DE2749491A1 - POLYURETHANE COMPOUNDS AND ITEMS MANUFACTURED FROM THEM - Google Patents

Description

Polyurethane compounds and articles made therefrom

The invention relates to polymer compositions referred to as polyurethanes, in particular polyurethanes made from a prepolymer of a multifunctional one Agent, such as castor oil, and an organic diisocyanate that is hardened with a crosslinking agent that the ester of a polyhydric alcohol with 2 or 3 hydroxyl groups and an aliphatic carboxylic acid with at least 12 Contains carbon atoms and one or more epoxy and / or hydroxyl groups per molecule.

Polyurethane compositions, which by implementing a corresponding Prepolymers of an organic diisocyanate with a curing agent, such as a polyalkylene glycol, are known In general, the organic diisocyanate with a suitable polyfunctional group containing active hydrogen atoms, converted to a prepolymer. The prepolymer is then treated with a suitable curing or crosslinking agent converted to polyurethane mass. For example, US Pat

809820/0790

3 362 921 describes an elastomeric polyurethane which is derived from a prepolymer that is produced by reacting castor oil with an organic diisocyanate, such as toluene diisocyanate, he " has been held. The prepolymer obtained is by reaction with a suitable ester of a polyhydric alcohol, the contains at least 4 hydroxyl groups, e.g. pentaerythritol monoricinoleate, networked. From this US-PS it is apparent that it is used to produce cured polyurethane with desired elastomeric Properties for embedding or potting purposes it is essential that a crosslinking or hardening agent is used, which is derived from esters of polyhydric alcohols containing at least 4 hydroxyl groups.

According to the invention, a polyurethane mass is made available, by reacting a diisocyanate polymer with an ester of a polyhydric alcohol having 2 or 3 hydroxyl groups and one aliphatic carboxylic acid with at least 12 carbon atoms and one or more epoxy and / or hydroxyl groups per molecule can be obtained.

A. prepolymer

Prepolymer compositions which can be used according to the invention are prepared by adding an active hydrogen-containing polymer material, whose molecular weight and acid number are within a certain range, with a controlled amount of a diisocyanate reacts, the diisocyanate being present in excess of stoichiometric amounts. Examples of polymer materials with active Hydrogen are polyester, castor oil, polyester amides and polyalkylene ether glycols. A more detailed description of prepolymer compositions made by reacting a diisocyanate with active Hydrogen-containing materials are found in U.S. Patents 2,625,531, 2,625,532, 2,625,535, 2 692 873 and 2 702 797-

To produce the prepolymer, organic diiso-

809820/0790

cyanates that are known to be used in manufacture such masses are suitable by reaction with active hydrogen-containing materials. To be favoured Arylene diisocyanates from the group of the diisocyanates of benzene and naphthalene or mixtures of these compounds are used. Below specific examples of corresponding arylene diisocyanates are listed: tolylene diisocyanate (2.4 / 2.6), toluene-2,4-diisocyanate, Toluene-2,6-diisocyanate, m-phenylene diisocyanate, xenylene-4,4'-diisocyanate, Naphthalene-1,5'-diisocyanate, 3,3'-bitolylene-4,4 -'-diisocyanate, Diphenylenemethane-4-, 4-diisocyanate, 4-chlorophenylene-2,4-diisocyanate, Dianisidine diisocyanate, diphenylene ether-4-, 4 · '-diisocyanate and polymeric isocyanates such as polymethylene polyphenylene isocyanate. Further usable arylene diisocyanates are the corresponding, derivatives substituted by lower alkyl radicals, halogen atoms and lower alkoxy radicals. It can also be used by others aromatic hydrocarbons derived diisocyanates and aliphatic isocyanates can be used.

Examples of active hydrogen-containing polymer materials are castor oil, glycol or polyglycol monoesters of hydroxycarboxylic acids having at least 12 carbon atoms, polyalkylene ether glycols and mixtures of these compounds.

Glycol and polyglycol monoesters of hydroxycarboxylic acids with at least 12 carbon atoms are obtained by reacting a hydroxycarboxylic acid with at least 12 carbon atoms with divalent ones lower aliphatic alcohols or ether alcohols, such as ethylene glycol, Propylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, Hexamethylene glycol and polyethylene and polypropylene glycols, by known methods, for example by direct Esterification. The hydroxymonocarboxylic acids can be saturated or unsaturated. Specific examples of appropriate Hydroxycarboxylic acids are ricinoleic acid, 12-hydroxystearic acid, Hydroxypalmitic acid, hydroxypentadecanoic acid, hydroxymyristic acid and hydroxycerotic acid.

809820/0790

Preferred esters for preparing these prepolymers are Propylene glycol monoricinoleate, ethylene glycol monoricinoleate and propylene glycol 12-hydroxystearate. To make the prepoly _ " mers, other esters are also suitable, including diethylene glycol monoricinoleate, Polyethylene glycol monoricinoleate, dipropylene glycol monoricinoleate, polypropylene glycol 12-hydroxystearate and propylene glycol hydroxypalmitate.

The esters of hydroxycarboxylic acids with at least 12 carbon atoms can with respect to the castor oil in a weight ratio of about 80 to 40 percent ester to about 20 to 60 percent Castor oil can be used. The preferred weight ratio is about 61 to 63 percent ester and 39 to 37 percent Castor oil.

It was also found that when using about 2 to NCO equivalents of the organic diisocyanate per 1 equivalent Hydroxyl group can be obtained in a mixture of castor oil and ester valuable prepolymer.

Any commercially available castor oil can be used as castor oil to produce the prepolymers. Preferably will Castor oil is used with a low content of acidic and volatile components. Such a product is under the Designation "DB" Ricinus Oil sold by NL Industries, Inc.

Polyoxypropylene derivatives of propylene glycol, trimethylolpropane, Glycerin or pentaerythritol can be used. Preferred polyoxypropylene polyols are propylene glycol derivatives with a Molecular weight from 200 to 800 and trimethylol propane derivatives with a molecular weight of 700 to 3000. The preparation of these polyalkylene ether glycols and their reaction with organic Diisocyanates with the formation of prepolymer compositions can be carried out according to the processes of US Pat. Nos. 2,702,797 and 2,692,873 will.

809820/0790

Preferred prepolymers are produced, for example, by reacting DB castor oil, polyoxypropylene glycol and an arylene diisocyanate. The mixture is heated ^{to 70 °} C. for 4 hours, for example. However, other temperatures of about 20 to 100 ^° C. can also be used with satisfactory results.

Leave the polyesters to be reacted with the organic egg isocyanate by reacting 2 bifunctional reactants, one of which is a dibasic carboxylic acid and the other is a Glycol is to produce. Polyester amides can be prepared by reacting a dibasic carboxylic acid with diamines or amino alcohols produce. The polyesters preferably have a hydroxyl number from about 40 to about 100 and an acid number from 0 to 7 on.

Below are specific examples of dibasic carboxylic acids with preferred carboxyl groups attached to the terminal carbon atoms listed that can be used to manufacture polyester and polyester amides: succinic acid, glutaric acid, Adipic acid, pimelic acid, maleic acid, malonic acid, fumaric acid, terephthalic acid and citric acid. Examples of glycols used for Manufacture of polyesters that can be used are ethylene glycol, propylene glycol, 1,3-tolylene glycol, triethylene glycol, Butylene glycol, hexamethylene glycol, decamethylene glycol and glycerol monoether. Can be used as diamines for the production of polyester amides corresponding compounds with at least one primary amino group can be used, such as ethylenediamine, propylenediamine, tetramethyl enediamine, m-phenylenediamine and 3,3'-diaminodipropyl ether. Examples of primary amino alcohols for the production of polyamides are 3-aminopropanol, 6-aminohexanol and 4-aminobutanol.

B. Crosslinking agents

It was found according to the invention that esters of polyvalent Alcohols with 2 or 3 hydroxyl groups and an ali-

809820/0790

COPY

phatic carboxylic acid with at least 12 carbon atoms and one or more hydroxyl and / or epoxy groups per molecule Curing of prepolymer masses are suitable, whereby products are obtained which in terms of physical and electrical properties Prepolymer compositions that have been cured with conventional curing agents are superior. The aliphatic hydroxy and / or epoxycarboxylic acids with at least 12 carbon atoms, which form an ester on reaction with polyhydric alcohols having 2 or 3 hydroxyl groups can be saturated or unsaturated be. Specific examples of compounds from this class of hydroxycarboxylic acids are ricinoleic acid, 12-hydroxystearic acid, Hydroxypalmitic acid, hydroxypentadecanoic acid, hydroxymyristic acid and hydroxycerotic acid and the epoxy derivatives of these acids. The length of the carbon chain of the aliphatic hydroxy and / or epoxy carboxylic acids is only relevant subject to a restriction that commercially only aliphatic Carboxylic acids up to about 22 carbon atoms are available. However, there are also aliphatic carboxylic acids with more than 22 carbon atoms suitable.

The following are examples of polyhydric alcohols with 2 or 3 hydroxyl groups, those with the aliphatic hydroxyl and / or Epoxycarboxylic acids can be converted, listed: ethylene glycol, Propylene glycol, glycerine, diethylene glycol, dipropylene glycol, Trimethylolpropane (TMP) and trimethylolethane (TME).

The esters suitable as curing agents for the prepolymers are prepared by customary processes, for example by direct esterification of an aliphatic hydroxy and / or epoxy carboxylic acid with a polyhydric alcohol with 2 or 3 hydroxyl groups. However, other known processes for the preparation of esters can also be used. Preferred curing agents for the prepolymers are ethylene glycol monoricinoleate, Trimethylolpropane monoricinoleate and trimethylolethane monoricin

809820/0790

oleate and the di- and triesters and mixtures of these esters. Examples of further esters that can be used are propyl glycol monoricinoleate, dipropylene glycol monoricinoleate and Glycerol monoricinoleate. It is also possible to use other esters which are obtained by reacting the polyvalent ones mentioned above Alcohols and aliphatic carboxylic acids result.

Furthermore, it was found according to the invention that castor oil which has been polymerized oxidatively, ie “oxidized” (“blown”) castor oil, can be used as part of the hardening mixture. Thereby, the flexibility is still more increased, as is the case in the absence of the polymerized or "oxidized ¹¹ castor oil.

The cured polyurethanes according to the invention are particularly suitable for embedding and encapsulating electronic components, for example for embedding underwater ultrasonic devices. The products according to the invention are also suitable as coating systems and in particular for embedding hollow fibers of liquid separation devices used for ultrafiltration, reverse osmosis, hemodialysis or the like. For example, hollow fiber separation devices are used for dialysis, ultrafiltration, reverse osmosis, hemodialysis, hemoultrafiltration and used oxygen delivery to the blood. In general, the separator is composed of a plurality of fine ones Hollow fibers, the end parts of which are embedded in a tube sheet and the open fiber ends in a tube sheet front (tube-sheet face), which allows liquid access to the inside of the fibers, end. The dividers are in one Enclosed housing, so that a separation cell is created with one or more fluid openings that allow the flow of a Allow liquid through the fibers and the inflow of another liquid into the area around the fibers without a Mixture of both liquids occurs. The separating element can have two tube sheets or a single tube sheet, with im

809820/0790

in the latter case the fibers are bent over so that all ends end together. The general structure of the separator and the separation cell is similar to that of a shell and tube heat exchanger. U.S. Patents 2,972 34-9, 3,228,876, 3,228,877, 3,4-22,008, 3,423 4-91, 3,339 34-1, and 3,503,515 are examples given for conventional hollow fiber cutting devices.

The tube sheet material is intended to fill the space between the hollow fibers and do not deform them. In addition, the cut edge must of the hollow fibers remain substantially circular after cutting. Furthermore, the tube sheet material must be easy to handle and can be processed into solid and permanent parts. In addition, the material is allowed to be used for biological and non-toxic for medical purposes.

The cured polyurethane of the invention satisfies the aforementioned requirements and is thus a valuable material for manufacture from tube sheet.

Many of the aforementioned separation devices must be used before they can be used be rinsed with ethanol. Thus, the tube sheet material must have good alcohol resistance, but may not be so hard or stiff that it is difficult to cut. Surprisingly, it was found that esters of polyvalent Alcohols with 2 or 3 hydroxyl groups and an aliphatic carboxylic acid with at least 12 carbon atoms and one or more hydroxyl and / or epoxy groups per molecule are particularly suitable as curing agents for the inventive Prepolymers are suitable and a favorable combination in terms of superior flexibility and excellent ethanol resistance result.

The examples illustrate the invention. All parts and percentages relate to weight, unless otherwise stated.

8 0 9 8 2 Π / 0790

The polymers obtained according to the examples below and moldings are examined according to the following methods:

hardness

The Shore D durometer readings are in accordance with ASTM D 2240 certainly. The samples are kept for 16 to 20 hours at tree temperature, an additional 2 hours at 75 ° C and an additional 5 to 7 days Hardened at room temperature.

Alcohol strength

The ethanol strength of the cured polymer samples is determined in accordance with ASTM D 543. The samples will last 16 to 20 hours Room temperature and an additional 8 hours at 75 ° C and cured cooled to room temperature.

Manufacture of prepolymers

A. A mixture of 204 g of polyoxypropylene glycol with a molecular weight of 400, 205 g of castor oil and 795 g of 4,4 ^I -diphenylenemethane diisocyanate (MDI) are placed in a reaction vessel under nitrogen and stirred. The temperature is slowly increased to 75 ° C and held for 7 hours at 70 to 8O ⁰ C, optionally under cooling. The prepolymer obtained has an NCO content of about 16.2 percent and a viscosity of 6000 cp.

B. According to the method of A, a prepolymer is made from the following Components manufactured:

Polyoxypropylenetriol derived from trimethylolpropane with a molecular weight of 1560 519 g

Polyoxypropylene glycol (molecular weight 400) 343 g 4,4'-diphenylene methane diisocyanate 1331 g

809820/0790

This prepolymer has an NCO content of about 15 percent and a viscosity of 32,000.

The prepolymer masses are made by adding a curing agent, which is an ester of a polyhydric alcohol with 2 or 3 hydroxyl groups an aliphatic carboxylic acid with at least 12 carbon atoms and one or more hydroxy and / or Contains epoxy groups or mixtures of these esters, cured to form an elastomeric product. Curing can take place at room temperature or elevated temperatures.

The following are methods of making urethane elastomers indicated under curing at room temperature or at elevated temperatures.

Curing at room temperature

The curing agent and the prepolymer are used in the corresponding Proportions mixed to a completely homogeneous mixture. The mixture is then degassed at 5 torr for 3 to 5 minutes. The degassed mixture is then poured into molds and cured at room temperature.

Hardening with heating

The prepolymer and the curing agent are separately degassed for about 30 minutes at 5 torr or at least until the foam initially formed collapses. The prepolymer and curing agent can be heated to facilitate degassing. Then, the prepolymer and the curing agent are thoroughly mixed in the appropriate proportions and then brought about 5 minutes at 6O ⁰ C again to a pressure of 5 Torr, to the introduced during mixing to remove air. The degassed mixture is then poured into molds and ^{cured at 100 °} C. for 4 hours.

809820/0790

Curing is used in Examples 1 to 16 below to illustrate the cured urethane elastomers of the invention carried out with heating. The amounts of the ingredients of Examples 1 to 16 are given in parts by weight.

example 1

Prepolymer A 272 Trimethylolpropane monoricinoleate 220 NCO / OH ratio 1.1 B e i s ρ i e 1 2 Prepolymer A 272 Trimethylolpropane tricinoleate 391 NCO / OH ratio s 1.1 B e i s ρ i e 1 3

Prepolymer A 272

Trimethylolpropane monoricinoleate

Trimethylolpropane tricinoleate 117 NCO / OH ratio s 1.1 B e i s ρ i e 1 4- Prepolymer A 272 Trimethylolpropane monoricinoleate 132 Trimethylolpropane tricinoleate 156 NCO / OH ratio s 1.1 B e i s ρ i e 1 5 Prepolymer A 272 Trimethylolethane monoric inoleate 221 NCO / OH ratio 1.1

809820/0790

Example 6

. Prepolymer A 272 Propylene glycol monoricinoleate 193 NCO / OH ratio s 1.1 B e i s ρ i e 1 7 Prepolymer A 272 Ethylene glycol monoricinoleate 215 NCO / OH ratio s 1.1 B e i s ρ i e 1 8 Prepolymer A 272 Glycerol monoricinoleate 162 NCO / OH ratio s 1.1 B e i s ρ i e 1 9 (comparative example) Prepolymer A 272 Castor oil 342 NCO / OH ratio s 1.1 B e i s ρ i e 1 10 (comparative example) Prepolymer A 272 Pentaerythritic bonoricin oleate 169 NCO / OH ratio s 1.1 B e i s ρ i e 1 11 Prepolymer B 302 Propylene glycol monoricinoleate 193 NCO / OH ratio s 1.1 B e i s ρ i e 1 12 Prepolymer B 302 Ethylene glycol monoricinoleate 215 NCO / OH ratio ^ _ηη ^ _ηιηηηΛ 1.1

Example 1? (Comparative example)

Prepolymer B 302 Pentaerythritol oricin oleate 169 NCO / OH ratio 1.1 Example 14- (comparative example) Prepolymer B 302 Castor oil 342 NCO / OH ratio s 1.1 Example 15 Prepolymer A 272 Ethylene glycol monoricinoleate 151 oxidized castor oil 105 NCO / OH ratio s 1.1 Example 16 Epopolymer A 272 Ethylene glycol monoric inoleate 173 oxidized castor oil 70 NCO / OH ratio 1.1

In Examples 1 to 16 it is 16 to 20 hours at room temperature and additionally hardened for 8 hours at 75 ° C. It is then cooled to room temperature and a microsection is made. The micro-cuts are microscopic to the contact of the connection for embedding to the hollow fibers and to the Maintaining the fiber geometry investigated. In all cases there is excellent contact between the hollow fibers, whereby the geometric arrangement of the fiber ends is maintained. The hardness and alcohol resistance of the individual polymers are compiled in Table I.

809820/0790

As can be seen from the table, the polymers of Comparative Examples 10 and 13 have good alcohol resistance, _- ■ but are too hard or inflexible. The polymers of Comparative Examples 9 and 14 show good flexibility but poor alcohol resistance. The products according to the invention show a favorable and unexpected combination in in terms of good flexibility and excellent alcohol resistance.

809820/0790

Table I.
Example J_JLJLJL-JLJL-Z-.JLJl. 10 11 12 13 14 15 16

Shore D hardness

initially 72 29 62 55 70 72 67 74 46 72 72 64 75 31 53 62

10 sec. 66 14 48 37 62 64 60 65 18 70 58 50 73 16 25 45

cDÄthanolo strength

Source volume, ι

%% 9.5 13.8 10.5 10.8 10.9 14.6 11.2 15.130.2 6.6 14.6 11.2 10.3 28.4 15.0 10.5

O O

(D

Claims (1)

Claims 1. Hollow fiber cutting device with a hollow fiber bundle that a plurality of fine hollow fibers, the end parts of which are embedded in a tube sheet and the open ends of which are embedded in a End tube sheet front, and which in a housing to form a separation cell with one or more liquid openings that allow the flow of a liquid through the Fibers and allow another liquid to flow into the area around the fibers without mixing the two Liquids entering, is included, characterized in that the tube sheet is a hardened polyurethane mass contains, which essentially consists of A. a prepolymer from the reaction product of castor oil and polyoxypropylene glycol with at least 1 mole of an organic Diisocyanate per polyol hydroxyl group and B. a crosslinking agent containing an ester of I. a polyhydric alcohol with 2 or 3 hydroxyl groups and 809820/0790 ORIGINAL INSPECTED II. An aliphatic carboxylic acid with at least 12 carbon atoms and one or more hydroxyl and / or epoxy groups per molecule or mixtures of these esters and _ ~~ optionally oxidized eicinus oil. 2. Device according to claim 1, characterized in that the organic diisocyanate in the prepolymer is diphenylene methane-4,4'-diisocyanate is present. 3. Device according to claim 1, characterized in that the polyurethane mass consists essentially of A. a prepolymer made from the reaction product of castor oil and polyoxypropylene glycol with at least 1 mole of toluene-2,4-diisocyanate, Toluene-2,6-diisocyanate or mixtures thereof, diphenylene methane-4,4'-diisocyanate or m-phenylene diisocyanate per polyol hydroxyl group and B. a crosslinking agent containing a monoester and / or diester of ethylene glycol and ricinoleic acid and Trimethylolpropane or trimethylolethane or mixtures of these mono-, di- or triesters. Cured polyurethane containing the reaction product from (1) the reaction product from (a) a polyester which has been produced from bifunctional components including at least one dibasic carboxylic acid and at least one bifunctional reactant with hydroxyl groups as functional groups, the polyester having a hydroxyl number of 40 to 100 and an acid number of 0 to 7, and (b) an arylene diisocyanate and
(2); a curing agent consisting essentially of an ester of a polyhydric alcohol with 2 or 3 hydroxyl groups and an aliphatic hydroxyl and / or 809820/0790 Epoxycarboxylic acid with at least 12 carbon atoms consists. 5. Cured polyurethane according to claim A, characterized in that that the curing agent ethylene glycol monoricinoleate, Ricinoleic acid trimethylolpropane ester, ricinoleic acid trimethylolethane ester or a mixture of these compounds. 6. Cured polyurethane, consisting essentially of the reaction product from (1) the reaction product of a polyalkylene ether glycol with a molecular weight of at least 200, a polyalkylene ether triol with a molecular weight of at least 15OO and an arylene diisocyanate, where the arylene diisocyanate in an amount of about 2 to 12 equivalents per 1 equivalent of polyalkylene ether glycol has been used, and (2) a curing agent consisting essentially of an ester of a polyhydric alcohol having 2 or 3 hydroxyl groups and an aliphatic hydroxy or epoxy carboxylic acid having at least 12 carbon atoms. 7. Cured polyurethane according to claim 6, characterized in that that the polyalkylene ether glycol is polyoxypropylene glycol. 8. Cured polyurethane according to claim 6, characterized in that that the curing agent is ethylene glycol monoricinoleate, ricinoleic acid trimethylolpropane ester, ricinoleic acid trimethylolethane ester or a mixture of these compounds. 9. Cured polyurethane, consisting essentially of the reaction product from (1) the reaction product of castor oil, an alkyl glycol 809820/0790 Ester of a hydroxycarboxylic acid with at least 12 carbon atoms and an arylene diisocyanate, which has been prepared by reacting about 2 to about 3 NCO equivalents of the diisocyanate per 1 equivalent of hydroxyl groups in the mixture of castor oil and ester, the ester and the castor oil in a weight proportion esters have been used by about 80 to 40 percent and about 20 to 60 percent of castor oil and i has been carried out the reaction of castor oil, esters and diisocyanate at temperatures of about 20 to 100 ⁰ C st, and
(2) a curing agent consisting essentially of a Esters of a polyhydric alcohol with 2 or 3 hydroxyl groups and an aliphatic hydroxy and / or epoxy carboxylic acid having at least 12 carbon atoms consists. 809820/0790