JPH01131229A - Production of hydrophylic polyurethane polymer - Google Patents

Abstract

PURPOSE: To obtain a hydrophilic polyurethane polymer for coating, etc., contg. carboxyl groups by reacting a diol such as diethylene glycol with specified multifunctional lactones and an org. polyisocyanate and then opening the lactone rings by hydrolysis.

CONSTITUTION: One or more diols having an equiv. of 100-3,000 such as diethylene glycol, a long chain polyoxyalkylene diol and a linear polyester diol as a condensation product of a diol and a dibasic acid are reacted with a multifunctional lactone of formula I [where R₁ is H or a monovalent group such as CH₂NH₂ and R₂ is a divalent group of formula II (where (m) is an integer of 2-10)] and/or an ether derived from the lactone and a urethane precursor such as an org. polyisocyanate or nitrile carbonate to form a polymer having lactone groups, etc., in the principal chain and having a mol.wt. of ≥6,000, ≥10% water absorptivity and ≤275°C pour point. The lactone rings are then opened by hydrolysis to obtain the objective polymer.

COPYRIGHT: (C)1989,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for making lactone-modified hydrophilic polyurethane resins that are water-insoluble but swell in water and other solvents. More specifically, the present invention is a polyether urethane resin having active and effective lactone groups in the polymer backbone, and the lactone groups are ring-opened in an alkaline solution.
This invention relates to a manufacturing method for forming a carboxylate group or a carboxyl group in a polymer main chain.

A large number of polymer systems containing free carboxylic acid groups are known in the art. However, it is difficult to produce polyurethanes with free carboxylic acid groups because isocyanates, which are necessary components in any polyurethane system, are also highly reactive with carboxylic acid groups.

One approach to introducing carboxylic acid groups into polyurethane resin chains is described in US Pat. No. 3,412.054. According to this method, a 2,2-di(hydroxymethyl)alkanoic acid such as 2,2-di(hydroxymethyl)propionic acid is reacted with an organic isocyanate to form a polyurethane containing unreacted carboxylic acid groups. generate.

The method of the present invention comprises (A) (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) one or more dibasic acids. From the group consisting of a bifunctional linear polyester derived from the condensation of the above diol and one or more dibasic acids, and a reaction product of one or more alkylene diols. Approximately 10 selected
One or more diols having an equivalent weight ranging from 0 to about 3000; (B) formula [wherein R is -H, -CHNH-8OCH3゜1
22'2 -CHOHCOOH and -(CHOH). CH20H
is a monovalent group selected from the group consisting of; n is an integer of 0 to 5; and R2 is a divalent group of -(CHOH)□-; m is an integer of 2 to 10. ]; and an ether derived from the lactone; and (C) a urethane precursor selected from the group consisting of zero-functional polyisocyanates and nitrile carbonates. It can be produced by forming a combination and further opening the lactone ring by hydrolysis.

The long chain water-soluble diols should have a molecular weight of at least about 200, preferably 1450-6000 or more, and can be ether, ester and ether-ester block containing resins. Suitable diols consist primarily of oxyethylene or oxypropylene groups, but may contain small proportions of other oxyalkylene groups. Also useful are block copolymer polyols obtained by adding ethylene oxide to polyoxypropylene chains. Linear polyester diols derived from the condensation of one or more diols and one or more dibasic acids, and one or more diols and one
Reaction products with difunctional linear polyesters derived from condensation with a species or two or more dibasic acids are useful.

Representative examples of polyfunctional lactones are those derived from polysaccharides and monosaccharides, such as monolactone, delta gluconolactone, solbolactone and D-glucuronactone.

The lactone used preferably has at least three, preferably four or more, hydroxyl groups in the molecule, or preferably at least one more hydroxyl group than is required to form a linear polyurethane chain. These free (
The unreacted hydroxyl groups remain in the polymer and are effective in crosslinking the polymer. The lactone ring is also reactive, i.e., opens by hydrolysis,
Carboxylate or carboxyl groups can be formed in the polymer backbone.

The number of carboxylic acid groups present in the polymer chain will be determined by the amount of lactone present in the reaction mixture. This amount can be from 0.1 to 30% of the weight of the total reaction mixture. Preferably the weight of lactone will be 0.5-15% of the weight of the total reaction mixture.

The polyisocyanate used in the present invention has the formula R (
NGO), where n is greater than 1, preferably from 2 to 4, and R is aliphatic, alicyclic, aliphatic-alicyclic, aromatic, or aliphatic-aromatic carbonized It is a hydrogen compound and has 4 to 26 carbon atoms, more preferably 6 to 20 carbon atoms, and generally 6 to 13 carbon atoms. Representative examples of the above isocyanates are: tetramethylene diisocyanate; hexamethylene diisocyanate; trimethylhexamethylene diisocyanate; dimeric acidic diisocyanates; isophorone diisocyanate; diethylbenzene diisocyanate; decamethylene-1,10-diisocyanate; cyclohexylene -1,2-diisocyanate and cyclohexylene-1,4-diisocyanate; and aromatic isocyanates such as 2,4- and 2-diisocyanate;
．． 1.5-naphthalene diisocyanate; dianisidine diisocyanate; toluidine diisocyanate; polymeric polyisocyanates, such as neopentyl tetraisocyanate; m-xylene diisocyanate; tetrahydronaphthalene -1,
5-diisocyanate; and bis(4-isocyanatophenyl)methane.

A preferred isocyanate is methylene di(cyclohexyl isocyanate-1.). Other less preferred diisocyanates are trimethylhexamethylene diisocyanate and isophorone diisocyanate.

Other compounds for a are isocyanate equivalents that form urethane linkages, ie adiponitrile carbonates of the formula.

In producing the polyurethane resins of the invention, low molecular weight glycols such as diethylene glycol and dipropylene glycol or aromatic glycols can be added to the reaction mixture.

Preferred low molecular weight aromatic polyols are bisphenol A and 4,4'-sulfonyldiphenol.

The proportion of long chain polyglycols and low molecular weight glycols, ie diethylene glycol, used depends on the hydrophobic-hydrophilic balance present in each and desired in the final product. Increasing the molecular weight and/or amount of long chain polyoxyalkylene glycol imparts strong hydrophilic properties to the final product. This effect can be counterbalanced by increasing the proportion of low molecular weight glycols, ie diethylene glycol or dipropylene glycol.

Considering the above (i.e., the number of polyalkylene oxide groups in the polymer chain which determines the hydrophilicity, and that polyethylene oxide groups are more hydrophilic than polypropylene oxide groups), the final product is It is easy to select a mixture of reactants with specific properties. By selecting the molecular weight of the polyalkylene glycol or using two types of polyalkylene glycol with different molecular weights, a wide range of properties can be satisfied.
It is possible to create customized products.

Amphoteric hydrophilic polyurethane polymers can be prepared by adding a dialkanol tertiary amine, such as jetanol methylamine, to the reaction mixture.

In producing the polyurethane resin of the present invention, the glycol is mixed with the lactone and the polyisocyanate is reacted with the mixture, although other techniques can also be used.

This reaction is catalyzed with catalysts known for such reactions. Suitable catalysts include tin salts and tin esters, e.g.
dibutyltin dilaurate, tertiary amines such as diethyldiamine (DABCD), N,N,N',N'-tetramethyl-1,3-butanediamine and other recognized compounds for urethane reactions well known in the art. It is a catalyst. This reaction can be carried out in the presence or absence of a diluent or solvent.

Due to its unique physical properties, the polyurethane ether resin of the present invention is suitable for dressing burns.
s) can be advantageously used. This resin is a powder for burns,
It can be applied as a film or from solution in a volatile non-toxic solvent and will form a permeable barrier to liquids. In this way, the physician can select drugs that can be applied prior to forming the resin coating or added to the resin for timed release. A particularly advantageous burn dressing comprises from about 1 to about 80 parts by weight of polyvinylpyrrolidone-iodine and from about 20 to about 90 parts by weight of a polyether polyurethane resin having free hydroxyl and carboxylate groups in the polymer backbone. at low temperature [v! It is a powder obtained by crushing.

Single-act polyurethane polyether resins are also useful in the following and applications: coatings, molding compounds, absorbents, controlled release agents, ion exchange resins, skin abrasion treatment, dialysis. Manufacturing of membranes, dentures, cannulae, contact lenses, solubilized packaging ingredients, hair sprays, cosmetics, burn dressings, contraceptive devices, sutures, surgical implants, blood oxygenators, intrauterine devices, vascular grafts, oral Emission systems, battery separators, eye patches, hair removal compositions, artificial corneas, fragrances, deodorants, anti-fog coatings, cloth for surgical hooks, oxygen exchange membranes, artificial nails for fingers, compatibility, adhesives, gas permeability. resistant membranes, and protective and drag-resistant membranes.

The implementation of the present invention will be explained using the following reference examples.

The present invention is not limited to these reference examples.

Parts are by weight unless otherwise indicated.

Reference Example 1 Molecular weight 145 of 109.2 parts (0,075 mol) in 17.4 parts (0.1t 54 mol) of diethylene glycol
A diethylene glycol solution of polyethylene glycol is prepared by heating and stirring 0 polyethylene glycol. The solution was cooled to below 60°C and added 1.0% of the solution in 46.4 parts of dimethyl sulfoxide.
A solution of delta gluconolactone prepared by dissolving 1.6 parts (0,065 moles) of delta gluconolactone is added. Add 80.8 parts (0,316 parts) to this mixture.
methylene biscyclohexyl-4,4'-isocyanate (H from II DuPont de Nimoers & Co., Wilmington, Praue)
(product labeled as YLENE W) while stirring. 0.5 parts by weight of an organotin catalyst solution; dibutyltin dilaurate (a product designated as T1□ manufactured by Metal and Thermite Company of Rahway, New Jersey) was added to the reaction mixture at 4 parts by weight.
Addition with stirring at a temperature below 5° C. prevents undesirable temperature increases caused by the heat of reaction. 2
After stirring for 0 minutes, the temperature rises to 80°C.

The reaction mixture is then transferred to a tray and placed in a 90° C. oven for 1 hour to complete the reaction. This polymer is soft, pliable and pliable in the wet state.

Reference Example 2 A polymer that is water-insoluble but soluble in a mixture of a major portion of alcohol and a minor portion of a base (1,ON sodium hydroxide) is produced from the following components by the method described in Reference Example 1. 3469 parts (2,37 mol) of polyethylene glycol (molecule 11450) 254 parts (2,39 mol) of diethylene 116 parts (0,65 mol) of delta gluconolactone (as a 20% solution in dimethyl sulfoxide) HY
LENE W 808 parts (3.16 mol) Dibutyltin dilaurate 5 parts A piece of this polymer, cast into a cylinder with a volume of 10 ml, was weighed, immersed in water at room temperature for 12 hours, dried with a paper towel. Remove surface moisture and reweigh.

The weight increase was 100%.

Reference Example 3 A lactone group-containing polymer containing a small amount of dissolved base or soluble in a small amount of alcohol with the addition of a small amount of water or other carrier is prepared by the method described in Reference Example 1 from the following ingredients: 2000 parts (1,37 mol) of polyethylene glycol (molecular weight 1450) 107.5 parts (1,64 mol) of diethylene glycol 116 parts (0,65 mol) of delta gluconolactone (20% solution in dimethyl sulfokilad) HYL
ENE W 808 parts (3.18 moles)
Tin octoate (T) * 5 parts * T9 is manufactured by Metal & Thermite Company (
of Rahway), a trademark of New Jersey.

Reference Example 4 This reference example illustrates the preparation of a polymer that is soluble in alkaline solution using a 5% excess of cyanate groups. The manufacturing method is described in Reference Example 1.

Polyethylene glycol (molecular weight 1450) 1097 parts (0.75 mol) Diethylene glycol 174 parts (1.64 mol)
Delta gluconolactone (as a 20% solution in dimethyl sulfoxide) 116 parts (0.65 mol) HY
L E N E W 102.4 copies (0,
4 moles) * Tin octoate (T ) 5 parts * Trademark of Metal & Thermite Company, New Jersey.

Reference Example 5 Polyurethane polyether resin 5 described in Reference Example 1
0 g and 17.4 ml of 29% ammonium hydroxide in a
Add to 500ml of nailing aqueous solution. The solution is stirred at 90° C. until all the polymer is dissolved. Add 1 part of a 20% aqueous solution of ammonium dichromate to this polymer solution.
Add 0 ml (2.0 g of (NH4)2Cr204). Apply this solution to the cellulose acetate film with a doctor knife and dry in low light or darkness at room temperature. A yellow, tough film of the photosensitive complex is formed. It adheres well to the cellulose acetate support. A photographic image is projected onto the film using an S-1 sunlamp as the light source with an exposure time of 60 seconds. The film is washed in water at room temperature. The photographic image is then developed by dissolving the unexposed, uncrosslinked parts of the photographic image.The polymers that form the photographic image are dyed directly by ink, so the developed film can be used in lithography processes.

Reference Example 6 An antifouling marine paint is formulated by ball milling the following ingredients for 3 hours: Polyurethane resin of Reference Example 2 150 parts 5% ammonium hydroxide in ethanol 500 parts Potassium dichromate 2 titanium dioxide
50 parts Acetic acid Water 3 parts Silver The product thus obtained is applied to wood and other surfaces to form a film which is crosslinked by sunlight to form an adherent insoluble protective coating.

The product is particularly nail-resistant when applied to the hull of a boat. Because of the hydrophilic nature of urethane resins, mercury salts are released slowly, preventing the growth of herniapods or algae on the paint surface.

Reference Example 7 A polyurethane polyether resin with a molecular weight of 4,750 obtained by adding a poly(oxyethylene) group to a poly(oxyethylene) chain with a molecular weight of 950 instead of polyethylene glycol by the method described in Reference Example 1 above. Manufactured using block copolymers.

Block copolymer (molecular weight 4750) 3577 parts diethylene glycol 174 parts delta gluconolactone (20% solution in dimethyl sulfoxide) 116 parts HYLENE W 808 parts dibutyltin dilaurate 5 parts Reference Example 8 The polyurethane polyether resin was mixed with the reference example 1 described above. A molecule obtained by adding a poly(oxyethylene) group to a poly(oxyethylene) chain with a molecular weight of 2250 instead of polyethylene glycol according to the method described above! 7500
manufactured using a block copolymer of

Block copolymer (molecular weight 7500) 1157.4
parts diethylene glycol 32.75 parts delta gluconolactone (as a 20% solution in dimethyl sulfoxide) 116 parts HYLENE W 808 parts dibutyltin dilaurate 5 parts Reference Example 9 A polyurethane polyether resin was prepared by the method described in Reference Example 1 above. Instead of polyethylene glycol, it is produced using a block copolymer with a molecular weight of 6500 obtained by adding poly(oxyethylene) groups to the poly(oxypropylene) chains of the molecule 'ff13250.

Block copolymer 325 parts diethylene glycol 21.76 parts delta gluconolactone (20% solution in dimethyl sulfoxide) 41.41 parts HYL
ENE W 132 parts Dibutyltin dilaurate 0.5 parts Reference Example 10 Polyurethane polyether resin was added in place of polyethylene glycol by the method described in Reference Example 1 above.
A molecule obtained by adding a poly(oxyethylene) group to a poly(oxypropylene) chain with a molecular weight of 4000! 13,333 block copolymer.

Block copolymer 1004 parts Diethylene glycol 17.4 parts Delta gluconolactone*11.6 parts Dimethyl sulfoxide 46.4 parts HYL
ENE W 80.8 parts Dibutyltin dilaurate 3 parts *Dissolved in dimethyl sulfoxide.

After stirring for 1 hour, the reaction mixture was transferred to a tray and
Place in the oven at 0°C overnight.

Reference Example 11 A series of three polyurethane polyether resins are prepared by the method of Reference Example 1 with varying amounts of delta gluconolactone.

After the initial reaction, instead of curing the resins in a furnace, the three resins (3 g each) were injected into 100 mg of Rutandrolone (N
ilcvar), 1.3cm x 2.5cm
The mixture was cast into a cylindrical shape and polymerized at 80°C for 30 hours. After removing from the mold, it is implanted into a living body and ruthandrolone (N
A cylinder suitable for the long-term release of ilavar is obtained for use in animal husbandry.

Reference Example 12 Delta gluconolactone (14.28 parts) is ground into a fine powder and mixed well with 29.15 parts of polyethylene glycol (molecular weight 200). The mixture was heated to 60°C and added with 56.57 parts of HYLENE W and 0.5 parts of HYLENE W.
Add 5 parts stannous octoate with stirring. After the exothermic reaction has stopped, the resin is transferred to a tray and placed in a 90° C. oven for 1 hour to complete the reaction.

Reference example 13 Polyethylene glycol with a molecular weight of 1450 (218,4
1 part) with 34.8 parts of diethylene glycol and the mixture is heated with stirring to the melting point.

Add 161.6 parts of HYLENE W to this melt.

A solution of delta gluconolactone is prepared by dissolving 23.2 parts of delta gluconolactone in 77 parts of dimethyl sulfoxide. Add the delta gluconolactone solution to the glycol and HYLENE W mixture with stirring and cool the reaction mixture to 50°C. 0.8 parts of dibutyltin dilaurate catalyst is added to the reaction mixture and stirring is continued until the exothermic reaction has ceased.

The resin is then cured in an oven at 90°C for 1 hour.

The cured resin (2.6 parts) was mixed with alkaline methanol (7 parts).
, 4 parts) and add 2.5 parts of a 2% aqueous ammonium dichromate solution. This dichromic acid catalyzed resin solution is injected through a 4 foot (122 cm) long 5+n+w Pyrex glass tube to form a uniform coating on its interior surface. Air dry the coating in ambient light for 5 minutes.

One end of the coated tube is closed with a cork passed through a fine hypodermic needle. The tube is filled with tap water and then held upside down to allow the tap water to drip out. The time it took for all the water to drip from the tube was 24 seconds. This experiment was repeated 10 times.

The time required to drain the tube was always 24 parts 1 second.

In control experiments, uncoated length <4 ft.
122 cm) of 5 mm Pyrex tubing is washed thoroughly with detergent solution, rinsed with distilled water, and air dried. Close this tube with the same cork passed through the narrow hypodermic end,
Fill with tap water. When this uncoated tube was inverted (10 experiments), it took 38 parts and 1 second to drain the tube.

In this reference example, the dichromate catalyzed resin composition described above is applied to the hull and centerboard of a light sailboat and exposed to sunlight for 6 minutes to bridge the coating.

Light breezes allow this yacht to outperform other yachts in its class.

Reference Example 14 A diethylene glycol solution of polyethylene glycol is prepared by heating and stirring 249.3 parts (0,172 mol) of polyethylene glycol having a molecular weight of 1450 and 79.5 parts (0,883 mol) of diethylene glycol. Add 52.9 parts (0,296 parts) to this melt.
249.3 parts (0.8 mole) of delta gluconolactone
part mole) of diethylene glycol adipate and 52
Add 0 parts (1.85 moles) of methylene biscyclo-4,4'-isocyanate. The mixture was stirred with heating to form a homogeneous melt, then 45
Cool to °C. A solution of 2.1 parts of dibutyltin dilaurate is added to the reaction mixture with rapid stirring to avoid an undesirable rise in temperature due to the heat of reaction. After stirring for 20 minutes, the temperature is 85°C. The reaction mixture is then transferred to a tray and placed in a 90° C. oven for 1 hour to complete the reaction.

The resulting polymer contains 21% by weight of adipate ester, is harder and more rigid than the polymer of Reference Example 1, and is insoluble in water and aqueous alkaline solutions. When immersed in water, the weight gain due to water absorption is less than 20%.

Reference Example 15 A polyurethane polymer derived from a linear polyester diol is produced by reacting the following components: Polyethylene glycol (0,005 mol) 7.9
5 parts delta gluconolactone (0,29 mol) 5.2 parts diethylene glycol adibate (0,172 mol) 49.88 parts HYLENE W (0,241 mol>6
The mixture of 8.0 parts reactants was stirred and heated until homogeneous and 0.24 parts Nailer Tin catalyst solution;

(manufactured in New Jersey, labeled ``12'') is added to the reaction with stirring to avoid an undesirable rise in temperature due to the heat of reaction. After stirring for 20 minutes, the temperature is 80°C.
rises to ℃. The reaction mixture was then transferred to a tray and placed at 90°
The reaction was completed by placing it in a furnace of C for 1 hour. The resulting polymer has 38% by weight of adipate ester F+H and is harder and more rigid than the polymer of Reference Example 14.

It is insoluble in basic solutions and methanol. The water absorption of this polymer is less than 15% by weight.

Reference Example 16 The Reference Example 16 is repeated, but the amount of diethylene glycol adipate present in the reaction mixture is increased from 49.86 parts to 1
．． 15 parts (1.4% by weight of the reaction mixture). When 1 g of the polymer of this reference example is immersed in water, it swells and
Absorbs 0.48g of water. 9ml of 1g of this polymer
of methanol and 1 ml of 2N aqueous sodium hydroxide solution.

Reference Example 17 A mixture of 90 parts by volume of ethanol and water (70:30
) to which 10 parts of the polymer of Reference Example 1 and 1 part of sulfadiazine were added. Add sodium hydroxide IN to reduce the p of the solution.
Adjust H to 7.0 and dissolve the polymer by stirring. This polymer solution is applied directly to the burn area as a burn dressing, and when the solvent evaporates, it forms a protective film that is permeable to gases and fluids, but
It prevents the growth of anaerobic organisms under the membrane and therefore does not interfere with treatment.

Reference Example 18 A polymer having the composition described in Reference Example 2 above is prepared by heating and stirring polyethylene, diethylene glycol, delta gluconolactone and HYLENE W to form a homogeneous mixture. The catalyst was added to the reaction mixture at 40°C and stirring continued until the exothermic reaction ceased (temperature began to drop), then 2
Add 32 parts (5% by weight) of cortisone with good stirring to ensure even distribution. This polymer is 1.5
It is cast into a cylinder of cm x 3 cm and cured at 70°C. After curing, the cylinders are removed from the mold. These are suitable for implantation for long-term cortisone release.

Example 1 15 parts of the polymer described in the previous reference example 3 are placed in 70 parts by volume of a mixture of isopropanol and water (50:50) and 10 parts by volume of IN sodium hydroxide solution are added. The mixture is refluxed to open the lactone ring and dissolve the polymer. The solution was titrated to pH 5.0 with IN hydrochloric acid and the solids content of the polymer was reduced to 15% with isopropanol.
Adjust to Add 15,000,000 units of phenoxyethylpenicillin to the polymer solution. The resulting solution can be applied to the abraded surface to seal this surface against irritating physical and biological substances.

Reference Example 19 A 20% solution of the polymer described in the previous Reference Example 7 was prepared in a mixture (50:50) of ethanol and water with the addition of 1 min of IN sodium hydroxide to cause dissolution. prepared by dissolving the polymer in

The pH of this solution is adjusted to 6.0 with IN hydrochloric acid. The solution thus obtained is applied topically to form a hypoallergenic base for cosmetic preparations. The polymer composition effectively covers skin blemishes and allows the skin to breathe.

Reference example 20 Hair Sera! - A composition is prepared by dissolving the polyurethane polyether resin of Reference Example 8 above in 95% ethanol. Add enough IN sodium hydroxide to effect dissolution and adjust the pH of the final composition to 7.0. The resulting solution is applied to the hair in the form of a spray, which gives excellent hold with a soft feel.

Reference Example 21 20 parts of the unsaturated polyether resin of Reference Example 1 were dissolved in 80 parts of ethanol-water (70:30) and a sufficient amount of IN sodium hydroxide was added to adjust the pH to 9.5.
Adjust to 5.6 parts of calcium thioglycolate are added to the solution thus obtained while stirring.

The resulting composition can be used as a depilatory agent.

Reference Example 22 The polymer 16 of Reference Example 16 above was extruded to a length of 1.5 m.
Form a pipe of 10 diameters. Dry nitrogen gas is passed through this tube and into the dry ice trap. Water vapor absorbed by the nitrogen as it flows through the tube precipitates as ice within the trap.

Reference Example 23 A series of three polyurethane polyether resins are prepared with varying amounts of delta gluconolactone.

Polyethylene glycol and diethylene glycol are melted together at 70°C in the absence of solvent and mixed. Then add delta gluconolactone and HYLENE W and continue stirring until the mixture is homogeneous. The mixture is cooled to 45° C. and the dibutyltin dilaurate is rapidly mixed with stirring. Stirring was continued for about 15 minutes, during which time the temperature rose to about 85°C due to the exothermic reaction.
Viscosity increases. The polymer is poured into a cold ready-to-drink pan while still viscous and placed in a 75°C oven for 20 minutes. The bread is then removed from the oven and cooled to room temperature. The polymer can be removed from the pan and stored indefinitely at room temperature or used immediately as a molding resin. This resin swells in methanol and can be dissolved in alkaline solutions.

Reference Example 24 The resin (a) of Reference Example 23 above was poured into a water-cooled mold in an amount equivalent to seven times the amount to fill the cavity, and the resin (a) was heated to 15% at 125°C.
,000 psi (1,055 kg/cJ) of pressure to form a lens. The mold is cooled and the optically clear polymer is removed.

Reference Example 25 One part of lutandrolone (Nilcvar) was added to Reference Example 2.
Blend with 30 parts of the resin (b) of No. 4 in a band mill at 40°C. This composition was put into the cavity of a cylindrical mold, and the pressure was set at 15,000 psi (1,055 kg/cn?).
and molded at 125° C. to form a cylinder of polyurethane polyester resin having a pharmacologically effective dose of lutandrolone uniformly distributed throughout its body.

Reference Example 26 An artificial esophagus is made from a tube woven from polyethylene terephthalate monofilament. The tube was slid onto a cylindrical rod of somewhat smaller diameter, and the assembly was immersed in a 15% isopropanol solution of the polyurethane polymer of Reference Example 3 prepared as described in Example 1, and air-filled. dry. By repeating dipping and drying, a 2 mm thick coating is formed on the outer surface 1- of the cloth tube.

A monofilament of polypropylene with a diameter of 1.5 mm is helically wound around the coated tube at a pitch of 5 turns/cm and the assembly is heat set by placing it in an oven at 80 °C for 15 minutes. The support rod was then removed from the tube, the tube was repeatedly dipped in a 15% isopropanol solution of polyurethane polymer as described in the previous section to coat the polypropylene monofilaments with polyurethane polymer, and The inner surface of the cloth tube - 2 m of polyurethane polymer coating
The thickness shall be m.

Reference Example 27 The polyurethane polymer of Reference Example 3 is dissolved in alkaline ethanol to form a 10% by weight solution, and a pair of polycarbonate safety glasses is immersed in the solution and dried at room temperature. The coating deposited on the polycarbonate lenses of safety glasses had improved fogging properties when compared to a similar pair of untreated safety glasses.

Reference Example 28 Resin (b) of Reference Example 23 was heated at 110°C and 15,000°C.
Surgical ligatures were made by extrusion through an orifice at 0 psi (1,055 kg/c/). The extruded monofilament was stretched 4 times, wound on a rack, and
Heat at 0'C for 30 min and cool to room temperature. The resulting zero-ply yarn is cut into lengths, packaged, and sterilized with gamma rays.

If an iodinated suture is desired, the suture is soaked in a 10% by weight solution of iodine in ethanol to absorb the desired amount of iodine into the suture. The multifilament suture was prepared in Reference Example 23, as described above in this Reference Example.
It can be produced by extruding the polymer of (b) through a spinneret containing the desired number of orifices, and braiding the multifilament after heat treatment.

Reference Example 29 The polymer solution described above in Reference Example 17 is cast onto a flat glass surface to form a film, which is air dried at room temperature. The dry film can be peeled off from the glass surface and applied directly to the burn surface as a burn dressing, or the film can be pulverized and applied to the burn in powder form.

Reference Example 30 1 part Neo B-vitamin A and 30 parts Reference Example 23 (a
) of polyurethane polyether resin and a band mill.
The surgical implant is made by compounding at 0.degree. Put this composition into the cavity of the inner cylindrical mold, 15.
000psi (1,055kg/cJ) and 125℃
to form a cylinder with an effective dose of Neo B-vitamin A evenly distributed throughout its body. In a similar manner, surgical implants containing pharmacologically effective doses of hormones, drug protagonists, anti-tubercular drugs, or steroids can be formed.

Reference Example 31 1 part of lactic acid is blended with 30 parts of the polyurethane polyether resin (C) of Reference Example 23 at 45°C in a band mill. This composition was put into the annular mold cavity, and
．． 000psi (1,055kg/cJ) and 125
C. to form a nail-like polymeric ring as an intrauterine device.

Reference Example 32 Resin (c) of Reference Example 23 was heated at 20.000 psi (1,4
06 kg/cJ) and 125° C. through an annular orifice to form a cannula. The cannula is immersed in a 10% by weight solution of iodine in ethanol for 24 hours, after which the iodine is distributed throughout the resin body. The cannula is then removed from the iodine solution and air dried.

Reference Example 33 A woven fiber tube with a diameter of 3 mm was repeatedly immersed in the solution of the polyurethane polyether resin described in Reference Example 17,
After air drying, the interstices between the strands are filled with polyurethane polymer to produce a surgically useful cannula.

A tube of larger diameter woven polyethylene terephthalate strands is similarly treated to fill the gaps between the woven strands. The resulting product can be used by surgeons as a vascular graft.

Reference Example 34 An 8 mm tube of woven collagen strands was coated with a solution of the polyurethane polyether resin described in Reference Example 17 and air dried at room temperature to fill the gaps between the strands and form the inner and outer walls of the tube. An artificial blood vessel is manufactured by coating. The tube is then immersed in heparin to absorb the heparin into the polyurethane coating, dried, and sterilized with gamma radiation.

Reference Example 35 In a ball mill, 75 parts by weight of the polyurethane polyether resin of Reference Example 10, 5 parts by weight of opium benzoin tincture, 10 parts by weight of bismuth suboxide and 1 OTrl part by weight were mixed.
A composition effective in inhibiting dehydration in humans and animals is prepared by milling together the seeds of P. plantago with dry ice. This composition can be administered orally to livestock suffering from infectious diarrhea.

Reference Example 36 2 parts by weight of Red Dye No. 2 was added to 98 parts of the polymer solution of Reference Example 19, and the mixture was ball milled for 2 hours. The resulting composition can be used as a cosmetic agent.

Reference Example 37 A black braided silk ti yarn is passed through the polymer solution of Reference Example 19, wound on a rack, and air dried.

The damaged suture has improved hand and tie-down properties compared to black braided silk 11-ply thread that was not treated in this manner.

Reference Example 38 The polymer solution described in Example 1 is adjusted to pH 7 and cast onto a glass surface to form a film, which is air dried. This dry film can be applied directly to the eye as an eye bandage.

Reference Example 39 Put the resin (a) of Reference Example 23 into a press and press 15,000
psi (1,055 kg/cJ) and 115° C. to form battery separators.

Reference Example 40 To the hair set composition of Reference Example 20, 2% by weight of fragrance essence is added. When you apply this composition to your hair,
While the solvent evaporates rapidly, the perfume binds to the polyurethane polymer and is slowly released over a 24 hour period.

Reference Example 41 A household deodorant composition is prepared by mixing 10 parts of phenol and 50 parts of the polymer solution described in Reference Example 19 above, 5 parts of perfume and 35 parts of water.

Reference Example 42 Coating on one surface of a woven cotton fabric with the polyurethane polyether solution described in Reference Example 19 above (4, thus making a surgical wrap fabric).

Reference Example 43 Resin (b) of Reference Example 23 was heated at 15,000 psi (1,0
55kg/co? ) and pressed in a hydraulic press at 110°C to form a polyurethane polyether film with utility as a dialysis membrane. Films thus produced can be advantageously used as carbon dioxide-oxygen exchange membranes in blood oxygenators, with minimal degradation of blood cells.

Reference Example 44 109.2 parts (0,075 mol) of polyethylene glycol with a molecular weight of 1450 was added to 17.4 parts (0.1 part 4 mol)
A diethylene glycol solution of polyethylene glycol is prepared by heating with stirring in diethylene glycol. The solution was cooled to 60°C,
To this is added a solution of delta gluconolactone prepared by dissolving 11.6 parts (0,065 moles) of delta gluconolactone in 46.4 parts of dimethyl sulfoxide. 80.0 parts (0.31 parts mol) of methylenebiscyclohexyl-4,4'-isocyanate (E.
i du pont de nimoas and Φ company,
City of Wilminto, Prauea.

A product labeled HYLENE W, sold by HYLENE W Inc.) and 0.4 part dietatoluamine are added to the mixture with stirring. 0.5 parts by weight of an organotin catalyst solution; dibutyltin dilaurate (Metal and Thermite Company, φ of Rahway, NJ) is added to the reaction mixture with stirring at a temperature below 45°C to reduce the heat of reaction. Avoid unfavorable temperature rises caused by After stirring for 20 minutes, the temperature rises to 80°C. The reaction mixture is then transferred to a tray and placed in a 90° C. oven for 1 hour to complete the reaction. This polymer is amphoteric and is soft, pliable, and pliable in the wet state.

Patent applicant Francis E. Gould (2 others)
”' Procedures Amendment 2, Title of invention Process for producing hydrophilic polyurethane polymer 3, Relationship with the person making the amendment Patent applicant address Name Francis E. Gould 4, Agent
, 6. Contents of amendment (1) The following is added between lines 6 and 4 from the bottom of page 61 of the specification.

"Example 6 100g of the resin produced in Reference Example 1 was cut into small pieces, and
Place in a container containing 1 ky of 0% ethyl alcohol and allow to swell for 60 minutes. A solution of KOH2,5& in 50 g of water is prepared and sprinkled onto the swollen polymer. Stir the mixture to completely dissolve the polymer. If the temperature is below 25°C, 2 to 6 hours are required for dissolution. The resulting solution has the desired pH. At pH=4, this resin is in the carboxylic acid form.

Example 7 Resin (a) ID 79 of Reference Example 11 is cut into small pieces and placed in a mixture of 90 parts of 95% aqueous ethanol and 10 parts of 70% aqueous isopropanol. After swelling the resin, 20 g of 10% by weight NaOH solution are added to the mixture. The batch is then stirred until the resin is dissolved.

The pH of this solution is then adjusted to 4±0.2. This solution is then gradually added to 101 of pure water. The resin is precipitated, separated and dried in a stream of hot air. This method removes the salts formed by V, neutralization, and eliminates the unpleasant odor of the dimethyl sulfoxide used in the preparation of the resin.

The dried resin is redissolved in ethanol and cast into a film. This carboxyl group significantly improves adhesion.

Example 8 123 g of resin (c) from Reference Example 11 are placed in 1.41 g of 90% aqueous methanol and treated with 10% Na0I (aqueous solution) sufficient to bring the pH to L2. The batch is stirred and Warm to 50-60° C. Continue stirring until the resin is dissolved.

This solution can be adjusted to any desired pH. At low pH, resins made with the stated amounts of delta gluconolactone become partially water soluble. (2) The statement will be amended as follows.

Page Line Before correction After correction 29 Bottom 7
Reference example 17 Example 130 4
〃18 Reference example 1730 Lower 6 Example 1 Example 2 Ro 1 10 Reference example 19
6 329N21 5 32 Lower 4 I 22 Reference example 183
2 Lower 6 Polymer 16 Polymer 36 5
Reference example 23 Reference example 1965 Lower 512
4 20 35 lower 4 I 26 l 196
6 2 l 25 l 21366～
4I24#20 Ro6 11 l 26
l 2266 Lower 6 Example 1
Example 267 Part 10 Reference Example 27
Reference example 2667 Lower 2 28, 24. 67 Lower 1 I 23 I 19
Page Line Before correction After correction 38 Bottom 7
Reference example 29 Reference example 2538 Lower 6
#17 Example 1391130
Reference example 26 69 2 I 26 I 1939
Lower 7 I 61 l 2739
Lower 6 l 23 I 19401
l32128 402 123. 19 409 133 #29 4010-17 Example 1 411134 Reference example 60 413117 Example 1 4110135 Reference example 61 41 Lower 2 l 36 #3
241 Lower 1 l 19 Example 64
24I37 Reference example 66 425-19 Example 6 4210I38 Reference example 34 4211 Example 1 Example 2 page Line Before correction After correction 42 Lower 6 Reference example 69 Reference example 3542 Lower 5 2311
9 42 lower 2 l 40 l 664
2 Lower 1 l 20 Example 443
5 141 Reference example 6743 6
119 Example Ro4310I42
Reference example 68 4311119 Example 6 43 Lower 6 #43 Reference example 394
6 lower 5 l 23 I 1944
3 144N40 or more

Claims (1)

[Claims] 1. (A) (a) diethylene glycol, (b) long chain polyoxyalkylene diol, (c) one or more diols and one or more dibasic acids; (d) a linear polyester diol derived from condensation, and (d) a difunctional linear polyester derived from condensation of one or more diols with one or more dibasic acids; or a reaction product with two or more alkylene diols.
One or more diols having an equivalent weight in the range of 3000; (B) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 is -H, -CH_2NH_2, -SO_2
CH_3, -CHOHCOOH and -(CHOH)_
is a monovalent group selected from the group consisting of nCH_2OH; n is an integer from 0 to 5; and R_2 is -(CHO
H) a divalent group of _m-; m is an integer of 2 to 10]; and/or an ether derived from the lactone; and (C) an organic polyisocyanate and a nitrile carbonate. A urethane precursor selected from the group consisting of A method for producing a hydrophilic polyurethane polymer, which comprises forming a polyurethane polymer having a group and a hydroxyl group, and further opening a lactone ring by hydrolysis. 2. One of the diols is a difunctional linear polyester derived from the condensation of one or more diols and one or more dibasic acids, Claim 1 Manufacturing method described. 3. The method according to claim 1, wherein one of the diols is a reaction product of a bifunctional linear polyester derived from the condensation of diethylene glycol and adipic acid and a polyoxyalkylene diol. 4. The diol is polyethylene glycol and diethylene glycol, the lactone is delta gluconolactone, the urethane precursor is methylene di(cyclohexyl isocyanate), and the reaction is carried out in the presence of a catalyst, according to claim 1 manufacturing method. 5. Diol is 54.6 parts of polyethylene glycol (
molecular weight 1450) and 8.7 parts of diethylene glycol, 5.8 parts of delta gluconolactone and 40.4 parts of methylene di(cyclohexyl isocyanate) and the catalyst comprised of 0.5 part of dibutyltin dilaurate. The manufacturing method according to claim 4.