RU2161629C2 - Method of film-forming agent - Google Patents

Abstract

FIELD: chemistry of polymers, more particularly technology of preparing film-forming materials by block oligomerization or telomerization. SUBSTANCE: described is technology of preparing film-forming materials by block cooligomerization or telomerization of cooligomers of unsaturated C₅-C₁₀ hydrocarbons with propylene oxide in the presence of titanium tetrachloride complex with promoting mixture of lower carbonyl compound with water and copromoter. Copolymer is aliphatic C₄-C₆ alcohol or mixture thereof with C₆-C₅₄ ester. Amount of propylene oxide is 2.3-9.1 wt % per C₅-C₁₀ cooligomer. Amount of titanium tetrachloride catalyst complex with promoting mixture and copromoter is 4.6-12.4% based on cooligomer. EFFECT: more efficient preparation method. 3 tbl

Description

The invention relates to a technology for producing film-forming materials by block oligomerization-telomerization of co-oligomers of C ₅ -C ₁₀ unsaturated hydrocarbons with propylene oxide in the presence of a complex of titanium tetrachloride with a promoting mixture of a lower carbonyl compound with water and a co-promoter.

 Such co-oligomers, due to the presence of functional groups in their molecules, have increased, in comparison with hydrocarbon, hardness and adhesion to substrates, which makes it possible to effectively use them as substitutes for edible vegetable oils in the production of composite paints and varnishes [R. M. Livshits, L. A. Dobrovinsky. Substitutes for vegetable oils in the paint and varnish industry. "Chemistry", M. 1987, p. 85].

A known method of producing a film former by cationic co-oligomerization of conjugated dienes or mixtures thereof with (co) cyclopentadiene (DCPD) dimers and vinyl aromatic hydrocarbons in the presence of TiCl ₄ complexes, followed by its deactivation with a mixture of 10 - 80 wt.% Propylene oxide with 10-70 wt.% Methanol, and also 20 - 80 wt.% chloroparaffin with a mass ratio of the mixture to TiCl ₄ equal to 4-10: 1, degassing of the deactivate from light hydrocarbons. The film-forming solutions in hydrocarbon solvents (white spirit or nefras) are characterized by: color in units of an iodometric scale of 10 - 20, transparency as a percentage of the transparency of refined vegetable oil with the same color value 120 hours after preparation and storage at room temperature 80 - 92.

 A uniform transparent glossy coating formed upon drying 24 hours after application and storage at room temperature is characterized by: bending strength in mm according to ShG-1 20, adhesion to metal in points 2-4 [Auth. St. USSR, N 1229205, cl. C 09 D 3/36, 1986].

 The film former thus obtained is characterized by insufficient transparency, low adhesion and elasticity of a uniform transparent glossy film.

The closest in technical essence is a method for producing a film-forming agent by co-oligomerization of monomer-containing mixtures containing conjugated dienes, vinyl aromatic compounds, olefins in the presence of titanium tetrachloride as a catalyst with a promotion mixture containing a carbonyl compound (phenol and / or acetone), water, and a co-promoter, with using a mixture of the latter phenol with c ₁ -C ₈ -alkyl ester of acetic acid, methacrylic acid or phthalic acid at a molar ratio TiCl _4: carbonyl at union of a water: co-promoter being 1: 0,01-0,33: 0,0001-0,0090. [RF Patent N 2050371: IPC C 08 F 240/00, 1995].

 Film-forming solution is characterized by: color 10 -12 units. IMSh, acidity (acid number) in mg KOH / g 0.3 - 1.5, transparency 98 - 99, drying time in hours at room temperature to "3" grade 3 - 20.

 A uniform transparent glossy coating formed upon drying 24 hours after application and storage at room temperature is characterized by: bending strength in mm according to ShG-1 1-15 mm, hardness according to M-3 in arbitrary units 0.4-0.6, water resistance at room temperature 24 - 120 hours, acid resistance at room temperature in 10% HCl 15 - 72 hours, light resistance according to IPK-3 at room temperature in hours 350 - 850.

 The disadvantage of this method is the instability of the color of the film former.

 The aim of the invention is to stabilize the color of the film former and its processed products during storage.

The goal is achieved by using a C ₄ -C ₆ aliphatic alcohol or its mixture with a C ₆ -C ₅₄ ester as a copromotor at a molar ratio of TiCl ₄ : carbonyl compound with water: a co-promoter of 1: 1.2 - 2.5: 5 - 10.

We found that when using co-oligomers of unsaturated C ₅ -C ₁₀ hydrocarbons containing DCPD fragments, the film former during storage in the presence of TiCl ₄ complexes with a carbonyl compound, water and well-known co-promoters with significant Lewis acidity releases cyclopentadiene (CPD), which at the moment of formation, linear low-molecular-weight products are oligomerized into yellow-raspberry-colored (containing carotenoid structures) [B. Eisler, A. Wassermann, SD Fomworth, D. Kodrick, R. Schnurmann. Nature, 1951, v. 459, p. 459; J. Polym. Sci. 1952, v. 3, p. 157], probably responsible for the insufficient resistance of the foaming agent to “yellowing” and exposure to light. When using the inventive copromotor, both Lewis acidity and the effective rate constant of the reduction of Ti (+ IV) to Ti (+ III) for the TiCl ₄ complex are significantly reduced, most likely due to the rehybridisation of Ti (IV) from sd to d sd and a greater decrease Gibbs free energy during the formation of octahedral complexes of titanium with molecules of the claimed co-promoters, which have a much greater Lewis basis [5. U. Mayer. Pure Appl, Chem. 1979, v. 51, p. 1697]. All this is likely to achieve a positive effect.

The film former is prepared under the conditions of the prototype using the same starting components and analysis methods (solutions) of the film former, but instead of the known, claimed copromotors and ratios TiCl ₄ : carbonyl compound with water: copromotor.

As in the case of the prototype, due to the telomerization of the components of the catalytic complex and the high degree of conversion of propylene oxide, the deactivation nodes of the TiCl ₄ complex and the release of the film former from the polymerizate are usually absent, since the concentration of free toxic components with a low flash point of the promoting mixture and propylene oxide Do not exceed the maximum permissible. The part of the co-promoter that has not entered into co-oligomerization is used as a solvent component of the film-forming solution, since its flash point (in a closed crucible) exceeds the maximum permissible +29 ^o C, and the toxicity does not exceed that of hydrocarbon solvents.

 The film-forming solution is characterized by: a film-forming concentration of 55 - 70 wt.%, A color of 10 - 20 units. IMSh, acid number 0.1 - 0.2 mg KOH / g, transparency 98 - 99. The relative reflection coefficient of white paint is 97 - 99, the drying temperature to "3" degree 3 - 20 hours

 A uniform transparent glossy coating formed upon drying 24 hours after application and storage at room temperature is characterized by: bending strength in mm according to ShG-1 2-10, hardness 0.62 - 0.80 srvc. units according to M-3, water resistance 72 - 192 hours, acid resistance 24 - 48 hours, light resistance 960 - 1080 hours

 The essence is confirmed by the following examples.

 Example 1

To a temperature-controlled reactor at 80 ^° C with conventional stirring containing 40.19 g of co-oligomers of unsaturated hydrocarbons C ₅ -C ₁₀ obtained by cationic co-oligomerization in the presence of a complex of TiCl ₄ with a carbonyl compound and water, 1: 1 mixture by weight of C ₅ fractions and C ₉ flexible pyrolysis of petroleum products in ethylene mode and containing, wt.%, in total, the following monomer fragments: 16.6 isoprene, 3.4 piperylene, 3.3 CPD, 14.6 iso-olefins C ₅ -C ₁₀ , 26.1 vinylaromatic hydrocarbons, 25.7 DCPD 1.1 acetylenic hydrocarbons C ₅ -C ₁₀ and 9.3 n-olefins C ₁ -C _{5 0,} 8.47 g of alkylbenzenes C ₈ -C _10, 1.5 g of saturated and aromatic hydrocarbons unidentified C ₈ -C _10, 28.42 g of petroleum ether-150/200 C and 1,75 TiCl ₄ solution was introduced 1.24 g of 4.7 wt. % water in technical acetone, 4.77 g of technical butanol (GOST 5208-81) and 2.1 g of propylene oxide. The molar ratio of TiCl ₄ : carbonyl compound with water: butanol is 1: 2.5: 7. After 10 minutes, the obtained polymerizate is subjected to analysis. It contains: 46.96 g of film former, 8.45 g of alkylbenzene, a total of 29.92 g of nephras and OST, 3.07 g of free butanol and less than 0.01 g of other free components of the promoting mixture and propylene oxide. The output of the film former 99.9 wt.%. The film former is characterized by: Mn = 4270, Mw / Mn = 1.5.

 Examples 2, 3 (tables 1, 2).

 The initial composition of the reaction mixture, co-promoter, temperature and co-oligomerization time are varied within the claimed limits.

 In example 2, technical isopentanol (GOST 5830-89) and butyl acetate (GOST 8981-88) are used as components of the co-promoter, and in example 3, a mixture of technical cyclohexanol (GOST 6021-85) and sunflower oil (GOST 1129-83).

Carrying out copolymerization under known conditions, but using the claimed copromotors and TiCl ₄ ratios: carbonyl compound with water:: the co-promoter is more resistant to yellowing, as well as to the action of water and light, with a film former that is not inferior to that obtained under known conditions.

If the molar ratio of TiCl ₄ : carbonyl compound with water is reduced to less than 1: 2.5 (example 5 of comparative table 3), and the molar ratio of TiCl ₄ : co-promoter is less than 1: 10 (example 5, table 3 ) and / or to use aliphatic alcohol C ₃ and lower (Example 6, Table 3), the transparency is reduced when stored at room temperature due to the competing chemical interaction of TiCl _{4 with the} oxygen-containing component of the promotion mixture.

If the molar ratio of TiCl ₄ : carbonyl compound with water is increased to more than 1: 1.2 (example 8, table 3), and the molar ratio of TiCl ₄ : co-promoter to more than 1: 5 (example 9, table 3) and / or to use aliphatic alcohol C ₇ and higher (Example 10, Table 3), the reflection coefficient of white paint decreases, probably due to an excessive increase in Lewis acidity of the TiCl ₄ complex.

 In table 3, the results of obtaining and the properties of the film former, not beyond the values of examples 1 to 3, are omitted.

As follows from the table, the use of transcendental molar ratios of TiCl ₄ , carbonyl compounds with water and co-promoter does not allow to achieve the goal of the invention in full.

 The use of the present invention allows to reduce the cost of composite paints prepared using such film-forming agents by reducing vegetable oil in them, and also to improve quality.

Claims (1)

A method of producing a film former, which consists in block oligomerization of co-oligomers of unsaturated hydrocarbons C ₅ - C ₁₀ with propylene oxide in the presence of 4.6 - 12.4% by weight of a co-oligomer C ₅ - C _{10 of a} catalytic complex of titanium tetrachloride with a promoting mixture of a lower carbonyl compound with water and a co-promoter in this case, a C ₄ - C ₆ aliphatic alcohol or its mixture with a C ₆ - C ₅₄ ester at a molar ratio of TiCl ₄ : lower carbonyl compound with water: co-promoter 1: 1.2 - 2.5: 5 - is used as a co-promoter 10, with the number of propylene oxide 2.3 - 9.1 wt.% on the co-oligomer C ₅ - C ₁₀ .

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