JPS63238157A - Water absorbable polyurethane composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyurethanes, and in particular to hydrophilic polyether-polyurethanes with excellent mechanical performance.

Hydrophilic polyurethane polymers have high water absorption properties and can be produced by reacting polyethylene ether glycol and polyisocyanate.

The mechanical properties of these polyurethanes in the wet state can be further improved.

It has now been discovered that hydrophilic polyether-polyurethanes with excellent mechanical performance in the wet state can be achieved by mixing a certain amount of hydrophobic polyester-polyurethane with the above-mentioned polymers. The provision of these hydrophilic polyurethane polymer blends and their uses, together with their manufacturing methods, constitute the main aim and object of the present invention.

The hydrophilic polyurethane composition of the present invention is a hydrophilic polyether polyurethane which is a reaction product of A, diethylene glycol and polyethylene ether glycol having a molecular weight of about 1,000 to 8,000, and a polyisocyanate.
B, from about 75% to about 25% by weight of a hydrophobic polyester derived from the condensation of a polyol, a polybasic acid, and a polyisocyanate;

Surprisingly, this polymer blend retains the desired surface hydrophilic properties. In this respect they are essentially comparable to hydrophilic polyether-polyurethane components. Furthermore, the simultaneous presence of the hydrophobic polyester polyurethane results in a significant increase in the tensile strength of the polymer blend in the wet state. Typically, the increase in tensile strength is due to the blend having a polyether composition of 25%.
% (from 0%) and becomes significant as the polyester approaches 75% (from 100%). As the above-mentioned values increase and decrease, respectively, the tensile strength approaches the maximum, and then as the polyether approaches 75% and the polyester approaches 25%, the tensile strength decreases, resulting in a bell-shaped curve. This behavior is unexpected and the reason for it has not yet been elucidated to date.

In addition, the polymer blend exhibits good hardness in both dry and wet conditions as measured by a Durometer A hardness tester. A further preferred property is reduced swelling of the blend compared to the hydrophilic polyether-polyurethane itself.

The hydrophilic polyurethane blend herein is prepared by forming a mixture of a hydrophilic polyether-polyurethane and a hydrophobic polyester-polyurethane using conventional mixing techniques. A typical method of operation is to take the required amounts of each of polyether and polyester polymers and dissolve them in a solvent. A film of the polymer blend is then obtained by applying the resulting solution to a suitable support and evaporating the solvent. Commonly used solvents include chloroform, cyclohexanone, diethylformamide, tetrahydrofuran, dimethylcol (eg, carbon 1-4) alone or in mixtures of these solvents. When casting a film, the solution should be about 5% to 10% by weight.
% solids, but if soaked, the solids content is about 3% to about 5%.

Polymer blends can also be formed by mixing chopped polyethers and polyester-polyurethanes of the invention in an extruder and extruding them into the desired structure or shape.

The hydrophilic polyether-polyurethane component of the polyurethane described herein is prepared by reacting a large amount of polyoxyethylene glycol (having a molecular weight of about 1000 to about 8000, or a mixture thereof), a small amount of diethylene glycol, and a polyisocyanate. .

Typical polyoxyethylene glycols are various commercially available carbowaxes available in a range of molecular weights from Union Carbide. Typical "carbowaxes" are PEG
(Carbowax 1450: Trademark) and P E
G (Carbowaxsooo: trademark), and the numbers in this product correspond to the molecular weight. The degree of hydrophilicity is determined by the ratio of long chain polyglycol and low molecular weight diethylene glycol present in the polyether-polyurethane. Increasing the molecular weight and/or amount of long chain polyethylene glycol promotes strong hydrophilic properties in the final product. An increase in the proportion of low molecular weight glycol, in this case diethylene glycol, results in a decrease in hydrophilic properties.

Generally speaking, polyether-polyurethane contains about 45% to 85% polyoxyethylene glycol and about 2% polyoxyethylene glycol.
．． 25%~11.0% diethylene glycol and about 15~
It is proposed to consist of 40% polyisocyanate. The polyisocyanate used to prepare the hydrophilic polyether-polyurethane in the polyurethane blend can be represented by R(NGO), where n is 1
Preferred boron compounds have 4 to 26 carbon atoms, but more suitable ones have 6 to 20 carbon atoms, and generally 6 to 13 carbon atoms. Typical examples of the above isocyanates include tetramethylene diisocyanate; hexamethylene diisocyanate; trimethylhexamethylene diisocyanate; diisocyanate of dimer acids; isophorone diisocyanate; diethylbenzene diisocyanate; decamethylene-1,10-diisocyanate; cyclohexylene 1.
2-diisocyanate and cyclohexylene 1.4-
Diisocyanates and 2,4- or 2,6-toridine diisocyanate, 4,4-diphenylmethane diisocyanate; 1,5-naphthalene diisocyanate: dianisidine diisocyanate; toridine diisocyanate; polymerized polyisocyanates such as neopentyl tetraisocyanate; m-xylene isocyanate; Tetrahydronaphthalene-1,5 diisocyanate and bis(4
-isocyanatophenyl)methane.

A preferred isocyanate is methylene di(cyclohexyl isocyanate). As other diisocyanates, trimethyl-hexamethylene diisonanate and isophorone diisocyanate are preferred, although they are slightly inferior.

Other useful compounds include nitrile carbonates which form urethane bonds corresponding to isocyanates. An example is adiponitrile carbonate having the following molecular formula.

To produce the hydrophilic polyether polyurethane component, glycols and polycyanates are reacted under known catalysts. The methods described herein use tin salts and organotin esters as catalysts.

For example, dibutyltin-dilaurate, quaternary amines (e.g. triethyldiamine (DABCO), N, N, N'
, N'-tetramethyl-1,3-butanediamine)
and other catalysts used in known urethane reactions.

The hydrophobic polyester polyurethane components used in the polymer blends described herein are commonly known polymers whose disclosures and methods of manufacture are described in the technical and patent literature.

These products are obtained by condensing a polyisocyanate with a polyester resin precursor having two or more active hydrogens when producing a polyurethane polymer by a known method. These polyesters can be regarded as esterification products of polybasic carboxylic acids and polyols having a large number of OH groups, such as polymeric diols. Examples of these diol compounds mentioned above are polytetramethylene-ether glycol and propylene/ethylene oxide block copolymers and propylene oxide based polyols. Polybasic acids are generally polycarboxylic acids, and the more familiar ones include adipic acid, mellitic acid, pyromellitic acid, trimellitic acid, succinic acid, itaconic acid, maleic acid, fumaric acid, mesaconic acid, There are azelaic acid, pimelic acid, and others. The polyester resin is selected to react with polyisocyanate to produce polyester polyurethane. This polyester polyurethane absorbs almost no water and has no tendency to absorb water.

Hydrophobic polyesters Polyurethanes are usually produced when the polymerized diol contains oxy-alkylene units with 3 or more carbons (eg oxypropylene).

The hydrophilic polyurethane-polyene composition of the present invention is stable with no dimensional change even after repeated exposure to boiling water, and is therefore advantageous when used in the production of soft contact lenses. It has unique physical properties.

The above-mentioned hydrophilic polyurethane polyene resin compositions can also be used as coatings, molding preparations, absorbent-adjustable sustained release agents, ion exchange resins, dialysis membrane manufacturing, dentures, cannulae, contact lenses, packaging materials. Burn dressings, contraceptive devices, sutures, surgical tubes, blood oxidizers, intrauterine devices, vascular prostheses, oral delivery systems, battery separators, eye bandages, corneal prostheses, anti-fog coatings, surgery It is effective as surgical gowns, oxygen exchange membranes, artificial finger nails, finger nails, adhesives, gas permeable membranes, other protective membranes, and chemical-resistant coatings.

The invention is further illustrated in the following examples. Unless otherwise specified, each component is in parts by weight.

[Production of polyether polyurethane]

[Example 1] A mixture of 49.0 parts of Carbowax 1450J (polyethylene glycol average molecular weight FFI 1450 Union Force - sold by Baite, Inc., New York, NY 10017) and 11.0 parts of diethylene glycol was heated for about 70 minutes until a homogeneous melt was obtained. Heat to °C with stirring.

While further stirring, methylene-biscyclohexyl-4,
4-Incyanate ([Desmodur: Trademark (DESM)
ODUR) WJ MOBAY Chemical Co. Pennsylvania Cloudy Pittsburgh, Penn Lincoln.

Parkway West/15205, 140 items for sale.
0 parts were added, during which time the temperature decreased. The temperature is about 50°
When C was reached, 0.15 ml of tin-octoate (
Metal and Thermite
Hermite New Chassis, Rahway, a product equivalent to T9), the whole body heats up and the temperature rises to about 7.
The temperature has reached 0℃. The whole was poured into a polypropylene pan. The volume temperature of this injection continued to rise to about 80° C. and foaming occurred. After the injection operation was completed, the pan was placed in an oven and maintained at 100°C for approximately 1 hour to complete the polymer reaction.

[Manufacture of polyether/polyester urethane blends and other products]

Polyether polyurethane and polyester polyurethane were dissolved in chloroform and the resulting solution was used to make films of polymer blends.

Polyester polyurethane is made of toluene diisocyanate, dicarboxylic acid having 6 to 10 carbon atoms, and 3 to 4 carbon atoms.
polyester obtained from alkylene diols
Produced by condensation with polyols. Basically, diisocyanates and polyester-polyols are the same. A film of the polymer blend was cast by applying the above solution to a suitable support, after which the solvent was evaporated. Films can also be produced by dipping a mandrel in the desired shape into a solution, then pulling the mandrel up and allowing the solvent to evaporate. Mandrels of various shapes are used to make gloves, finger plugs, and condoms.

For cast films, the solution can contain about 5% to 10% solids, while for dipping methods it can contain 3% to 5% solids.

The blend is made by mixing finely ground particles of the polymer in an extruder and extruding it into the desired shape, such as a nasal tube, a gastric tube, a cannula, or a film. The polyether/polyester polyurethane blends described above may be mixed with drugs or other pharmaceutical agents to provide controlled release when placed in solution, saline, or body fluids. Can also be used for encapsulation. Drug delivery can be made in a variety of convenient forms. For example, it can be made into a tablet for oral ingestion implant, or into a flattened shape.

Example 2 The procedure of Example 1 was repeated except that the polyether-polyurethane consisted of the following components.

PEG (r Carbowax 8000J')...
41.0 parts diethylene glycol ・・・・・・
...9.0 part "Desmodua W" ・
・・・・・・・・・・・・33.0 parts tin octoate (T
9) ......0.15 ml [Example 3] The operation of Example 1 was repeated except that the polyether-polyurethane consisted of the following components.

PEG (r carbowax 8000J) *...8
2.0 parts diethylene glycol ・・・・・
... Part 3.0 "Desmodua W" ...
・・・・・・・・・・・・15.0 parts Dibutyltin diraliurate (T12)・・・・・・・・・0.20 m1* Polyethylene glycol has an average molecular weight of 7,500 to 8,000 and is manufactured by Union Carbide Co., Ltd. Use what is sold at.

The polyether/polyester blend was soaked in room temperature water for 24 hours. It was then drained and wiped with a paper towel to remove surface moisture. Moisture content was determined from the weight increase of the sample. Durometer A hardness was determined for both dry and wet samples. Tensile strength was measured on both dry and wet samples.

The polyether/polyester polyurethane of the example was further tested for water absorption by the following procedure.

The sample was heated to approximately 300℃ with a diameter of 0.25cm and a wall thickness of 0.058cm.
It was heated and extruded into a cm tube shape. Tubular sample (length 4cm)
The weight, diameter and wall thickness were measured in a dry state. 2 samples
The sample was left in water at room temperature for 4 hours to remove surface moisture.

Thereafter, the weight, diameter, and wall thickness were measured to calculate the amount of change in volume. The water absorption rate, diameter, wall thickness, and volume change were calculated using the following equations.

Although the water absorption of the polymer blend was essentially the same as that of the hydrophilic polyether-polyurethane itself,
Mechanical strength was improved in this state (5 other people)

Claims (25)

[Claims] (1) A, diethylene glycol and molecular weight approximately 1000
from about 25% to about 75% by weight of a hydrophilic polyether polyurethane, which is the reaction product of polyoxyethylene glycol of up to about 8,000% with a polyisocyanate, and of polyoxyethylene glycol derived from the condensation of B, a polyol and a polybasic acid. Approximately 75% by weight of hydrophobic polyester polyurethane, which is a reaction product of functional polyester and polyisocyanate.
A water-absorbing polyurethane composition comprising a blend of about 25% by weight. (2) The composition according to claim 1, wherein the polyethylene glycol has a molecular weight of about 1,450. (3) The molecular weight of polyethylene glycol is about 7500~
8,000. (4) The composition according to claim 1, wherein A is 40% by weight and B is 60% by weight. (5) The composition according to claim 1, wherein A is 60% by weight and B is 40% by weight. (6) The composition according to claim 1, wherein the polyester-polyurethane is a condensation product of a polyisocyanate and a polyester-polyol derived from a polycarboxylic acid and a fatty acid diol. 7. The composition of claim 6, wherein the polyester-polyol is derived from a dicarboxylic acid having 6 to 10 carbon atoms and an alkylene diol having 3 to 4 carbon atoms, and the polyisocyanate is toluene diisocyanate. (8) A, diethylene glycol and molecular weight approximately 2000
from about 25% by weight to about 7% by weight of a hydrophilic polyether-polyurethane, which is the reaction product of polyoxyethylene glycol of about 8,000% and polyisocyanate.
5% by weight, and about 75% by weight of B, a hydrophobic polyester-polyurethane which is the reaction product of a polyisocyanate and a polyfunctional polyester derived from condensation with a polyol and a polybasic acid.
A three-dimensional structured molded article formed from a water-absorbing polyurethane composition comprising a blend of ~25% by weight. (9) The article according to claim 8, wherein the structure is a film. (10) The article according to claim 8, wherein the structure is a film-like burn covering. (11) The article according to claim 8, wherein the structure contains a drug. (12) The article according to claim 11, wherein the drug is a hormone. (13) Claim 11 in which the drug is a steroid
Items listed in section. (14) The article according to claim 8, wherein the structure is in the shape of an intrauterine device. (15) The article according to claim 14, wherein the intrauterine device also includes a composition of a contraceptive device. (16) Claim 8, wherein the structure is in the shape of a diaphragm.
Items listed in section. (17) The article according to claim 8, wherein the structure is in the shape of a cannula. (18) The article according to claim 17, wherein the cannula is capable of sufficiently separating and dispensing the drug from the aggregate. 19. The article of claim 8, wherein the structure is in the form of an oral delivery system containing a pharmacologically active agent. (20) The article according to claim 8, wherein the structure is in the form of a membrane permeable to humid vapor. (21) The article according to claim 8, wherein the structure is molded. (22) The article according to claim 8, wherein the structure is a contact lens. (23) The article according to claim 8, wherein the structure is a corneal prosthesis. (24) The article according to claim 8, wherein the structure is a film-like surgical gown. (25) The article according to claim 8, wherein the structure is in the shape of a dialysis membrane.