RU2089554C1 - 1,3,5-trimethyl-1,3,5-tres (hexafluoroalkyl) cyclotrisiloxanes for preparing thermo- and oil resistant fluorine containing siloxane polymers - Google Patents

Abstract

FIELD: synthetic rubber industry, more particularly manufacture of fluorine containing siloxane polymers. SUBSTANCE: present invention describes 1,3,5-trimethyl-1,3,5-tris (hexafluoroalkyl) cyclotrisiloxanes of general formula: [R_fSi(CH₃)O]₃ wherein R_f is

Description

которые могут использоваться как промежуточные соединения в синтезе фторсилоксановых полимеров, применяемых для изготовления резино-технических изделий, использующихся в кабельной, авиационной, автомобильной и других отраслях промышленности.The invention relates to organosilicon compounds, and in particular to the field of fluorine-containing cyclotrisiloxanes of the general formula:
[R _f Si (CH ₃ ) O] ₃
Where

which can be used as intermediate compounds in the synthesis of fluorosiloxane polymers used for the manufacture of rubber products used in cable, aviation, automotive and other industries.

где n 1-10
(пат. ФРГ 3.248.546А1, СА, 101, 172333 F, 1984), получаемые гидролизом соответствующих (полифторалкил)метилдихлорсиланов. По данным (Pierce O.R. Holbrook G.W. Iohannson O.K. Ind. Eng.Chem. 1960, 52, 783-784), полимеры на основе данных циклосилоксанов обладают хорошей маслобензостойкостью - набухание в толуоле за 24 ч при 20 ^oC составляет 21 25 об. Однако термостойкость таких полимеров невысока, так, по данным авторов настоящей заявки, 13 -я потеря в весе наступает уже при 200 ^oC.Known 1,3,5-trimethyl-1,3,5 tris (polyfluoroalkyl) cyclotrisiloxanes of the General formula:

where n 1-10
(US Pat. Germany 3.248.546A1, CA, 101, 172333 F, 1984) obtained by hydrolysis of the corresponding (polyfluoroalkyl) methyldichlorosilanes. According to (Pierce OR Holbrook GW Iohannson OK Ind. Eng. Chem. 1960, 52, 783-784), polymers based on these cyclosiloxanes have good oil and petrol resistance - swelling in toluene for 24 hours at 20 ^o C is 21 25 vol. However, the heat resistance of such polymers is low, so, according to the authors of this application, the 13th weight loss occurs already at 200 ^o C.

получаемый гидролизом соответствующего 2,2,3,3-циклобутилметилдихлорсилана. Однако полимер, полученный на основе данного циклотрисилоксана, обладает недостаточной маслобензостойкостью. Так, по данным авторов настоящей заявки, набухание в толуоле за 24 ч при 20 ^oC составляет 38 39 об.Known 1,3,5-trimethyl-1,3,5 tris (2 ', 2', 3 ', 3'-tetrafluorocyclobutyl) cyclotrisiloxane (US Pat. UK 706 201, CA, 51, 14796i, 1957) of the formula

obtained by hydrolysis of the corresponding 2,2,3,3-cyclobutylmethyldichlorosilane. However, the polymer obtained on the basis of this cyclotrisiloxane has insufficient oil and petrol resistance. So, according to the authors of this application, the swelling in toluene for 24 hours at 20 ^o C is 38 39 about.

(Iarrant P. Dycker G.W. Dunmire R. Butler G.B. JACS, 79, 6536, 1957), получаемый гидролизом соответствующего (3,3,3 - трифторпропил)метилдихлорсилана с выходом 30 Полимер на основе данного циклотрисилоксана обладает хорошей маслобензостойкостью: набухание в толуоле за 24 ч при 20 ^oC составляет 21 об. (Pierce O.R. Hopbrook G.W. Johannson O.K. Ind. Eng. Chem. 1960, 52, 783-784). Однако по данным (Коршак В.В. Термостойкие полимеры, М. "Наука", 1969, с.78), термостойкость их невысока: 13-я потеря в весе наступает при 270 ^oC, интервал рабочих температур от -68 ^oC до +205 ^oC (там же, с.338).The closest analogue in its purpose to the proposed compounds is 1,3,5-trimethyl-1,3,5-tris (3,3,3 trifluoropropyl) cyclotrisloxane of the formula:

(Iarrant P. Dycker GW Dunmire R. Butler GB JACS, 79, 6536, 1957) obtained by hydrolysis of the corresponding (3,3,3 - trifluoropropyl) methyldichlorosilane in 30 yield. The polymer based on this cyclotrisiloxane has good oil resistance: swelling in toluene for 24 h at 20 ^o C is 21 vol. (Pierce OR Hopbrook GW Johannson OK Ind. Eng. Chem. 1960, 52, 783-784). However, according to (Korshak V.V. Heat-resistant polymers, M. "Nauka", 1969, p. 78), their heat resistance is low: the 13th weight loss occurs at 270 ^o C, the temperature range from -68 ^o C to +205 ^o C (ibid., P. 338).

 The aim of this invention is the synthesis of available fluorine-containing alkylmethylcyclotrisiloxanes that can be used to obtain polymers that combine high heat resistance and good oil and oil resistance.

 This goal is achieved by the synthesis of compounds of General formula I.

The compounds described are obtained by hydrolysis of the corresponding methyl (hexafluoroalkyl) dichlorosilanes with sodium bicarbonate in the presence of pyridine in a molar ratio of reactants 1 1 1 in acetone at 20 - 25 ^° C. The reaction mixture is stirred for 3 hours, after which the precipitate of the salts is filtered off, the acetone and vacuum are removed. rectification emit the target product. The output is 50-60
The composition and structure of the obtained compounds are confirmed by elemental analysis and ¹ H, ¹⁹ F and ²⁹ Si NMR spectroscopy. All assignments are based on (Emsley J. Finney J. Sutcliff L. High Resolution NMR Spectra, T.1.2. M. Mir, 1968). The starting methyl (hexafluoroalkyl) dichlorosilanes are obtained by hydrosilylation of the corresponding hexafluoroolefins with methyldichlorosilane at a molar ratio of reactants 1: 1.05-1.25, respectively, in the presence of a Spyer catalyst at 150 ^° C.

Example 1. In a 1 L flask equipped with a stirrer, dropping funnel and thermometer, 84 g (1 mol) of NaHCO ₃ , 79.1 g (1 mol) of pyridine and 420 ml of acetone are placed. 235 ml (319 g, 1 mol) of methyl- (2,2,3-trifluoro-3-trifluoromethylcyclobutyl) ethyl dichlorosilane in 80 ml of acetone are added to the mixture over 1 h at 20-25 ^° C with stirring. The mixture is then stirred for another 3 hours, filtered off from the salt precipitate, acetone is distilled off in a water bath and 251 g (95) of the hydrolyzate are obtained. Cyclotrisiloxane is isolated by vacuum distillation. 132 g (50) of the expected product are obtained. T bale. 220 ^o C / 2 mm Hg n $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{d}}$ 1.3950, d $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{4}}$ 1.3632.

 Calculated, Si 10.94; C 36.23; F 43.03; O 6.03; H 3.77.

 Found Si 10.95; C 36.15; F 43.11; O 6.10; H- 3.90.

 Mol.weight 265.

¹⁹ F NMR spectrum (in (CD ₃ ) ₂ CO, δ ppm): 73.87 (3F, 3-CF ₃ ).

AV spectrum: d _A -100.25, δ _B -116.67, J _AB 228 Hz (2 F, 2-CF ₂ ); 170.67 (1F, 3-CF).

¹ H NMR spectrum (in (CD ₃ ) ₂ CO, δ ppm): 0.45 (3H, Si-CH ₃ ), 0.64 (2H, 1-CH ₂ ), 1.4 (2H, 2-CH ₂ ); 1.65 (1H, 1'-CH); 2.18 (2H, 4'-CH ₂ ).

NMR spectrum ²⁹ Si (in (CD ₃ ) ₂ CO s (a _c a _c ) ₃ Cr, d ppm) -9.51 and -9.61 (cis and trans isomers).

и представляет собой 1,3,5-триметил-1,3,5-трис-(2-(2',2',3'-трифтор-3'-трифторметилциклобутил)этил)циклотрисилоксан.According to the analysis, the isolated compound corresponds to the formula I-1,

and represents 1,3,5-trimethyl-1,3,5-tris- (2- (2 ', 2', 3'-trifluoro-3'-trifluoromethylcyclobutyl) ethyl) cyclotrisiloxane.

Example 2. In a 1 L flask equipped with a stirrer, dropping funnel and thermometer, 84 g (1 mol) of NaHCO ₃ , 79.1 (1 mol) of pyridine and 420 ml of acetone were placed. 235 ml (319 g, 1 mol) of methyl (2,3,3-trifluoro-2-trifluoromethylcyclobutyl) ethyl dichlorosilane in 80 ml of acetone are added to the mixture over 1 hour at 20-25 ^° C with stirring. The mixture is then stirred for another 3 hours, filtered off from the salt precipitate, acetone is distilled off in a water bath and 251 g (95) of the hydrolyzate are obtained. Cyclotrisiloxane is isolated by vacuum distillation. 132 g (50) of the expected product are obtained. T _bale. 220 ^o C / 2 mm Hg n $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{d}}$ 1,3951, d $\genfrac{}{}{0ex}{}{\text{twenty}}{\text{4}}$ 1,363.

 Calculated, Si 10.94; C 36.23; F 43.03; O 6.03; H 3.77.

 Found, Si 10.81; C 36.16; F 43.08; O 6.00; H 3.84.

 Mol.weight 265.

¹⁹ F NMR spectrum (in (CD ₃ ) ₂ CO, δ ppm): 78.58 (3F, 2-CF ₃ ).

AB spectrum d _A -105.26, δ _B -105.72, _AB 225.5 Hz (2F, 3-CF ₂ ), 193.7 (1F, 2-CF).

¹ H NMR spectrum (in (CD ₃ ) ₂ CO, δ ppm)
0.44 (3H, Si-CH ₃ ), 0.63 (2H, 1-CH ₂ ), 1.41 (2H, 2-CH ₂ ); 1.66 (1H, 1'-CH); 2.2 (2H, 4'-CH ₂ ).

NMR spectrum of ²⁹ Si (in (CD ₃ ) ₂ CO, Cr (a _c a _c ) ₃ , d ppm) -9.54 and 9.63 (cis and trans and isomers).

и представляет собой 1,3,5-триметил-1,3,5 - трис-(2-(2',3',3'-трифтор-2'-трифторметилциклобутил)этил)циклотрисилоксан.According to the analysis, the isolated compound corresponds to the formula I-2, where

and represents 1,3,5-trimethyl-1,3,5-tris- (2- (2 ', 3', 3'-trifluoro-2'-trifluoromethylcyclobutyl) ethyl) cyclotrisiloxane.

Example 3. In a 1 L flask equipped with a stirrer, dropping funnel and thermometer, 84 g (1 mol) of NaHCO ₃ , 79.1 g (1 mol) of pyridine and 420 ml of acetone are placed. To the mixture, 228 ml (331 g, 1 mol) of methyl (3,4,4-trifluoro-3-trifluoromethylbicyclo [2.2.1 ^2.5 ] heptyl) dichlorosilane is added over 1 hour at 20-25 ^° C while stirring. in 80 ml of acetone. The mixture is then stirred for another 3 hours, filtered from a precipitate of salts, acetone is distilled off in a water bath and 262 g (95) of hydrolyzate are obtained. Vacuum distillation emit cyclotrisiloxane. 166 g (60) of the expected product are obtained. T _bale. 250 ^o C / 2 mm Hg T _pl. 55 ^o C.

 Calculated, Si 10.47; F 41.16; C 38.98; H 3.61; O 5.78.

 Found, Si, 10.40; F 41.28; C 38.81; H 3.52; O 5.62.

 Mol.weight 277.

¹⁹ F NMR spectrum (in (CD ₃ ) ₂ CO, δ ppm): 76.18 (3F, 3-CF ₃ ).

AB spectrum d _A -110.08, δ _B -110.61, J _AB 253 Hz (2F, 4-CF ₂ ), -180.95 (1F, 3-CF).

¹ H NMR Spectrum (in (CD ₃ ) ₂ CO, δ, ppm): 0.9 (3H, Si-CH ₃ ), 1.78 (2H, 7-CH ₂ ), 2.00 (2H 6-CH ₂ ), 2.18 (1H, 1-CH), 2.82 (2H; 2-CH, 5CH).

NMR spectrum of ²⁹ Si (in (CD ₃ ) ₂ CO c Cr (a _c a _c ) ₃ , d ppm): -10.28 and 10.75 (cis and trans isomers).

и представляет собой 1,3,5-триметил-1,3,5-трис -(3',4',4'-трифтор-3'-трифторметилбицикло[2.2.1^2,5] гептил)циклотрисилоксан.According to the analysis, the allocation corresponds to the formula I-3, where

and represents 1,3,5-trimethyl-1,3,5-tris - (3 ', 4', 4'-trifluoro-3'-trifluoromethylbicyclo [2.2.1 ^2,5 ] heptyl) cyclotrisiloxane.

Example 4. In a 1 L flask equipped with a stirrer, dropping funnel and thermometer, 84 g (1 mol) of NaHCO ₃ , 79.1 g (1 mol) of pyridine and 420 ml of acetone are placed. To the mixture was stirred for 1 hour at 20-25 ^o C with stirring was added 228 mL (331 g, 1 mole) of methyl (3,3,4-trifluoro-4-triftormetilbitsiklo [2.2.1 ^2.5] heptyl) dichlorosilane in 80 ml of acetone. The mixture is then stirred for another 3 hours, filtered from a precipitate of salts, acetone is distilled off in a water bath and 262 g (95) of hydrolyzate are obtained. Vacuum distillation emit cyclotrisiloxane. 166 g (60) of the expected product are obtained. T _bale. 250 ^o C / 2 mm RT. Art. T _pl. 55 ^o C.

 Calculated, Si 10.47; F 41.16; C 38.98; H 3.61; O 5.78.

 Found Si 10.41; F 41.24; C 38.79; H 3.50; O 5.64.

 Mol.weight 277.

¹⁹ F NMR spectrum (in (CD ₃ ) ₂ CO, δ ppm): 75.4 (3F, 4-CF ₃ ),
AB spectrum d _A -120.9; δ _B -121.40, J _AB 252 Hz, (2F, 3-CF ₂ ), 178.4 (1F, 4-CF).

¹ H NMR spectrum (in (CD ₃ ) ₂ CO, δ, ppm): 0.91 (3H, Si-CH ₃ ), 1.80 (2H, 7-CH ₂ ); 2.05 (2H, 6 CH ₂ ), 2.30 (1H, 1-CH), 3.01 (2H; 2-CH, 5-CH).

²⁹ NMR spectrum (in (CD ₃ ) ₂ CO c Cr (a _c a _c ) ₃ , d ppm): -10.25 and 10.80 (cis and trans isomers).

и представляет собой 1,3,5-триметил-1,3,5-трис-(3',3',4'-трифтор-4'-трифторметилбицикло[2.2.1.^2,5]гептил) циклотрисилоксан.According to the analysis, the isolated compound corresponds to the formula I-4, where

and represents 1,3,5-trimethyl-1,3,5-tris- (3 ', 3', 4'-trifluoro-4'-trifluoromethylbicyclo [2.2.1. ^2.5 ] heptyl) cyclotrisiloxane.

 The described methyl (hexafluoroalkyl) cyclotrisiloxanes of formula I were used as monomers for the synthesis of methyl (hexafluoroalkyl) polysiloxanes containing a vinyl group.

 The polymers are obtained by polymerization of the corresponding cyclotrisiloxanes with an alkali metal siloxanolate, taken in an amount of 0.004-0.007 wt. calculated on cyclotrisiloxane.

 The table shows the properties of the obtained polymers, as well as polymers based on 1,3,5-trimethyl-1,3,5-tris- (3,3,3-trifluoropropyl) cyclotrisiloxane (IV), 1,3,5-trimethyl- 1,3,5-tris- (polyfluoroalkyl) cyclotrisiloxane (II) and 1,3,5-trimethyl-1,3,5-tris (2,2,3,3-tetrafluorocyclobutyl) cyclotrisiloxane (III).

 As can be seen from the table, the use of methyl (hexafluoroalkyl) cyclosiloxanes of the general formula I allows one to obtain fluorine-containing siloxane polymers with high thermal and oil resistance.

 In addition, the method of synthesis of the claimed compounds is based on a fairly simple technology, does not require expensive solvents and allows you to get the target products with fairly high yields. Thus, the proposed compounds are affordable products and can be used for the industrial production of fluorosiloxane polymers.

Claims (1)

1. 3,5-Trimethyl-1,3,5-tris (hexafluoroalkyl) cyclotrisiloxanes of the general formula
[R _f Si (CH ₃ ) O] ₃
Where

to obtain thermo- and oil-resistant fluorine-containing siloxane polymers.

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