RU2280652C1 - Method for production of polyalkylmethacrylate additive (variants) and polyalkylmethacrylate additive (variants) - Google Patents

Abstract

FIELD: polymer chemistry, in particular production of polyalkylmethacrylate additives to mineral oils.

SUBSTANCE: claimed additive is obtained by (co)polymerization of alkylmethacrylate in inert solvent medium in presence of laurylmercaptane and polymerization initiator at 110-130°C. As alkylmethacrylate ester of general formula CH₂=C(CH₃)COOR is used, wherein R represents C₈-C₁₀-, C₁₂-C₁₄-, C₁₂-C₁₈-, C₁₆-C₂₀-alkyl, obtained by transesterification of methylmethacrylate from fraction of high fatty C₈-C₁₀-, C₁₂-C₁₄-, C₁₂-C₁₈-, C₁₆-C₂₀-alcohols in presence of alkali catalyst such as potassium carbonate and mixture of phenol inhibitors such as p-methoxyphenol and 2,6-ditertbuthyl-4-methylphenol in ratio of (5.0-6.0):1, in air flow, and in methylmethacrylate/high alkohol molar ratio of (2.0-2.5):1. In one embodiment ester of general formula CH₂=C(CH₃)COOR is polymerized with monomer of monomer mixture selected from group containing methylmethacrylate, buthylmethacrylate, 2-ethylhexylmethacrylate, styrene, alkylmaleinate in laurylmercaptane/copolymerization initiator mass ratio of (0.013-0.075):1. Polyalkylmethacrylate additives having desired properties also are disclosed.

EFFECT: effective polyalkylmethacrylate additives to mineral oils of improved characteristic and simplified method for production thereof.

9 cl, 124 ex, 4 tbl

Description

The invention relates to the chemistry of polymers, in particular to methods for producing and compositions of polyalkyl methacrylate additives used as additives, for example, mineral oils for thickening, increasing viscosity, and also to lower the pour point of oils and improve their color.

A known method for producing acrylic polymers that can be used as additives to oils (USSR copyright certificate No. 378403, M. Cl. With 10 M 1/28, C 08 F 3/64, publ. 04/18/1973). Acrylic polymers are obtained by radical polymerization of acrylic or methacrylic acid esters and a mixture of synthetic alcohols of normal structure with the number of carbon atoms 7-20 containing 2-30% isostructural alcohols, when heated in the presence of an organic solvent - toluene, taken in an amount of 120-350% by weight monomer, and benzoyl peroxide as a polymerization initiator. The polymer yield is 81-92%. The starting monomers are prepared by the esterification reaction of (meth) acrylic acid with mixtures of synthetic alcohols of normal structure with the number of carbon atoms 7-20 containing 20-30% isostructural alcohols in the presence of an acid catalyst in an organic solvent. It should be noted that the method of producing monomers is characterized by a large amount of acidic wastewater and the presence of an organic solvent, which requires significant energy costs when it is removed after the polymerization stage and the additive.

The viscosity index of the additive (obtained polymer and oil brand DS-11) is 90-108, pour point -22 ÷ -30 ° C; the viscosity index of the additive (obtained polymer and oil grade IS-12) does not exceed 93-131, pour point -40 ÷ -46 ° C; color additives 2.5-3.0.

Known polymer additive that improves the viscosity index, and a method for its production (RF patent No. 2102402, IPC 6 C 08 F 220/18, C 10 M 145/14, publ. 01.20.1998). The polymer additive obtained by copolymerization of unsaturated esters of the General formula:

,

,

,

,

,

,

where R` is H, alkyl; R _a = linear or branched C ₆ -C ₂₅ alkyl;

R _a = R _a - C ₁ -C ₄ alkyl; R _c = 2,2,6,6-tetramethyl-piperidin-4-ol, a linear, branched or cyclic radical containing 1 or 2 nitrogen atoms and from 4 to 20 carbon atoms, with a mass content of esters of the general formula I, II, III no more than 95%, no more than 12% and no more than 8%, respectively; in an inert solvent in the presence of a molecular weight regulator and a radical initiator in the presence of a molecular weight regulator and a radical initiator when heated.

The viscosity index of the additive is 183-184 (in mineral oil SN No. 150). However, the used complex mixture of monomers, including nitrogen-containing, with a pungent odor, gives the copolymer a dark color, reduces its stability over time. The color of the polymer additive is 2.5-3.

The closest in technical essence to the present invention are a polymer additive and a method for producing copoly (meth) acrylate (RF patent No. 2154091, IPC 7 C 10 M 145/14, C 08 F 220/10, publ. 10.08.2000, prototype ) A polymer additive consisting of a copolymer of (meth) acrylate is obtained by copolymerization of a monomer composition, including:

a) 85-98 wt.% (meth) acrylates of the general formula I CH ₂ = C (R) -COOR ₁ ;

where R = H, CH ₃ ; R ₁ is an alkyl radical C ₆ -C ₂₅ ;

b) 1-6 wt.% (meth) acrylates of the general formula II CH ₂ = C (R) -CO-XR ₂ , where R = H, CH ₃ ; X = 0, -NH, NR ₃ ,

where R ₃ is an alkyl radical of C ₁ -C ₃ , R ₂ is an alkyl radical of C ₄ -C ₂₀ and the number of tertiary nitrogen atoms is 1-2;

c) 1-9 wt.% (meth) acrylates of the general formula III CH ₂ = C (R) -COOR ₄ , where R = H, CH3; R4 is a C ₄ -C ₂₀ alkyl radical, a hydroxyl and / or alkoxyl radical with 1-2 oxygen atoms, wherein the alkoxyl group is OR ₅ , where R ₅ is a C ₁ -C ₄ alkyl radical. The copolymerization is carried out in an inert solvent at a temperature of 75-130 ° C in the presence of a radical initiator taken in an amount of 0.2-3.0 parts by weight per 100 parts of monomer. The reaction mixture may include sulfur-containing compounds in order to control the molecular weight of the copolymer, in an amount of 0.01-0.5 parts per 100 parts of monomers. Monomer conversion 98%.

The obtained additive is transparent, however, the presence of nitrogen in the composition of the obtained products significantly affects its stability over time; in addition, during storage, the product acquires an undesirable dark color. The obtained additive is characterized by the following properties: viscosity index 189-191 (in mineral oil SN 150), pour point minus 33 ° C, color 2.5-3.0 (see table 2, example 24 and table 4, example 101) .

The present invention solves the problem of creating effective polyalkyl methacrylate additives for mineral oils.

The technical result of the invention is to simplify the technology for producing polymer additives and improve its operational characteristics (for example, increasing viscosity, lowering pour point, improving color).

To achieve the specified technical result in the method for producing a polyalkyl methacrylate additive by polymerization of an alkyl methacrylate in an inert solvent in the presence of lauryl mercaptan and a polymerization initiator when heated, an alkyl of the general formula CH ₂ = C (CH ₃ ) COOR obtained by transesterification of methyl methacrylate of one of the higher fatty alcohol fractions is used as an alkyl methacrylate selected from the group C ₈ -C _10, C _12, C _14, C ₁₂ -C _18, C ₁₆ -C ₂₀ in an air stream at a temperature of 110-130 ° C at a molar ratio of methyl methacrylate and fraction higher fatty alcohols, equal to (2.0-2.5): 1, in the presence of an alkaline catalyst - potassium carbonate (potash) and a mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditret-butyl-4-methylphenol in their mass ratio (5.0-6.0): 1. The polymerization of alkyl methacrylate is carried out at a mass ratio of lauryl mercaptan and polymerization initiator equal to (0.013-0.075): 1.

The above technical result can be achieved by the fact that in the method for producing a polyalkyl methacrylate additive by copolymerization of an alkyl methacrylate in an inert solvent in the presence of lauryl mercaptan and a copolymerization initiator, a mixture of alkyl methacrylates is used in which the alkyl methacrylate is an ether of the general formula CH ₂ = C (CH ₃ ) COOR obtained by transesterification of methyl methacrylate of one of the higher fatty alcohol fractions selected from the group C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in an air stream at a temperature 110-130 ° C and a molar ratio of methyl methacrylate to higher fatty alcohols equal to (2.0-2.5): 1, in the presence of an alkaline potassium carbonate catalyst and a mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditret-butyl-4 -methylphenol in their mass ratio (5.0-6.0): 1. A mixture of alkyl methacrylates is copolymerized at a weight ratio of lauryl mercaptan and copolymerization initiator (0.013-0.075): 1.

The above technical result can also be achieved by the fact that in the method for producing a polyalkyl methacrylate additive by copolymerization of an alkyl methacrylate in an inert solvent in the presence of lauryl mercaptan and a copolymerization initiator during heating, an ether of the general formula CH ₂ = C (CH ₃ ) COOR obtained by transesterification is used as an alkyl methacrylate methyl methacrylate one of the higher fatty alcohol fractions selected from the group C ₈ -C _10, C _12, C _14, C ₁₂ -C _18, C ₁₆ -C _20, in an air stream at a temperature of 110-130 ° C at a molar Aspect and methyl methacrylate and fractions of higher fatty alcohols equal to (2.0-2.5): 1, in the presence of an alkaline potassium carbonate catalyst and a mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditretbutyl-4-methylphenol in their mass ratio (5 , 0-6.0): 1, which is copolymerized in an amount of 50-95 wt.% With a monomer or a mixture of monomers selected from the group consisting of methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, styrene, alkyl maleate, where C ₈ -C ₁₀ alkyl , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ .

The copolymerization of alkyl methacrylate with the monomer or mixture of monomers described above is carried out at a weight ratio of lauryl mercaptan and copolymerization initiator (0.013-0.075): 1.

The technical result of the invention may also be achieved by the fact that in the production method of the poly dopant methacrylate copolymerization in an inert solvent in the presence of lauryl mercaptan and initiator is copolymerized with heating copolymerization of 50-95 wt.% Of a mixture of alkyl methacrylates, wherein the alkyl methacrylate is an ester of the general formula CH ₂ = C (CH ₃₎ COOR, obtained by transesterification of methyl methacrylate one of the fractions of higher fatty alcohols, chosen from the group of C ₈ -C _10, C _12, C _14, C ₁₂ -C _18, C ₁₆ -C _20, air flow at a temperature of 110-130 ° C and a molar ratio of methyl methacrylate and higher fatty alcohols equal to (2.0-2.5): 1, in the presence of an alkaline potassium carbonate catalyst and a mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditret -butyl-4-methylphenol in their mass ratio (5.0-6.0): 1 with a monomer or a mixture of monomers selected from the group consisting of methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, styrene, alkyl maleate, where C ₈ -C alkyl ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ . A mixture of alkyl methacrylates is copolymerized with a monomer or a mixture of monomers, above, with a weight ratio of lauryl mercaptan to polymerization initiator (0.013-0.075): 1.

The polyalkyl methacrylate additive was obtained by polymerization in an inert solvent in the presence of lauryl mercaptan and a polymerization initiator by heating an alkyl methacrylate of the general formula CH ₂ = C (CH ₃ ) COOR obtained by transesterification of methyl methacrylate from one of the higher fatty alcohol fractions selected from the group C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in a stream of air at a temperature of 110-130 ° C at a molar ratio of methyl methacrylate and the fraction of higher fatty alcohols equal to (2.0-2.5): 1, in the presence of an alkaline potassium carbonate catalyst and a phenol mixture ol inhibitors of p-methoxyphenol and 2,6-ditret-butyl-4-methylphenol in their mass ratio (5.0-6.0): 1.

The polyalkyl methacrylate additive can also be obtained by heating in an inert solvent in the presence of lauryl mercaptan and the initiator of the copolymerization of a mixture of alkyl methacrylates of the general formula CH ₂ = C (CH ₃ ) COOR, in which the alkyl methacrylate is obtained by transesterification of methyl methacrylate from one of the higher fatty alcohol ₈ fractions, selected -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in a stream of air at a temperature of 110-130 ° C and a molar ratio of methyl methacrylate and the fraction of higher fatty alcohols equal to (2.0-2, 5): 1, in the presence of an alkaline catalyst potassium carbonate and mixtures of phenolic inhibitors of p-methoxyphenol and 2,6-di-tert-butyl-4-methylphenol at a weight ratio of (5.0-6.0): 1.

The polyalkyl methacrylate additive can also be obtained by copolymerization by heating in an inert solvent in the presence of lauryl mercaptan and a copolymerization initiator of 50-95 wt.% Alkyl methacrylate of the general formula CH ₂ = C (CH ₃ ) COOR obtained by transesterification of methyl methacrylate from one of the higher fatty alcohol fractions selected groups C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in a stream of air at a temperature of 110-130 ° C with a molar ratio of methyl methacrylate to the fraction of higher fatty alcohols equal to (2.0 -2.5): 1, in the presence of an alkaline catalyst ka carbon dioxide and a mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditretbutyl-4-methylphenol in their weight ratio (5.0-6.0): 1 with a monomer or a mixture of monomers selected from the group consisting of methyl methacrylate, butyl methacrylate, 2 ethylhexyl methacrylate, styrene, alkyl maleate, where alkyl is C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ .

The polyalkyl methacrylate additive can also be obtained by heating in an inert solvent in the presence of lauryl mercaptan and a copolymerization initiator of 50-95 wt.% A mixture of alkyl methacrylates of the general formula CH ₂ = C (CH ₃ ) COOR, in which alkyl methacrylate is obtained by transesterification of methyl methacrylate of one of the higher alcohol fractions selected from the group C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in a stream of air at a temperature of 110-130 ° C at a molar ratio of methyl methacrylate and the fraction of higher fatty alcohols (2, 0-2.5): 1 in the presence of alkaline catalysis potassium carbonate and a mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditret-butyl-4-methylphenol in their mass ratio (5.0-6.0): 1 with a monomer or a mixture of monomers selected from the group consisting of methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, styrene, alkyl maleate, where alkyl is C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ .

A comparative analysis of the proposed technical solution with the prototype allows us to conclude that the claimed method of producing polyalkyl methacrylate additives (options) (co) polymerization of alkyl methacrylate ether of the General formula CH ₂ = M (CH ₃ ) COOR, where R is alkyl C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ obtained by transesterification of methyl methacrylate with higher fatty alcohols of the fraction C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ in certain conditions using certain ingredients. The proposed polyalkyl methacrylate additive (options) obtained by (co) polymerizing the indicated alkyl methacrylate differs from the known one as the alkyl methacrylate used is the ester of the above formula synthesized by transesterification of methyl methacrylate with higher fatty alcohols of the fraction C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , under certain conditions, using certain ingredients. This allows us to conclude that the proposed method for producing polyalkyl methacrylate additives (options) and the composition of the proposed polyalkyl methacrylate additives (options) are new.

The authors are aware of methods for producing acrylic and methacrylic acid esters by transesterification of methyl methacrylate, a di- and polyhydric alcohol. Such esters are used, for example, in the production of synthetic rubbers and latexes, flocculants, adhesives, sealants, in the paint and varnish industry (USSR author's certificate No. 910598, MKI C 07 C 69/54, publ. 07.03.1982), in the manufacture of optical glasses ( application of Germany No. 3423443, MKI C 07 C 69/54, publ. 02/01/1986), as monomers for the production of polymer molding materials, thickeners and adhesives (GDR patent No. 272067, MKI C 07 C 69/54, publ. 27.09 .1989).

It turned out to be unexpected the possibility of implementing a method for producing polyalkyl methacrylate additives (options) (co) polymerization of alkyl- (C ₈ -C ₁₀ ), - (C ₁₂ -C ₁₄ ), - (C ₁₂ -C ₁₈ ), - (C ₁₆ -C ₂₀ ) methacrylates synthesized by transesterification of methyl methacrylate with higher fatty alcohols of the fraction C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ under certain conditions, to obtain polyalkyl methacrylate additives (variants) with a certain set of properties. In this, the authors perceive the inventive step of their proposed technical solutions.

The essence of the invention is illustrated by the following examples.

To implement the methods for producing alkyl methacrylates according to examples 1-36, methyl methacrylate (GOST 20370-74), potash (GOST 4221-76), p-methoxyphenol (TU 6-09-1248-78), 2,6-di-tert-butyl are used -4-methylphenol (TU 38-101459-75), higher fatty alcohols fraction C ₈ -C ₁₀ , higher fatty alcohols fraction C ₁₂ -C ₁₄ , higher fatty alcohols fraction C ₁₂ -C ₁₈ and higher fatty alcohols fraction C ₁₆ - C ₂₀ (TU 38.107119-85).

In the proposed examples 1-16 and taken for comparison examples 17-36, as well as table 1, methods for producing alkyl (C ₈ -C ₁₀ ) -, alkyl (C ₁₂ -C ₁₄ ) -, alkyl (C ₁₂ -C ₁₈ ) - and alkyl (C ₁₆ -C ₂₀ ) methacrylates. The number of alkyl methacrylates synthesized by the authors is not limited to the examples 1-16 of table 1 given in the description of the hare.

Example 1

In a two-liter round-bottom four-neck reactor equipped with a mechanical stirrer with a speed of 60-80 rpm, an air supply tube, a thermometer, a Christmas tree column with electric heating and a complete condensation head with a methyl methacrylate-methanol azeotrope receiver, load 400 g (4 mol) of methyl methacrylate, 260 g (2 mol) of higher fatty alcohols of the fraction C ₈ -C ₁₀ , 6.6 g (1 wt.%) Potassium carbonate, 0.168 g (0.026 wt.%) P-methoxyphenol and 0.032 g (0.005 wt.%) 2 , 6-di-tert-butyl-4-methylphenol (weight ratio 5.2: 1.0). Turn on the mixer, give a flow of air of 0.3 l / h per 1 kg of reaction mass and turn on the heating. The temperature in the reactor is increased to 110-130 ° C and incubated for 1 hour. The contents of the reactor are brought to a boil and at a temperature of 63-80 ° C in pairs and a reflux ratio of 2-4: 1, the selection of the methyl methacrylate-methanol azeotrope begins. 104.7 g of azeotrope are collected. The reaction time is 15 hours. Then, at a temperature of a heating bath of 90-95 ° C, an excess of methyl methacrylate is distilled off in vacuo. The catalyst is filtered off. 383 g of alkyl (C ₈ -C ₁₀ ) methacrylate are obtained, yield 92%.

Example 2

Alkyl (C ₈ -C ₁₀ ) methacrylate is obtained in the reactor according to Example 1, but methyl methacrylate is transesterified at a molar ratio of methyl methacrylate: higher fatty alcohols of the C ₈ -C ₁₀ fraction equal to 2.3: 1.0 (460 g of methyl methacrylate and 260 g higher fatty alcohols of fraction C ₈ -C ₁₀ ), with an air flow of 0.2 l / h per 1 kg of reaction mass. 386 g of monomer are obtained with a yield of 93.5%.

Example 3

Alkyl (C ₈ -C ₁₀ ) methacrylate is produced in the reactor according to Example 1, but methyl methacrylate is transesterified with a methyl methacrylate: higher fatty alcohol fraction of C ₈ -C ₁₀ fraction equal to 2.5: 1.0 (500 g methyl methacrylate and 260 g higher fatty alcohols of the fraction C ₈ -C ₁₀ with an air flow of 0.5 l / h per 1 kg of reaction mass, 386 g of monomer are obtained with a yield of 93.5%.

Example 4

Alkyl (C ₈ -C ₁₀ ) methacrylate is prepared under the conditions of Example 1, but methyl methacrylate is transesterified in the presence of 0.133 g (0.020 wt.%) P-methoxyphenol and 0.026 g (0.004 wt.%) 2,6-di-tert- butyl-4-phenol (weight ratio 5.0: 1.0). 383 g of monomer are obtained in a yield of 92%.

Example 5

Alkyl (C ₈ -C ₁₀ ) methacrylate is prepared under the conditions of Example 1, but the transesterification of methyl methacrylate is carried out in the presence of 0.199 g (0.030 wt.%) P-methoxyphenol and 0.033 g (0.005 wt.%) 2,6-di-tert- butyl-4-phenol (mass ratio 6.0: 1.0). 383 g of monomer are obtained in a yield of 92%.

Example 6

In the reactor of example 1, the transesterification of methyl methacrylate with higher fatty alcohols of fraction C ₁₂ -C _{14 is} carried out. Download 400 g (4 mol) of methyl methacrylate, 390 g (2 mol) of higher fatty alcohols fractions C ₁₂ -C ₁₄ , 7.9 g (1 wt.%) Potassium carbonate, 0.199 g (0.026 wt.%) P-methoxyphenol, 0.038 g (0.005 wt.%) Of 2,6-di-tert-butyl-4-methylphenol (weight ratio 5.2: 1.0). Turn on the mixer, give a flow of air of 0.3 l / h per 1 kg of reaction mass and turn on the heating. The temperature in the reactor is increased to 110-130 ° C and incubated for 1 hour. The contents of the reactor are brought to a boil and at a temperature in pairs of 63-80 ° C and a reflux ratio of 2-4: 1, the selection of the methyl methacrylate-methanol azeotrope begins. The reaction time is 15 hours. Then, at a temperature of a heating bath of 90-95 ° C, an excess of methyl methacrylate is distilled off in vacuo. The catalyst is filtered off. 500 g of alkyl (C ₁₂ -C ₁₄ ) methacrylate are obtained in a yield of 93.5%.

Example 7

Alkyl (C ₁₂ -C ₁₄ ) methacrylate is prepared under the conditions of Example 6; transesterification of methyl methacrylate is carried out at a molar ratio of methyl methacrylate: higher fatty alcohols of the C ₁₂ -C ₁₄ fraction equal to 2.3: 1.0 (460 g of methyl methacrylate and 390 g of higher fatty alcohols of the C ₁₂ -C ₁₄ fraction) in the presence of 0.160 g (0.020 wt.%) p-methoxyphenol and 0.032 g (0.004 wt.%) of 2,6-di-tert-butyl-4-methylphenol (weight ratio 5.0: 1.0). 500 g of monomer are obtained with a yield of 93.0%.

Example 8

Alkyl (C ₁₂ -C ₁₄ ) methacrylate is prepared under the conditions of Example 6, transesterification of methyl methacrylate is carried out at a molar ratio of methyl methacrylate: higher fatty alcohols of the C ₁₂ -C ₁₄ fraction equal to 2.5: 1.0 (500 g of methyl methacrylate and 390 g of higher fatty alcohols fraction C ₁₂ -C ₁₄ ), in the presence of 0.236 g (0.030 wt.%) p-methoxyphenol and 0.0329 g (0.005 wt.%) 2,6-di-tert-butyl-4-methylphenol (mass ratio 6.0: 1.0). 500 g of monomer are obtained with a yield of 93.0%.

Example 9

In the reactor of example 1, the transesterification of methyl methacrylate with higher fatty alcohols of the C ₁₂ -C ₁₈ fraction is carried out. Download 400 g (4 mol) of methyl methacrylate, 384 g (2 mol) of higher fatty alcohols fractions C ₁₂ -C ₁₈ , 8 g (1 wt.%) Potassium carbonate (potash), 0.24 g (0.026 wt.%) P methoxyphenol and 0.046 g (0.005 wt.%) of 2,6-di-tert-butyl-4-methylphenol (weight ratio 5.2: 1.0). Turn on the mixer, give a flow of air of 0.5 l / h per 1 kg of reaction mass and turn on the heating. The temperature in the reactor is increased to 110-130 ° C and incubated for 1 hour. The contents of the reactor are brought to a boil and at a temperature in pairs of 63-80 ° C and a reflux ratio of 2-4: 1, the selection of the methyl methacrylate-methanol azeotrope begins. 118.8 g of azeotrope are collected. The reaction time is 15 hours. Then, at a temperature of a heating bath of 90-95 ° C, an excess of methyl methacrylate is distilled off in vacuo. The catalyst is filtered off. 503.2 g of alkyl (C ₁₂ -C ₁₈ ) methacrylate are obtained in a yield of 92.5%.

Example 10

Alkyl (C ₁₂ -C ₁₈ ) methacrylate is prepared under the conditions of Example 9, transesterification of methyl methacrylate (460 g) is carried out at a molar ratio of methyl methacrylate: higher fatty alcohols of the C ₁₂ -C ₁₈ fraction (380 g) 2.3: 1.0 at current air 0.3 l / h per 1 kg of reaction mass. 503.2 g of alkyl- (C ₁₂ -C ₁₈ ) methacrylate are obtained in a yield of 92.5%.

Example 11

Alkyl (C ₁₂ -C ₁₈ ) methacrylate is prepared under the conditions of Example 9, transesterification of methyl methacrylate is carried out at a molar ratio of methyl methacrylate (500 g): higher fatty alcohols of the C ₁₂ -C ₁₈ fraction (380 g) 2.5: 1.0 at current air 0.3 l / h per 1 kg of reaction mass. 503.2 g of monomer are obtained with a yield of 93.0%.

Example 12

Alkyl (C ₁₂ -C ₁₈ ) methacrylate is prepared under the conditions of Example 9, transesterification of methyl methacrylate is carried out at a molar ratio of methyl methacrylate (400 g): higher fatty alcohols of the C ₁₂ -C ₁₈ fraction (380 g) 2.0: 1.0 in the presence of 0.159 g (0.020 wt.%) P-methoxyphenol and 0.032 g (0.004 wt.%) 2,6-di-tert-butyl-4-methylphenol (mass ratio 5.0: 1.0), with an air flow of 0, 3 l / h per 1 kg of reaction mass. 503.2 g of monomer are obtained with a yield of 92.0%.

Example 13

Alkyl (C ₁₂ -C ₁₈ ) methacrylate is prepared under the conditions of Example 9, transesterification of methyl methacrylate is carried out at a molar ratio of methyl methacrylate: higher fatty alcohols of the C ₁₂ -C ₁₈ fraction of 2.0: 1.0 in the presence of 0.239 g (0.030 wt.%) p-methoxyphenol and 0.03 g (0.005 wt.%) 2,6-di-tert-butyl-4-methylphenol (mass ratio 6.0: 1.0), with an air flow of 0.3 l / h per 1 kg of reaction mass. Obtain 592.1 g of monomer with a yield of 92.0%.

Example 14

In the reactor of example 1, the transesterification of methyl methacrylate with higher fatty alcohols of the C ₁₆ -C ₂₀ fraction is carried out. Download 400 g (4 mol) of methyl methacrylate, 500 g (2 mol) of higher fatty alcohols of the C ₁₆ -C ₂₀ fraction, 9 g (1 wt.%) Potassium carbonate (potash), 0.227 g (0.026 wt.%) P-methoxyphenol and 0.044 g (0.005 wt.%) of 2,6-di-tert-butyl-4-methylphenol (weight ratio 5.2: 1.0). Turn on the mixer, give a flow of air of 0.3 l / h per 1 kg of reaction mass and turn on the heating. The temperature in the reactor is increased to 110-130 ° C and incubated for 1 hour. The contents of the reactor are brought to a boil and at a temperature in pairs of 63-80 ° C and a reflux ratio of 2-4: 1, the selection of the methyl methacrylate-methanol azeotrope begins. The reaction time is 15 hours. Then, at a temperature of a heating bath of 90-95 ° C, an excess of methyl methacrylate is distilled off in vacuo. The catalyst is filtered off. 610 g of alkyl (C ₁₆ -C ₂₀ ) methacrylate are obtained in a yield of 92.5%.

Example 15

Alkyl (C ₁₆ -C ₂₀ ) methacrylate is prepared under the conditions of Example 14, transesterification of methyl methacrylate is carried out at a molar ratio of methyl methacrylate (460 g): higher fatty alcohols of the C ₁₆ -C ₂₀ fraction (486 g) 2.3: 1.0, in the presence of 0.182 g (0.020 wt.%) p-methoxyphenol and 0.036 g (0.004 wt.%) 2,6-di-tert-butyl-4-methylphenol (mass ratio 5.0: 1.0), with an air flow of 0 2 l / h per 1 kg of reaction mass. 608 g of monomer are obtained with a yield of 92.0%.

Example 16

Alkyl (C ₁₆ -C ₂₀ ) methacrylate is prepared under the conditions of Example 14, transesterification of methyl methacrylate is carried out at a molar ratio of methyl methacrylate (500 g): higher fatty alcohols of the C ₁₆ -C ₂₀ fraction (486 g) 2.5: 1.0, in the presence of 0.272 g (0.030 wt.%) p-methoxyphenol and 0.045 g (0.005 wt.%) 2,6-di-tert-butyl-4-methylphenol (mass ratio 6.0: 1.0), with an air flow of 0 5 l / h per 1 kg of reaction mass. 610 g of monomer are obtained with a yield of 92.5%.

Examples 17-21 for comparison

Alkyl (C ₈ -C ₁₀ ) methacrylate is prepared under the conditions of Example 1, but the conditions for the transesterification of methyl methacrylate are different from those stated in Examples 1-5 (see table 1).

Examples 22-26 for comparison

Alkyl (C ₁₂ -C ₁₄ ) methacrylate obtained in the reactor according to example 1, but the conditions for the transesterification of methyl methacrylate are different from those stated in examples 6-8 (see table 1).

Examples 27-31 for comparison

Alkyl (C ₁₂ -C ₁₈ ) methacrylate obtained in the reactor according to example 1, but the conditions for the transesterification of methyl methacrylate are different from those stated in examples 9-12 (see table 1).

Examples 32-36 for comparison

Alkyl (C ₁₆ -C ₂₀ ) methacrylate obtained in the reactor according to example 1, but the conditions for the transesterification of methyl methacrylate are different from those stated in examples 14-16 (see table 1).

When transesterifying methyl methacrylate with higher fatty alcohols, fractions C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ in the absence of air flow or at a flow rate of less than 0.2 l / h per 1 kg reaction mass alkyl (C ₈ -C ₁₀ ) -, (C ₁₂ -C ₁₄ ) -, (C ₁₂ -C ₁₈ ) -, (C ₁₆ -C ₂₀ ) methacrylate is polymerized in the reactor. The flow of air at a speed of more than 0.5 l / h per 1 kg of reaction mass is impractical.

Table 1 №№ pp Source components Product yield,% Note Molar Inhibitors Higher fatty alcohols fraction ratio of methyl methacrylate: higher fatty alcohols fraction p-methoxyphenol 2,6-di-tert-butyl-4-methylphenol mass ratio of inhibitors wt.% one 2 3 four 5 6 7 8 Proposed one. C ₈ -C ₁₀ 2.0: 1.0 0,026 0.05 5.2: 1.0 92.0 Monomer is stable during storage. 2. C ₈ -C ₁₀ 2.3: 1.0 0,026 0.005 5.2: 1.0 93.5 - "- 3. C ₈ -C ₁₀ 2.5: 1.0 0,026 0.005 5.2: 1.0 93.5 - "- four. C ₈ -C ₁₀ 2.0: 1.0 0,020 0.004 5.2: 1.0 92.0 - "- 5. C ₈ -C ₁₀ 2.0: 1.0 0,030 0.005 6.0: 1.0 92.0 - "- 6. C ₁₂ -C ₁₄ 2.0: 1.0 0,026 0.005 5.2: 1.0 93.5 - "- 7. C ₁₂ -C ₁₄ 2.3: 1.0 0,020 0.004 5.0: 1.0 93.0 - "- 8. C ₁₂ -C ₁₄ 2.5: 1.0 0,030 0.005 6.0: 1.0 93.0 - "- 9. C ₁₂ -C ₁₈ 2.0: 1.0 0,026 0.005 5.2: 1.0 92.5 - "- 10. C ₁₂ -C ₁₈ 2.3: 1.0 0,026 0.005 5.2: 1.0 92.5 - "- eleven. C ₁₂ -C ₁₈ 2.5: 1.0 0,026 0.005 5.2: 1.0 93.0 - "- 12. C ₁₂ -C ₁₈ 2.0: 1.0 0,020 0.004 5.0: 1.0 92.0 - "- 13. C ₁₂ -C ₁₈ 2.0: 1.0 0,030 0.005 6.0: 1.0 92.0 - "- fourteen. C ₁₆ -C ₂₀ 2.0: 1.0 0,026 0.005 5.2: 1.0 92.5 - "- fifteen. C ₁₆ -C ₂₀ 2.3: 1.0 0,020 0.004 5.0: 1.0 92.0 - "- 16. C ₁₆ -C ₂₀ 2.5: 1.0 0,030 0.005 6.0: 1.0 92.5 - "- For comparison 17. C ₈ -C ₁₀ 1.7: 1.0 0,020 0.004 5.0: 1.0 81.0 eighteen. C ₈ -C ₁₀ 3.0: 1.0 0,020 0.004 5.0: 1.0 - Product removal reduction 19. C ₈ -C ₁₀ 2.3: 1.0 0.012 0.003 4.0: 1.0 - Polymer formation twenty. C ₈ -C ₁₀ 2.3: 1.0 0,032 0.005 6.4: 1.0 - Painted Monomer 21. C ₈ -C ₁₀ 3.0: 1.0 0.012 0.003 4.0: 1.0 - Polymer formation 22. C ₁₂ -C ₁₄ 1.7: 1.0 0,020 0.004 5.0: 1.0 80.0 23. C ₁₂ -C ₁₄ 3.0: 1.0 0,020 0.04 5.0: 1.0 - Product removal reduction 24. C ₁₂ -C ₁₄ 2.3: 1.0 0,120 0.003 4.0: 1.0 - Polymer formation 25. C ₁₂ -C ₁₄ 2.3: 1.0 0,032 0.005 6.4: 1.0 - Painted Monomer 26. C ₁₂ -C ₁₄ 3.0: 1.0 0.012 0.003 4.0: 1.0 - Polymer formation 27. C ₁₂ -C ₁₈ 1.7: 1.0 0,026 0.005 5.2: 1.0 80.0 28. C ₁₂ -C ₁₈ 3.0: 1.0 0,020 0.004 5.0: 1.0 - Product removal reduction 29. C ₁₂ -C ₁₈ 2.3: 1.0 0.012 0.003 4.0: 1.0 - Polymer formation thirty. C ₁₂ -C ₁₈ 2.3: 1.0 0,032 0.005 6.4: 1.0 - Painted Monomer 31. C ₁₂ -C ₁₈ 3.0: 1.0 0.012 0.003 4.0: 1.0 - Polymer formation 32. C ₁₆ -C ₂₀ 1.7: 1.0 0,020 0.004 5.0: 1.0 80.0 33. C ₁₆ -C ₂₀ 3.0: 1.0 0,020 0.004 5.0: 1.0 - Product removal reduction 34. C ₁₆ -C ₂₀ 2.3: 1.0 0.012 0.003 4.0: 1.0 - Polymer formation 35. C ₁₆ -C ₂₀ 2.3: 1.0 0,032 0.005 6.4: 1.0 - Painted Monomer 36. C ₁₆ -C ₂₀ 3.0: 1.0 0.012 0.003 4.0: 1.0 - Polymer formation

From the data shown in table 1, it can be seen that when transesterifying methyl methacrylate with higher fatty alcohols, the fractions C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ under the claimed conditions receive monomers with a yield of 92.0- 93.5%, storage stable (see examples 1-16). When transesterifying methyl methacrylate with higher fatty alcohols, the fractions C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , or C ₁₆ -C ₂₀ in a reduced (undeclared) molar ratio of methyl methacrylate is the indicated higher fatty alcohol, but with the claimed mass ratio of inhibitors the yield of the final product is reduced (see examples 17, 22, 27, 32). With an increase in the content of methyl methacrylate, but the claimed mass ratio of inhibitors, the removal of the final product from a unit volume of the reactor decreases sharply, which is economically disadvantageous (see examples 18, 23, 28, 33). If the transesterification of methyl methacrylate is carried out with a mass ratio of phenolic inhibitors lower than the declared, but with the claimed molar ratio of methyl methacrylate: higher fatty alcohol, then alkyl (C ₈ -C ₁₀ ) -, (C ₁₂ -C ₁₄ ) -, (C ₁₂ -C ₁₈ ) - and (C ₁₆ -C ₂₀ ) methacrylate is polymerized (see examples 19, 24, 29, 34); when the mass ratio of phenolic inhibitors is greater than the claimed, but with the claimed molar ratio of methyl methacrylate: higher fatty alcohol, alkyl methacrylate is colored, which is undesirable (see examples 20, 25, 30, 35). The polymer is formed during the transesterification of methyl methacrylate with higher fatty alcohols in a molar ratio greater than the claimed, when using phenolic inhibitors in a ratio lower than the declared (see examples 21, 26, 31, 36).

In the proposed examples 1-23 and table 2, methods for preparing various polyalkyl (C ₈ -C ₁₀ ) -, polyalkyl (C ₁₂ -C ₁₄ ) -, polyalkyl (C ₁₂ -C ₁₈ ) -, and polyalkyl (C ₁₆ - C ₂₀ ) methacrylates and their properties.

To implement the proposed methods using various alkyl methacrylates obtained in examples 1-16 of the description of the application from table 1. As an inert solvent in the polymerization of alkyl methacrylates, for example, toluene (GOST 5789-78), industrial oil of the brand I-20A (GOST 20799-88 ), molecular weight regulator lauryl mercaptan (TU 6-09-13-930-87), polymerization initiator, for example, 2,2 ^1- azodi-isobutyric acid dinitrile (ADN, TU 6-09-3840-74), tert butyl perbenzoate (TBPB, TU 6-05-1997-85).

The resulting polymers are analyzed according to the following indicators: kinematic viscosity at a temperature of 50 ± 0.1 ° C according to GOST 33-82, viscosity index according to GOST 25371-97, color according to GOST 20284-74, oil pour point (for example, grade I-20A) containing the additive - the resulting polymer, according to GOST 20287-91. The kinematic viscosity at a temperature of 50 ± 0.1 ° C of the obtained polymers is 900-15500 mm ² / s. Other properties of polyalkyl methacrylates are shown in table 2.

Example 1

The polymerization of alkyl (C ₈ -C ₁₀ ) methacrylate obtained in Example 1 of Table 1 is carried out in a one-liter four-neck reactor equipped with a mechanical paddle stirrer, a thermometer, a nitrogen bubbler and a dropping funnel. 300 g of an inert solvent, industrial oil I-20A, are loaded into the reactor, heated to 65 ° C and nitrogen is passed through it at a rate of 20 ml / min for 30 minutes. 2.9 g (1.45 wt% of the monomer) of the ADN polymerization initiator, 0.17 g (0.075 wt% of the monomer) of the molecular weight regulator of lauryl mercaptan and 208.3 g of alkyl (C ₈ -C ₁₀ ) methacrylate are added. The contents of the reactor are heated to 80 ° C and polymerization is carried out. The process ends at 100-105 ° C. The total reaction time is 11 hours. Unreacted monomer and residual alcohol are distilled off on a rotary-film evaporator at a pressure of 4 kPa and a temperature of 170 ° C. Get 480 g of a 4 -% transparent solution of the polymer in industrial oil I-20A. Conversion 98.5%.

Example 2

The polymerization of alkyl (C ₈ -C ₁₀ ) methacrylate obtained in example 4 of table 1 and taken in the amount of 326.1 g is carried out as in example 1, but 200 g of industrial oil I-20A, 4.5 g, are loaded into the reactor 1.50 wt.% Of the monomer) of the ADN polymerization initiator and 0.25 g (0.083 wt.% Of the monomer) of lauryl mercaptan. Get 526 g of a 60% transparent solution of the polymer in industrial oil I-20A. Conversion 98.7%.

Example 3

The polymerization of alkyl (C ₈ -C ₁₀ ) methacrylate obtained in example 3 of table 1 and taken in an amount of 208.3 g is carried out as in example 1, but 3.1 g (1.55 wt.% Of the monomer) are loaded into the reactor ) ADN polymerization initiator and 0.180 g (0.10 wt.% of the monomer) of lauryl mercaptan. Get 510 g of a 40% transparent solution of the polymer in industrial oil I-20A. Conversion 98.5%.

Example 4

The polymerization of the alkyl (C ₈ -C ₁₀ ) methacrylate obtained in Example 2 of Table 1 and taken in an amount of 208.3 g is carried out analogously to Example 1, but 3 g (1.50 wt.% Of the monomer) of the ADN polymerization initiator are charged and 0.175 g (0.087 wt% of the monomer) of lauryl mercaptan. Get 510 g of a 40% transparent solution of the polymer in industrial oil I-20A. Conversion 98.5%.

Example 5

The polymerization of alkyl (C ₈ -C ₁₀ ) methacrylate obtained in example 5 of table 1 and taken in an amount of 434.8 g is carried out as in example 1, but 100 g of industrial oil I-20A, 6 g, are loaded into the reactor (1, 50 wt.% Of the monomer) of the polymerization initiator ADN and 0.35 g (0.087 wt.% Of the monomer) of lauryl mercaptan. 520 g of an 80% clear polymer solution in industrial oil I-20A are obtained. Conversion 98.9%.

Example 6

The polymerization of alkyl (C ₈ -C ₁₀ ) methacrylate obtained in example 2 of table 1 and taken in an amount of 208.1 g is carried out as in example 1, but 4.6 g (2.3 wt.% Of monomer) are charged into the reactor ) initiator of polymerization of TBPB and 0.06 g (0.030 wt.% of the monomer) of lauryl mercaptan. Get 510 g of a 40% transparent solution of the polymer in industrial oil I-20A. Conversion 98.5%.

Example 7

The polymerization of alkyl (C ₈ -C ₁₀ ) methacrylate obtained according to Example 1 of Table 1 and taken in an amount of 208.3 g is carried out as in Example 1, but 300 g of industrial oil I-20A, 5 g, are loaded into the reactor (2, 5 wt.% Of the monomer) of the polymerization initiator TBPB and 0.07 g (0.035 wt.% Of the monomer) of lauryl mercaptan. The polymerization is carried out at 115 ° C for 8 hours. Get 509 g of a clear 40% solution of the polymer in industrial oil I-20A. Conversion 98.5%.

Example 8

The polymerization of alkyl (C ₈ -C ₁₀ ) methacrylate obtained in example 3 of table 1 and taken in an amount of 209 g is carried out as in example 1, but 5.4 g (2.7 wt.% Of the monomer) of the initiator are charged into the reactor polymerization of TBPB and 0.08 g (0.044 wt.% of the monomer) of lauryl mercaptan. Receive 510 g of a clear 40% solution of the polymer in industrial oil I-20A. Conversion 98.5%.

Example 9

The polymerization of alkyl (C ₁₂ -C ₁₄ ) methacrylate obtained in accordance with Example 7 of Table 1 and taken in an amount of 216 g is carried out as in Example 1, but 300 g of industrial oil I-20A, 2.14 g (2, 5 wt.% Of the monomer) of the ADN polymerization initiator and 0.015 g (0.075 wt.% Of the monomer) of lauryl mercaptan. The polymerization is carried out at 115 ° C for 8 hours. Obtain 517 g of a clear 40% solution of the polymer in industrial oil I-20A. Conversion 98.4%.

Example 10

The polymerization of alkyl (C ₁₂ -C ₁₄ ) methacrylate, obtained according to example 6 of table 1 and taken in an amount of 216 g, is carried out as in example 1, but 300 g of industrial oil I-20A, 2 g (1.0 wt. % of the monomer) of the polymerization initiator ADN and 0.145 g (0.072% by weight of the monomer) of lauryl mercaptan. Obtain 517 g of a clear 40% solution of the polymer in industrial oil I-20A. Conversion 98.4%.

Example 11

The polymerization of alkyl (C ₁₂ -C ₁₄ ) methacrylate obtained in example 8 of table 1 and taken in an amount of 217.5 g is carried out as in example 1, but 2.32 g (1.16 wt.% Of the monomer) are loaded into the reactor ) ADN polymerization initiator and 0.176 g (0.087 wt% of the monomer) of lauryl mercaptan. Get 517 g of a 40% solution of the polymer in industrial oil I-20A. Conversion 98.5%.

Example 12

The polymerization of alkyl (C ₁₂ -C ₁₄ ) methacrylate obtained in accordance with Example 7 of Table 1 and taken in an amount of 215 g is carried out as in Example 1, but 300 g of industrial oil I-20A, 4.6 g, are loaded into the reactor (2, 3 wt.% Of the monomer) of the polymerization initiator TBPB and 0.064 g (0.032 wt.% Of the monomer) of lauryl mercaptan. The polymerization is carried out at 115 ° C for 8 hours. Obtain 513 g of a clear 40% solution of the polymer in industrial oil I-20A. Conversion 98.5%.

Example 13

The polymerization of alkyl (C ₁₂ -C ₁₈ ) methacrylate obtained according to example 13 of table 1 and taken in an amount of 425.5 g is carried out as in example 1, but 100 g of industrial oil I-20A, 4.7 g, are loaded into the reactor 1.10 wt.% Of the monomer) of the ADN polymerization initiator, 0.3 g (0.070 wt.% Of the monomer) of lauryl mercaptan. 523 g of an 80% clear polymer solution in industrial oil I-20A are obtained. Conversion 98.8%.

Example 14

The polymerization of alkyl (C ₁₂ -C ₁₈ ) methacrylate obtained in accordance with Example 10 of Table 1 and taken in an amount of 217 g is carried out as in Example 1, but 300 I-20A industrial oils, 2.1 g, are loaded into the reactor (1, 07 wt.% Of the monomer) initiator ADN, 0.150 g (0.075 wt.% Of the monomer) lauryl mercaptan. Obtain 518 g of a 40% clear solution of polyalkyl (C ₁₂ -C ₁₈ (methacrylate in industrial coat I-20A. Conversion 98.5%.

Example 15

The polymerization of alkyl (C ₁₂ -C ₁₈ ) methacrylate obtained in example 10 of table 1 and taken in an amount of 216 g is carried out as in example 1, but 300 g of toluene, 2.14 g (1.07 wt.% From the monomer) of the polymerization initiator ADN and 0.15 g (0.075 wt.% of the monomer) of lauryl mercaptan. Obtain 517 g of a 4% solution of polymer in toluene. Toluene is distilled off in vacuo at 40-45 ° C and a residual pressure of 40 mm Hg. The resulting polymer is mixed with 300 g of industrial oil I-20A, obtaining a 40% polymer solution. Conversion 98.8%.

Example 16

The polymerization of alkyl (C ₁₂ -C ₁₈ ) methacrylate obtained in Example 9 of Table 1 and taken in an amount of 217 g is carried out as in Example 1, but 300 g of industrial oil I-20A are loaded into the reactor. 2.1 g (1.0 wt.% Of the monomer) of the ADN initiator and 0.145 g (0.072 wt.% Of the monomer) of lauryl mercaptan. Get 518 g of a 40% transparent solution of the polymer in industrial oil I-20A. Conversion 98.4%.

Example 17

The polymerization of alkyl (C ₁₂ -C ₁₈ ) methacrylate, obtained according to example 9 of table 1 and taken in the amount of 216 g, is carried out as in example 1, but 300 g of toluene, 2 g (1.0 wt.% Of monomer) are loaded into the reactor ) ADN polymerization initiator and 0.145 g (0.072 wt% of the monomer) of lauryl mercaptan. Obtain 517 g of a 40% solution of the polymer in toluene. Toluene is distilled off in vacuo at 40-45 ° C and a residual pressure of 40 mm Hg. The resulting polymer is mixed with 300 g of industrial oil I-20A to obtain a 4% polymer solution. Conversion 98.7%.

Example 18

The polymerization of alkyl (C ₁₂ -C ₁₈ ) methacrylate obtained in Example 11 of Table 1 and taken in an amount of 319 g is carried out as in Example 1, but 200 g of industrial oil I-20A, 3.5 g (1.16) are charged into the reactor wt.% from the monomer) of the polymerization initiator ADN and 0.263 g (0.087 wt.% from the monomer) of lauryl mercaptan. Obtain 520 g of a 60% clear polymer solution in in-tri-I-20A oil. Conversion 98.5%.

Example 19

The polymerization of alkyl (C ₁₂ -C ₁₈ ) methacrylate obtained in example 12 of table 1 and taken in an amount of 316 g is carried out as in example 1, but 200 g of toluene, 2.32 g (1.16 wt.% From the monomer) of the polymerization initiator ADN and 0.176 g (0.087 wt.% of the monomer) of lauryl mercaptan. Obtain 517 g of a 60% solution of the polymer in toluene. Toluene is distilled off, as in example 15. The conversion of 98.5%.

Example 20

The polymerization of alkyl (C ₁₂ -C ₁₈ ) methacrylate obtained in Example 10 of Table 1 and taken in an amount of 217 g is carried out as in Example 1, but 300 g of industrial oil I-20A, 5.2 g (2.6 g) are loaded into the reactor wt.% from the monomer) of the polymerization initiator TBPB and 0.076 g (0.038 wt.% from the monomer) of lauryl mercaptan. The polymerization is carried out at 115 ° C for 8 hours. Obtain 519 g of a clear 40% solution of the polymer in industrial oil I-20A. Conversion 98.5%.

Example 21

The polymerization of alkyl (C ₁₆ -C ₂₀ ) methacrylate obtained in Example 14 of Table 1 and taken in an amount of 215 g is carried out as in Example 1, but 300 g of industrial oil I-20A, 2.9 g (1.16) are charged into the reactor wt.% from the monomer) of the polymerization initiator ADN and 0.14 g (0.075 wt.% from the monomer) of lauryl mercaptan. Get 515 g of a 40% solution in industrial oil I-20A. Conversion 98.4%.

Example 22

The polymerization of alkyl (C ₁₆ -C ₂₀ ) methacrylate obtained in example 15 of table 1 and taken in an amount of 215 g is carried out as in example 1, but 300 g of industrial oil I-20A, 3.0 g (1.5 g) are loaded into the reactor wt.% from the monomer) of the polymerization initiator ADN and 0.16 g (0.087 wt.% from the monomer) of lauryl mercaptan. Get 515 g of a 40% solution of the polymer in industrial oil I-20A. Conversion 98.5%.

Example 23

The polymerization of alkyl (C ₁₆ -C ₂₀ ) methacrylate obtained in example 16 of table 1 and taken in an amount of 215 g is carried out as in example 1, but 300 g of industrial oil I-20A, 2.9 g (1.45) are charged into the reactor wt.% from the monomer) of the polymerization initiator ADN and 0.186 g (0.093 wt.% from the monomer) of lauryl mercaptan. Get 515 g of a 40% solution of the polymer in industrial oil I-20A. Conversion 98.8%.

table 2
The method of producing polyalkyl (C ₈ -C ₁₀ ) -, polyalkyl (C ₁₂ -C ₁₄ ) -, polyalkyl (C ₁₂ -C ₁₈ ) - and polyalkyl (C ₁₈ -C ₂₀ ) methacrylates and their properties №№ pp Source components Monomer Conversion,% Properties of Polyalkyl Methacrylates Note Alkyl Methacrylate Polymerization initiator The mass ratio of the molecular weight regulator and the polymerization initiator Viscosity index Color, units CTN Pour point, ° C one 2 3 four 5 6 7 8 9 Proposed one. C ₈ -C ₁₀ ADN 0.051: 1.0 98.5 189 0.5 minus 35 In examples 1-4, 16, 18, 20-23, the solvent is industrial oil 2. - "- - "- 0.055: 1.0 98.7 190 0.5 minus 36 3. - "- - "- 0.064: 1.0 98.5 190 0.5 minus 36 four. - "- - "- 0.058: 1.0 98.5 190 0.5 minus 38 5. - "- - "- 0.058: 1.0 98.9 190 0.5 minus 38 6. - "- TBPB 0.013: 1.0 98.5 189 1,5 minus 38 7. - "- - "- 0.014: 1.0 98.5 190 1,5 minus 38 8. - "- - "- 0.016: 1.0 98.5 189 1,5 minus 38 9. C ₁₂ -C ₁₄ ADN 0.070: 1.0 98.4 190 1,0 minus 38 10. - "- - "- 0.072: 1.0 98.4 190 1,0 minus 38 eleven. - "- - "- 0.075: 1.0 98.5 189 1,0 minus 38 12. - "- TBPB 0.014: 1.0 98.5 189 1,5 minus 38 13. C ₁₂ -C ₁₈ ADN 0.063: 1.0 98.8 195 1,0 minus 40 fourteen. - "- - "- 0.070: 1.0 98.5 195 1,0 minus 40 fifteen. - "- - "- 0.070: 1.0 98.8 190 1,5 minus 38 In examples 15,17,19 the solvent is toluene 16. - "- - "- 0,0726: 1,0 98.4 195 1,0 minus 40 17. - "- - "- 0.072: 1.0 98.7 189 1,5 minus 38 eighteen. - "- - "- 0.075: 1.0 98.5 195 1,0 minus 40 19. - "- - "- 0.075: 1.0 98.5 189 1,5 minus 40 twenty. - "- TBPB 0.015: 1.0 98.5 189 1,5 minus 38 21. C ₁₆ -C ₂₀ ADN 0.051: 1.0 98.4 189 1,5 minus 39 22. - "- - "- 0.058: 1.0 98.5 189 1,5 minus 39 23. - "- - "- 0.064: 1.0 98.6 189 1,5 minus 39 For comparison 24. According to the prototype 98.0 189-191 2.5-3.0 minus 33

From the data shown in table 2, it is seen that during the polymerization of alkyl methacrylates obtained according to examples 1-16 of the description of table 1, in the claimed conditions, the conversion of monomers is 98.4-98.9%. The obtained transparent polymers are characterized by the following indicators: viscosity index 189-195, color 0.5-1.5 units. CNT, pour point (-35) ÷ (40) ° С.

When carrying out the polymerization of alkyl methacrylates under conditions different from the declared ones (when the mass ratio of the molecular weight regulator and the polymerization initiator is less than or greater than the claimed), the conversion of monomers sharply decreases, and it is inappropriate to determine the performance of the obtained polymers.

The copolymerizable monomers and some compositions (mixtures) of copolymerizable monomers are shown in Table 3. The remaining compositions of the copolymerizable monomers are not listed in Table 3.

In the proposed examples 1-100 and taken for comparison examples 102-124, as well as table 4, methods for producing various polyalkyl (C ₈ -C ₁₀ ) -, polyalkyl (C ₁₂ -C ₁₄ ) -, polyalkyl (C ₁₂ -C ₁₈ ) - and polyalkyl (C ₁₆ -C ₂₀ ) methacrylates by copolymerization: mixtures of alkyl methacrylates; alkyl methacrylate with various monomers or a mixture of monomers; mixtures of alkyl methacrylates with various monomers or a mixture of monomers; and properties of polyalkyl methacrylates.

For the implementation of the proposed methods use various alkyl methacrylates obtained in examples 1-16 of the description of the application from table 1; methyl methacrylate (MMA, GOST 20370-74), butyl methacrylate (BMA, TU 6-01-2-784-86), 2-ethylhexyl methacrylate (2-EGMA, obtained in the laboratory), styrene (GOST 10003-90), alkyl ( C ₈ -C ₁₀ ) -, (C ₁₂ -C ₁₄ ) -, (C ₁₂ -C ₁₈ ) - and (C ₁₆ -C ₂₀ ) maleates (obtained in laboratory conditions); other components were indicated above.

The resulting copolymers are analyzed according to the following indicators: kinematic viscosity at a temperature of 50 ± 0.1 ° C according to GOST 33-82, viscosity index according to GOST 25371-97, color according to GOST 20284-74, pour point of I-20A brand oil containing an additive - the resulting copolymer according to GOST 20287-91. The kinematic viscosity at a temperature of 50 ± 0.1 ° C of the obtained copolymers is 1660-12700 mm ² / s, viscosity index 179-186. Other properties of polyalkyl methacrylates are shown in table 4.

The number carried out by the authors of the methods for producing various polyalkyl methacrylates is not limited to the examples 1-100 of table 4 indicated in the application description.

Example 1

The copolymerization of alkyl (C ₈ -C ₁₂ ) methacrylate obtained in example 1 of table 1, and alkyl (C ₁₂ -C ₁₈ ) methacrylate obtained in example 9 of table 1, is carried out in a one-liter four-neck reactor equipped with a mechanical paddle stirrer, thermometer, bubbler for supplying nitrogen and a dropping funnel. 150 g of an inert solvent — I-20A industrial oil — are loaded into the reactor, heated to 65 ° C and nitrogen is passed through it at a rate of 20 ml / min for 30 minutes. 2.25 g (1.5 wt.% Of monomers) of ADN initiator are added, 0.122 g (0.082 wt.% Of monomers) of lauryl mercaptan, 75 g (50 wt.%) Alkyl (C ₈ -C ₁₀ ) methacrylate, 75 g (50 wt.%) Ayakyl (C ₁₂ -C ₁₈ ) methacrylate. The contents of the reactor are heated to 80 ° C and polymerization is carried out. The process ends at 100-105 ° C. The total reaction time is 11 hours. Unreacted monomers and residual alcohol are distilled off on a rotary-film evaporator at a pressure of 4 kPa and a temperature of 170 ° C. Obtain 295 g of a 50% solution of the copolymer in the industrial mal I-20A. Conversion 98.5%.

Examples 2-11

The copolymerization of mixtures of alkyl methacrylates (150 g) is carried out in the reactor according to example 1. The number of starting components and their ratio are shown in table 4.

Examples 12-33

The copolymerization of alkyl methacrylate with a monomer or a mixture of monomers (in an amount of 150 g) from table 3 is carried out in the reactor of example 1. The number of starting components and their ratio are shown in table 4.

Examples 34-100

The copolymerization of a mixture of alkyl methacrylates with a monomer or a mixture of monomers (in an amount of 150 g) from table 3 is carried out in the reactor according to example 1. The number of starting components and their ratio are shown in table 4.

Examples 102-109

The copolymerization of alkyl methacrylate with a monomer or a mixture of monomers from table 3 is carried out in the reactor of example 1 under conditions different from those stated in examples 12-33 of table 4.

Examples 110-124

The copolymerization of a mixture of alkyl methacrylates with a monomer or a mixture of monomers from table 3 is carried out in the reactor of example 1 under conditions different from those stated in examples 34-100 of table 4.

From the data shown in table 4, it is seen that during the copolymerization of mixtures of alkyl methacrylates obtained according to examples 1-16 of table 2, or alkyl methacrylate with the monomer or mixture of monomers from table 3, or a mixture of alkyl methacrylates according to examples 1-16 of table 1 with a monomer or mixture of monomers from table 3 in the claimed conditions, the conversion of (co) monomers is 98.5-98.8%. The obtained transparent copolymers have a color of 1.0-2.0 units of CNT, pour point (-36) ÷ (-42) ° C (see examples 1-100). When carrying out the copolymerization of alkyl methacrylates under conditions different from the declared ones (when the mass ratio of the molecular weight regulator and the initiator of copolymerization is lower or greater than the claimed), the conversion of comonomers sharply decreases, and it is impractical to determine the indicators of the obtained copolymers. When copolymerizing alkyl methacrylate with a monomer or monomer mixture from the table 3 or a mixture of alkyl methacrylates with a monomer or a mixture of monomers from table 3, taken in an amount less than the declared, but with the claimed mass tion ratio of the molecular weight regulator and initiator copolymerizable comonomer conversion is 82,0-82,4%, a decrease in the kinematic viscosity, thus deteriorating color copolymers and increases the pour point (see. Examples 102-124). A similar effect also occurs during the copolymerization of other alkyl methacrylates with the monomer or mixture of monomers from Table 3 or a mixture of alkyl methacrylates with the monomer or mixture of monomers taken in an amount less than the declared amount, but with the claimed weight ratio of the molecular weight regulator and the copolymerization initiator. These examples are not shown in table 4. When copolymerizing alkyl methacrylates with a monomer or a mixture of monomers from Table 3 or a mixture of alkyl methacrylates with a monomer or a mixture of monomers taken in an amount greater than the declared amount (with the stated mass ratio of the molecular weight regulator and the copolymerization initiator), the properties of the resulting copolymers are close to the properties of the polymers according to Table 2.

Claims (9)

1. A method of producing a polyalkyl methacrylate additive by polymerization of an alkyl methacrylate in an inert solvent in the presence of lauryl mercaptan and a polymerization initiator by heating, characterized in that an ether of the general formula CH ₂ = C (CH ₃ ) COOR obtained by transesterification of methyl methacrylate of one of the higher fatty fractions is used as an alkyl methacrylate alcohols selected from the group C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in a stream of air at a temperature of 110-130 ° C, with a molar ratio of methyl methacrylate to the fraction of higher fatty alcohols, equal m (2.0-2.5): 1, in the presence of an alkaline potassium carbonate catalyst and a mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditret-butyl-4-methylphenol in a weight ratio of 5.0-6.0 ):one. 2. A method of producing a polyalkyl methacrylate additive by copolymerization of alkyl methacrylates in an inert solvent in the presence of lauryl mercaptan and a copolymerization initiator by heating, characterized in that they use a mixture of alkyl methacrylates in which the alkyl methacrylate is an ether of the general formula CH ₂ = C (CH ₃ ) COOR obtained by methyl methacrylate fractions of higher fatty alcohols, chosen from the group of C ₈ -C _10, C _12, C _14, C ₁₂ -C _18, C ₁₆ -C _20, in an air stream at a temperature of 110-130 ° C and a molar ratio of methyl methacrylate fraction of higher fatty alcohols equal to (2.0-2.5): 1, in the presence of an alkaline potassium carbonate catalyst and a mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditret-butyl-4-methylphenol in their mass ratio (5, 0-6.0): 1. 3. A method for producing a polyalkyl methacrylate additive by copolymerization of an alkyl methacrylate in an inert solvent in the presence of lauryl mercaptan and a copolymerization initiator by heating, characterized in that an ether of the general formula CH ₂ = C (CH ₃ ) COOR obtained by transesterification of methyl methacrylate of one of the higher fat fractions is used as an alkyl methacrylate alcohols selected from the group C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in a stream of air at a temperature of 110-130 ° C, with a molar ratio of methyl methacrylate to the fraction of higher fatty alcohols, (2.0-2.5): 1, in the presence of an alkaline potassium carbonate catalyst and a mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditret-butyl-4-methylphenol in their mass ratio (5.0-6.0 ): 1, which is copolymerized in an amount of 50-95 wt.% With a monomer or a mixture of monomers selected from the group consisting of methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, styrene, alkyl maleate, where alkyl is C ₈ -C ₁₀ , C ₁₂ -C ₁₄ C ₁₂ -C ₁₈ C ₁₆ -C ₂₀ . 4. A method of producing a polyalkyl methacrylate additive by copolymerization of an alkyl methacrylate in an inert solvent in the presence of lauryl mercaptan and a copolymerization initiator by heating, characterized in that a mixture of alkyl methacrylates is used, in which the alkyl methacrylate is an ether of the general formula CH ₂ = C (CH ₃ ) COOR obtained by transesterification from fractions of higher fatty alcohols selected from the group C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in a stream of air at a temperature of 110-130 ° C and a molar ratio of methyl methacrylate and fraction of higher fatty alcohols equal to (2.0-2.5): 1, in the presence of an alkaline potassium carbonate catalyst and a mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditret-butyl-4-methylphenol in their mass ratio (5, 0-6.0): 1, which is copolymerized in an amount of 50-95 wt.% With a monomer or a mixture of monomers selected from the group consisting of methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, styrene, alkyl maleate, where C ₈ -C ₁₀ alkyl, C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ . 5. A method of producing a polyalkyl methacrylate additive according to claims 1 to 4, characterized in that (co) polymerization of the alkyl methacrylate is carried out at a weight ratio of lauryl mercaptan and polymerization initiator (0.013-0.075): 1. 6. Polyalkyl methacrylate additive obtained by polymerization by heating in an inert solvent in the presence of lauryl mercaptan and an initiator of polymerization of an alkyl methacrylate of the general formula CH ₂ = C (CH ₃ ) COOR obtained by transesterification of methyl methacrylate of one of the higher fatty alcohol fractions selected from the group C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in a stream of air at a temperature of 110-130 ° C, with a molar ratio of methyl methacrylate to the fraction of higher fatty alcohols equal to (2.0-2.5) : 1, in the presence of an alkaline potassium carbonate catalyst and a mixture and phenolic inhibitors of p-methoxyphenol and 2,6-ditret-butyl-4-methylphenol in their mass ratio (5.0-6.0): 1. 7. Polyalkyl methacrylate additive obtained by copolymerization by heating in an inert solvent in the presence of lauryl mercaptan and a copolymerization initiator of a mixture of alkyl methacrylates of the general formula CH ₂ = C (CH ₃ ) COOR, in which alkyl methacrylate is obtained by transesterification of methyl methacrylate from one of the higher fatty alcohol fractions ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in a stream of air at a temperature of 110-130 ° C and a molar ratio of methyl methacrylate and the fraction of higher fatty alcohols equal to (2.0-2 , 5): 1, in the presence of an alkaline catalyst Ator potassium carbonate and mixtures of phenolic inhibitors of p-methoxyphenol and 2,6-di-tert-butyl-4-methylphenol at a weight ratio of (5.0-6.0): 1. 8. Polyalkyl methacrylate additive obtained by copolymerization by heating in an inert solvent in the presence of lauryl mercaptan and a copolymerization initiator of 50-95 wt.% Alkyl methacrylate of the general formula CH ₂ = C (CH ₃ ) COOR obtained by transesterification of methyl methacrylate from one of the higher fatty alcohol fractions selected groups C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in a stream of air at a temperature of 110-130 ° C, with a molar ratio of methyl methacrylate and a fraction of higher fatty alcohols equal to (2, 0-2.5): 1, in the presence of an alkaline potassium carbon catalyst the syllable and mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditret-butyl-4-methylphenol in their weight ratio (5.0-6.0): 1 with a monomer or a mixture of monomers selected from the group consisting of methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, styrene, alkyl maleate, where alkyl is C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ . 9. Polyalkyl methacrylate additive obtained by copolymerization by heating in an inert solvent in the presence of lauryl mercaptan and a copolymerization initiator of 50-95 wt.% A mixture of alkyl methacrylates of the general formula CH ₂ = C (CH ₃ ) COOR, in which alkyl methacrylate is obtained by transesterification of methyl methacrylate fat fractions of one of the fractions alcohols selected from the group C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ , in a stream of air at a temperature of 110-130 ° C and a molar ratio of methyl methacrylate to the fraction of higher fatty alcohols (2 , 0-2.5): 1 in the presence of alkali potassium carbonate and a mixture of phenolic inhibitors of p-methoxyphenol and 2,6-ditret-butyl-4-methylphenol in their mass ratio (5.0-6.0): 1 with a monomer or a mixture of monomers selected from the group consisting of methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, styrene, alkyl maleate, where alkyl is C ₈ -C ₁₀ , C ₁₂ -C ₁₄ , C ₁₂ -C ₁₈ , C ₁₆ -C ₂₀ .