DE1520624C - Process for the production of a liquid copolymers from ethylene and ethyl acrylate, methyl acrylate or methyl methacrylate lat - Google Patents

Description

Various processes are already available for the production of copolymers of ethylene with acrylic acids has been proposed, including in U.S. Pat. No. 2,200,429 and in US Pat British patents 579,884 and 703,252. All of these processes are characterized in that the Interpolymerization requires a relatively long time, although relatively high temperatures and pressures and the cheapest free radical initiators and catalysts used will. For example, according to the process of US Pat. No. 2,200,429, copolymers of ethylene are obtained with methyl methacrylate, ethyl acrylate or methyl acrylate at temperatures from 100 to 400 ° C and Pressures of at least 500 at, for example 1500 at or even 2500 at, can be produced. That way The copolymers obtained are solid substances with a hard to rubbery character and high Molecular weights from 3000 to about 10,000.

In contrast, the invention has set itself the task, proceeding from the same, last-mentioned To produce comonomers, liquid copolymers with low molecular weights, which are completely, particularly suitable as a lubricant and as a plasticizer for synthetic resins based on vinyl and are by characterized by low viscosities and low acid numbers.

The inventive method for the production of copolymers from ethylene and ethyl acrylate, Methyl acrylate or methyl methacrylate through copolymerization of the monomers at temperatures up to 400 ° C and high pressures is characterized in that a temperature of 150 to 400 ° C and a pressure of 72 to 720 atm is applied, the residence time of the reactants in the reaction zone is limited to 30 seconds to 30 minutes the process up to the formation of a copolymer with an acid number of at most 3, a molecular weight of 500 to 1500 and a molar ratio of ethylene to acrylate of 1 to 3 carried out is, the upper limit of the molar ratio of the molecular weight according to the formula

X + 0.25

1500 \
Molecular weight /

is dependent and X has the value 1.75 for the case of ethyl acrylate and methyl methacrylate and the value of 2.25 for the case of methyl acrylate, and the liquid reaction products are immediately removed from the reaction zone.

The method carried out according to the invention has the advantage of being more convenient to carry out, because it can be carried out under relatively low pressures, but with high throughputs be achieved. Above all, however, the considerable shortening of the residence times from 18 to 20 hours according to US Pat. No. 2 200 429 for 30 seconds to 30 minutes of undesirable secondary and degradation reactions are largely prevented or even completely eliminated. Such reactions are unavoidable when ethylene is exposed to an acrylic ester under high pressures and temperatures during is copolymerized relatively long reaction times. As a result, the present invention provides Process uniform reaction products that do not require any additional cleaning measures. In addition, high conversions and yields are achieved.

An understanding of the process of the present invention is best understood from the schematic of an apparatus designed to carry out the process. The main parts of this apparatus are a storage tank for ethylene gas, e.g. B. a gas metering cylinder 1, a mixer 2, in which all reactants are mixed with stirring and optionally under the action of cooling devices -. can, an adjustable metering pump 3, which leads the mixture of the reactants to the reaction vessel, a heated pipe 4, which ^{is calibrated to pressures up to 703 kg / cm 2} , and an expansion and collecting vessel 5 for collecting the process product and the unreacted monomers. The dosing cylinder 1, the autoclave 2 and the dosing pump 3 are known commercially available apparatus parts.

so The heatable reaction tube can have various shapes. In the ones below For example, the heating coils consist of either a 6mm standard high pressure pipe or a 4.7mm Ermeto tube. Such pipes have a

* 5 volumes of 8.20 or 40 ecm. Each tube is equipped with several thermocouples, appropriately spaced along its length, to measure the temperature in the tube. The relaxation and collection unit 5 consists of three main parts, namely a pneumatic control element, which is operated by a suitable compressed air source with about 0.63 kg / cm ^a , a sensor which converts the impulses from the high pressure system into a signal that actuates the control element, and a check valve, which either maintains the pressure or vents to the outside space, in accordance with the pulses given by the control element via the sensor. These three organs are also available on the market. With reference to the scheme, the method of the invention is generally carried out as follows:

The mixer 2 and the metering pump 3 are cooled to about -30 ° C. by pumping acetone cooled with dry ice around them. The reaction tube 4 is held in a heating bath made of silicone oil or molten salts, which is heated to the desired temperature by means of a thermoregulated heating unit. The dosing cylinder for the ethylene is filled from a suitable storage container. It is allowed to assume a temperature equilibrium at about 25 ^° C. with the aid of a thermostatically regulated water bath. The mixer 2 is a pressure vessel which is placed under vacuum and then filled with ethylene. The pressure drop is measured to thereby calculate the amount of moles introduced. The other reactants, namely the acrylate, the catalyst and optionally a solvent, are brought into a cylinder not shown in the diagram and from there are injected into the mixer 2 with nitrogen under pressure.

The pressure usually does not exceed 35.2 kg / cm ² .

The contents of the mixer are then stirred for at least 2 minutes and then the stirrer can be used switch off.

The apparatus arrangement described represents only one embodiment and can be modified in many ways will. So can be replaced by a device which two or more streams in such a way Dosing pump injects that separate streams

mixed thoroughly before entering the hot reaction coil.

As soon as the metering pump 3 starts up, the desired pressure is built up in a few minutes. The reaction mixture passes through the reaction tube 4, where it remains at a temperature of about 150 to 400 ^° C. and a pressure of at least 70.3 kg / cm ^{3 for} 30 minutes to 30 seconds, preferably 2 to 20 minutes. .

The mixture is released through the check valve as soon as the desired pressure is reached, and from that point on - the valve opens and closes continuously to vent both the liquid and the gas. Under no circumstances should the pressure exceed ^{703 kg / cm 2.} The liquid is collected in a modified fraction separator while the gases are passed through a moisture measuring device. During the process, usually the temperatures of the thermocouples, the data of the humidity measurement arrangement, the speed of the attack of the condensed phase, the pressure at the check valve and the temperatures of the cooling bath (typically about -30 ⁰ C) read.

The liquid process product is freed from volatile constituents by heating in a simple still with take-off overhead, usually under vacuum. The final temperature and pressure conditions to be observed during this procedure will depend on the intended use. For example, driving off the volatile constituents at about 200 ^° C. and about 1 mm Hg pressure is suitable for obtaining many products that are suitable as plasticizers. The residue from this distillation serves as the basis for calculating the yields and conversion and for the physical and analytical values. The analytical values include a determination of the carbon content in order to calculate the ratio of ethylene to monomeric acrylate in the copolymer.

If appropriate, a known initiator, the free radicals, can be used in the process according to the invention forms, can be applied, e.g. B. di-tert-butyl peroxide or tert-butyl peracetate. These initiators can be in Quantities of 1 to 20 mole percent, calculated per mole of total monomers, are used. Is beneficial the range of 1 to 5 mole percent. Usable · products can also be prepared without the presence of an initiator, but higher conversion rates are formed in the presence of a free radical Initiator reached. The reaction mixture can.ein diluent such as cymene, hexane or methyl isobutyl ketone, to reduce the exothermicity of the reaction and the reaction mixture to keep flowing. Such diluents should generally not exceed 200 percent by weight, calculated on the amount of acrylic monomer. Under certain extreme conditions with regard to temperature, pressure and / or catalyst concentration can despite the inventive short residence time secondary and degradation reactions take place, but these are caused by the addition of small amounts such diluents can be effectively prevented. The obtained by the method according to the invention Products are characterized by extremely low molecular weights and a flowable State off. In addition, they do not contain any by-products or breakdown products. Your superiority as soft

Makers in comparison to previously known copolymers of ethylene and acrylates is likely due to the fact that no chain terminators are present in their production.

The products according to the invention are characterized by the following properties:

1. Molecular weight (measured ebulliometrically) between 500 and 1500,

2. Viscosity in the range H to Z ₅ Gardne r - Ho 1 dt, equivalent 2 to 98.5 poise,

3. Color shade generally 1, but never more than 3, according to the Gardner-Holdt scale 1933,

4. Acid numbers generally below 1 and not * 5 if higher than 3.0,

5. The molar ratio of ethylene to acrylate, depending on the acrylic monomer used, 1.0 to 3.0.

The preferred ranges of the molar ratios and the molecular weight of the process products can can be taken from the following table I:

Methyl acrylate
general
preferably ... Table I. Molecular weight 25th Ethyl acrylate
general
preferably ... 500 to 1500
700 to 900 Methyl methacrylate
general
preferably ... 500 to 1500
700 to 900 500 to 1500
500 to 800 Ethylene acrylic
Molar ratio
in the product 1.0 to 3.00
1.7 to 2.2 1.0 to 2.5
1.3 to 2.0 1.0 to 2.5
2.0 to 2.5

It is characteristic that the molecular weight of the Material, the lower, the greater the proportion of ethylene introduced into the copolymer. So is

in the case of the copolymer of ethylene and methyl acrylate an average molecular weight of about 500 is suitable for a plastic composition in which the molar ratio of ethylene to methyl acrylate is 3.0. However, the value must be reduced to 2.25 as soon as one approaches an average molecular weight of 1500: these Circumstances are taken into account in the table reproduced above, which is the permissible upper limit the ethylene content as a function of the molecular weight.

The products manufactured according to the present process can be used for certain purposes can be additionally improved if the acid number of the copolymers is kept low by For example, an acid number of no more than 3.0 is ensured. This is particularly meaningful when the process products are used as lubricants or as plasticizers for such polymeric substances be like them in. electrical insulation

and the like. In these applications it is necessary, in part, undesirable corrosive Acids? .Us keep away from lubricants and other f-. on the one hand to achieve a high volume resistance,

if the repaired product is to be used as an electrical insulating means.

The examples below illustrate embodiments of the invention Procedure.

The residence time is the time in which the reactants are present in the reaction tube and effectively undergo interpolymerization. To illustrate, it should be stated that the entire duration of the entire process was 108 minutes and resulted in a total of 373 g of liquid product. If you divide the product weight over time, the result is 3.46 g / minute. Take a specific one If the weight of the product is about 1, this value can also be interpreted as 3.46 ccm / minute. The The volume of the reaction coil of Example 1 was 8 ecm. If you divide this by 3.46 cc / minute, this gives the reaction time during which the reactants are actually in the reaction tube linger. This results in a residence time of 2.3 minutes.

In order to discuss the residence time, it should also be taken into account that the reaction participants are all are liquid when they enter the reaction tube. The one emerging at the other end of the reaction tube The product of these reactants is also a liquid. The measurement of the obtained liquid however, does not include the unreacted ethylene which is volatilized. In the present example 1 more than 3.46 ccm / minute of starting materials flows through the reaction tube. If you have a Dividing the volume of the reaction tube by this larger value results in even shorter residence times, as Table II and Examples indicate. The information in Table II about the residence times, which are already considerably below the effective residence times of the known mixed polymerization processes, therefore actually represent maximum values that are actually even undercut. It is evident that the hot reaction coil, when the process is carried out on a larger scale, for example, to be carried out in continuous manufacturing operations, a volume many times over the values of 8.20 or 40 ecm given in the examples below. Elevated If the capacity of the reaction queue is increased, there is at the same time a reduction in dei for Measurement of a certain amount of ethylene and acrylate required time, as each of these operations

ίο Unit supplied a larger amount of the monomers can be. Regardless of the diameter, shape or length of the reaction tube or the rate at which the monomers are passed through the reaction tube, that remain critical residence times practically unchanged. Of course, productivity increases with the increase the capacity of the reaction space. Those prepared according to the following examples Products are all liquid, generally light colored, make useful lubricants or lubricants: additives and are primarily suitable as plasticizers for synthetic resin compositions based on vinyl. ■ Table II shows the properties of a number of copolymers from the examples.

25. posed. The copolymers are by the Number of the example. In the spring case there is 40 parts by weight of the interpolymer of the invention with 60 parts by weight of polyvinyl chloride and 1 part of co-precipitated barium cadmium laurate in usually mixed by known methods.

The test methods mentioned in Table II for

the various plastics made from polyvinyl chloride are known. As a precaution, however, the full

. constant description of these tests is referred to in a publication "Plasticizers" (Rohm & Haas Company. Philadelphia, Pennsylvania, 1954, pp. 66 to 70). Those listed in Table II Properties make clear the good suitability of the products of the invention for plasticization from vinyl resins.

Table II
Properties of copolymers of the invention for plasticizing PVC plastics compositions

Hot example Shore "A" hardness
10 seconds Torsional modulus
V '135001')
"C 90 '"C
Soapy water
extraction
% Hexane -
extraction
% Activated carbons
volatility
° / o loss. . 2 76 - 19 ^{1 line} ₂ 5.2. 25.2. 3.6 3 82 - 1 8.4 22.9 4.2 4th 76 - 6 6.8 9.8 3.2 . 5 79 - 4. ^{1 line} ₂ 12.7 8.6 4.5 6th 83 - 3 ^l / ₂ 3.9 4.2 2.0 9 87 + IV ₂ 5.5 6.5 ■ 2.1 · 10 77 -18 6.2 22.6 5.6 H 77 - 7th 11.9 ' 12.0 4.4 15th 79 - ίο ¹ /. 4.1 15.9 1.0 DOP 69 - 35 9 30th . 10

The last cross column gives the corresponding values for the commercially available plasticizer dioctylphtha-

As already mentioned, the properties of the invention can be used for certain purposes Products can be improved by one.die ■ acidity of the copolymers low, z. B. the Acid number below 3.0, holds. In this case, the products have a higher tolerance and a lower soapy water extractability, this is particularly of importance for a use for electrical insulation and the like. A low acid number is crucial for. good volume resistance. This is shown in Table III below.

Table III Volume resistivity (ohms - cm · 10 ¹² )

Example 2 Product according to
Example 4 j Example 15 1.2 X * More commercially available
Polyester** DPO *** 90 ⁰ C dry 3.2.
6.0 6.7 12.8! 1.5 0.10
0.42 about 0.1
about 0.1 1.9
3.0 60 ⁰ C wet

The column X * gives the values for a mixed polymer of ethylene and ethyl acrylate (molar ratio 1.50, molecular weight 743, acid number 11), which was not produced according to the present invention has been, again. The column »Polyester **« gives the values for known plasticizers made from glycols and dibasic acids again. The "DOP ***" column gives the values for the known plasticizer dioctyl phthalate on.

Dioctyl phthalate is an electrotechnically good one Plasticizer, but a little too volatile. The known polyesters, e.g. B. Polypropylene sebacatej have good resistance, but unsatisfactory electrical properties. From both points of view considered, on the other hand, the products produced by the process according to the invention represent a This is a valuable addition to the technology, because with a lower acid number they are more stable in mass than dioctyl phthalate and at the same time have equivalent or even better electrotechnical properties stocks. '

In summary, it can be stated that the invention improves over the prior art Copolymers are made available. In terms of process technology, a large part of the Previously required processing time and the cost of the thermal energy to be saved. The process is characterized by the unusually rapid reaction of the monomers as soon as they are Reach the part of the apparatus where the conditions for the desired interpolymerization prevail. The process according to the invention only requires a simple mixture of the reactants, which in relatively small quantities continuously the. heated reaction coil. Man As a result, saves the effort for a system that is specially resistant to high pressures and temperatures Apparatus heretofore required when mixing large quantities of reactants must be, while the polymerization takes place slowly in successive batches of the monomeric mixture. In the case of the present proceedings, at any point in time are only proportionate small amounts of the monomer mixture the high polymerization temperatures in the reaction tube exposed, the conditions being chosen so that the reaction is very rapid, in some cases is almost explosive. This almost instantaneous polymerization of the monomers, from the first The moment they are exposed to the polymerization conditions prevailing in the hot reaction tube are, and the immediate removal of the reaction products from the reaction area suppresses the formation of mining or other by-products to a minimum. As a result, one can see considerable Sets of. Monomers polymerize in very short times and also achieve much higher Conversion rates and yields.

B e i s ρ i e 1 1

In a quenched at ⁰ C -4o container is brought 525 g (18.75 mol) of ethylene, then sets 215 g (2.5 mol) of methyl acrylate, 74.8 g of a 75 ° / _o by weight benzene solution of tert-butyl peracetate and 53.75 g of cymene are added, these substances are mixed with the ethylene by stirring, the container is pressurized to 35.2 kg / cm ² with the nitrogen and the entire reaction mixture is fed with the aid of a high-pressure metering pump into a reaction coil of 8 ecm Capacity, which is kept at 250 ° C by means of a constant temperature bath and a pressure of 352.0 kg / cm ^{2 is maintained} absolutely by means of a high pressure relief valve. The feed of the reaction mixture is adjusted so that about 3 ecm of condensed phase per minute are collected from the reaction coil via the expansion valve. The emerging gaseous components are allowed to escape into the open. The total duration of the operation is 108 minutes. A total of 373 g of liquid product are obtained. This product is cleaned of volatile constituents by heating to 200 ^° C. at a pressure of about 1 mm Hg. The distillation residue has the following properties:

Viscosity at 25 ° C

(G ard η er - H ο 1 dt) T- (5.5 Poise)

Molecular weight 625 ± 4

Molar ratio

Ethylene (E) / Acrylate (MA) 2.72 / 1.0

Yield according to analysis 55.0 ° / ₀

Acid number 0.5

Color tint '. 1 (Gardner

1933-SkaIa).

B ei s ρ i e 1 2

The method of Example 1 is used.

Approach:

Ethyl acrylate 300 g

- Ethylene .- ·. 420 g

75 ° / ₀ tert-butyl peracetate 63.4 g

Working conditions:

Bath temperature ........ 20O ⁰ C

Volume of the reaction tube .... 40 ecm
Running time 135 minutes.

208 g of liquid crude product are obtained.

Features of the product:

Viscosity: .. R] -

Molecular weight 746

Molar ratio 1-97

Yield; 74 ° / ₀

Acid number 0.8

Color shade 1 -

109 636/119

• ■ 1

B e i s ρ i e 1 3

-You work according to the method of example approach:.

Methyl methacrylate 250 g

Ethylene 525 g

Cymol: ... 125g

75% tert-butyl peracetate

Running time 156 minutes, accumulation 480.3 g of crude product.

Features of the product:

Viscosity .... Z ₅ -

Molecular weight 670

Molar ratio: 1.75

Yield 59.0%

Acid number ... 0.5

Color shade: ..... 1+

Example 4

One works according to the method of example

Approach: . ^; ...

Ethyl acrylate '. .. 300 g ^a 5

Ethylene 420g

75% tert-butyl peracetate., .. 63.4g

Reaction pressure 1125 kg, running time 176 minutes, 357 g of crude product accumulated.

Features of the product:

Viscosity Y—

Molecular weight '. 878

Molar ratio 1.00

Yield 67.6%

Acid Number 0.4

Color shade 1 -

Example 5

One works according to the method of example approach:

Methyl acrylate .. 258 g

Ethylene 252 g

75% tert-butyl peracetate 42.3 g,

Bath temperature 150 ⁰ C, running time of 158 minutes, seizure 373 g of crude product. '

5 °

Features of the product: · '

Viscosity Y

Molecular weight 661

Molar ratio ...: 1.44

. Yield 72.0%

Acid number 0.8

Color 1- | -

B is ρ ie 1 6 g ₀

The method of Example 1 is used.

Approach:

Ethyl acrylate 300 g ".,

Ethylene 336 g -

. 75% tert-butyl peracetate 21.2 g

Running time 180 minutes, 335 g of crude product accumulated.

624

Features of the product:

Viscosity "Z ₄ -

Molecular weight 1290

Molar ratio 1.10

Yield 71.8%

Acid number 1.5

Color shade '..... 1 -

B e i s ρ i e 1 7

One works according to the method of example approach:

Ethyl acrylate .. 300 g

Ethylene 252 g

Cymol 300g

75% tert-butyl peracetate 42.3 g

G ⁰ bath temperature 200 C, running time of 185 minutes, crude 652nd

Features of the product:

. Viscosity ............ Z ₁

Molecular weight .......... 959 ·, ■ · .-

Molar ratio 1.34

Yield ............... 76.0%

Acid number ^ 0.5

Color shade 1,

Examples

One works according to the method of example Approach: ' . ■

Methyl methacrylate 250 g

Ethylene 350 g

75% cymene hydroperoxide 30.6g

Cymene; 250 g

Bath temperature 290 ° C., running time 237 minutes, accumulation 619 g of crude product.

Features of the product:

Viscosity Z—

Molecular weight 614

Molar ratio 2.24

'Yield .;'. 58%

Acid number 0.5

Color shade ...... '1 +

Example9

One works according to the method of example

Approach:

Ethyl acrylate 252g

Ethylene 300 g

Methyl ethyl ketone peroxide 28 g

Running time 167 minutes, accumulation 370 g of crude product.

Features of the product:

Viscosity, Z ₃ -

Molecular weight _; ... 1095

Molar ratio 1.0

Yield .. .. 78.8%.

Acid number 1.0 -j.

■ Shade I -

■. . B e i s ρ i e 1 10

The method of Example I is used.

Approach:

Ethyl acrylate 300 g

Ethylene 420 g

di-tert-butyl peroxide (97%) 35.1 g

Hexane 150 g

Bath temperature 290 ° C., running time 181 minutes, accumulation 568 g of crude product.

Features of the product:

Viscosity N-,

Molecular weight 663

Oil ratio 1.96

Yield: 74%

Acid number 2.0

Color shade 1 -

B e i s ρ i e 1 11 The method of Example 7 is used.

Approach:

Methyl acrylate ..: 344 g

Ethylene 56Og

Methyl propionate .... <. 68.8 g

75% tert-butyl peracetate ........... 84.5 g

Running time 178 minutes, accumulation 579 g of crude product.

Features of the product:

Viscosity ...; :. X +

. Molecular weight: ..... 649

Molar ratio 1.74

Yield 64.2%

Acid number 0.5

Color shade 1 +

Example 12

The method of Example 1 is used.

Approach:

Methyl acrylate ..., '...' 215g

Ethylene ... 250g

Hexane ..: 215 g

di-tert-butyl peroxide (97%) "22.6 g

Bath temperature 350 ° C., running time 200 minutes, accumulation 568 g of crude product.

Features of the product:

Viscosity W

Molecular weight 65 L

Molar ratio '.. 2.55

Yield 72%

Acid number 1.0

Color shade 3

B e i s ρ i e 1 13

One works according to the method of example

Approach:

Methyl methacrylate ....; 50 g

Ethylene ■ .., 140 g

Methyl isobutyl ketone 21.3 g

tert-butyl peracetate (75%) 13.9 g

Capacity of the reaction coil 20 ecm, reaction pressure 703 kg / cm ² .

Features of the product:

Viscosity W | -

Molecular weight 500

Molar ratio 1.90

Yield 54%

Acid number. ■ 1.0

Color shade 1

Example 14

The method of Example 1 is used.

Approach: ■ .. ■. ■. . .

Methyl methacrylate 344 g

Ethylene, 56Og

Methyl propionate 68.8 g

75% tert-butyl peracetate 169 g

Reaction pressure 176.0 kg / cm ^a , absolute, duration 183 minutes, 611 g of crude product accumulated.

Features of the product:

Viscosity ............ Y-

Molecular weight 589

Molar ratio 1.38

Yield 60%

Acid number: ....... 0.5

Color shade 1 -

Example 15

The method of Example 1 is used.

Approach:

Ethyl acrylate 300 g

Ethylene: 420 g

Hexane 150 g

di-tert-butyl peroxide 40.6 g

Badtemperatiir 200 ° C, running time of 260 minutes, 556 g of crude product seizure, distillation at 23O ^C C / 0.3 mm Hg.

Features of the product:

Viscosity>. K-

Molecular weight 915

Molar ratio 1.73

Yield 54%

Acid number 0.8

Color shade 1

Claims (6)

Patent claims: 1. Process for the production of copolymers from ethylene and ethyl acrylate. Methyl acrylate or methyl methacrylate by copolymerization of the monomers at temperatures up to 400 ^° C and high pressures, characterized in that a temperature of 150 to 400 ^° C and a pressure of 72 to 720 atm are used, the residence time of the '' reactants in the reaction zone is 30 Seconds to 30 minutes, the process is limited to /.11 r formation of a liquid copolymer with an acid number of at most 3, a molecular weight of 500 to 1500 and a molar ratio of ethylene to acrylate of 1 to 3 is carried out, \\ obci is the upper limit of the M oil ratio to the molecular weight according to the formula I- 0.25 (- ¹⁵⁰ ° \ Molecular weight is dependent and X has the value 1.75 for the case of ethyl acrylate and methyl methacrylate and the value of 5.25 for the case of methyl acrylate, and the liquid reaction products are immediately removed from the reaction zone. 2. The method according to claim 1, characterized in that that the reaction in the presence of a free radical initiator in quantities of up to 20 mol percent, based on the total monomers, performs. 3. The method according to claim 1 or 2, characterized in that the process is carried out in the presence of cymene, hexane, methyl propionate or methyl isobutyl ketone in amounts of no more than 20 percent by weight, based on the acrylate. 4. The method according to claim 1 to 3, characterized in that there is a heated reaction zone Coiled pipe used with a capacity of at least 8 ecm. 5. Use of the prepared according to claim 1 to 4 Copolymers as lubricants. 6. Use of the copolymers prepared according to claims 1 to 4 as plasticizers for Vinyl based synthetic resins. 1 sheet of drawings