SU602503A1 - Tetrakis-(hydroxyalkyleneoxy) titanium as catalyst of interesterification and polycondensation and method of preparing same - Google Patents

Description

polycondensation in the preparation of a range of polyesters, for example, polydiethylene alpha marate, polyethylene succinate and polyethylene terephthalate.

The table shows the conditions for the preparation of polyesters in the presence of tetrakis (hydroxyalkyleneoxy) titanium. As follows from the tables received

The novel compounds catalyze both the polyesterification reaction and the polycondensation reaction. Reakic at both stages proceeds relatively quickly (no more than 2.5 hours), at low temperatures. The polyesters obtained contain a small amount (mea 1%) of OH groups.

1 Diethyl fumarate Tetrakis Diethylene - (hydroxyglycol diethyleneHyroquinoneoxy) titanium 0.06 150-170 195-210

I Dimethyltere-Tetrakisphthalate (hydroxytriene, ethylene glycol oxy) -titan 0.05 180-210 260-280

The molar ratio of I: II everywhere 1

The main advantage of the proposed: compounds as a catalyst for the production of polyesters is that they can be used immediately without hydrolysis, which simplifies the process.

A known method for producing titanium diglycols by reacting alkyl orthotitanium with glycols of the formula HO-C-CH -) - OH, where is -2-6.10 at a temperature of 80-220 ° C ZD.

The products obtained by this method are insoluble, non-meltable powders or glassy solid insoluble substances that easily soften when heated. With etch, the reaction proceeds, depending on the starting glycol, only by 44-81% (according to the liberated alcohol).

The proposed method for the preparation of tetrakis- (hydroxyalkyleneoxy) titanium is that the alkyl orthotitanate is reacted with a glycol of the formula HORH where 1 is -CH2CH20 -) (, P "1, 2, 3 at 2080 ° C, molar ratio in organic solvent These organo-titanium compounds are prepared under the usual instrumental conditions adopted when working with methylorganic compounds using organic solvents such as methyl chloride.

0.94

thirty

60

0.31

G20

thirty

butyl orthotitolate is used predominantly in the alkylortotitan class. The reaction with ethylene glycol is carried out at room temperature (20-25 ° C), with other glycols at elevated temperatures (40-;). Removal of the solvent and the alcohol formed in the reaction is carried out by vacuum distillation. The desired product is obtained with a 100% -HtM yield.

The resulting tetrakis (hydroxyalkens of lenoxy) titans are viscous, transparent resins, light yellow, soluble in alcohols, glycols, pyridine, insoluble in diztile ether, benzene, dioxane. The only exception is the first homologue of this series, tetrakis (hydroxyethyl) and titanium, which is obtained as a colorless transparent glassy substance insoluble in pyridine, ethanol, methylene chloride.

The composition and structure of tetrakis- (hydroxyalkyleneoxy) titans are confirmed / denoted by elementary analysis, using IR-ray spectroscopy.

Example. Tetrakis- (hydroxyethylenoxy) titanium.

The synthesis is carried out under conditions that exclude moisture from the air.

Claims (3)

To 3.24 g (0.0522 mol) of ethylene glycol in 20 ml of methylene chloride, 4.44 g (0.017305 mol) of butyl orthotitanium are added dropwise. The mixture is stirred at room temperature for 3 hours. Then the solvent and the butyl alcohol resulting from the reaction are gradually distilled off with a gradually increasing vacuum. The product is dried to constant weight at room temperature in a vacuum of 2-3 mm Hg. 3.83 g (100%) of a transparent, colorless glassy substance, insoluble in methylene chloride pyridine, ethanol is obtained. Found,%: C 32.65; H 6.86; Ti 16.61. Holy GoT. Calculated,%: C, 32.89; H, 6.90; Ti 16.40. PRI mme R 2. Tetrakis- (hydroxy diethylenoxy) titanium. The synthesis is carried out under conditions that exclude moisture from the air. A solution of 11.4 g (0.1072 mbl) of diethylene glycol in 30 m of methylene chloride is poured into 9.1 g (0.0268 mol) of butyl orthotitanium, the mixture is stirred and heated at 40 ° C for 2 hours. Then, with a gradually increasing vacuum, the solvent is distilled off and the butyl alcohol formed as a result of the reaction is dried. The product is dried to a constant weight of br 60-80 ° in a vacuum of 3-4 mm Hg. 12.6 g (100%) of the substance are obtained in the form of a viscous transparent resin of light yellow color, soluble in alcohols, glycol, methylene chloride, pyridine, insoluble in diethyl ether, beola, dioxane. Found,%: C 40.99; H 7.89; Ti 10.26.Ci6 j60 «-Ti Calculated,% t С 41,10; H 7.70; PM 10.28. Example Tetrakis- (hydroxyriethylenoxy) titanium. The synthesis is carried out analogously to example 2. 10.8 g (0.0720 mol) of triethylene glycol dissolved in 30 ml of methylene chloride are poured into 6.1 g (0.0180 mol) of butyl orthotitanate. 11.6 g (100%) of the substance is obtained in the form of a viscous transparent resin of a light yellow rip, soluble in alcohols, glycols, pyridine, insoluble in diethyl ether, benzene, dioxane. Found,%: C 44.47; H 8.60; T-f 7.16. Cr4H52 ° 1b Calculated,%: C 44.72; H 8.13; TI 7.43. Claim 1. Tetrak is (hydrostatin and oleoic) titanium of the general formula T: ((OTc) 4, where T is C-CHjCHjO-) n, 2 or 3, as a catalyst for transesterification and polycondensation. 2. A method of producing compounds POP.1, characterized in that the alkyl orthotitanate is subjected to reaction with a glycol of the general formula HORH, where R C — CH 2 CH 20 -) n, an ”1.2 or 3, at a temperature of 20-80 ° C at a molar ratio of 1 ; 4 in the environment of an organic solvent. Sources of information, taking into account in the examination: 1. Author's certificate of the USSR 417448, cl. C 08 5 63/52, 1974. 2.Japanese patent tt 14235, cl. .26 D 6. 1968. S-ieEuzacebe A., AA-Orthotiianate ioEcohoEeet 3e and pst-ocatechine.BotC-Soc. him.de France, 96i, 3.Si7.