rise ,¦ caused by the heat of reaction.' After stirring for 20 minutes~
¦ the temperature increases to 80 CO The reaction mixture is I then trans~erred to a tray and placed in an oven at 90 C. for l hour to complete the reactionO This polymer~ in the wet state/ is soft~ compliant and flexibleO
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¦ A polymer -that is insoluble in wa-ter but soluble in a I mixture of a major portion of alcohol and a minor portion of ¦ aqueous base (1.0 N sodium hydroxide) is prepared by the method S ¦ described in Example 1 from:
Polyethylene Glycol (M. Wt. 1450) 3469 par-ts (2.37 mole) ¦ Diethylene254 parts (2.39 mole) ¦I Delta Gluconolactone (as a 20%
. ¦ solution in dimethyl sulfoxide) 116 parts (0.65 mole) HYLENE W ~trade mark)808 parts (3.16 mole) . . Dibutyl tin dilaurate 5 parts .A piece of this polymer, cast in the form of a cylinder .. ¦ having a volumn of 10 ml. is wei~hed, immersed in wate:r at room .
. I temperature for 12 hours, dried with a paper towel to remove ¦ surface moisture and again welghed~ rrhe increase in weight was 100%.
A pol~me.r containing lactone groups that is soIuble in ¦ a ma~or portion of al.cohol ha~ing a minor amount of base dissolve .
!¦ therein, or added with a minor amount of water or other carrier ¦l is prepared by the method described above in Example 1 from:
. I Polyethylene Glycol (M. Wt~ 1450) 2000 parts (1. 37 mole) Diethylene Glycol107.5 parts (1.64 mole) Delta Gluconolactone (as a 20%
solution in dimethyl sulfoxide) 116 parts (0.65 mole) . HYLENE W (trade markl808 parts (3.16 mole) : ¦ Stannous Octoate (Tg)*S parts ¦ *Tg is a trademark o~ the Metal and Thermite Company of Rahway, . I New Jersey.
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~XAMPLE 4 This example illustrates the preparation of a polymer soluble in alkaline solutions using a 5~ excess o cyanate ¦ groups. The me-thod of preparation is described in Example 1.
¦ Polyethylene Glycol (mol~ wto 1450) 1097 parts (0.7S mole) Diethylelle Glycol 174 parts (1.64 mole) Delta Gluconolactone (as a 20%
solution in dimethyl sulfoxid~ 116 parts (0.65 mole) 1~ HYLENE W (trade mark) 102.4 parts (0.4 mole) 10 ¦¦ Stannous Octoate (T~)* 5 parts Fifty grams of the polyurethane polyether resin described above in Example 1 is added to 500 ml of an aqueous solution containing 17.4 ml of 23% ammonium hydro~ide~ The ¦ solution is stirred at 90 CO until all of the polymer dissolves.
To the polymer solution is added 10 ml of an a~ueous 20% solution of ammonium dichromate 12.0 g (NH9)2Cr204]. The solution is applied to cellulose acetate film with a doctox knife and dried at room temperature in subdued light or darkness. A tough film of the photosensitive comple~ light yellow in color, is deposited that adheres well to the cellulose acetate substrate.
¦ A photographic image is proje~ted onto the film using a S-l sun lamp as the light source and an exposure time of 60 seconds.
The film is developed by washing in water at room temperature to dissolve ancl remove the unexposed and uncross-linked portion of the photographic image. Since the polymer that forms the photographic imaye is substantative to ink the developed film I may be used in lithography printing processes.
¦ *Tg is a trademark of the Metal and Thermite Company of I Rahway, New Jersey.
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E~AMPL~ 6 ~n anti-fouling marlne paint is formula-ted by grinding in a ball mill fo.r three hours:
I Polyurethane resin of Example 2 150 parts 5 I Five percent ammonium hydroxide . in ethanol 500 parts ¦ Potassium dichromate2 parts Titanium dioxide 50 parts Mercury:acetate 3 parts . The produc-t so ob-tained may be applied to wood and other surfaces ¦ to form a film that is cross-linked by sun light to an adherent ¦ insoluble protective coating. The product is particularly ¦ effective when applied to the hull of a boat as a hydrophylic ¦ nature of the urethane resins permits the slow release of the 1 mercury salts and prevents barnacle or algae formation on the ¦ painted surfaces.
EXAMPLE 7 .
¦~ A polyurethane polyether resin is prepared by the method described in Example 1 above substituting for the 1¦ polyethylene ylycol a block copolymer having a molecular we.ight of 4750 obtainecl by adding poly(oxyethylene) groups to a poly~oxypropylene~ chain having a molecular weight of ~50. .
.. Block copolymer ~M. Wt. 4750) . 3577 parts ll Diethylene glycol 174 parts .
25 I Delta gluconolactone (as.a 20%
solution in dimethyl sulfoxide) 116 parts ~YLENE W (.trade m~rk~ 808 parts Dibutyl tin dilaurate 5 parts I 1 ~ 5 5 ~ 1 EX~MPLE 8 A polyure-thane polyether resin is prepared by the method described in Example 1 above subs-tituting for the polyethylene ylycol a block copolymer having a molecular weight of 7500 obtained by adding poly(oxyethylene) groups to a poly(oxypropylene) chain having a molecular weight of 2250u Block copolymer (M. Wt. 7500) 1157.4 parts ; Diethylene Glycol 32O75 parts Delta gluconolactone (as a 20~
10 ~ solution in dimethyl sulfoxide) 116 parts HYLENE W ~trade markl 808 parts Dibutyl tin dilaurate 5 parts A polyurethane polyether resin is prepared by t,he lS method described in Example 1 above substituting for the polyethylene ylycol a block copolymer having a molecular weight of 6500 obtained by adding poly(oxyethylenel yroups to a .
poly(oxypropylenel chain having a molecular weight of 32500 " Block copolymer 325 parts Diethylene glycol 210 76 parts Delta gluconolactone (as a 20%
solution in dimethyl sulfoxide)41.41 parts HYLENE W (trade mark) 132 parts Dibutyl tin dilaurate 0.5 parts ~12-l i 5 ~ 5~ ~
I
¦ EXAMPLE 10 ¦ A polyurethane polyether resin is prepared by the method described in Example 1 above substituting for the polye-thylene glycol a block copolymer having a molecular weight j of 13,333 obtained by adding poly(oxyethylene) groups to a ¦ poly(oxypropylene) chain having a molecular weight of about 4000.
Block copolymer 1004 parts Diethylene glycol 170 4 parts Delta qluconolactone* llo 6 parts . Dimethyl sulfoxide 46.4 parts HYLENE W ~trade ma~k~ 80.8 parts Dibutyl~tin dilaurate 3 parts .
After stirring ~or one hour~ the reaction mixture is transferred to a tray and placed in an oven at 90 C. overnightO
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~XAMPL~
¦ A series of three polyurethane polyether resins is ¦ prepared by the procedure of Example 1 in which the amount of ¦ Delta glucono-lactone is varied.
S ¦ Polyethylene Diethylene Delta HYLENE* Dibutyl tin ¦ glycol glycol glucono- W dilaurate ¦ (~. Wt. 1450) lactone#
¦ Resin (a) 54.6 g8.7 g 2.9 g 40.4 g 0.5 g ¦ Resin (b) 54.6 y8.7 g 5.8 g 40.4 g 0.5 g 10 ! Resin (c) 54.6 g8.7 g 11.6 g 48.5 g 0.5 g ¦ After the initiai reaction, instead of curing the resin ¦ in an oven the three resin (3 g. of each) were mixed with 100 mg ¦ of norethandrolone (Nileva~), cast in the form of cylinders 1.3 c ¦ by 2.5 cm and polymerized at 80 C. for 30 hours. After removing lS ¦ from the mold, cylinders suitable for in vivo implantation to ¦ provide prolonged release of the norethandrolone (Nilevar*~ are - ¦ obtained for use in animal husbandry.
¦ EXAMPLE 12 Delta glucanolactone ~14.28 parts) is ground to a fine powder and thoroughly mixed with 29.15 parts of polyethylene glycol (M. Wt. 200). The mixture is heated to 60 C. and to it is added 56.57 parts of E~NE~ W and 0.5 parts of stannous octoat~
with stirring. After the exothermic reaction subsides, the resin is transferred into a tray and placed in an oven at 90 C. for one hour to complete the reaction.
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dissolved in dimethyl sulfoxide . . . .
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Polyethylene glycol of molecular weighit 1450 (218.4 ¦Iparts) is mixed with 34.8 parts of diethylene glycol and the llmixture is heated with stirrlng to the melting point. To this S ~Imelt is added 161~6 parts of HYL~ W.
A solution of delta gluconolactone is prepared by ¦Idissolving 23.2 parts of delta gluconolactone in 77 parts of dimethyl sulfoxide. The dleta gluconolactone solution is added to the mixture of glycols and ~IYLENE W with sti.rring and the reaction mixture is cooled ko 50 C. Eight tenths parts of dibutyl tin dilaurate catalyst is adde~ -to the reaction mixture, and stirring is continued until the exothermic reaction subsidesO
The resin is then cured in an oven at 90C. for one hourO
The cured resin (2.6 parts) is dissolved in alkaline methanol ~/.4 parts) and 2.5 parts o~ a 2% aqueous ammonium dichromate solution is addedO The dichromate catalyzed resin ~solution is poured through a S mm pyrex glass tube 4 feet in llen~th to form a uniform coating on the interior surface thereofO
¦The coating is air ~ried in ambient light for 5 minutesO
I One end of the coated tube is closed with a cork . pierced by a fine hypodermic needle~ The tube is filled with `
tap water and then in~erted to p~rmit the tap water to drain . out. The time required for all water to drain from the tube . iwas 24 seconds. The experiment was repeated ten timesO The 5 ¦Itime required for the tube ~o drain was always 24 ~ 1 secondsO
. In a control experiment an uncoated 5 mm pyrex -tube 4 feet in length is washed thoroughly with a detergent solution, ¦rinsed with distilled water and air driedO The tube is closed jwith the same cork pierced by a fine hypodermic needle referred * trade mark -15-,. ' .
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to above and filled with tap water. When this uncoated tubeis inverted (10 trials) it required 38 ~ 1 seconds for the water to drain from the tube.
¦ The dichromate catalyzed resin composition described ¦above in this example is applied to the hull and center-board of a Lightning Class sailboat and exposed to the sunlight for 6 minutes to cross-link the coating. In a light breeze the sailboat outperforms other boats in her class.
A diethylene glycol solution of polyethylene glycol is prepared by heating and stirring 249.3 parts tO.172 mole) of polyethylene glycol having a molecular weight of 1450 with 79.5 parts (O.g83 mole) o~ diethylene glycol. To this melt is added S2.9 parts (0.296 mole) of delta gluconolactone, 249.3 parts tO.86 mole) of diethylene glycol adipate and 520 parts (1.85 moles) of methylene bis cyclohexyl-4,4'-isocyanate. The mixture is stirred with heating to form a homogeneous melt and then cooled to 45 C. Two and one tenth parts of a solution of dibutyl tin dilaurate is added to the reaction mixture with rapid stirring to avoid undue temperature rise caused by the heat of reaction. After stirring for twenty minutes, the temperature is 85 C. The reaction mixture is then transferred to a tray and placed in an oven at 90 C. for one hour to complete the reaction. The resultinq polymer contains 21 weight percent adipic acid ester, is harder and more rigid than the polymer of Example 1 and is insoluble in water and aqueous alkaline solutioas. When immersed in water the increase in weight, due to the water take up, is less than 20 percent.
. .
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¦l A polyurethane polymer derlved from a lincar polyester diol is prepared by reacting:
¦ polyethylene glycol (0.005 mole) 7.95 parts 5 ¦ delta glucanolactone (0.29 mole) 5.2 parts diethylene glycol adipate (0.172 mole) 49.86 parts ¦ HYLENE ~ (0.241 mole) 68q0 parts ¦The mixture of reactants is heated with stirring until homogeneous ¦and 0.2'1 parts of an organic tin catalyst solution; dibutyl tin Idilaurate (a product identified as T12* manufactured by Metal and IThermite Company of Rahway, New Jersey) is added to the reaction ¦with st~rring at a temperature below 45 C. to avoid undue temperature rise caused by the heat of reaction. After stirring for 20 minutes, the temperature increases to 80 CO The reaction mixture is then transerred to a tray and placed in an oven at 90 C. for l hour to complete the reaction. The resulting polymer contains 38 we.ight percent adipic acid ester and is ¦harder and more rigid than ~he pol~mer of Example 14. It is linsoluble in basic aqueous solutions and methanolO The water !take up of this polymer is less than lS weight percent.
E~AMPLE 16 Example 15 above is repeated but the amount of the diethylene glycol adipate present in the reaction mixture is Ireduced from 49.86 parts to 1.15 parts (1.4 weight percent of 2S Ithe reaction mixture). One gram of the polymer of this example rhen immersed in water swells and absorbs 0.48 g waterO One gram ~of this polymer may be dissolved in a mixture of 9 ml methanol iand 1 ml of 2 N aqueous sodium hydroxide.
trade mark Il .
11$5~1 EX~PLE 17 To 90 parts by volumn of a mixture of ethanol and ¦water (70:30) is added lO parts oE the polymer of Example l and !l part of sulfadia~ine. The polymer is dissolved by stirring !with the addition of l N sodium hydroxide to adjust the pH of ¦,the solution to 7Ø The polymer solution may be applied as a l! burn dressing directly to a burn area and upon evaporation of the I solvent forms a protective skin that does not interfere with ¦ healing because of its permeability to gases and fluids but ~prevents the growth of anerobic organisms under the dressing.
¦j EXAMPLE l8 A polymer having the composition set forth in Example 2 above is prepared by heating and stirring the polye-thylene ~lycol, diethylene glycol, delta glucanolactone and HYLENE W
1! to form a homogeneous mixture. The catalyst is added to the ¦' reaction mixture at 40 C. and stirring is continued until the ¦ exothermic reaction subsides (temperature starts to drop) at which time 232 parts (5 weight percent) of cortisone is added I with thorough stirring to assure uniform dispersion. The polymer ' is cast in the form of cylinders l.5 cm by 3 cm and is cured ~ at 70 C. After curing, the cylinders are removed from the ¦¦ mold and are suitable for implantation to provide prolonged jl release of cortisone.
I EXAMPLE l9 1 .
i Fifteen parts of the polymer described in Example 3 I above is placed in 70 parts by volumn of a mixture of isopropanol ¦ and water (50:50) and lO parts by volumn of l N sodium hydroxide solution is added. The mixture is refluxed to hydrolyse the ¦ lactone ring and dissolve the polymer. The solution is titrated to pH 5.0 with l N hydrochloric acid and the polymcr solids content adjusted to 15 percent with isopropanol. To this polymer * trade mark 1 i 5 5 ~ ~ 1 solution is added 15,000,000 units of phenoxyethyl penicillin.
The resulting solution may be applied to an abraided skin area to seal off the area from irritating physical and biological substances. The deposited film allows the free passage of gases and moisture from the area covered.
A twenty percent solution of the polymer described in Example 7 above is prepared by dissolving that polymer in a mixture of ethanol and water (50:50) with the addition of sufficient 1 N sodium hydroxide to effect solution. The pH of ¦the solution is adjusted to 6.0 with 1 N hydrochloric acid. The . solution so obtained may be applied topically to form a hypoallergenic base for cosme-tics. The polymer composition effectively covers skin blemishes and allows the skin to breathe.
A hair set composition is prepared by dissolving the polyurethane polyether resin of Example 8 above in 9S percent ethanol. Sufficient 1 N sodium hydroxide is added ~o effect solution and the pH of the final composition adjusted to 7Ø
The resulting solution may be applied to the hair in the form of a spray and provides superior holding with a soft feel.
Twenty parts of the unsaturated polyether resin of Example 1 is dissolved in 80 parts of ethanol-water (70:30) and sufficient 1 N sodium hydroxide to adjust the pH to 9.5. To the solution so obtained is added with stirring 5.6 parts of calcium thioglycolate. The resulting composition finds use as a dipillatory agent.
5 5 9 ~
¦ EXAMPLF ~3 I The polymer of Example 16 above is extruded to form ¦la tube 1.5 m in leng-th and 10 mm in diameter. Dry nitrogen ¦Igas is passed through this tube and into a dry ice trap. The ¦Itube is then immersed in a trough of water. Water vapor which ¦lis picked up by the nitrogen as it flows through the tube is ¦!deposited in the trap as ice.
il EXAMPLE 24 A series of three polyurethane polyether resins is prepared in which ~he amount of Delta glucano-lactone is varied.
Polyethylene Delta glycol Diethylene glucono- HYLENE* Dibutyl tin '~M. Wt. 1450) glycollactone W dilaurate ~ _ ¦Resin (a) 54.6 g 8.7 g 2.9 g 40.4 g ODO4 g IResin ~b) 54.6 g 8.7 g 5.8 g 40.4 g 0.04 g IResin (c) 54.6 g 8.7 g 11.6 g48.5 g 0.04 g IlThe polyethylene glycol and diethylene glycol are melted and ~jmixed together in the absence of a solvent at 70 C. The ~Delta glucanolactone and E~ * W are then added and stirring is ¦continued until the mixture is homogeneous~ The mixture is cooled to 45 C. and the dibutyl tin dilaurate is added rapidly ¦with stirringO Stirring is continued for about 15 minutes ¦during which time the exothermic heat of reaction causes the ¦¦temperature to rise to about 85 C. and the viscosity increases.
¦IThe polymer is poured while still viscous into a chilling pan and placed in an oven at 75 C. for ~0 minutes. The pan is then removed from the oven and cooled to room temperature. The polymer may be removed from the pan and stored indefinitely at -2~-¦',* trade mark 'l ' .
room temperature or used immediately as a molding resin. The resin will swell in me~hanol and may be dissolved in alkaline solutlons.
! EXAMPLE 25 I The resin (a~ of Example 24 above is molded in the ¦shape of a lens by placing in a water cooled mold sufficient resin to fill the cavity and applying 15,000 psi pressure at ~125 C~ The mold is cooled and the optically clear polymer llens is removed.
One part of norethandrolone (Nilevar*~s blended with 30 parts of resin (b~ of Example 25 on a Band mill at 40 CO
This composition is placed in the cavity of a cylindrical mold and molded at 15,000 psi and 125 C. to form a cylinder of the polyurethane polyester resin having uniformly distributed Ithrouyhout its mass a pharmacologically effective dosage of ¦,norethandrolone O
¦I EXAMPLE 27 1~ An esophageal prosthesis is prepared from a tube woven ¦of polyethylene terphthalate monofilament. The tube is slipped ¦over a cylindrical rod of slightly smaller diameter and the assembly is dipped in a 15% isopropanol solution of the polyure-thane polymer of Example 3 prepared as described in Example 19 jand air dried. The dipping and drying procedure is repeated until a coatiny 2 mm in thickness is built up on the external Isurface of the fabric tube.
¦ A polypropylene monofilament 1.5 mm in diameter is ¦spirally wound around the coated -tube with a pitch of 5 turns per I ., ~r~ trade ma k -21-~ 5 ~ ~ ~
Icentimeter and heat set by placing the assembly in an o~en for ¦15 minutes at 80 C. The supporting rod is then removed from ¦the tube and the tube is repeatedly dipped in the 15~ isopropanol ¦solution polyurethane polymer as described above in the preceding paragraph until the polypropylene monofilament is aovered with the polyurethana polymer and the coating of polyurethane polymer on the interior surface of the fabric tube is 2 mm in thickness.
10The polyurethane polymer of Example 3 is dissolved in alkaline ethanol to form a 10 weight percent solution and a pair of polycarbonate safety goggles are dipped in the solution and allowed to dry at room temperature. The coating deposited on the polycarbonate lenses of the safety goggles resulted in a marked improvement in fogging characteristics when compared with a slmilar pair of safety goggles not so treated.
i EXAMPLE 29 A surgical suture is prepared by extruding the resin ; (b) of Example 24 through an orifice at 110 C. and 15,000 psi.
The extruded monofilament is stretched four times, wound on a rack, annealed at 100 C. for one-half hour and cooled to room temperature. The resulting su'cure may be cut to length, packaged and sterilized by gamma irradiation. If an iodized suture is desired, the suture is immersed in a 10 weight percent solution of iodine in ethanol until the desired amount of iodine has been taken up by the suture. Multifilament sutures may be produced as described above in this example by extruding the polymer of ~ample Ib~ througù a spinnerette containing the ` -2~- _ ~_ .
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desired number of orifices and braiding the multifilament after it llas been annealed.
eX~MPLe 30 The polymer solution described above in Example 17 is cast on a flat glass surface to form a film that is air ! dried at room temperature. The dry film may be removed from ¦the glass surface and applied directly to the surface of a burn ~as a burn dressing or the film may be comminuted and applied to ¦the burn in the form o a powder.
¦ EXAMPLE 31 ¦ A surgical implant is prepared by blending one part of r . I neo-3-vitamin A with 30 parts of the polyurethane polyether resin of Example 24 ~a) on a band mill at 40 C. This composition is placed in the cavity of a cylindrical mold and molded at 15,000 psi and 125 C. to form a cylinder having uniformly ! distributed throughout its mass an effective dosage of neo-B-vitamin ~. In a similar manner surgical implants may be molded containing a pharmacologically effective dosage of a hormone, a drug protagonist, an anti-tubercular drug or a steroid.
One part of lactic acid is blended with 30 parts of the polyurethane polyether resin (c) of Example 24 on a band 1 mill at 45 CO The composition is placed in the cavity of , an annular mold and molded at 15,000 psi and 125 C. -to Eorm a polymer ring useful as an intrauterine device.
The resin ~c) of Example 24 is extruded through an annular orifice at 20,000 psi and 135 C. to form a cannula.
The cannula is immersed for 24 hours in a 10 weight percent solution of iodine in ethanol after which time the iodine is I
;' ~distributed throughou~ the resin mass. The cannula is then removec ¦from the iodine solution and air dried.
¦ EXAMPLE 3~
I A woven tube of textile fibers 3 mm in diameter is ¦ repeatediy dipped in the solution of polyurethane polyether Iresin described in Example 17 and air dried to fill the inter-¦stices between the strands with polyurethane polymer and produce a cannula useful in surgery.
I Larger diameter tubes of woven polyethylene terphthalate strands may be similarly treated to fill the interstices between the woven strands. The resulting product may be used by the ? ' surgeon as a vascular prosthesis.
A vascular prosthesis is prepared by coating an 8 mm - 15 tube of woven collagen strands with the solution of polyurethane polyether resin described in Example 17 and air drying at xoom temperature to fill the interstiCes between the 9trands and coat the interior and eXterior walls of the tube. The tube is then dipped in heparin which is absorbed by the polyurethane coating, dried, packaged and sterilized by gamma irradiation.
EXAMPLE_36 A compoSition effective in the control of dehydration in humans and animals is prepared by grinding together in a ball ; . mill with dry ice 75 parts by weight of the polyurethane polyether resin of Example 10, 5 parts by weight of paregoric, 10 parts by weight bismuth suboxide and 10 parts by weight of psyllium (p}antago) seeds. ~he composition may be administered orally to cattle afflicted With the scours.
~_' - ' . __ _ EX~MPLE 37 To 98 parts of the polymer solution of Example 20 is added 2 parts by weight of a Red Dye No. 2 and the mixture is ball milled for 2 hours. The resulting composition may be ¦ used as a cosmetic.
A black braided silk suture is passed through -the polymer solution of E~ample 20 wound on a rack and air dried.
The resulting suture has an improved hand and tie down properties when compared with black braided silk that has not been so treated . I The polymer solution described in Example 19 is adjusted to pH 7 and cast on a glass surface to Por~ a film that is air dried. The dry film may be applied directly to the lS eye as an eye bandage.
~XAMPLE 40 The resin (a) of Example 24 is placed in a press and molded at 15,000 psi and 115 C. to forrn a hattery separator plate.
To the hair set composition of Example 21 is added 2 weight percent of a perfume essence. When this composition is applied to the hair the solvent rapidly evaporates but the perfume is bound to the polyurethane polymer and is slowly ¦released over a period of 24 hours.
~XAMPLE 42 ' ................................ _ .
A household deodorant composition is prepared by mixing 10 parts of phenol with 50 parts of the polymer solution described . ' ., - _. .. ~ . ..
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1~5~91 ~! in :~ample 20 abovc, 5 par-ts of perfume alld 35 parts of water.
Il A surgical drape is prepared by coating one surface ¦lof a woven cottvn cloth wi-th the polyurethane polyether solu-tion l~described in E~ample 20 above.
ll EXAMPLE 44 I
The resin (b) of Exampie ~4 is pressed at 15,000 ¦psi and 110 C. in a hydraulic press to form a polyurethane ¦polyether film having utility as a dialysis membraneO The film Iso prepared may be advantageously used as the carbon dioxide -¦oxygen exchange membrane in a blood oxygenator with minimum .destruction of blood cells.
I - .
. A diethylene glycol solution of polyethylene glycol is.prepared by heating 109.2 parts (0.075 mole) of polyethylene glycol having a molecular weight of 1450 in 17.4 parts ~0.164 mole) ¦lof diethylene glycol with stirring. The solution is cooled to i below 60 C. and to it is added a solution of delka glucono-I ~ lacto-ne prepared by dissolving 11.6 parts (0.065 mole) of delta 20. gluconolactone in 46.4 parts of dimethyl sulfoxide. Eighty ¦and eight tenths parts (0.316 mole) of methylene bis cyclohexyl-¦4,4'-isocyanate ~a product identified as E~ * W sold by E. Io DuPont de Nemours & Co., Wilmington, Delaware) and 0.4 parts of diethanol amine are added ~o the mixture with skirring. One half part by weight of an organic tin catalyst solution; dibutyl ~tin dilaurate (a product identified as T12* manufactured by Metal ¦ancl Thermite Cornpany of Rahway, New ~erseyj is added to the . Ireaction mixture with stirring at a temperature below 45 C. to i ~ ~* trade mark ~1 i~5.
!
~avoid undue temperature rise caused by the heat of reaction.
,After stirring for 20 minutes, the temperature increases to ¦80 C. The reaction mixture is then transferred to a tray jand placed in an oven at 90 C. for 1 hour to complete the S reaction. This polymer is amphoteric and, in the wet state, is soft, compliant and Elexible.
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Claims (92)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A hydrophilic polyurethane polymer comprising the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids:
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids:
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
2. The polyurethane polymer of claim 1, wherein one of said diols is a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids.
3. The polyurethane polymer of claim 1, wherein one of said diols is the reaction product of a polyoxyalkylene diol with a difunctional linear polyester derived from the condensation of diethylene glycol with adipic acid.
4. A surgical suture comprising a hydrophilic poly-urethane polymer obtained by reacting.
(A) one or more diols having an equivalent weight in the range of from about 100 to 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
5. The suture of claim 4, wherein said hydrophilic polyurethane polymer is in the form of a monofilament.
6. The suture of claim 4, wherein said hydrophilic polyurethane polymer is in the form of a braided multifilament.
7. The suture of claim 4, having present in said hydrophilic polyurethane polymer a medicament.
8. The suture of claim 7 wherein said medicament is iodine.
9. A burn dressing comprising a hydrophilic polyurethane polymer obtained by reacting:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-m being an integer from 2 to 10; and ethers derived from said lactones: and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-m being an integer from 2 to 10; and ethers derived from said lactones: and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
10. The burn dressing of claim 9 wherein said hydrophilic polyurethane polymer is in the form of a film.
11. The burn dressing of claim 9 wherein said hydro-philic polyurethane polymer is in powder form.
12. The burn dressing of claim 9 wherein said hydrophilic polyurethane polymer is in solution.
13. The burn dressing of claim 10 having present in said hydrophilic polyurethane polymer a medicament.
14. The burn dressing of claim 13 wherein said medica-ment is sulfadiazine.
15. The burn dressing of claim 11 wherein a medicament is distributed throughout the powder.
16. The burn dressing of claim 12 wherein a medicament is dissolved in said solution.
17. A surgical implant comprising a solid hydrophilic polyurethane polymer obtained by reacting:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates;
said polyurethane polymer having distributed throughout its mass a medicament.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates;
said polyurethane polymer having distributed throughout its mass a medicament.
18. The implant of claim 17 wherein said medicament is an anti-tubercular drug.
19. The implant of claim 17 wherein said medicament is a drug protagonist.
20. The implant of claim 17 wherein said medicament is a hormone.
21. The implant of claim 17 wherein said medicament is a steroid.
22. The implant of claim 17 wherein said medicament is a vitamin.
23. An intrauterine device comprising a hydrophilic polyurethane polymer obtained by reacting:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000 selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2-NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000 selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2-NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
24. The intrauterine device of claim 23 in the shape of a ring.
25. The intrauterine device of claim 23 having distributed throughout said polyurethane polymer a contraceptive.
26. The intrauterine device of claim 25 wherein the contraceptive is lactic acid.
27. A canula, the walls of which are formed of a hydrophilic polyurethane polymer obtained by reacting:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH20H; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH20H; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
28. The canula of claim 27 wherein said polyurethane polymer has distributed throughout its mass a medicament.
29. The canula of claim 28 wherein said medicament is iodine.
30. A canula woven of textile fiber in the form of a tube having external and internal walls, at least one wall of which is coated with a film of a hydrophilic polyurethane polymer obtained by reacting:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH20H; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH20H; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
31. A vascular prosthesis comprising textile strands woven in the form of a tube; the intersticies between said woven strands being filled with a hydrophilic polyurethane polymer comprising the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10, and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10, and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
32. The vascular prosthesis of claim 31 wherein said poly-urethane polymer has distributed throughout its mass a medicament.
33. The vascular prosthesis of claim 31 wherein said textile strands are polyethylene terphthalate strands.
34. The vascular prosthesis of claim 31 wherein said textile strands are collagen strands.
35. The vascular prosthesis of claim 32 wherein said medi-cament is heparin.
36. An oral delivery system comprising a pharmacologically active agent and a hydrophilic polyurethane polymer as a carrier vehicle therefor, said hydrophilic polyurethane polymer being the re-action product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consis-ting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones;
and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consis-ting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones;
and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
37. A solution effective in the repair of skin abrasions comprising a hydrophilic polyurethane polymer dissolved in a volatile non-toxic organic solvent, said polyurethane polymer being the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
38. A cosmetic adapted for topical application comprising a solution of a non-toxic dye and a hydrophilic polyurethane polymer in a volatile non-toxic organic solvent, said-polyurethane polymer being the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
39. A surgical suture coated with a hydrophilic polyurethane polymer comprising the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-:
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-:
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
40. An eye bandage comprising a hydrophilic polyurethane polymer film obtained by reacting:
(a) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of: H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(a) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of: H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
41. A battery separator plate formed of a hydrophilic polyurethane polymer comprising the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids, (B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids, (B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
42. A hair spray composition comprising a solution in a volatile non-toxic solvent of a hydrophilic polyurethane polymer obtained by reacting:
(a) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10, and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(a) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10, and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
43. A gas permeable membrane formed of a hydrophilic polyurethane polymer comprising the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol) (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol) (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
44. A depilatory liquid comprising a solution in a non-toxic solvent of a depilatory agent and a hydrophilic polyurethane polymer obtained by reacting:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-, m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-, m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
45. A solution of perfume and a hydrophilic poly-urethane polymer in a non-toxic solvent said polyurethane polymer comprising the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids.
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2H2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids.
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2H2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
46. A corneal prosthesis comprising a solid transparent hydrophilic polyurethane polymer obtained by the reaction of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2,-SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates, said polyurethane polymer being in the shape of a lens and characterized by a refractive index in the range of from about 1.39 to about 1.55; dry.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2,-SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates, said polyurethane polymer being in the shape of a lens and characterized by a refractive index in the range of from about 1.39 to about 1.55; dry.
47. A deodorant composition comprising a solution of a disinfectant, a perfume and a hydrophilic polyurethane polymer obtained by reacting:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
48. A method of imparting moisture to a dry gas which comprises passing the gas through a tube formed of a hydrophilic polyurethane polymer obtained by reacting:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
49. An antifogging liquid containing in solution a hydrophilic polyurethane polymer comprising the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
50. A surgical drape comprising a fabric coated on at least one side with a hydrophilic polyurethane polymer obtained by reacting:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-, m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-, m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
51. A dialysis membrane formed of a hydrophilic polyurethane polymer comprising the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
52. In a blood oxygenator the improvement which comprises a carbon dioxide - oxygen exchange membrane formed of a hydrophilic polyure-thane polymer comprising the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-, m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-, m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
53. An amphoteric hydrophilic polyurethane polymer comprising the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3, 000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) difunctional linear polyesters derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-, m being an integer from 2 to 10; and ethers derived from said lactones;
(C) a.urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates; and (D) a dialkanol tertiary amine.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3, 000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) difunctional linear polyesters derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-, m being an integer from 2 to 10; and ethers derived from said lactones;
(C) a.urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates; and (D) a dialkanol tertiary amine.
54 59. An esophageal prosthesis constructed of a fabric tube reinforced with a spirally wound polypropylene monofilament and coated on at least one side with a hydrophilic polyurethane polymer obtained by reacting:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difullctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group conslsting of -H, -CH2NH2, -SO2CH3, CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difullctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group conslsting of -H, -CH2NH2, -SO2CH3, CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
55. A contact lens comprising a molded hydrophilic polyurethane polymer obtained by reacting:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-:
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000, selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2NH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-:
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
56. The polyurethane polymer of claim 1 characterized by a flow point below 275° C.
57. The polyurethane polymer of claim 1 characterized by the presence of lactone groups and hydroxyl groups in the polymer backbone.
58. The polyurethane polymer of claim 1 characterized by the presence of carboxyl groups and hydroxyl groups in the polymer backbone.
59. The polyurethane polymer of claim 1 which has been molded to form a desired shape.
60. A coated device consisting of a substrate coated with a hydrophilic polyurethane polymer comprising the reaction product of:
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000 selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2CH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
(A) one or more diols having an equivalent weight in the range of from about 100 to about 3,000 selected from the group consisting of:
(a) diethylene glycol, (b) long chain polyoxyalkylene diols, (c) linear polyester diols derived from the condensation of one or more diols with one or more dibasic acids, and (d) the reaction product of one or more alkylene diols with a difunctional linear polyester derived from the condensation of one or more diols with one or more dibasic acids;
(B) a polyfunctional lactone having the formula wherein R1 is a monovalent radical selected from the group consisting of -H, -CH2CH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-;
m being an integer from 2 to 10; and ethers derived from said lactones; and (C) a urethane precursor selected from the group consisting of organic polyisocyanates and nitrile carbonates.
61. The coated device of claim 60 wherein the substrate is a catheter.
62. A polyurethane polyether resin having lactone groups in the polymer backbone.
63. The polyurethane polyether resin of claim 62 having hydroxyl groups in the polymer backbone.
64. A carrier system comprising an active agent and a hydrophilic polymer as a carrier vehicle therefore, said carrier vehicle comprising a polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone.
65. In a method for releasing an active agent in a medium in which said active agent is used the improvement comprising:
incorporationg said active agent in a polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone;
exposing said polyurethane with said active agent to said medium; and releasing said active agent into said medium at a predetermined rate.
incorporationg said active agent in a polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone;
exposing said polyurethane with said active agent to said medium; and releasing said active agent into said medium at a predetermined rate.
66. The method of claim 65 wherein the medium is-water.
67. The method of claim 65 wherein the medium is a gas.
68. The method of claim 67 wherein said gas is air.
m~b/ ~J~
m~b/ ~J~
69. A polyurethane polyether resin characterized by a molecular weight above 6000 and having lactone groups in the polymer backbone, said urethane polymer comprising the reaction product of:
(a) a polyfunctional lactone having the formula wherein Rl is a monovalent radical selected from the group consisting of -H, -CH2MH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-m being an integer from 2 to 10; and ethers derived from said lactones.
(b) a polyalkylene oxide glycol; and (c) an organic polyisocyanate;
said urethane polymer being soluble in alkaline solutions.
(a) a polyfunctional lactone having the formula wherein Rl is a monovalent radical selected from the group consisting of -H, -CH2MH2, -SO2CH3, -CHOHCOOH, and -(CHOH)nCH2OH; n being an integer from 0 to 5; and R2 is a divalent radical -(CHOH)m-m being an integer from 2 to 10; and ethers derived from said lactones.
(b) a polyalkylene oxide glycol; and (c) an organic polyisocyanate;
said urethane polymer being soluble in alkaline solutions.
70. The polyurethane polyether resin of claim 69 wherein said lactone is delta gluconolactone.
71. The polyurethane polyether resin of claim 69 wherein said lactone is mannolactone.
72. The polyurethane polyether resin of claim 69 wherein said lactone is sorbolactone.
73. The polyurethane polyether resin of claim 69 wherein said lactone is D-glucuronolactone.
74. The polyurethane polyether resin of claim 69 wherein said polyalkylene oxide is polyethylene glycol having a molecular weight of 1450.
75. The polyurethane polyether resin of claim 69 wherein said polyalkylene oxide glycol is a mixture of polyethylene glycol and dietllylerle glycol.
76. The polyurethane polyether resin of claim 69 wherein said polyalkylene glycol is a block copolymer polyol characterized by a molecular weight of about 4750; said block copolymer polyol being obtained by adding poly(oxyethylene) groups to a poly(oxypropylene) chain having a molecular weight of about 950.
77. The polyurethane polyether resin of claim 69 wherein said polyalkylene glycol is a block copolymer polyol characterized by a molecular weight of about 7500; said block copolymer polyol being obtained by adding poly(oxyethylene) groups to a poly(oxypropylene) chain having a molecular weight of about 2250.
78. The polyurethane polyether resin of claim 69 wherein said polyalkylene glycol is a block copolymer polyol characterized by a molecular weight of about 6510; said block copolymer polyol being obtained by adding poly(oxyethylene) groups to a poly(oxypropylene) chain having a molecular weight of about 2250.
79. The polyurethane polyether resin of claim 69 wherein said polyalkylene glycol is a block copolymer polyol characterized by a molecular weight of about 13,333; said block copolymer polyol being obtained by adding poly(oxyethylene) groups to a poly(oxypropylene) chain having a molecular weight of about 4000.
80. The polyurethane polyether resin of claim 69 wherein said polyalkelene oxide glycol is polypropylene glycol.
81. The polyurethane polyether resin of claim 69 wherein said polyisocyanate is methylene di(cyclohexylisocyanate).
82. The polyurethane polyether resin of claim 69 wherein said polyalkylene oxide is a polyethylene oxide having a molecular weight in the range of 200 to
83. A photosensitive coating composition comprising an alkaline solution of a polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone and a catalyst which accelerates the cross-linking of said resin when exposed to light.
84. The coating composition of claim 83 wherein the catalyst is ammonium dichromate.
85. A photosensitive film comprising a layer of a dichromate catalysed polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone supported on a substrate to which it adheres.
86. A method of protecting and reducing the hydrostatic drag of a surface which comprises applying thereto a coating of a catalysed polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone and exposing said resin coating to light.
87. A polyurethane polyether resin obtained by reacting a mixture of polyethylene glycol, diethylene glycol, delta gluconolactone and methylene di(cyclohexylisocyanate) in the presence of a catalyst.
88. The polyurethane polyether resin of claim 87 obtained by reacting a mixture of about 54.6 parts of polyethylene glycol (M. Wt. 1450), about 8.7 parts of diethylene glycol, about 5.8 parts of delta gluconolactone and about 40.4 parts of methyl-ene di(cyclohexylisocyanate) in the presence of about 0.5 parts dibutyl tin dilaurate.
89. A hydrostatic drag resistant coating composition comprising an alkaline solution of a polyurethane polyether resin having free hydroxyl groups and carboxylate groups in the polymer backbone and a catalyst that accelerates the cross-linking of said resin when exposed to light.
90. The coating composition of claim 89 having present therein an effective amount of an anti-fouling agent.
91. A composition useful in the treatment of burns comprising from about 1 to about 80 parts by weight of polyvinyl-pyrolidone-iodide and from about 20 to about 99 parts by weight of a polyether polyurethane resin having free hydroxyl and carboxylate groups in the polymer backbone.
92. The polyurethane polyether resin of claim 62 whlch has been hydrolyzed to form carboxylate groups or carboxyl groups in the polvmer backbone.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/809,260 US4156066A (en) | 1977-06-23 | 1977-06-23 | Polyurethane polymers characterized by lactone groups and hydroxyl groups in the polymer backbone |
| US809,260 | 1977-06-23 | ||
| US05/864,715 US4156067A (en) | 1977-06-23 | 1977-12-27 | Polyurethane polymers characterized by lactone groups and hydroxyl groups in the polymer backbone |
| US864,715 | 1977-12-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1155591A true CA1155591A (en) | 1983-10-18 |
Family
ID=27123205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000303879A Expired CA1155591A (en) | 1977-06-23 | 1978-05-23 | Polyurethane polymers characterized by lactone groups and hydroxyl groups in the polymer backbone |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JPS5410398A (en) |
| CA (1) | CA1155591A (en) |
| DE (1) | DE2827450A1 (en) |
| FR (1) | FR2440380A1 (en) |
| GB (1) | GB1605079A (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4156066A (en) * | 1977-06-23 | 1979-05-22 | Tyndale Plains - Hunter Ltd. | Polyurethane polymers characterized by lactone groups and hydroxyl groups in the polymer backbone |
| WO1983003549A1 (en) * | 1982-04-08 | 1983-10-27 | Smith And Nephew Associated Companies P.L.C. | Surgical adhesive dressing |
| CA1205745A (en) * | 1982-07-02 | 1986-06-10 | John D. Dell | Film-forming composition containing an antimicrobial agent and method |
| US4542012A (en) * | 1982-07-02 | 1985-09-17 | Minnesota Mining And Manufacturing Company | Film-forming composition containing an antimicrobial agent and methods |
| NL8202894A (en) * | 1982-07-16 | 1984-02-16 | Rijksuniversiteit | POLYESTER FILAMENT MATERIAL. |
| NL8202893A (en) * | 1982-07-16 | 1984-02-16 | Rijksuniversiteit | ORGANIC Tolerant, ANTHITHROMBOGENIC MATERIAL, SUITABLE FOR RECOVERY SURGERY. |
| GB8309993D0 (en) * | 1983-04-13 | 1983-05-18 | Smith & Nephew Ass | Surgical adhesive dressing |
| IL72041A (en) * | 1984-06-05 | 1990-01-18 | Elka Touitou | Preparation for controlled release of iodine |
| US4780488A (en) * | 1986-08-29 | 1988-10-25 | Ciba-Geigy Corporation | Wettable, flexible, oxygen permeable, substantially non-swellable contact lens containing polyoxyalkylene backbone units, and use thereof |
| US5634946A (en) | 1988-08-24 | 1997-06-03 | Focal, Inc. | Polymeric endoluminal paving process |
| JP2836878B2 (en) | 1988-08-24 | 1998-12-14 | スリピアン，マービン，ジェイ | Intraluminal sealing with biodegradable polymer material |
| DE19912648A1 (en) | 1999-03-20 | 2000-09-21 | Aesculap Ag & Co Kg | Flat implant, method for its production and use in surgery |
| JP3450810B2 (en) * | 2000-01-31 | 2003-09-29 | キヤノン株式会社 | Aliphatic polyester, method for producing aliphatic polyester and method for recycling cellulose |
| KR20020065180A (en) * | 2001-02-06 | 2002-08-13 | 엘베테크놀로지 주식회사 | A biodegradable polyester urethanes and method for the production thereof |
| US7964696B2 (en) * | 2005-09-20 | 2011-06-21 | Polynovo Biomaterials Pty Limited | Chain extenders |
| JP4767137B2 (en) * | 2006-09-08 | 2011-09-07 | 株式会社オートネットワーク技術研究所 | Seal wire waterproofing method and structure |
| JP5530057B2 (en) * | 2006-09-15 | 2014-06-25 | 三井化学株式会社 | Method for producing water-disintegrable block copolymer, and water-disintegrable block copolymer obtained by the method |
| GB2470088B (en) | 2009-11-10 | 2011-06-29 | Landmark Innovations Ltd | Root canal therapy |
| JP2019112595A (en) * | 2017-12-26 | 2019-07-11 | Dic株式会社 | Thermosetting urethane resin composition for cellulose ester film coat, and cellulose ester film coat agent composition using the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3658939A (en) * | 1968-12-11 | 1972-04-25 | Usm Corp | Polyurethane and adhesive solution of a polyurethane |
| GB1408141A (en) * | 1971-12-09 | 1975-10-01 | Laporte Ind | Polymeric compositions |
| CA977493A (en) * | 1971-12-13 | 1975-11-04 | Goodyear Tire And Rubber Company (The) | Post-curable cured polyurethane |
-
1978
- 1978-05-23 CA CA000303879A patent/CA1155591A/en not_active Expired
- 1978-05-31 GB GB2468478A patent/GB1605079A/en not_active Expired
- 1978-06-22 DE DE19782827450 patent/DE2827450A1/en not_active Withdrawn
- 1978-06-22 FR FR7818726A patent/FR2440380A1/en active Granted
- 1978-06-23 JP JP7631778A patent/JPS5410398A/en active Granted
-
1988
- 1988-10-13 JP JP63258319A patent/JPH01131229A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2440380B1 (en) | 1982-12-17 |
| GB1605079A (en) | 1981-12-16 |
| JPS5410398A (en) | 1979-01-25 |
| JPH01131229A (en) | 1989-05-24 |
| JPH0314848B2 (en) | 1991-02-27 |
| DE2827450A1 (en) | 1979-01-11 |
| JPS6237651B2 (en) | 1987-08-13 |
| FR2440380A1 (en) | 1980-05-30 |
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