SU973551A1 - Process for producing oligourethane epoxydes - Google Patents

Description

This invention relates to the synthesis of polyurethane epoxides, which can be used to produce optically active films, adhesives and binders, as well as structuring additives or modifiers of polymeric materials.

A known method for producing urethanes with terminal epoxy groups is carried out by reacting polyols, diisoctanates and epoxy alcohols. As polyols, simple and complex oligoesters C are used. However, the synthesized oligourethane epoxidises are linear compounds containing no more than 2 epoxy groups per oligomer macromolecule, which does not provide a high crosslink density per unit volume, and, consequently, high strength properties.

The closest in technical essence to the present invention is a method for producing oligourethane epoxides by reacting a diisocyanate with a polyol and glycidol in the presence of an organotin catalyst. The resulting oligourethane epoxides can be used to obtain polymers of f2j.

However, they do not possess optical activity.

The purpose of the invention is to impart optical activity to the polymers obtained on the basis of oligourethane epoxides.

Said object is achieved in that in the preparation oligouretanzpoksi10 rows diizotsiana .ta by reacting a polyol and glycidol in the presence of an organotin catalyst is used as a polyol levoglyukaean oksipropi15-insulated or its derivatives, and reacting the diisocyanate with levoglyukazanom or its derivatives oksipropilirovynnymi osusaestvl dissolved to a conversion degree of NCO-groups equal to 50 ± 1% 20 in the environment of dioksan at 30-6O C.

Levogluko is used as a hydroxyl-containing compound, occupied (1) or its oxypropylated derivative (I):

25

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CIS9

n he

thirty

(eleven)

(one)

w R-fcHj-dH-o n

L I Jn

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1,6-hexamethylene diisocyanate or 2,4-toluene diisocyanate is used as isocyanates. The reaction proceeds in the presence of organotin catalysts at a concentration of: 2, 2, mol / l. The ratio of the INSPECTION of the compounds (in mol x) of levoglucosane, diisocyanate, and glycidyl alcohol is 1: 3: 3-1: 3: 6, respectively. Purification of the final products is performed by reprecipitation from dioxane solution to diethyl ether.

Oligourethane epoxides are powdered or waxy products containing from 6 to 15% epoxy groups having a specific BpameHHelJo J. (in acetone} from -12 to -30. Characteristic absorption bands according to IR spectra: 910 cm epoxy, 1735 cm - urethane group. The resulting products are cured with maleic anhydride and various amine compounds, for example, polyethylene polyamine, capable of opening an epoxy ring.

Example 1. In a three-necked flask equipped with an EHR cooler, a dropping funnel and a mechanical stirrer, 6.48 g (0.04 mol) of levoglucosane, 80 f / ui absolute dicosan are placed, the contents are heated to, 2-10 mol / l of catalyst is added {diethyl di-laurinate tin) and pour 17.08 mp (0.12 mol) Rolliol diisocyanate. The reaction is carried out until the conversion of NCO-groups is 50%. Next, 7.95 ml (0.12 mol) of glycidyl alcohol is added and the reaction is continued until all free NCO-groups are completely consumed. The reaction mixture is cooled and precipitated into diethyl ether. The precipitate is filtered, washed and dried to a constant weight. Output - 32.5 g (90.0%), Mm-1440, the content of epoxy groups - 10.20%, specific rotation (in acetone) With 3-18.0 °.

Example 2. According to the procedure of Example 1, 6.48 g (0.04 mol) of levoglucosane, 80 ml of absolute dioxane, containing 5e are heated to a flask, 2-1СГ mol of catalyst (tin diethyldyl uurinate) are added, 19.38 ml are added (0.12 lgol) of hexamethylene diisocyanate and the reaction is carried out until the conversion of the NCO-groups is 50%. Next, 8.75 ml (0.12 mol) of glycidyl alcohol is added and the reaction is continued until the free NCO-groups disappear. Purification of the products is carried out as in Example 1. The yield is 29.1 g (80.1%), the content of epoxy groups is 10.53%. specific rotation (in dioxane) "-17,2.

Example 3. According to the procedure of Example 1, 1.62 g (0.01 mol) of levoglucosane, 20 ml of absolute dicosane are placed in a flask, the contents are heated with 40®, 4.27 ml (0.03 mol) of toluene diisocyanate and 2-10 mol are added / l of catalyst (tin dithyl dilurinate). The reaction is brought to the conversion of MCO-groups equal to 50%. Next, 5.00 ml (0.07 mol) of glycidyl alcohol is added and the reaction is continued until the free NCO-groups disappear. Purification of the products is carried out as in Example 1. The yield is 10.9 g (88.0%), Mm - 1940, the content of epoxy groups is 9.39% specific rotation (in acetone), -14.2.

Example 4. According to the procedure of Example 1, 30 g (0.09 mol) of hydroxypropylated levoglucosane with a molecular weight of 300.50 ml of dioxane and 38.2 ml (0.27 mol) of 2,4-toluene diisocyanate are placed in a flask. Mol / l of catalyst (tin diethyldylurinate), the contents of the flask are heated to 60 and the reaction is carried out until the conversion of the NCO groups to 50%. Next, 17.8 ml (0.27 mol) of glycidyl alcohol is added and the reaction is continued until complete free MSO groups disappear. Cleaning products is carried out as in example 1. Output 94.0 g (97.5%) Mm - 1550, the content of epoxy groups is 9.06%, the specific rotation (in acetonum) GO / J2o is 10.9.

Example 5. According to the procedure of Example 1. 30 g (0.09 mol) of hydroxypropylated levoglucosane with a molecular weight of 330, 60 ml of absolute dioxane are placed in a flask, the contents are heated to 60, 2-10 mol / g of catalyst (tin diethyldyl dialurinate) are added , 43.6 ml (0.27 mol) of glycidyl alcohol is added and the reaction is continued until the free NCO groups disappear. the products are cleaned as in example 1. The yield is 82.4 g (88.3%), the content of epoxy groups is 9.66, the specific rotation (in dioxane) |: o; j ° -11.3.

Claims (2)

Example 6. According to the procedure of Example 1, 16.5 (0.033 mol) of hydroxypropylated levoglucosane with a molecular weight of 500.60 ml of absolute dioxane are placed in a flask, the contents are heated to 60, 210 mol / l of catalyst (tin diethyldyl dialurinate) are added and 14 are poured 26 ml (0.10 mol) of toluene diisocyanate. The reaction is carried out until the conversion of HC07Group is 50%. Next, 6.64 ml (0.10 mol) of glycidyl alcohol is added and the reaction is continued until the free NCO-rpynn disappears completely. Purification of the products is carried out as in Example 1, Yield 44, 6 g (86.9%), the content of epoxy groups is 7.21%, Mm - 1940, specific rotation (in acetone) CofJ -8.1 ° Example 7 According to the procedure of Example 1, 20 g (0.024 mol) of hydroxypropyl levoglucoean with a molecular weight of 840, 35 ml of absolute dioxane are placed in a flask, the contents are heated to 40, the catalyst (tin diethyldyl-dilurinate tin) is added and 10.4 ml (0.072 ml) are added. they say) toluylenediisodianata. The reaction is carried out until the conversion of NCO-rpynn is 50%. Next, 4.86 ml (0.073 mol) of glycidyl alcohol is added and the reaction is continued until the free NCO-rpynn is completely dissolved. After completion of the reaction, the solvent is distilled off. The yield is 38.2 g (99.8%), the content of epoxy groups is 6.81%. Example 8. A solution of the product obtained according to example 2, dissolved in 6 ml of acetone, was added 0.327 g of hexamethylenediamine and the film was cast. After removal of the solvent, the film is left for 18 hours at room temperature and then maintained at POR for 3 hours. Film properties: 163 kg / cm 135, specific rotation -15.2 °. Thus, the proposed method of producing oligourethane epoxides makes it possible to obtain polymers q with predetermined optical activity, and also expands the raw material base for their synthesis by using the left-glucosane product of thermal depolymerization of wood and plant waste as the hydroxyl-containing component. The method of obtaining oligourethane epoxides by reacting a diisocyanate with a polyol and glycidol in the presence of an organotin catalyst, characterized in that, in order to impart optical activity to the polymers obtained on the basis of the oligourethane epoxides, as a polyol, they are used to act on the current patterns, to go to the target, if you are using the polyol used to obtain optical activity of the polymers obtained on the basis of oligourethane epoxides its hydroxypropylated derivatives are carried out to a degree of conversion for N CO-groups of 50 ± 1% in dioxins Points on at Bo C. Sources of information received note in the examination 1.Patent US 3828005, cl. 260-77.5, publ. 1974. 2. USSR author's certificate number 283569, cl. C 08 G 18/62, 1967 (prototype).