DE4415353A1 - Diols - Google Patents

Abstract

Diols of the formula I <IMAGE> in which the variables have the following meaning: A is an unsubstituted tetramethylene group or one substituted by 1 or 2 C1- to C4-alkyl groups; Z is the bis-yloxy radical of a mono- or disaccharide group or sugar alcohol group whose remaining hydroxyl groups are protected as ethers, esters or acetals; m is a value from 2 to 150; n is a value from 1 to 150; and diols of the formula II <IMAGE> in which the variables have the following meaning: A is an unsubstituted tetramethylene group or one substituted by 1 or 2 C1- to C4-alkyl groups; Z is the bis-yloxy radical of a sugar alcohol, mono- or disaccharide group whose remaining hydroxyl groups are protected as ethers, esters or acetals; m is a value from 2 to 150; n is a value from 2 to 150, processes for the preparation of these diols and their use for the preparation of polyurethanes.

Description

The present invention relates to new diols of general Formula I.

in which the variables have the following meaning:
A is an unsubstituted or a tetramethylene group substituted with 1 or 2 C₁ to C₄ alkyl groups;
Z is the bis-yloxy residue of a mono- or disaccharide group or sugar alcohol group, the remaining hydroxyl groups of which are protected as ethers, esters or acetals;
m has a value from 2 to 150;
n has a value from 1 to 150,
Diols of the general formula II

in which the variables have the following meaning:
A is an unsubstituted or a tetramethylene group substituted with 1 or 2 C₁ to C₄ alkyl groups;
Z the bis-yloxy residue of a sugar alcohol, mono- or disaccharide group, the remaining hydroxyl groups of which are protected as ethers, esters or acetals;
m has a value from 2 to 150;
n has a value from 1 to 150,
and processes for the preparation of these diols.

In addition, the invention relates to polyurethanes from polyvalent Isocyanates, polyhydric alcohols and, if desired, more valuable amines, which is the component of the polyhydric alcohol 5 to 100 mol% consists of a diol I or a diol II.

The invention further relates to the use of the poly urethanes for the production of moldings and coatings as well as these moldings and coated with the polyurethanes Objects.

It is generally known that poly-tetrahydrofurans as diol Building blocks for polyurethanes are well suited because they are the poly urethanes have a particularly favorable low-temperature behavior lend. A disadvantage, however, is the relatively high viscosity of the Poly-tetrahydrofurans that are difficult to process there is occasion.

In WO-A 86 01 512 there are liquid monoglucosides made from saccharides or polysaccharides and poly-tetrahydrofuran.

These known carbohydrate derivatives are indeed suitable for manufacturing position of polymers, in particular of polyurethanes, their However, processing properties still leave something to be desired.

The present invention was therefore generally new poly urethanes with improved application properties underlying.

In particular, the task extended to new diols based on Poly-tetrahydrofuran as polyurethane building blocks, which the poly Give urethanes the desired properties.

Accordingly, the diols I and II and a defined at the outset Processes for the preparation of these compounds were found.

Furthermore, polyurethanes were made from polyvalent isocyanates, more valuable alcohols and, if desired, polyvalent amines found, which are characterized in that the component 5 to 100 mol% of the polyhydric alcohol from a diol I. consists. Furthermore, the use of the polyurethanes for the production of moldings and coatings as well as these Molded articles and objects coated with the polyurethanes found.  

The variables of the diols I and II according to the invention have the following meaning:
A is an unsubstituted or a tetramethylene group substituted by 1 or 2 C₁ to C₄ alkyl groups, e.g. B. the grouping

-CH₂-CH- (CH₃) -CH₂-CH₂-,

but preferably the unsubstituted tetramethylene group;
Z the bis-yloxy residue of a sugar alcohol, mono- or disaccharide group, the remaining hydroxyl groups of which are protected as ethers, esters or acetals, preferably a correspondingly derivatized sugar alcohol group, in particular the 1,4- derived from the sugar alcohol sorbitol by etherification Dioxa-3,6-bisyloxibicyclo [3.3.0] octane group of the formula

m has a value from 2 to 150, preferably from 3 to 70,
and the degree of condensation
n has a value from 1 to 150, preferably from 1 to 20.

The diols I are prepared according to the invention by using a Polyoxyalkylene glycol of the general formula III

in which A and m have the meaning given above, with which to Generation of the above-mentioned, desired degree of condensation n defined amount of a dichloroformate of the general Formula IV

in which Z has the meaning given above, in the presence of a base implements.  

The diols II are prepared according to the invention by using a Polyoxyalkylene glycol derivative of the general formula V

in which A and m have the meaning given above and X one is a nucleophilically substitutable leaving group with which to Generation of the above-mentioned, desired degree of condensation n defined amount of an alkali metal dialcoholate of a mono- or disaccharide or a sugar alcohol and the end permanent groups X of the reaction product in known per se Conversion to a base with hydroxyl groups.

To prepare the diols I, the starting material III is poly tetrahydrofuran is particularly preferred.

The starting dichloroformates IV are usually by reacting the mono- or disaccharides or of sugar alcohol obtained with phosgene (see e.g. DE-A 22 51 206, EP-A 250 773 or DE-A 29 38 464).

The bis-yloxi residues of sugar alcohols, mono- or Disaccharides in the diols I and the starting material III underlying stem bodies are monosaccharides, such as glucose, Mannose, galactose, gulose, fructose and arabinose, disaccharides, such as preferably maltose, lactose and sucrose, and sugar alcohols, such as in particular sorbitol, mannitol and xylitol.

Those hydroxyl groups of these sugar alcohols, mono- or Disaccharides that do not react with phosgene should be in a conventional manner prior to phosgenation protected by etherification, esterification or acetalization.

Acetate protection is preferably used as the ester protecting group group, as ether protecting groups are the methyl, ethyl, benzyl and phenyl ether protecting groups are preferred.

Vicinal hydroxyl groups of the mono- or disaccharides or Sugar alcohols can be obtained by acetalization, for example with Acetone or benzaldehyde.

Methods for esterification, etherification or acetalization of the Hydroxyl groups are e.g. B. in T. Greene, Protective Groups in Organic Chemistry, Wiley, New York, 1981.  

A particularly preferred starting material for production the compounds IV and the diols I is the commercial one 1,4-dioxa-3,6-dihydroxy-bicyclo [3.3.0) octane, the double inner Ether of the sugar alcohol sorbitol as it is particularly uniform Diolen I leads.

To set the desired degree of condensation n sets the compounds III and IV in a manner known per se with each other in the amount required by the desired Degree of condensation n is defined. The molar ratio III to IV is generally 1 to 2, but is preferred Molar ratio of 1.05 to 2, corresponding to a condensation degree n from 20 to 1.

The reaction of III with IV takes place with the help of a base, preferably tertiary nitrogen bases such as trimethylamine, Cyclohexyldimethylamine, pentamethyldiethylenetriamine, pyridine, N-methylpiperidine, diazabicycloundecane and especially triethyl amine. The molar ratio of the base to the starting materials IV is preferably 2: 1. However, an excess of base can also be used up to 100 mol% can be added.

The reaction of III with IV is preferably carried out in solution. Suitable solvents are, for example, tetrahydrofuran, Dioxane, methylene chloride, chloroform, carbon tetrachloride, N-methyl-pyrrolidone, dimethylformamide, diethyl ether, xylene, Mesitylene and preferably toluene.

The reaction is generally carried out at 0 to 200 ° C., preferably as at 20 to 150 ° C, and most preferably at 60 to 120 ° C through.

The reaction is expediently carried out under normal pressure, however one can also with reduced or increased pressure work, a pressure range of 1 to 50 bar is preferred.

The response times are usually 1 to 12 hours, usually 2 to 8 hours.

In terms of process engineering, the procedure is expediently such that component III and the base heated and in the feed process with the dissolved component IV. To complete the reaction is then turned on for some time set temperature stirred.  

Working up to the diols I is carried out in the usual manner, and by separating the salt formed during the reaction and distilling off the solvent. The so available he Diols I according to the invention are distinguished by low viscosities even with high average molecular weights and thus through good ones application properties. They are therefore suitable preferably as a diol building block for the production of polymers such as Polyurethanes.

According to the invention, polyoxy is used to prepare the diols II alkylene glycol derivatives of the general formula V are used. In For the starting materials V, the variable X denotes a nucleophile substitutable leaving group, preferably a halogen atom, such as Chlorine, bromine or iodine, or an alkyl or aryl sulfonate, such as p-toluenesulfonate, trifluoromethanesulfonate and especially methane sulfonate.

As the polyoxyalkylene derivative V to be used according to the invention in particular the poly-tetrahydrofuran bismesylate is preferred.

The polyoxyalkylene derivatives V are known or can be obtained by known methods especially easy by using poly-tetrahydrofuran Chlorinating agents such as B. PCl₅ SOCl₂ or phosgene to the poly oxyalkylene dihalides (see J. Am. Chem. Soc, 60 (1938), 2540) or by reacting polyoxyalkylene glycols with alkyl or Arylsulfonic acid halides to the corresponding polyoxyalkylene sulfonates (see DE-A 38 34 265).

The dialcoholates required for the preparation of the diols II Sugar alcohols, mono- or disaccharides are commonly used by implementing the protected sugar alcohols, mono- or Disaccharides with an alkali metal hydride, alkali metal amide, Alkali metal hydroxide or alkali metal alcoholate produced (see S. Patai, "The Chemistry of the Ether Linkage", p. 445, 1967). For economic reasons it is mainly alkali metal Methanolate is preferred as the base. The Her the dialcoholates in solution. Suitable Solvents are e.g. B. toluene, tetrahydrofuran, dioxane and ins special N-methylpyrrolidone, dimethylformamide and above all Alcohols such as methanol or ethanol.

The dialcoholates are derived from sugars or sugar alcohols, the remaining hydroxyl groups by etherification, esterification or acetalization are protected.  

The parent bodies underlying these connections are Monosaccharides such as glucose, mannose, galactose, gulose, fructose and arabinose, disaccharides, such as preferably maltose, lactose and sucrose and sugar alcohols, such as in particular sorbitol, Mannitol and xylitol.

Those hydroxyl groups of these sugar alcohols, mono- or Disaccharides that are not converted into alcoholate groups should be, before the implementation with the Alkali metal base in a conventional manner by Ver etherification, esterification or acetalization protected.

Acetate protection is preferably used as the ester protecting group group, as ether protecting groups are the methyl, ethyl, benzyl and phenyl ether protecting group are preferred.

Vicinal hydroxyl groups of the mono- or disaccharides or Sugar alcohols can be obtained by acetalization, for example with Acetone or benzaldehyde.

Methods for esterification, etherification or acetalization of the Hydroxy groups are e.g. B. in T. Greene, Protective Groups in Organic Chemistry, Wiley, New York, 1981.

A particularly preferred starting material for the production of Dialcoholates and, as a consequence, diols II is the commercially available 1,4-dioxa-3,6-dihydroxy-bicyclo [3.3.0) octane, the double inner Ether of the sugar alcohol sorbitol as it is particularly uniform Diolen II leads.

To set the desired degree of condensation n, the dialcoholate and the compound V in a manner known per se with each other in the amount required by the desired Degree of condensation n is defined. The molar ratio of dialcoholate / Compound V is generally 1 to 2, is preferred however, a molar ratio of 1.05 to 2, corresponding to one Degree of condensation n from 20 to 1.

After the reaction of the dialcoholate with compound V, the two terminal groups X of the reaction product in itself converted in known manner with a base in hydroxyl groups. Preferred bases are alkali solutions such as potassium hydroxide and especially Caustic soda.

To accelerate the reaction, it is recommended to use phase trans fer catalysts or crown ethers as catalysts.  

The reaction is generally carried out at 0 to 200 ° C., preferably as at 20 to 150 ° C, and most preferably at 60 to 120 ° C through.

The reaction is expediently carried out under normal pressure, however one can also work at reduced or increased pressure ten, a pressure range of 1 to 50 bar being preferred.

The response times are usually 1 to 12 hours, usually 2 to 8 hours.

It may be appropriate to implement the implementation using a Solvent. Here are z. B. toluene, Tetrahydrofuran, dioxane, N-methyl-pyrrolidone and dimethyl formamide.

In terms of process engineering, the procedure is usually such that Dialcoholate in the solvent to the reaction temperature heated and in the course of the progressive implementation with the poly oxyalkylene derivative V. After completing the reaction the base is added and again for a while at the one temperature set.

The reaction mixture is worked up in itself known manner, usually by adding an acid for adjusting the pH value, removing the solvent, Extraction of the residue and subsequent drying of the Extract phase.

The polyurethanes according to the invention are produced in in a manner known per se, by stepwise polyaddition from polyvalent isocyanates to polyvalent alcohols. More details are the plastics handbook, vol. VII, "Polyurethane", 1983 and the specialist literature cited therein. As catalysts one usually uses tertiary in the production of polyurethane Amines such as dimethylbenzylamine and organotin compounds such as Tin diethyl hexanoate, dibutyl tin dilaurate and dibutyl tin bis-dodecyl mercaptide.

The polyurethanes of polyvalent isocyanates according to the invention, polyhydric alcohols and, if desired, polyhydric amines are characterized in that the component of the polyvalent Alcohol to 5 to 100 mol% from a diol I or diol II consists.  

Examples of polyvalent isocyanates are aliphatic, alicyclic and aromatic di-, tri- and polyisocyanates in Question.

Preferred diisocyanates are 2,4-bis [isocyanate] toluene, 2,6-bis [isocyanate] toluene, 1,4-bis [2-isocyanatethyl] cyclohexane and 1,3-bis [isocyanatmethyl] cyclohexane.

Particularly preferred diisocyanates are bis- [4-isocyanate-phenyl] methane, 1,6-bis [isocyanate] hexane and 5-isocyanate-3- (isocyanate methyl) -1,1,3-trimethylcyclohexane (isophorone diisocyanate).

Preferred triisocyanates are tris [4-isocyanatphenyl) methane and those from the triisocyanurate series and 2,4,6-trioxo-1,3,5-tris [3-isocyanate-4-methylphenyl] hexahydro-1,3,5-triazine.

Preferred polyhydric alcohols are polyester polyols and above all polyether polyols from alkylene oxides such as tetrahydrofuran, 1,3-propylene oxide or 1,2- and 2,3-butylene oxide and two or trihydric alcohols as starters such as ethanediol, 1,2- and 1,3-propanediol, diethylene glycol and dipropylene glycol.

Polyether polyols from the alkylene oxides are particularly preferred 1,2-propylene oxide and ethylene oxide and the starter trimethylol propane.

In addition, ethylene glycol, glycerol, Sugar alcohols, sugar, polycarbonate polyols and polyoxypropylene polyols.

According to the invention, there is the component of the polyhydric alcohol in the polyurethanes from 5 to 100 mol% from one of the diols I or II. The alcohol component preferably contains 5 to 50 mol% of diol I or diol II.

It may be appropriate to use polyvalent chain extension Amines to form urea bridges for manufacturing to use the polyurethanes of the invention.

Examples of such multivalent amines are diethyltoluylene diamine, 4,4′-diamino-3,3′-dichloro-diphenyl-methane, 3,5-diamino-4- Isobutyl chlorobenzoate, hexamethylenediamine and 1-amino-3- aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine).

The polyurethanes according to the invention are used to produce Shaped bodies and coatings and can vary depending on use purpose contain the usual auxiliary substances. Such auxiliaries are  for example foam stabilizers, hydrolysis and oxidation stabilizers, UV stabilizers and blowing agents, flame retardants medium, dyes, fillers and reinforcing agents such as ins special glass fibers.

In general, the polyurethanes according to the invention are notable good processing properties such as a favorable low temperature behavior.

Examples

The average molecular weight was determined osmometrically.

The OH number was determined by the acetylation of the invention Compounds with the system pyridine / acetic anhydride / diazabicyclo octane and the subsequent titration of the applied acet excess anhydride by means of aqueous alkali hydroxide solution certainly. The dimension of the OH number is mg KOH / g substance.

example 1 Implementation of poly-tetrahydrofuran bismesylate with 1,4-dioxa-3,6-dihydroxy-bicyclo [3.3.0] octane bis-alcoholate

43.2 g (0.29 mol) of 1,4-dioxa-3,6-dihydroxy-bicyclo [3.3.0] octane were reacted with 31.9 g (0.58 mol) of sodium methoxide in 1000 ml of toluene to give the dialcoholate. After removal of the toluene and addition of 500 ml of dimethylformamide, the mixture was heated to 80 ° C., and 189.1 g (0.39 mol) of poly-tetrahydrofuran bismesylate V ("poly-THF 250 '' = poly-THF of molecular weight 250, corresponds to m ∼ 3. After a period of 4 hours, 39.0 g (0.19 mol) of 20% sodium hydroxide solution were added and the mixture was stirred again for one hour, after which the solution was dissolved in 13 ml of concentrated acetic acid the pH was adjusted to 5 and the dimethylformamide was distilled off, the residue was taken up in 200 ml of n-butanol and 200 ml of water, the aqueous phase was extracted twice with n-butanol and the combined organic phases were finally dried received Diol II as an oil in a yield of around 88%.
Analyzes:
OH number: 185
MG: 605
Freezing point: ∼ 10 ° C.

A practically the same product was made using Obtained sodium hydride instead of sodium methoxide.  

The diol was ideal for the production of poly urethanes.

Example 2 Reaction of poly-tetrahydrofuran with 1,4-dioxa-3,6-dihydroxy bicyclo [3.3.0] octane bischloroformate

21.8 g (0.087 mol) of poly-tetrahydrofuran III ("Poly-THF 250 '') and 13.9 g (0.138 mol) of triethylamine were heated to 45 ° C and with a solution of 17.4 g (0.0642 mol) of 1,4-dioxa-3,6-dihydroxy bicyclo [3.3.0] octane bischloroformate IV in 50 ml of toluene within of 1 hour in the feed process. Then became Completion of the implementation at the reak another 3 hours tion temperature kept.

The usual work-up gave the diol I as a light oil in a yield of 100%.
Analyzes:
OH number: 112
: 1000.

The diol was ideal for the production of poly urethanes.

Claims (13)

1. Diols of the general formula I in which the variables have the following meaning:
A is an unsubstituted or a tetramethylene group substituted by 1 or 2 C₁ to C₄ alkyl groups;
Z the bis-yloxy residue of a mono- or disaccharide group or sugar alcohol group, the remaining hydroxyl groups of which are protected as ethers, esters or acetals;
m has a value from 2 to 150;
n a value from 1 to 150. 2. Diols according to claim 1, in which the variables have the following meaning:
A is an unsubstituted tetramethylene group;
Z the bis-yloxy residue of a mono- or disaccharide group or sugar alcohol group, the remaining hydroxyl groups of which are protected as ethers, esters or acetals;
m has a value from 3 to 70;
n has a value from 1 to 20. 3. Diols according to claim 1 or 2, in which Z is the 1,4-dioxa-3,6-bisyloxy-bicyclo [3.3.0] octane group of the formula derived from the sugar alcohol sorbitol by etherification is. 4. Diols of the general formula II in which the variables have the following meaning:
A is an unsubstituted or a tetramethylene group substituted by 1 or 2 C₁ to C₄ alkyl groups;
Z the bis-yloxy residue of a sugar alcohol, mono- or disaccharide group, the remaining hydroxyl groups of which are protected as ethers, esters or acetals;
m has a value from 2 to 150;
n a value from 1 to 150. 5. Diols according to claim 4, in which the variables have the following meaning:
A is an unsubstituted tetramethylene group;
Z is the bis-yloxy residue of a sugar alcohol group, the remaining hydroxyl groups of which are protected as ethers, esters or acetals;
m has a value from 3 to 70;
n has a value from 1 to 20. 6. Diols according to claim 4 or 5, in which Z is the 1,4-dioxa-3,6-bisyloxi-bicyclo [3.3.0] octane group of the formula derived from the sugar alcohol sorbitol by etherification is. 7. A process for the preparation of the diols I according to claims 1 to 3, characterized in that a polyoxyalkylene glycol of the general formula III in which A and m have the meaning given in Claims 1 and 2, with the amount of a dichloroformate of the general formula IV defined to produce the desired degree of condensation n in which Z has the meaning given in claims 1 to 3, in the presence of a base. 8. A process for the preparation of the diols II according to claims 4 to 6, characterized in that a polyoxyalkylene glycol derivative of the general formula V in which A and m have the meaning given in Claims 4 and 5 and X is a nucleophilically substitutable leaving group, with the amount of an alkali metal dialcoholate of a mono- or disaccharide or of a sugar alcohol, the amount of which is defined to produce the desired degree of condensation, the remaining hydroxyl groups are protected as ethers, esters or acetals, and the terminal groups X of the reaction product are converted into hydroxyl groups with a base in a manner known per se. 9. Polyurethanes from polyvalent isocyanates, polyvalent Alcohols and, if desired, polyvalent amines, thereby characterized in that the component of polyhydric alcohol 5 to 100 mol% of a diol I according to the claims 1 to 3 or from a diol II according to claims 4 to 6 consists.   10. Polyurethanes according to claim 9, in which the polyvalent Isocyanate bis- [4-isocyanatphenyl] methane, 1,6-bis- [iso cyanate] hexane or 5-isocyanate-3- (isocyanate methyl) -1,1,3- is trimethylcyclohexane. 11. Polyurethanes according to claim 9 or 10, which in addition to the Diols I or II or 1,2-propylene oxide, ethylene oxide or Trimethylolpropane included. 12. Use of the polyurethanes according to claims 9 to 11 for the production of moldings and coatings. 13. Moldings made of the polyurethanes according to the claims 9 to 11 and counter coated with these polyurethanes stands.