A method of obtaining a film-forming oligomer of styrene

 

(57) Abstract:

The invention relates to the production of film-forming oligomers of styrene, which can be used to prepare coatings. A method of obtaining a film-forming oligomer of styrene by oligomerization in the mass in the presence of sulfuric acid at 20 to 50°C. , wherein the process is conducted in the presence of 88% H2SO4when the ratio of monomer:acid 100:0,2, when the desired conversion of styrene to the reaction mass injected toluene in an amount of 10 vol.%, as a monomer used steroidogenesis distillate formed in the production of polystyrene according to the method of incomplete conversion of the monomer. The technical result - obtaining the oligomer of styrene unpainted convenient for processing with a high degree of stability during storage, and disposal of waste. table 1.

The invention relates to methods for film-forming oligomers of styrene, which can be used to prepare coatings.

Known methods for producing oligomers of styrene in the presence of sulfuric acid as a catalyst for oligomerization [1. J. Kennedy. Cationic polymerization Olev is the process of oligomerization in the environment of the solvent, which must be separated from the oligomer.

The closest is the method of obtaining the oligomer of styrene by oligomerization of styrene in bulk in the presence of sulfuric acid concentration 75-92% at a temperature of 20-50oC [3. P. Plech. Cationic polymerization. Ed. Mir, M., 1966, 229-231 C. - prototype].

The disadvantage of this method is to obtain an oligomer, painted in brown color in crystalline form or in the form of a highly viscous fluid, which causes difficulty in processing. Due to residual catalyst in the mass of the obtained oligomer unstable during storage and after a few hours crystallizes.

The basis of the invention the task is improving the method of producing film-forming, in which due to oligomerization in concentrated sulfuric acid at a certain ratio of the monomer and the acid provides the oligomer of styrene easily pererabatyvajushhego, unpainted, with a high degree of stability during storage, which allows to obtain the paint with improved performance characteristics and disposed steroidogenesis waste production.

The problem is solved by a method of obtaining linkables are in the presence of 88% H2SO4when the ratio of monomer acid, 100:0,2, when the desired conversion of styrene to the reaction mass injected toluene in an amount of 10 vol.%, as the monomer used steroidogenesis distillate formed in the production of polystyrene according to the method of incomplete conversion of the monomer.

The proposed method of producing film-forming allows to obtain an oligomer of styrene unpainted, suitable for processing liquid form, neizmeryaemym its properties over a long period of storage. When it is used for coatings significantly improved their luster, does not require the introduction of plasticizers, reduced content of volatile released into the atmosphere during the drying of coatings. This effect is due to the fact that in contrast to the known, the proposed method claimed concentration of H2SO4and its dosage provide a control process of the synthesis, the specified degree of oligomerization and the depletion of monomer styrene; the remains of the catalyst is spent on sulfonation of toluene, ensuring the stability of the product during prolonged storage. Smooth process flow, reducing the viscosity of the reaction medium on the proposed method obespechivayuschee serves also as a plasticizer and modifier and increases in the share of non-volatile in the composition of the coatings.

The composition steroidogenesis waste, wt.%: styrene 69 - 95; polystyrene 3 - 4; polygard 0.2 to 1.0; medical vaseline oil (MBM) 1,0 - 1,5; benzaldehyde from 0.2 to 0.33; acetophenone 0,03 - 0,07; heavy residue 0,77 - 24,1.

The invention is illustrated by the following examples.

Example 1. In a reactor with a stirrer download 100 volumes steroidogenesis waste and 0.2 volume of H2SO488% concentration.

The composition steroidogenesis waste, wt.%: styrene 69, polystyrene 4, polygard 1, MVM, 1,5, benzaldehyde 0,33, acetophenone 0,07, heavy residue 24,1. The index of refraction at 25oC - 1,5475. The mixture under continuous purging with nitrogen, stirred for 10 min at 202oC. the mixture is Then heated to 44 - 45oC and oligomerization are growing at the rate of index of refraction on the value 0,0015 - 0,0025 for 0.5 hour. When increasing the index of refraction higher than 0,0025 for 0.5 hour, the temperature at 2 to 3oC reduce. By reducing the index of refraction lower than 0,0015 for 0.5 hour, the temperature of the reaction mixture increased to 2 to 3oC. When reaching the index of refraction 1,5850 - 1,5900 in the reaction mixture is injected with 10 volumes of toluene. The mixture is then cooled and analyze: color - visually, the content of residual monomer of the styrene - chromatographies is some viscosity. For the preparation of the paint coating mix 20% solution of polystyrene in toluene in the amount of 50% with 30% of film-forming (oligomer of styrene and 20% pigment (iron oxide red). The mixture fray in kraskoterke or ball mill to milling degree not more than 20 μm. The resulting paint experience by current standards. The results are shown in the table.

Example 2. Analogously to example 1. The composition steroidogenesis waste, wt.%: styrene 85, polystyrene 3, polygard 0,5, MVM, 1,0, benzaldehyde 0.3, the acetophenone of 0.05, heavy residue 10,15. The index of refraction at t = 25oC - 1,5488. The results are shown in the table.

Example 3. Analogously to example 1. The composition steroidogenesis waste, wt.%: styrene 95, polystyrene 3, polygard 0,2, MVM, 1,0, benzaldehyde 0,2, acetophenone 0,03, heavy residue of 0.77. The index of refraction at t = 25oC - at 1.5490. The results are shown in the table.

Example 4. Analogously to example 1. As a monomer used styrene according to GOST 10003-81. Mass fraction of styrene and 99.8%. The index of refraction at t = 25oC - 1,5440. The results are shown in the table.

Example 5. Analogously to example 1. Toluene at a given conversion of styrene is not administered. The results are shown in the table.

Example 6. Analogously to example 1. The concentration of H2SO4- 92%. The results are shown in the table.

Example 8. For the preparation of the paint coating film-forming oligomer of styrene do not use. The paint is prepared analogously to example 1 by mixing 75% 20%-aqueous solution of polystyrene in toluene with 5% dioctylphthalate (plasticizer) and 20% iron oxide red. The results are shown in the table.

Data presented in table show that the proposed method (examples 1 to 3) are styrene oligomer with a degree of oligomerization of 4 to 5 with a low content of residual monomer of styrene 0.1 to 0.15%, with a dynamic viscosity of 220 - 270 SP that creates convenience when using it, the product is not painted and is stable when stored for at least 3 months. With the introduction of the obtained oligomer in the composition of the paint coating on the basis of polystyrene film-forming, compared to published industry paint without oligomer (example 8), improves gloss coating from 8 to 50%, reduced mass fraction of volatile from 60 to 43% during drying of the paint coatings, is excluded from the formulation of scarce plasticizer dioctylphthalate.

By carrying out control experiments, beyond the claims of the applicant, the following is established:

- With the exception of the recipes toluene (example 5) the viscosity of the final product increases in 6 - 7 times, which makes unloading and use of the product. The resulting product is unstable during storage and after 3 hours it turns into a crystalline state.

- When using 75% H2SO4(example 6) obtained crystalline product with a higher degree of oligomerization and high residual monomer content, the full cycle is lengthened, work with a crystalline product is difficult.

- When using 92% H2SO4(example 7) obtained crystals, painted in brown color, the process is rapidly and getting a low concentration of residual monomer difficult.

A method of obtaining a film-forming oligomer of styrene by oligomerization in the mass in the presence of sulfuric acid at 20 - 50oC, wherein the process is conducted in the presence of 88% H2SO4when the ratio of monomer : acid 100 : 0,2, when the desired conversii distillate, formed in the production of polystyrene according to the method of incomplete conversion of the monomer.

 

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