Agents of suppressing the formation of growth, method of production thereof, the composition comprising the agent, a method of suppressing the formation of growth, method of polymerization, the polymerization reactor


 

(57) Abstract:

The invention relates to agents suppressing the formation of growth on the walls of the reactor during polymerization of vinyl chloride or vinyl acetate. The agent is a condensation product of aldehyde, phenolic compounds and aromatic carboxylic acid replacement on the aromatic nucleus. Agents are in the acid form or in the form of the corresponding salts with basic agents. Compositions containing the above agents and used as agents against the formation of the knot, include the solvent, the substance bonding surface of the reactor at a concentration of agent is 0.2-15 wt. % of the solution. The polymerization is carried out in the reactor, the inner walls of which are covered by these agents. The technical result - the prevention of deposits of polymeric formations on the walls of the polymerization reactor, the receiving agent from the available materials. 6 C. and 5 C.p. f-crystals, 11 PL.

The invention relates to agents suppressing the formation of growth, as well as to compositions containing such agents suppress, prevent smearing in the polymerization of vinyl chloride or vinyl acetate which polymerization is carried out in aqueous suspension, in aqueous emulsion or in mass.

All the above mentioned methods of polymerization of the resulting polymer is firmly stick to the walls of the reactor, forming a so-called "growth" (in other words, "scale"), which has a deleterious effect on the final product due to the fact that small fragments of growth during their separation from the walls of the reactor can be included in the polymer product, as well as on the security of the reaction, since the formation of growth slows down heat transfer wall, thereby creating security problems due to overheating.

This smearing is the lack of polymerization processes, because after each re-reaction it is necessary to clean the walls.

This cleanup is costly because it reduces the performance of the installation and dangerous for operators due to the toxicity of the monomers, particularly vinyl chloride.

To reduce this problem have developed many products and methods, all of them based on the coating of the walls of the reactor materials, which should prevent the adhesion or even smearing, for example, by offsetting the polymerization of monomers on the walls of the reactor. In the UK 1439339; the Japan patent 54-107991; patent Canada 1181899, patent EP 0052421) or a mixture of dyes (alizarin, xanthones, natural flavonoids, naftochinona, hydroxyanthraquinone and others) with such film-forming elements, such as, for example, polysaccharides, polyvinyl alcohols, polyvinylpyrrolidone. See, for example, the Japan patent 04342701; 04154804; 04154801; 04154805; 04108805; 04159302 and 04031402.

In the patent EP 0614915 propose to apply the product of condensation between quinones and heterocyclic compounds having at least two amino groups, whereas in the patent EP 0606013 described, in particular, condensation products between quinones and especially diaminodiphenylamine, substituted carboxyl group or sulfo. Finally, in the patent EP 0695761 described the use of products obtained by condensing compounds "phenol, such as phenol or 1-naphthol in the presence of aliphatic bicarbonate acid.

The more widely used products apparently are those described in patent EP 0052421. However, although achieved significant results in respect of suppressing the formation of growth, these agents do not allow a significant number of repeat polymerizate.

All of these agents for baking the ability to stick to the walls of the reactor.

The most typical ways to provide the coating by painting or spraying, in this case, it is necessary to prepare the corresponding solutions of the same products, for example aqueous solutions. In the case of sputtering can be used as a propellant, nitrogen or water vapor under a pressure of 5-15 bar.

As indicated, the characteristics of these products can be improved through the use of film-forming agents, such as polysaccharides or vysokomineralizovannyh polyvinyl alcohols.

Now installed and it is the aim of the present invention, agents for preventing the formation of growth, which is particularly effective in the polymerization of vinyl chloride or vinyl acetate, or mixtures thereof in the presence or absence of the polymerized with other monomers or polymers include condensation products of aldehyde (A), phenolic compounds (b) and aromatic carboxylic acids, oxetanemethanol on the aromatic nucleus (C). These agents as such or in the form of compositions suitable for coating, demonstrate their ability to suppress almost completely the formation of build-up on the inner walls of the reactor, and in General in the reaction systems, also TLAT re-polymerization without causing each time these agents prior to each operation and without significant changes in the smearing between the first and last reactions.

These agents gave more favorable property, that is, they have a reduced sensitivity to changes in pH in the polymerization processes and they have considerable life when stored.

Moreover, the obtained polymers show better physical properties.

Therefore, another objective of the present invention to provide compositions containing one or more of the above agents for preventing the formation of fouling in the polymerization of vinyl chloride or vinyl acetate, or mixtures thereof in the presence or in the absence of other monomers or polymers capable of polymerization with them.

Further another objective of the present invention is to develop a method of suppressing the formation of fouling in the polymerization of vinyl chloride or vinyl acetate, or mixtures thereof in the presence or absence of the polymerized with other monomers or polymers, which consists in coating the inner walls of the reactor for polymerization with one or more of the above agents for preventing the formation of the knot.

The present invention relates also to method of polymerization of vinyl chloride or vinyl acetate, or is in the reactor, the inner wall of which is covered by one or more of the above agents for preventing the formation of growth, and it also relates to the polymers obtained by this method.

Finally, the present invention is a reactor for polymerization, the inner wall of which is covered by one or more of the above agents for preventing the formation of the knot.

The compound (A) can be any aldehyde capable of condensation in the ortho and/or para-positions relative to the hydroxyl present on the aromatic nucleus. Many aldehydes showed that they are suitable for this purpose. Apply preferably formaldehyde or a source of a substance, such as paraldehyde is recommended or paraformaldehyde, aliphatic aldehydes having from 2 to 5 carbon atoms, benzaldehyde or heterocyclic aldehydes such as furfural. The connection of the phenol (B) can be any mono - or polyhydroxylated phenol, which are free at least two ortho - and/or parpolity relative to the hydroxyl group or groups, such as phenol, cresol, ethylphenol, resorcinol, pyrocatechol, hydroquinone, pyragollole or bisphenol a, or a compound of formula (I):

< / BR>
where m= 1, 2, or 3,(C1-5)alkoxy. Apply preferably phenol, resorcinol or 1-naphthol. Finally, the compound (C) is gidroksilirovanii aromatic carboxylic acid of the formula (II):

< / BR>
where R2selected from the group consisting of hydrogen, hydroxy, (C1-5)alkoxy, hydroxy (C1-5)alkyl, halogen, phenyl and hydroxyphenyl; R3has the same values as R2with the exception of hydrogen; X and dotted lines, taken together, are condensed in anthopology divalent residue with benzene ring of formula (III):

< / BR>
where p = 1 or 2, or they do not represent anything; under the following conditions:

a) when X and dotted lines, taken together, represent a residue according to formula III, at least two ortho - and/or parpolity relative to the hydroxyl group or groups should be free;

b) when X and dotted lines, taken together, anything is not present, then at least one of R2or R3represent hydroxy, and at least two ortho - and/or parpolity relative to the hydroxyl group or groups should be free.

Apply preferably monoaxially acids, such as salicylic acid lot, 2,5-deoxybenzoin acid, monooxigenase alkoxybenzenes acid, such as 2-hydroxy-5-methoxybenzoic acid, oxidative acid, such as 6-hydroxy-2-naphthoic acid.

Molar ratio of compounds (A), (b) and (C) as defined above, can be in very wide limits, but it does not affect all the exceptional properties of agents suppressing the formation of growth according to the present invention. Preferably the molar ratio of aldehyde (A), phenolic compounds (b) and aromatic carboxylic acids, oxetanemethanol on the aromatic nucleus (C), are respectively in the range between 0,6-1,2: 0,05-0,95: 0,95-0,05. Even more preferably, the aldehyde is used in a molar ratio not exceeding the amount of gram-molecules of compounds (b) and (C).

Agents of suppressing the formation of growth according to the present invention can be prepared according to various methods. In the first embodiment, these agents can be obtained by reaction of compounds (A), (b) and (C) in aqueous solution in the above molar relationship in the presence of a strong basic agent, for example sodium hydroxide or potassium, to perform the reaction in the pH value in the range of from about 8 to primer is o be catching the main solution of the compounds (b) and (C), and after heating it at the following temperatures add the component (A). The temperature at which the reaction is typically between about 40oWith and about 120oWith, and preferably between about 70oWith the 100oC. the reaction Time is not critical, and it may be predominantly between about 1 and about 8 hours.

Or add in aqueous basic solution (pH between about 8 and about 13.5) of the compound (V) or compound (s) or with an aqueous solution of the compound (A) at a temperature of between about 5 and about 30oC. After stirring for about 1-3 hours at room temperature the aqueous basic solution (pH as indicated), respectively, of the compound (s) or connection (In) is added to the thus obtained compound Dimethylol, and the resulting mixture is heated to a temperature and for time period above. These reactions can also be performed at the place, namely on the walls of the reactor or in General on any other part reaction system, which may be in contact with vinyl chloride or vinyl acetate, mixtures thereof, other monomers or polymers, polymerized with them, also in the form of vapor.

To facilitate coupling agents suppressing the formation of growth, in accordance with the present invention, with those parts of the reaction system, in which it is desirable that the coupling has taken place, you can apply the appropriate surfactant or film-forming agents such as polyvinyl alcohols with a high content of hydroxyl.

Preferred polyvinyl alcohols having a degree of hydrolysis of not less than 96% and 4% of water, and a viscosity of 20 mPas or more, preferably 40 mPas or more, measured by a viscometer of Hepler.

If they are used, these surfactants or coating agent is mixed with the received agents for preventing the formation of the growth in the amount of from about 2 to about 20% by weight, calculated on the agents for preventing the formation of the knot.

In addition to the advantages already indicated the m lies in the fact, that you can get them in solid form, they are easily transported and stored. Therefore, during their deposition on the walls of the reactor for polymerization or other reaction system in which it is desirable grip, you can apply one or more agents as such, obtained by the described methods, or you can use one or more agents learned in the solid state, and to prepare them with the appropriate composition.

This composition is preferably in liquid form, and it can be prepared by dissolving one or more agents suppress the formation of growth in accordance with the present invention, the water in the main agent at pH from about 8 to about 13.5, or in a suitable organic solvent, possibly in the presence of surfactants and the above-mentioned film-forming agents.

The concentration of agents suppressing the formation of growth in the compositions for use in applying them to the walls of the reactor or, in General, the reaction system is from about 0.2 to about 15%, preferably between about 0.4 and about 9%, calculated by weight of the solution.

The number of agent suppressing the formation of the growth in soybean 5 g of the active substance on m2the surface and not less than 0.02 g/m2surface, preferably to not more than 3 g/m2and to not less than 0.1 g/m2surface.

In the case of liquid water compositions agent suppressing the formation of growth after the dissolution of the basic agent, for example sodium hydroxide or potassium hydroxide, or with ammonia or a lower aliphatic amines or mono - or triethanolamine is usually applied by known methods of spraying a mist of water or nitrogen at high pressure, however it can also be applied by brush or, in the case of vinyl chloride, can be used as a carrier of the same monomer. The application can be carried out on cold or hot wall using solutions, pre-heated or at room temperature, although temperature is not critical. After application of the agent of suppressing the formation of the growth of the inner wall can also be heated.

Polymerization of vinyl acetate or vinyl chloride, which are dealing in the present invention, is homopolymerization or copolymerization among them in the presence or absence of one or more monomers or polymers, polymerized with them, such as other vinyl difficult EFI 3-15 carbon atoms, for example, methyl acrylate, butylmethacrylate, Acrylonitrile, Methacrylonitrile, unsaturated esters of dibasic acids, such as diethyl ether maleic acid, delloye esters, as, for example, ZIOC scientists-olefins, such as ethylene and propylene, vinyl esters and compounds of styrene. In addition, the copolymerization involves the polymerization of vinyl chloride in the presence of pre-formed polymers, possibly in the presence of agents for graft copolymer for the formation of grafted vinyl chloride polymers. Examples of these pre-molded polymers suitable for the production of grafted vinyl chloride polymers include poly-2-ethyl hexyl acrylate, poly-n-butyl acrylate and copolymers of olefin/vinyl esters, for example copolymers of ethylene/vinyl acetate.

Agents of suppressing the formation of growth, in accordance with the present invention, have shown that they are particularly effective in the case of polymerization in aqueous suspension or in aqueous emulsion, but also noted a significant reduction in the adhesion of scale to the walls and in the case of polymerization in mass.

Homo - and copolymerization of vinyl acetate and/or vinyl chloride in suspension can s polyvinyl acetate, cellulose ethers, gelatin, sorbitol esters of fatty acids.

Applied quantities vary usually between 0.05 and 2% by weight, calculated per total content of the monomers used.

In the emulsion polymerization used surfactants as emulsifiers, such as, for example, polyglycolide esters salts nonyphenol, sodium or ammonium C12-C18fatty acids, alkylphosphates, alkylsulfonates, alkylbenzenesulfonates, sulfonated olefins, esters of sulfuric acid of fatty alcohols.

Commonly used number varies between 0.05 and 5% by weight, calculated per total content of the monomers used.

You can apply any appropriate polymerization initiators soluble in the used vinyl monomers. Examples of these catalysts in the polymerization include peroxides, such as peroxide lauroyl, peroxide acetylcyclohexanone, azo-compounds, such as azo-bis(dimethylvaleronitrile), and PEROXYDICARBONATE, as, for example, dicetylperoxydicarbonate, diisopropylperoxydicarbonate, bis-(4-tert-butyl-cyclohexyl)-PEROXYDICARBONATE etc. These initiators and anyone who's monomers. In the emulsion polymerization it is possible to use initiators that are soluble in oil, for example peroxide diacyl or dialkylamines, for example peroxide lauroyl or benzoyl peroxide, complex periphery, such as t-butyl peroxypivalate or t-butyl per-2-ethylhexanoate, PEROXYDICARBONATE or dicetylperoxydicarbonate or system girorastvorimie Militello-reduction initiator based persulfates, hydrogen peroxide, hydroperoxides, United with sodium metabisulfite, formaldehyde-sulfoxylate sodium, etc.

Working conditions of polymerization are those which are known in the art and are typically used for polymerization of vinyl acetate and vinyl chloride in emulsion, suspension and bulk or in their mixtures in the presence or absence of one or more monomers or polymers, polymerized with them.

Temperatures are in the range between 40 and 80oC and the pressure is, in most cases, between 5 and 14 bar for vinyl chloride and between 65oWith 95oC at atmospheric pressure for vinyl acetate.

The present invention is illustrated further by the following examples.

EXAMPLE 1

Preparation agent suppression clicks what adalnikam with bubbling, downloaded 670 ml of water, 77 g (0.5 moles) of 3,5-deoxybenzoin acid [(-razorenova acid), compound (C)] , and 72 g (0.5 moles) of 1-naphthol [connect ()]. In the resulting suspension was added 62 g (of 1.55 moles) of NaOH pellets and continued stirring until complete dissolution. Then slowly added to 90 g of an aqueous solution of 30% aqueous formaldehyde [compound (A), 27 g, 0.9 moles] with continuous stirring while maintaining the temperature below the 50oC. After complete addition the temperature was brought to 85oC and at this temperature maintained, the reaction mixture in conditions of mixing for about 3 hours. Got an aqueous solution of an agent preventing the formation of growth with a concentration of 20% by mass.

This solution possible after cooling at room temperature, can be brought to the desired concentration for the intended use, as described above. If necessary, you can add the appropriate surfactant or film-forming agents. Or agent of suppressing the formation of growth can be obtained in solid form by acidification, filtration and drying.

EXAMPLES 2-7

Acting in accordance with the method described in the previous Example, you need a kitchen which situations the relationship.

EXAMPLE 8

Preparation agent suppressing the formation of the knot

Repeating the method of Example 1, starting from 0.1 mol of 2,4-deoxybenzoin acid (C) 0.9 moles of 1-naphthol (B) and 0.9 moles of formaldehyde (A).

EXAMPLES 9-18

Acting in accordance with the methods described in the previous Examples, starting with the following compounds (A), (b) and (C), prepared agents suppressing the formation of the knot. In table. In specified molar ratio of the three components.

EXAMPLE 19

Preparation agent suppressing the formation of the knot

In a glass reactor with a capacity of 2 liters equipped with a stirrer, thermometer and reflux condenser with bubbling, downloaded 660 ml of water, 13.8 g (0.1 moles) of 2-oksibenzoynoy acid [salicylic acid, the compound (C)], of 129.6 g (0.9 moles) of 1-naphthol [connect ()]. To the solution was added 32 g (0.8 moles) of NaOH pellets and stirred until complete dissolution. Then slowly added with stirring, 90 g of an aqueous solution of 30% aqueous formaldehyde [compound (A), 27 g, 0.9 moles], while the temperature was maintained below 50oC. At the end of the additives, the reaction mixture was heated to a temperature of 95oAnd for about 8 hours maintained under conditions of stirring the mixture at this temperature the Assos.

After a possible cooling at room temperature, this solution can be brought to the desired concentration for the intended use, as described above. You can add, if necessary, appropriate surfactants or film-forming agents. By acidification, filtration and drying, you can get an agent for suppressing the formation of a knot in the solid state.

EXAMPLES 20-23

Preparation agent suppressing the formation of the knot

Starting from the following compounds (A), (b) and (C) and acting in accordance with the methods described in the previous Example, prepared the agent for suppressing the formation of the knot. In table. With the specified molar ratio of the three components.

EXAMPLE 24

Preparation agent suppressing the formation of the knot

At a temperature in the range between 10oAnd 20oWith slowly added 40 g (0.4 moles) of 30% aqueous formaldehyde from 30.8 g (0.2 moles) of 3,5-deoxybenzoin acid [-razorenova acid, the compound (C)], dissolved in 100 g of 9% NaOH. After completion of addition the mixture was stirred for 2 hours at a temperature of between 20oAnd the 25oWith, then added 36 grams (0.25 moles) of 1-naphthol, dissolved in 220 g of 6.4% NaOH. Tenetehara 3 hours. Got an aqueous solution of an agent for suppressing the formation of growth at 20% concentration.

After a possible cooling at room temperature, this solution can be brought to the desired concentration for the intended use, as described above. You can add the appropriate surfactant or film-forming agents. Or by acidification, filtration and drying, you can get an agent for suppressing the formation of a knot in the solid state.

EXAMPLE 25

Preparation agent suppressing the formation of the knot

At temperatures below 30oWith slowly added 82 g (of 0.82 moles) of 30% aqueous formaldehyde in 61 g (0.4 moles) of 2,4-deoxybenzoin acid [-razorenova acid, the compound (C)] , dissolved in 476 11% NaOH. After completion of addition the mixture was stirred for about 30 minutes at a temperature between 20oC and 30oWith, then added 72 g (0.5 moles) of 1-naphthol and 400 g of water. The reaction mixture was heated at a temperature of 85oC and stirred it at this temperature for 4 hours. Got an aqueous solution of an agent for suppressing the formation of growth at 16% concentration by weight.

After a possible cooling at room temperature, this appropriate surfactants or film-forming agents, if you need it. Or an agent for suppressing the formation of growth can be obtained in solid form by acidification, filtration and drying.

EXAMPLES 26-29

Acting in accordance with the methods described in Examples 24 and 25 were prepared by the agent for suppressing the formation of build-up, starting from the following compounds (A), (b) and (C). In table. D also indicates the molar ratio of the three connections.

EXAMPLE 30

Polymerization of vinyl acetate monomer (VAM) in aqueous suspension

In a 25 liter reactor made of stainless steel, equipped with a reflux condenser and an anchor stirrer, was loaded with the following ingredients, parts by weight:

The monomer vinyl acetate - 100

Water - 50

Polyvinyl alcohol (26/88) - 0,05

Acetaldehyde - 0,4

Sodium acetate - 0,01

Benzoyl peroxide - 0,03

The mixture was subjected to reflux distilled at atmospheric pressure, and polymerization was carried out for 4 hours to achieve conversion of at least 99%.

According to this method is carried out separately polymerization in the presence and absence of the agent for suppressing the formation of growth in accordance with the present invention. These agents were applied in the amount of 0.3 g/m2the surface area. Soderzhaniya the results are presented in Table 1, and they are expressed in parts/million (hours/million) in relation to the downloaded monomers.

When applying agents for preventing the formation of build-up of Examples 1, 2, 3, 4, 7, 8, 19, 20 and 21 in an amount of 0.1 g of the ingredient, active on m2the surface area of the reactor, similar results were obtained.

EXAMPLE 31

Polymerization of vinyl chloride monomer (VCM) in aqueous suspension

In a 100-liter reactor made of stainless steel, lined on the inside with a glass lining, which was equipped with stirrer of Pfaudler, downloaded after removal of the oxygen by the following ingredients in parts by weight:

The monomer vinyl chloride - 100

Water - 150

POLEVIK S 404WTM(3V SIGMA, Italy) - 0,04*

POLEVIK SP 808TM(3V SIGMA, Italy) - 0,04*

Methoxypropylacetate - 0.04

Sodium bicarbonate - 0,03

Bis-(4-tert-butylcyclohexyl)PEROXYDICARBONATE - 0.04

* active ingredient

The system was heated to a temperature of 54oS, which corresponds to the temperature in degrees Kelvin polyvinylchloride polymer, equal to about 70, then as the pressure is increased to 7/8 ATM, and polymerization was carried out for about 7 hours. When the pressure has dropped to 2-3 ATM, the reaction stopped, too nemuritorii in the presence and in the absence of the agent for suppressing the formation of growth in accordance with the present invention.

Agents for preventing the formation of build-up is caused in the amount of 0.5 g/m2surface of the reactor. The amount of growth was determined after emptying and rinsing of the reactor, collecting and weighing. The results obtained are presented in Table 2, and they are expressed in parts/million (hours/million) in relation to the downloaded monomer.

The resulting polyvinyl chloride example V, D, F, H, and N stabilized against thermal oxidative degradation by calcium stearate and zinc and was subjected to molding under pressure to obtain plates having a thickness of 1.5 mm. Negative spectrophotometer measured the rate of yellowing of the plates (VI) with the values specified in Table 3.

The polymers obtained according to the present invention showed the best appearance.

EXAMPLE 32

For four successive times, carried out the polymerization, similar to the previous example, in the absence or presence of the agent for suppressing the formation of the knot. When the past was present, they were put in the amount of 0.5 g / m2surface of the reactor only once before the first polymerization. The number formed by outgrowth was determined after release and leaching reactor at the end of ceregene in parts/million (hours/million) in relation to the number of downloaded monomer.

Received polyvinylchloride was subjected to stabilization by calcium stearate and zinc against thermo-oxidative degradation, and they were molded under pressure to obtain plates with a thickness of 1.5 mm metric yellowing (VI) plates gave values imposed on those of the previous Example.

EXAMPLE 33

The copolymerization of esters of vinyl acetate monomer (VAM)/vinyl esters in water dispersion

In a 25 liter reactor made of stainless steel, equipped with a reflux condenser and an anchor stirrer, was loaded to 30% of a mixture of monomer and 50% of system redox initiator described below in parts by weight:

The monomer vinyl acetate - 70

Dibutylated - 30

Water - 70

Acetylcellulose (WP 300) - 2

Ethoxylated, nonyl-phenol - 2,3

Panso3- 0,07

tert-Butylhydroperoxide - 0,18

Formaldehyde of sulfoxylate sodium - 0,18

The mixture was subjected to reflux distilled at atmospheric pressure, and then loaded for 5 hours at a temperature of 85oWith the rest of the material.

After completion of the reaction, cooling and unloading of the last reactor was washed with water under a pressure of 5 ATM.

According to this method, carried out separate polymerization in the Pris is Alenia education of the growth in the amount of 0.3 g/m2. After discharge from the reactor and wash it, as well as the collection and weighing of growth is determined by its number.

The results obtained are presented in Table 5, and they are expressed in parts/million (hours/million).

EXAMPLE 34

A similar copolymerization of the previous Example was repeated for 3 consecutive times in the absence or presence of the agents of suppressing the formation of growth in accordance with the present invention. When working in the presence of the latter they were put in the amount of 0.3 g/m2surface of the reactor at one time before the first polymerization. The number of the resulting growth was determined after emptying and rinsing of the reactor at the end of the third load, gathering and weighing it. The results obtained are presented in Table 6, where they are expressed in parts/million (hours/million) in relation to the number of downloaded monomer.

The copolymer obtained from Examples 34B, D, E, and G were subjected to stabilization by calcium stearate and zinc against thermo-oxidative degradation, and then molded under pressure to obtain plates with a thickness of 1.5 mm, a Reflective spectrophotometer measured the rate of yellowing (VI) plates, having received the values specified in Table 7.

On the of chloride (VCM) in aqueous suspension

On the inner walls of the polymerization reactor of stainless steel with a capacity of 40 m3caused by spraying in the first phase aqueous strong alkaline solution of the compound from Example 25 in order to obtain a certain amount of suppressor of education growth, 0.75 g/m2. After spraying the walls of the reactor were heated for 1 minute at a temperature of about 60oC. subsequently downloaded the following ingredients, expressed in part/million:

The monomer vinyl chloride - 100

Water - 150

POLEVIKs 404W (3V SIGMA, Italy) - 0,05*

GARSENALKN 17 (NIPPON HANSEL, Japan) to 0.055

ALCOTEX72,5 (REVERTEX, UK) - 0,025

Sodium bicarbonate - 0,03

bis-(4-tert-Butylcyclohexyl)-PEROXYDICARBONATE - 0,03

Peroxide lauroyl - 0.04

* as an active substance

The system was heated to a temperature of about 54oWith corresponding temperature in degrees Kelvin vinyl polymer is about 70, with increasing pressure up to 7-8 atmospheres, and for approximately 6 hours spent polymerization. When the pressure has dropped to 2-3 atmosphere, the reaction was stopped, removed gases and recovered unreacted monomer.

EXAMPLE 36

The polymerization of the above Example was repeated in the reactor of stainless steel with a capacity of 100 m3equipped with a fridge; the inner wall of the reactor and the refrigerator covered with a layer of water in a strong alkaline solution of the compound from Example 1 by spraying in the vapor phase, so that the number of agent suppressing the formation of growth amounted to 0.63 g/m2. During these tests on an industrial scale has also implemented eighty consecutive polymerizati without cleaning the inner walls of the reactor and the refrigerator before each test, but before each polymerization process described above, they are simply washed with water and inflicted on them, the agent for suppressing the formation of the knot. The smearing was not observed. The same results were achieved when applying agents suppressing the formation of build-up of Examples 25 and 27.

EXAMPLE 37

Polymerization of vinyl chloride monomer (VCM) in aqueous suspension

On the inner wall of the reactor stainless steel polymerization tank is Example 25, pre-diluted with water in ratio of 1:10 (volume:volume) to get the number of agent suppressing the formation of the growth of 0.75 g/m2. After spraying the walls of the reactor were heated for 1 minute at a temperature of about 60oC. subsequently downloaded the following ingredients, the contents of which are expressed in parts/million:

The monomer vinyl chloride - 100

Water - 150

POLEVIKS 404W (3V SIGMA, Italy) - 0,04*

GARSENALKN 17 (NIPPON HANSEL, Japan) - 0,06

bis-(4-tert-Butylcyclohexyl)PEROXYDICARBONATE - 0,03

Peroxide lauroyl - 0.04

* as an active substance

The system was heated to approximately 59oS, which corresponds to a temperature value in degrees Kelvin polyvinylchloride polymer, i.e., about 65, the pressure was increased to 8-10 atmospheres. Within about 5 hours polymerization was carried out. When the pressure has dropped to 2-3 atmospheres, the reaction is stopped by the release of gases and unreacted monomer were removed. It was held at least eight consecutive polymerizati without causing agent of suppressing the formation of build-up before each test. Similar results were obtained srutowanie outgrowth, containing condensation products of acetaldehyde or formaldehyde, capable of condensation in the ortho - and/or paraprotex relative to the hydroxyl on the aromatic nucleus, phenolic compounds, which are mono - or polioksidony phenol in which at least two ortho - and/or parpolity relative to the hydroxyl group or groups are free or phenolic compounds is a compound of formula (I):

< / BR>
where m= 1, 2, or 3;

R and R1selected independently from the group consisting of hydrogen, halogen, (C1-C5)alkyl, hydroxy and Carbo(C1-5)alkoxy and benzoic or naphthoic acid, gidroksilirovanii on the aromatic nucleus, which is the compound of formula (II)

< / BR>
where R2selected from the group consisting of hydrogen, hydroxy, (C1-5)alkoxy, (C1-5)alkyl, hydroxy(C1-5)alkyl, halogen, phenyl and hydroxyphenyl;

R3has the same meaning as R2with the exception of hydrogen;

x and dotted lines, taken together, can represent either a bivalent radical, condensed in anthopology with the benzene ring of formula (III)

< / BR>
where p= 1 or 2

or they don't represent anything, under the following conditions: a) when x clusters relative to the hydroxyl group or groups should be free; b) when x and dotted lines, taken together, do not represent anything, at least one of R2or R3is hydroxy, and at least two of the ortho - and/or parpolity relative to the hydroxyl group or groups should be free.

2. Agents of suppressing the formation of growth under item 1, characterized in that they are in acid form or in the form of the corresponding salts with basic agents.

3. The method of receiving agent suppressing the formation of growth under item 1 or 2, navigated the interaction of the aldehyde, phenolic compounds and aromatic carboxylic acids, gidroksilirovanii on the aromatic nucleus in the presence of a strong alkaline agent, at a temperature of approximately 40oup to approximately 120oWith over a period of time from about 1 to about 8 o'clock

4. The method according to p. 3, characterized in that the aldehyde, compound phenol and an aromatic carboxylic acid, gidrauxilirovannaya on the aromatic nucleus, react with molar ratios, respectively 0,6-1,2: 0,05-0,95: 0,95-0,05.

5. The method according to PP. 3 and 4, characterized in that the first aldehyde is reacted with a compound of the phenol or alternatively with aromatic carboxylic Ki which are then reaction with carboxylic acid, gidroksilirovanii on the aromatic nucleus, or with the connection of phenol, respectively.

6. Agents of suppressing the formation of growth under item 1 and 2, characterized in that they are obtained according to the method according to PP. 3-5.

7. Composition having activity against the formation of build-up that contains one or more agents suppress the formation of growth according to any of paragraphs. 1, 2 or 6, the solvent and substances that provide the coupling agent with the surface of the reactor, and the concentration of the agent of suppressing the formation of build-up is between about 0.2 and about 15% based on the weight of the solution.

8. Agents of suppressing the formation of growth according to any of paragraphs. 1, 2 or 6, used in the method of polymerization of vinyl chloride or vinyl acetate or mixtures thereof in the presence or in the absence of other monomers or polymers, polymerized with them.

9. The method of suppressing the formation of build-up in the way of polymerization of vinyl chloride, vinyl acetate, in the presence or in the absence of polymers, polymerized with them, which are coated on the inner walls of the polymerization reactor with one or more agents suppressing the formation of growth according to any of paragraphs. 1, 2, or 6.

10. The way the polymer is th is carried out in the reactor, the inner wall of which is covered by one or more agents suppressing the formation of growth according to any of paragraphs. 1, 2, or 6.

11. The polymerization reactor, the inner wall of which is covered by one or more agents suppressing the formation of growth according to any of paragraphs. 1, 2 or 6.

 

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