RU2397994C1 - Hydroxymethylolphenyl-organosiloxanes and synthesis method thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry and technology of producing hydroxy-oganosiloxanes. The invention discloses novel hydroxymethylolphenyl-organosiloxanes of general formula R⁵Si(CH₃)₂O[SiR¹R²O]_n[SiR³R⁴O]_m Si(CH₃)₂R⁵, where R¹ is methyl or 3-(4-hydroxy-3-methylol-5-methoxyphenyl)propyl, R² -s methyl, ethyl, phenyl, vinyl, trifluoropropyl, methacryloxypropyl; R³, R⁴ denote methyl; R⁵ is methyl or 3-(4-hydroxy-3-methylol-5-methoxyphenyl)propyl; n-0-20; m=0-400; when n=m=0 R⁵ is 3-(4-hydroxy-3-methylol-5-methoxyphenyl)propyl. The invention also discloses a method for synthesis of the said compounds by reacting corresponding organosilicon phenols with 37% aqueous solution of formaldehyde in an aqueous-alkaline medium at pH 10-12 and temperature 20-60°C in the presence of carbamide in molar ratio of organisilicon phenol, formaldehyde and alkali equal to 1:(1.1-2)f:(1-1.2)f respectively, where f is the number of phenol groups in the phenol and ranges from 1 to 20.

EFFECT: efficient synthesis of novel hydroxy-organosiloxanes, which are suitable for imparting other organic and elementary organic compounds, including copolymers, thermal stability, frost resistance, hydrophobic properties and other valuable properties, and can also be used as a modifier of organic resins and compounds.

2 cl, 1 tbl, 3 dwg, 9 ex

Description

The invention relates to chemistry and technology for the production of hydroxyorganosiloxanes containing simultaneously different substituents at the ends or in the middle of the siloxane chain, including reactive hydroxy groups. Hydroxymethylolphenylorganosiloxanes are expediently used as starting compounds to impart organoelement and organic compounds, including copolymers, heat resistance, frost resistance, hydrophobicity and other valuable properties inherent in hydroxyorganosiloxanes, as well as modifiers of organic resins and compounds.

No information on the obtained and isolated organosilicon compounds containing simultaneously phenolic and methylol (hydroxymethyl) functional groups in the patent documentation and scientific literature was found.

In German patent No. 937555, 1956, NPK 39c / 30, Dow Corning describes a method for producing only organosiloxane phenol-formaldehyde resins based on the products of high-temperature condensation of alkoxysilanes and - siloxanes with organic diphenols and cocondensates of the mixture of phenoxyphenolorganosilane sulfanes obtained or resins with hydrolytically unstable Si-OC bond.

In 1968, in the journal Angewandte Makromolekulare Chemie (v. 4/5, No. 41, pp. 212-254), an article by Greber was published, which provides information on the preparation of copolymers by polycondensation of organosilicon phenols and organic methylolphenols.

Organosilicon phenols and the method for their preparation are also protected by patents: US 4923912 (1990, IPC C08G 59/00/40), Japan - 1887911 (1994, IPC C08L 63/00), Russia - 2211845 (2001, IPC C08G 59/00/40 )

The objective of the present invention is to obtain an effective method of previously unknown hydroxyorganosiloxanes, including both phenolic and methylol functional groups.

The problem is solved in that as a result of the studies we proposed 3- (4-hydroxy-3-methylol-5-methoxyphenyl) propylorganosiloxanes of a new chemical structure corresponding to the general formula

,

,

where R ¹ is methyl or 3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl, R ² is methyl, ethyl, phenyl, vinyl, trifluoropropyl, methacryloxypropyl;

R ³ , R ⁴ is methyl; R ⁵ is methyl or 3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl; n = 0-20, m = 0-400; when n = m = 0, R ⁵ -3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl, and the method for their preparation. The silicon atom is bonded to aryl or alkyl, including substituted halogens, as well as vinyl, methacrylic and other groups.

Moreover, in these compounds, the siloxane chain can be linear, cyclic or branched with a content of up to 400 or more units.

The structure of the obtained liquid hydroxyorganosiloxanes of various viscosities containing both phenolic and methylol groups in the structure of the molecule is confirmed by NMR and IR spectroscopy and the results of elemental analysis (see examples, Tables 1 and 1 - 3). IR spectra contain absorption bands characteristic of bonds: siloxane (1020-1100 cm ^-1 ),

ether (1240 cm ^-1 ) and hydroxyl (2750-3600 cm ^-1 ) groups.

Chemical shifts (δ) of atoms ¹ H ppm in hydroxyorganosiloxanes Group indicating (*) atom H Chemical shift (8) of H atoms, ppm Si-CH ₃ * 0.00-0.16 Si-CH ₂ * -CH ₂ -CH ₂ 0.45-0.65 Si-CH ₂ -CH ₂ * -CH ₂ 1.54-1.75 Si-CH ₂ -CH ₂ -CH ₂ * 2.45-2.66

4.60-4.74

5.45-5.55

3.70-3.85

7.00-7.10

6.75-6.79

The presence of a methylol group in oxymethylated eugenol (model compound) confirms the characteristic shift of the absorption band in the IR spectra (peak 3375 cm ^-1 ) compared to eugenol, in which there are no hydroxymethyl (3513 cm ^-1 ) groups (Fig. 1). When compared with the original organosilicon phenols in the hydroxymethylolphenylorganosiloxanes obtained by us, the same characteristic absorption bands are observed in the IR spectra (Fig. 2). The results of NMR- ¹ H analyzes of the obtained compounds indicate chemical shifts of proton nuclei, confirming the structure of the target hydroxymethylolphenylorganosiloxanes. These data are shown in table 1 and figure 3.

The proposed hydroxymethylolphenylorganosiloxanes are synthesized from various organosilicon phenols of the general formula

,

,

[where R ¹ is methyl or 3- (4-hydroxy-5-methoxyphenyl) propyl; R ² is methyl, ethyl, phenyl, vinyl, trifluoropropyl, methacryloxypropyl; R ³ , R ⁴ is methyl; R ⁵ is methyl or 3- (4-hydroxy-5-methoxyphenyl) propyl; n is 0-20; m is 0-400; when n = m = 0; R ⁵ - 3- (4-hydroxy-5-methoxyphenyl) propyl] by their interaction with a 37% aqueous solution of formaldehyde (B) and alkali (C) in an aqueous medium at a pH of 10-12 and at a temperature of 20-60 ° C, preferably 35-45 ° C, in the presence of urea in a molar ratio A: B: C = 1: (1.1-2) -f: (1-1.2) f, where f is the number of phenolic groups in phenol equal to 1 -20, and urea is taken in excess of formaldehyde in a double amount.

Then chloroform is added to the reaction mass until a 10-50% solution of hydroxyorganosiloxane in chloroform is formed, followed by separation of the organic phase and isolation of the target product from it by distillation of the solvent.

The pH values of the medium (10-12) found by us for the preparation of hydroxymethylolphenylorganosiloxanes, the process temperature range of 20-60 ° C, preferably 35-45 ° C, and the mass ratio of the starting reagents are optimal for synthesis and provide a high yield of the main product with a minimum amount of by-products. It should be noted that at pH <10 and pH> 12, the process of obtaining the main product proceeds slowly or is associated with the formation of a significant amount of by-products. At a process temperature of up to 20 ° C, the reaction lasts 7-8 hours, and at 35-45 ° C only 3-4 hours. Above 60 ° C, the reaction of the interaction of organosilicon phenol with formaldehyde is complicated by undesirable reactions. To minimize the latter during the process of producing hydroxyorganosiloxanes, we used urea in double amount relative to the excess of formaldehyde.

Example 1

Synthesis of 1,3-hexamethyl-2-methyl-3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl trisiloxane of the structural formula:

2.1 g (0.053 mol) of sodium hydroxide, 43.36 g of water are charged into the reaction flask, and 20 g (0.052 mol) are added dropwise with stirring.

1,3-hexamethyl-2-methyl- [3- (4-hydroxy-3-methoxyphenyl) propyl] trisiloxane. After the formation of a solution with a pH of 11.5, 8.416 g (0.104 mol) of a 37% aqueous formaldehyde solution are added. When the temperature of the reaction mass reaches 35-40 ° C, it is maintained with stirring for 3 hours. Then, 5.42 g of 35% hydrochloric acid was added to the flask to neutralize the alkali, and at pH 5 of the solution, 1.5 g of urea powder was added to it and the mass was stirred for 1 hour. After separation of the reaction mass, 50 ml of chloroform is poured onto it until a 50% solution is formed. In a separatory funnel, the upper aqueous layer is separated from the lower layer — the reaction product in chloroform, and the solution is washed with water to pH 7. The solvent at T = 80 ° C and P = 15 mm Hg. distilled off in a rotary evaporator. 21.5 g of 1,3-hexamethyl-2-methyl [3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl] trisiloxane are obtained in a yield of 93% by weight. The reaction product is a clear, dark yellow liquid. Physico-chemical characteristics of the product:

η _D ²⁰ = 1.4875; ρ = 1.5844 g / cm ³ . The gross formula is C ₁₈ H ₃₄ O ₅ Si ₃ , M.M.- 414 am.u. Composition in%, calculated / found: C = 52.17 / 55.17; H = 8.21 / 8.54; Si = 20.29 / 19.72; % CH ₂ OH groups by NMR spectroscopy is 7.49 / 7.05.

Example 2

Synthesis of 1,3-bis- [3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl] tetra-methyldisiloxane with the structural formula:

The course of the experiment is similar to that in Example 1. 4.86 g (0.12 mol) of sodium hydroxide, 48.6 g of water, 27.72 g (0.06 mol) of 1,3-bis-3- (4-hydroxy) are taken -3-methoxyphenyl) propyltetramethyldisiloxane and at a pH of 10.5, 14.63 g (0.18 mol) of a 37% aqueous formaldehyde solution are added to it. After 3 hours of reaction, 12.51 g of 35% hydrochloric acid, 3.6 g of urea are added to the mass, and the reaction mixture is diluted with 100 ml of chloroform to form a 30% solution. Obtain 31.85 g of the product (yield 85 wt.%), Which is a clear, viscous, dark yellow liquid.

Physico-chemical characteristics of hydroxyorganosiloxane:

η _D ²⁰ = 1.5285, µ = 843 cPz. The gross formula is C ₂₆ H ₄₂ O ₇ Si ₂ , M.M. = 522 am.u.

Composition in%, calculated / found: C = 67.82 / 68.10; H = 8.04 / 8.82; Si = 10.73 / 9.64; % CH ₂ OH groups by NMR spectroscopy is 12, 88 / 12.34.

Example 3

Synthesis of α, ω-hexamethyloligo [3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl] methyldimethylsiloxane of the structural formula:

The course of the experiment is similar to that shown in Example 1. Take 4.386 g (0.11 mol) of sodium hydroxide, 43.86 g of water, 43.19 g (0.01 mol) of α, ω-hexamethyl [3- (4-hydroxy-5 -methoxyphenyl) propyl] oligomethyldimethylsiloxane and 12.97 g (0.16 mol) of a 37% aqueous formaldehyde solution are added at pH 11, the reaction mixture is kept for 4 hours. 11.47 g of 35% hydrochloric acid, 4.8 g of urea and 100 ml of chloroform are added until a 50% solution of hydroxyorganosiloxane in chloroform is formed. 41.75 g of hydroxyorganosiloxane are obtained in a yield of 87% by weight, which is a clear, viscous, dark yellow liquid.

Physico-chemical characteristics of the product: η _D ²⁰ = 1.4534, µ = 3605 cPz. % CH ₂ OH groups by NMR spectroscopy is 5.52 / 5.38.

Example 4

Synthesis of α, ω-bis- [3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl] oligodimethylsiloxane of the structural formula:

The course of the experiment is similar to that in Example 1. Take 0.587 g (0.015 mol) of sodium hydroxide, 5.87 g of water, 19.07 g (0.0075 mol) of α, ω-bis- [3- (4-hydroxy-5- methoxyphenyl) propyl] oligodimethylsiloxane and 3.86 g (0.048 mol) of a 37% aqueous formaldehyde solution 2.1 g of 35% hydrochloric acid, 1.2 g of carbamide and 100 ml of chloroform are added at pH 12 to form 15% - solution of hydroxyorganosiloxane in chloroform. 17.43 g of product is obtained (yield 85 wt.%), Which is a clear, viscous, dark yellow liquid. Physico-chemical characteristic: η _D ²⁰ = 1.4270, µ = 2594 cPz. M.m. = 2592 a.m. % CH ₂ OH groups by NMR spectroscopy is 2.39 / 2.43.

Example 5

Synthesis of α, ω-bis- [3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl] oligodimethylmethylphenylsiloxane of the structural formula:

The course of the experiment is similar to that in Example 1. 1.16 g (0.029 mol) of sodium hydroxide, 15 g of water, 17.67 g (0.014 mol) of α, ω-bis- [3- (4-hydroxy-5-methoxyphenyl) are taken propyl] oligodimethylmethylphenylsiloxane and 2.4 g (0.03 mol) of a 37% aqueous solution of formaldehyde, 2.1 g of 35% hydrochloric acid, 1 g of carbamide and 100 ml of chloroform are added at pH 12 until a 15% solution is formed hydroxyorganosiloxane in chloroform. 17.88 g of product are obtained (yield 88 wt.%), Which is a clear, viscous, dark yellow liquid. Physico-chemical characteristic: η _D ²⁰ = 1.5270, µ = 3504 cPz. M.m. = 2308 a.m. % CH ₂ OH groups by NMR spectroscopy is 3.68 / 3.43.

Example 6

Synthesis of α, ω-bis- [3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl] oligodimethylmethylvinylsiloxane of the structural formula:

The experiment is similar to that in Example 1. 0.1 g (0.0025 mol) of sodium hydroxide, 25 g of water, 30 g (0.001 mol) of α, ω-bis- [3- (4-hydroxy-5-methoxyphenyl) are taken propyl] oligodimethylmethylvinylsiloxane and 2.4 g (0.03 mol) of a 37% aqueous solution of formaldehyde, 2.1 g of 35% hydrochloric acid, 1 g of urea and 100 ml of chloroform are added at pH 12 until a 30% solution is formed hydroxyorganosiloxane in chloroform. 30.1 g of product are obtained (yield 92 wt.%), Which is a clear, viscous, dark yellow liquid. Physico-chemical characteristic: η _D ²⁰ = 1.4080, µ = 4500 cps. M.m. = 30074 am.u. % CH ₂ OH groups by NMR spectroscopy is 0.21 / 0.18.

Example 7

Synthesis of α, ω-bis- [3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl] oligodimethylmethylmethacryloxypropylsiloxane of the structural formula:

The course of the experiment is similar to that in example 1. Take 0.244 g (0.0061) mol) of sodium hydroxide, 7 g of water, 13.54 g (0.003 mol) of α, ω-bis-3- (4-hydroxy-5-methoxyphenyl) propyloligodimethylmethylmethacryloxypropylsiloxane and 1 g (0.012 mol) of a 37% aqueous solution of formaldehyde, 1.1 g of 35% hydrochloric acid, 1.2 g of urea and 100 ml of chloroform are poured at a pH of 12 to form a 10% solution of hydroxyorganosiloxane in chloroform. Obtain 11.93 g of the product (yield 85 wt.%), Which is a clear, dark yellow liquid. Physico-chemical characteristic: η _D ²⁰ = 1.4220, µ = 159 cPz. M.m. = 5078 a.m. % CH ₂ OH groups by NMR spectroscopy is 2.22 / 1.88.

Example 8

Synthesis of α, ω-bis- [3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl] oligodimethylmethyl trifluoropropylsiloxane of the structural formula:

The course of the experiment is similar to that in Example 1. Take 0.244 g (0.0061 mol) of sodium hydroxide, 7 g of water, 10.25 g (0.003 mol) of α, ω-bis- [3- (4-hydroxy-5-methoxyphenyl) propyl] oligodimethylmethyl trifluoropropylsiloxane and 1 g (0.012 mol) of a 37% aqueous formaldehyde solution, 1.1 g of 35% hydrochloric acid, 1.2 g of carbamide and 100 ml of chloroform are added at pH 12 until a 10% solution is formed. 8.81 g of product is obtained (yield 86 wt.%), Which is a clear yellow liquid. Physico-chemical characteristic: η _D ²⁰ = 1.3890, µ = 280 cPz, M.m. = 3718 am.u. % CH ₂ OH groups by NMR spectroscopy is 2.67 / 2.12.

Example 9

Synthesis of α, ω-hexamethyloligo [3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl] ethyldimethylsiloxane of the structural formula:

The course of the experiment is similar to that in Example 1. Take 4.386 g (0.11 mol) of sodium hydroxide, 43.86 g of water, 64.02 g (0.01 mol) of α, ω-hexamethyl-3- (4-hydroxy-5 -methoxyphenyl) propyloligoethyl dimethylsiloxane and, at pH 11, 17.83 g (0.22 mol) of a 37% aqueous formaldehyde solution are added, the reaction mixture is kept for 4 hours. 11.47 g of 35% hydrochloric acid, 5 g of carbamide and 120 ml of chloroform are added until a 50% solution of hydroxyorganosiloxane in chloroform is formed. Obtain 64.85 g of the finished product with a yield of 92 wt.%, Which is a clear, viscous, dark yellow liquid. Physico-chemical characteristic of the product: η _D ²⁰ = 1.4740,% CH ₂ OH groups by NMR spectroscopy is 8.86 / 8.20.

Claims (2)

1. Hydroxymethylolphenylorganosiloxanes of the general formula

where R ¹ is methyl or 3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl, R ² is methyl, ethyl, vinyl, phenyl, trifluoropropyl, methacryloxypropyl; R ³ , R ⁴ is methyl; R ⁵ is methyl or 3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl; n = 0-20, m = 0-400; at n = m = 0, R ⁵ -3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl. 2. The method of producing hydroxymethylolphenylorganosiloxanes according to claim 1, characterized in that the organosilicon phenols of the general formula

where R ¹ is methyl or 3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl, R ² , R ³ , R ⁴ , n, m have the above meanings, R ⁵ is methyl or 3- (4-hydroxy -3-methylol-5-methoxyphenyl) propyl, at n = m = 0 R ⁵ -3- (4-hydroxy-3-methylol-5-methoxyphenyl) propyl, is reacted with a 37% aqueous formaldehyde solution (B) in the presence of sodium hydroxide (C) in an aqueous medium at a pH of 10-12 and a temperature of 20-60 ° C, preferably 35-45 ° C, in the presence of urea in a molar ratio A: B: C = 1: (1.1 -2) f: (1-1,2) f, where f is the number of phenolic groups in phenol equal to 1-20, and urea is taken for excess formaldehyde in duplicate and the reaction mixture was added chloroform to form a 10-50% strength solution in gidroksiorganosiloksana chloroform, followed by separation of the organic phase and isolating the desired product therefrom by distilling off the solvent.

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