DE1023227B - Process for the production of polyether resins - Google Patents

Description

GERMAN

It is known that aliphatic polyethers containing oxy groups by polymerizing glycide. The polyglycides are viscous to soft resin-like products and are characterized by good solubility, ζ. B. in methanol and acetic acid. Even in cold water they are easily soluble. It is also known that oxacyclobutane and its derivatives, in particular that obtainable from pentaerythritol 3,3-dimethyloltrimethylene oxide, by action polymerize acidic catalysts. This gives highly branched or cross-linked products, which are no longer soluble and no longer meltable. The polymerization of 3-methylol-S-chloromethyltrimethylene oxide also takes place to an insoluble resin. If one wants to be soluble and meltable by this method To produce polyethers, one must either use hydroxyl-free trimethylene oxide compounds or mask existing hydroxyl groups before polymerizing, e.g. B. by reacting the monomer Alcohol with acetone. The acetal groups of the polymer can then be cleaved, if necessary, and so can the hydroxyl groups free again.

It has now been found that new, technically interesting aliphatic polyethers can be obtained by that one polymerizes 3-methylol-3-alkyltrimethylene oxides and the polymers, if appropriate, into functional Derivatives transferred.

In contrast to the polyglycides, the polymerization products of these trimethylene oxide alcohols are proportionate high-melting, usually crystal-clear hard resins, surprisingly in most common Solvents such as water, alcohols, ketones, esters and hydrocarbons, both at room temperature as are also insoluble at elevated temperature. Some high boiling solvents, e.g. B. dimethylformamide, Glycol monomethyl ether, cyclohexanone and monomeric trimethylene oxide alcohols, however, have a some dissolving power, especially at higher temperatures. They are only readily soluble in a few strongly polar solvents, e.g. B. in pyridine, di- and triethanolamine and cresol.

However, the new polymerisation products differ in their property of still being meltable and soluble surprisingly from the known, crosslinked and therefore infusible ones mentioned and insoluble polymerization products derived from other hydroxyl-containing trimethylene oxide compounds have been received.

Trimethylene oxide of the type mentioned, e.g. B. 3-methyl- or S-ethyl-S-methyloltrimethylene oxide, are by reacting the corresponding trimethylolalkanes, for. B. of trimethylol ethane and trimethylol propane, with carbonic acid esters according to patent 950 850 or with phosgene according to patent application F 15 046 IVb / 12q technically particularly easily accessible.

Method of manufacture
of polyether resins

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen

Dr. Karl Raichle, Dr. Hermann Schnell,

Krefeld-Uerdingen,

and Dr. Wolfgang Biedermann, Krefeld-Verberg,
have been named as inventors

The polymerization of the trimethylene oxide alcohols, which proceeds with the opening of the ether ring, is caused by addition acidic catalysts triggered. Suitable for this

z. B. superchloric acid, sulfuric acid, phosphoric acid, cation exchangers, such as the resin obtained by sulfonating a styrene-divinylbenzene copolymer, also catalysts of the Friedel-Crafts type, such as aluminum chloride, tin tetrachloride, antimony pentachloride, Zinc chloride and boron trifmoride. Also the catalysts known for polymerizing tetrahydrofuran and catalyst combinations can be used to advantage. The amount of catalysts to be added fluctuates z. B. between 0.01 and 10 mole percent and depends on their effectiveness.

One can polymerize within a wide temperature range. So you can z. B. at room temperature start and let the reaction proceed with self-heating. In some cases it can also be beneficial be able to polymerize at lower temperatures. By adding an inert diluent the course of the reaction can be moderated. A refluxing diluent can also be used for discharge serve the heat released, whereby certain polymerization temperatures can be set. When using a diluent, the polymer separates out as a rule because, in contrast to the monomer is insoluble in most solvents.

After the end of the polymerization, the catalyst is optionally neutralized by treating the polymer with basic substances such as ammonia, alkali and alkaline earth hydroxides or carbonates, as well as organic Bases, e.g. B. methylamine and pyridine. if

709 850/448

3 4

the neutralizing agent and its reaction product Example 2 are water-soluble with the catalyst, the 3-methyloltrimethylene oxide in 680 parts by weight can be removed from a solution of 1160 parts by weight of 3-ethyl polymer by washing with water. Insoluble substances, on the other hand, are to be separated off by filtration, 10 parts by volume of a molar amount of solute benzene, preferably in the heat and optionally with the addition of a 5 solution of boron trifluoride diethyl etherate in an absolute amount of a solvent. Benzene added with stirring. Then the temperature rises. The products of the process represent a new kind of temperature in the reaction mixture to around 85 °, whereby the plastics, which have thermoplastic properties initially have a thin liquid solution to form a gelatinous, and, for example, deformed by pouring or pressing, solidify. After cooling to 60 ^c will be able to. The crystal clear resins can as such io the reaction mixture for 6 days at this temperature, for. B. can be used for optical purposes and are left suitable. The catalyst is then added to cement glasses, e.g. B. for the production of 500 parts by volume Q.lnormal sodium hydroxide ineffective of. Multilayer glasses or lens systems. made. After the benzene has been distilled off, the raw material is differentiated from plastics by repeatedly boiling with water, advantageously compared to the known epoxy inorganic substances, and from mineralizing, which is often cloudy and usually yellow to brownish Pressure at about 150 ¹¹ completely drained. One is colored, as well as compared to the known ones, receives 1120 parts by weight of a water-insoluble, clearly mentioned at the beginning, comparable, hydroxyl groups transparent, colorless resin with a softening-containing polymeric trimethylene oxide compound, point of 125 ". The hydroxyl number is 500, which is strongly crystallized and white in color 20 Additions of small amounts of water increase the properties of the products at a given rate of merization, while larger waterfalls have an inhibitory effect by adding other cyclic ethers of the same amount Ethylene oxide, with a percentage of water, reaches the polymerization tempepylene oxide, epichlorohydrin and tetrahydrofuran, at the temperature 115 °, and after only one day's residence, the polymerization mixture is modified. By adding 25 at 60 °, practically the same yield. Monomers, the two or more polymerizable ether rings ent hold, e.g. B. 2,6-Dioxaspiro-3,3-heptane, Example 3 can be crosslinked, completely insoluble and infusible products

can be obtained. In this case, a molding can contain 116 parts by weight of S-ethyl-S-methyloltrimethylene oxide only within the period of time during the polymerization are heated to 100 ° and then with stirring

gradually occurring viscous to plastic range 1 part by weight of concentrated sulfuric acid added,

take place. The specified temperature is maintained for 24 hours

Retain the polyethers which are polyhydric alcohols. Obtained after work-up according to Example 1

Like other high molecular weight polyalcohols, you can use 102 parts by weight of hard, water-insoluble resin

z. B. polyvinyl alcohol and cellulose, on a technical basis 35 a relative viscosity of 1.07, measured at 25 ° in

part way into a number of functional derivatives 0.5% cresol solution.

be transferred. So you get z. B. by um-.

Settlement with acid chlorides or anhydrides esters and example 4

with isocyanates urethanes. Others are known per se 116 parts by weight of 3-ethyl-3-methyloltrimethylene oxide The functional derivatives that can be prepared using the th methods are 40 with 10 parts by weight of a cation extract. B. ethers, acetals and xanthates. Here, exchangers can be used sulfonated crosslinked polydies Alcohol groups of the polyethers completely or only styrene in bead form for 8 hours at about 150 ° with stirring partly functionally converted. They can also be heated. After removal of the catalyst by fiI high molecular weight Side chains through implementation of the tration of the reaction hydroxyl groups, which are sufficiently thin at 150 ° with z. B. Ethylene oxide or propylene 45 mixture are volatile components at the same Temoxyd introduce. With the help of polyfunctional fabrics, temperature removed. 30 parts by weight of water are obtained as Dicarboxylic anhydrides, or diisocyanates, leave insoluble resin. It also becomes 82 parts by weight finally hardened, infusible products are produced - unreacted 3-ethyl-3-methyloltrimethylene oxide place. That obtainable by such reactions is recovered. A large number of derivatives make it possible to achieve the properties 50 Example 5 the polyether has a wide variety of uses

adapt. In one with a dry ice-methanol

. cooled reflux condenser equipped reaction vessel

Example 1 are 116 parts by weight of S-ethyl-S-methyloltrimethylene

100 parts by weight of 3-ethyl-3-methyloltrimethylene oxide 55 oxide with 40 parts by volume of liquid methyl chloride

are mixed with 0.15 parts by volume of oO'Yoiger while stirring. With stirring, 1 part by volume of that in Example 2

Superchloric acid combined. Heated catalyst solution used in about 40 minutes was added. The polymer

the reaction mixture to about 60 ° and solidifies to ization begins with boiling of the methyl chloride, and

a clear, transparent mass. This becomes 20 hours after a few hours the contents of the vessel become clear

Leave at the specified temperature and solidify in a transparent mass. Then you work

closing at about 140 ° to neutralize the catalyst according to Example 2 and receives 104 parts by weight of color

sators, while stirring with gaseous ammonia, solid resin with a softening point of 124 °.

acts. It is then distilled while maintaining. .

the temperature of about 140 ° volatile components under Example 6

reduced pressure. 92 parts by weight of 65 102 parts by weight of S-methyl-S-methyloltrimethylene oxide are obtained

of a colorless, hard resin with a softening of 1 part by volume of that used in Example 2

point of 117 °, measured by the mercury method combined catalyst solution. After the end of the

from Krämer-Sarnow. The relative viscosity is merization and work-up according to Example 1 is obtained

1.07, measured at 25 ° in 0.5% cresol solution, the 96 parts by weight of hard, colorless and water-insoluble

Hydroxyl number 505.70 resin with a softening point of 106 °.

Example 7

In a solution of 29 parts by weight of 2,6-dioxaspiro-3,3-heptane in 116 parts by weight of 3-ethyl-3-methyloltrimethylene oxide 0.8 parts by volume of the catalyst solution used in Example 2 are stirred in. After short Time the mixture heats up, the viscosity increasing rapidly. After a few hours one still has deformable colorless and clear transparent resin is formed. By prolonged heating to about 100 ° it will cured to a completely insoluble and infusible resin.

Example 8

To a refluxing mixture of 116 parts by weight of S-ethyl-S-methyloltrimethylene oxide, 22 parts by weight of epichlorohydrin and 40 parts by volume of liquid ethyl chloride are added to 0.2 parts by volume with stirring 60% excess chloric acid added. The mixture has solidified after several hours. After 24 hours working up as in Example 1 with distilling off the ethyl chloride. 98 parts by weight of one are obtained colorless resin with a softening point of 106 ° and a chlorine content of 3.1%.

25 Example 9

550 parts by weight of a resin prepared according to Example 2 are melted at 150 ° and in portions 750 parts by weight of benzoyl chloride are added with stirring. The specified temperature is maintained as long as until the initially vigorous evolution of hydrogen chloride has ended. It is then poured onto ice and rewashed xAoif taking in benzene with water neutral, separates from the aqueous layer, dried and the benzene was distilled off under reduced pressure. 770 parts by weight of a clear, transparent, visibly yellowish color are obtained Resin with a softening point of 68 °. The hydroxyl number is 0, the saponification number is 261. The resin is insoluble in methanol, readily soluble in benzene.

Example 10

In a solution of 10 parts by weight of sodium in 200 parts by weight of anhydrous methanol and 250 parts by weight 220 parts by weight of the resin obtained according to Example 2 are added to anhydrous xylene. Under Stirring, the methanol is first distilled off via a fractionation column until the boiling point is at the top of the column of xylene adjusts. Then, with further stirring at 120 °, 82 parts by weight of benzyl chloride added dropwise to the residue, with etherification occurring with the separation of sodium chloride. After further Stirring for 2 hours at the boiling point of the xylene is then the reaction product by means of steam freed from xylene and volatile organic substances, washed salt-free with water and finally at 120 to 140 ° completely dehydrated under reduced pressure. 237 parts by weight of a partially benzylated one are obtained Haizes with a hydroxyl number of 264.

Example 11

To 200 parts by weight of the obtainable according to Example 11, partially benzylated resin is added 1 part by weight of sodium and ethylene oxide is passed at 140 to 160 ° for this period one until 340 parts by weight are added. A pale brown colored resin is obtained, which in contrast to the partially benzylated resin obtained according to Example 11 is water-soluble.

Claims (1)

PATENT CLAIM: Process for the preparation of polyether resins by polyaddition of cyclic oxy groups Ethers, characterized in that 3-methylol-3-alkyltrimethylene oxides of the polyaddition reaction subject and optionally the reaction products by treatment with esterifying modified or etherifying agents. Considered publications:
U.S. Patent No. 2,462,048;
French patent specification No. 1 065 633. © 709 850/448 1.58