DE1301513B - Process for the polymerization of free-radically polymerizable ethylenically unsaturated monomers - Google Patents

Description

1 2

From the German Auslegeschrift 1026 959 the carbonyl compounds can be known through the that metal carbonyls can be used together with orga- formula Mn ₂ (CO) ₁₀ and niche halides to initiate polymerization reactions and that CH ₃ also does not take any precautionary measures to exclude 5

Air is required in the reaction. The effective S

most carbonyls are, however, under

Air access worsens. It has now become (OC) ₃ Fe Fe (CO) ₃

found that the effectiveness of specific metal carbonyls virtually unaffected as polymerization by the presence of air io S '' is. CH ₃ According to the invention, a method for

Polymerizing will normally be represented by a free-radical mechanism and will be in the total radical mechanism polymerizable ethylenic 15 description referred to as »metal carbonyls. Both unsaturated monomers in the presence of a super metal carbonyl change their activity with respect to Gangsmetallcarbonyls, an organic halogen on the various monomers, and the active compound and of atmospheric oxygen prudence of each carbonyl depends on the posted, which is characterized in that conditions averted; however, it was found as transition metal carbonyl Dimangandecacarbonyl 20 that most monomers polymer yields of or di ^^ - methylthio-diiron-hexacarbonyl use 80% without taking precautions for detachment. At the end of being hit by air.

The process according to the invention proceeds.

the polymerization of the ethylenically unsaturated metal carbonyl concentration generally material without any precautions or 35 to about 10 " ¹ mol / l reaction mixture. Although it can be stated that the possibility of removal, if any, results in little or no advantages and is not excluded from some oxygen is preferred Konzentravon ethylenically unsaturated material by commissioning functions of 1 × 10 ^-5 to 5 × 10 ^-2 mol / l Reaktionsrührungbringen with a metal carbonyl in counter mix to use.

War using an organic halide The polymerization can be carried out in a solvent

the previously operated processes in which large or in the presence of a diluent or Care should be taken to reduce the presence or absence of the dispersion medium Oxygen can be carried to a very low concentration like media, however it is (generally less than 0.01 percent by volume, particularly expedient, the metal carbonyl as the Lö- [100 parts per million by volume]) to admit, does not form part of the invention. Usable solvents, thinners or

The inventive method brings a 40 dispersion media include ether (for example outstanding technical progress with it. It is tetrahydrofuran), ester (e.g. ethyl acetate), namely particularly advantageous that the invention nitrile (for example benzonitrile) and water or Proper procedures without the aid of costly mixtures of the same. It should be noted, however, that ligen high vacuum devices or with inert not all solvents for both Carbonylverbin atmosphere operated devices are suitable, the best solvent can leads can be. A further application is easy in any case by a simple experiment of the method according to the invention is to be determined. Some solvents can be used as Field of air-drying paints and adhesive chain transfer agents in polymerisation processes. work.

The polymerization according to the invention 50 When the monomer with the diluent Ethylenically unsatiable is not miscible in accordance with a suitable method, an emulsifying agent can be used Monomers are those whose polymer increases the interface between the two sation can normally be used by free radical generating phases.

Catalysts initiated, especially those The organic halogen compound used

with an electron-attracting group, for example in the process according to the invention, preferably has a carboxylic acid or ester group attached to an ethylenically bonded carbon of 2 or more on the same carbon atom. lowing halogen atoms (-X), which are either chlorine examples of monomers with electron withdrawing atoms or bromine atoms. It is preferred that groups are acrylic monomers (for example acrylic- that if only 2 such halogen acid, methacrylic acid, hydroxymethacrylic acid and 60 atoms are present, there is also an electron-withdrawing or electrostatic butylaminoethyl methacrylic acid and its electron-accepting group (-Y) on the same atom, ester, amide, nitrile and homologues), arylalkenes (giving a compound of the structure (e.g. styrene) and mixtures thereof. -CX ₂ Y), while otherwise it is preferred that other monomers, e.g. vinyl chloride, the halogen compound is the group -CX ₃ , wherein X vinyl pyridine, vinyl ester (such as vinyl acetate) and vinyl 65 each represent chlorine and bromine, respectively. Beiidenchlorid can also be polymerized by the process according to the invention for useful halogen compounds. Carbon tetrachloride, chloroform, trichlorobromo-

The methane, bromoform, carbon tetrabromide, trichloride used in the process according to the invention

fluoromethane, chloral, trichloroacetonitrile, benzotrichloride (C ₆ H ₅ -CCl ₃ ) or mixtures thereof. Less strongly halogenated compounds such as methylene chloride and chloroacetamide can also be used, although these tend to be less effective.

Alternatively, the halogen compound can be a polymer containing halogen atoms in the has recurring units. Thus, graft polymers can be obtained by the process according to the invention be generated, for example with poly (vinyl trichloroacetate) or poly (vinyl monochloroacetate).

As a further alternative, the halogen compound can be an organosilicon compound, for example a haloorganosilane of the structure

X ₃ CY-SiX ₃

wherein X is halogen, generally chlorine or bromine, and Y is a direct bond or a divalent organic radical, for example a »° divalent hydrocarbon radical, means to be. A suitable compound of this type is p-trichloromethylphenyltrichlorosilane.

Silane derivatives have an affinity for glass and can be used in conjunction with the carbonyl and a suitable monomer to graft polymers onto glass. The effectiveness of initiation, however, depends considerably on the particular components used, and the value of any particular halogen compound will depend on the metal carbonyl with which it is used. The concentration of the halogen compound used is generally 5 x 10 ^-3 to 2 × ΙΟ ^"1 mol / l reaction mixture, although amounts as low as 10 ~ ⁵ mol l may be feasible / under some circumstances, and an upper limit is primarily by reasons Economics and also determined based on the effectiveness of the halogen compound as a chain transfer agent.

The polymerization can be promoted by heat or by photochemical effects.

The polymerization temperatures depend very much on the choice of monomer. Conveniently, the temperature is 20 to 100 ° C, preferably 40 to 9O ⁰ C, although possibly higher or lower temperatures can be used.

The photochemical effect can be brought about by UV radiation or visible light radiation or induced. Daylight can be used, but this does not allow the degree of control which is possible when a source of artificial radiation is used. It can also be a Combination of heat activation and photochemical activation can be applied.

The polymerization can be carried out essentially at atmospheric pressure, although optionally higher or lower pressures can be used, especially if the monomer is volatile. The time required for polymerization depends on several factors including individual components used, their concentration and the polymerization temperature.

The polymers can be isolated by conventional procedures, for example by Precipitation from solution by pouring the reaction mixture into a liquid in which the polymer is sparingly soluble, for example methanol or petroleum ether. Another option is that Polymerization product dissolved in a suitable solvent (for example chloroform) and then be precipitated again by diluting with a non-solvent. It can be useful simply isolating the polymer by evaporating the unpolymerized monomer.

The invention is explained in more detail with reference to the following examples, which are not to be interpreted as limiting. where the parts are parts by weight and the percentages are percentages by weight, unless otherwise is specified.

example 1

A mixture containing 0.03 part of dimanganese decacarbonyl and 0.8 part of carbon tetrachloride was obtained and 9.5 parts of monomeric methyl methacrylate or methyl methacrylate. This mixture was introduced into a polymerization vessel which was then sealed or sealed and heated to 80 ° C for 2 hours. There were no precautions or precautions taken to remove air. At the end of this time the tube was opened that Product was dissolved in chloroform and the chloroform solution was used to precipitate the polymer in Poured methanol. The resulting polymer weighed 8.81 parts (92.9 percent yield).

Example 2

It was the compound of the formula Fe ₂ (CO) ₆ S ₂ (CHa) ₂ , whose structure as

CH ₃

(CO) ₃ Fe;

Fe (CO) ₃

CH ₃

is believed to be made by reacting iron pentacarbonyl with dimethyl sulfide. Using the same by the procedure of Example 1 in place of the dimangandecacarbonyl 7.80 parts of polymer produced, representing a yield of 82.1%.

Example 3

For comparison purposes, the procedure of Example 2 was repeated, taking precautions or Precautions have been taken to exclude air. It became essentially the same Yield obtained.

Example 4

It was a mixture containing 9100 parts of styrene, 60 parts of poly (vinyl trichloroacetate) [made by polymerizing vinyl trichloroacetate] and 10.1 parts of dimanganese decacarbonyl manufactured. The mixture was introduced into a polymerization vessel which was then sealed or sealed, and irradiated with light having a wavelength of 4358 Å. There were

no precautions or precautions taken to remove air. After 9 minutes and The reaction mixture gelled for 50 seconds. In the case of an identical, but performed under vacuum During the experiment, the reaction mixture gelled in 3 minutes and 45 seconds.

Example 9 Example 5

A reaction mixture containing 910 parts of styrene and 1 part of Dimangandeca-5 carbonyl and 15 parts of p-trichloromethylphenyltrichlorosilane manufactured. This mixture was introduced into a polymerization vessel, which was then sealed sealed and heated to 80 ° C for 2 hours. No precautions were taken It became a mixture containing io or Air Removal Precautions

1 part dimanganese decacarbonyl, 79 parts tetrachloro taken. At the end of this time the pipe became carbon and 940 parts of methyl methacrylate and methyl methacrylate, respectively. This mixture was introduced into a polymerization vessel,

which then tightly closed or sealed and

Was irradiated with light having a wavelength of 4358 Å for 2 hours. No precautions were taken or precautions taken to remove air. At the end of that time the pipe was

opened and the product was dissolved in chloroform approximately 1 part dimanganese decacarbonyl, 320 parts solves. The resulting solution was used to precipitate methyl methacrylate or methyl methacrylate,

24 parts of carbon tetrachloride and the amount of the selected solvent indicated in the table Reaction mixtures prepared. In the case of water, 60 parts were used Water with 10 parts of sodium dodecylbenzenesulfonate or sodium dodecylbenzenesulfonate form an emulsion manufactured.

The mixture was poured into a polymerization vessel

10.7 parts of dimanganese decacarbonyl, 41.5 parts of 30 introduced, which tightly closed or sealed Poly (vinyl trichloroacetate) [by trichloroacetylation and heated to 80 ° C for 2 hours. It was from Polyvinyl alcohol produced] and 11,000 parts of the precautions or precautionary tert-butylaminoethyl methacrylate in any stage manufactured. These measures are taken to remove air. The mixture was poured into a polymerization vessel - at the end of this time, the polymer was introduced through which is then tightly closed or sealed, pour the product mixture into methanol, filter and isolated with light having a wavelength of 4358 Å and drying.

opens, the product was dissolved in chloroform and the chloroform solution was used to precipitate the polymer poured into methanol. The yield was 45.2%.

Examples 10-14

To determine the effect of varying the solvent, an

g g

Poured polymer into methanol, whereby the polymer was obtained in 94.5% yield. An identical experiment carried out under vacuum gave a yield of 94.9 ⁰ Io.

Example 6

A mixture with a content of 07 il idb 1 il

has been irradiated. No measures or precautions have been taken to remove air. The reaction mixture gelled in 28 minutes.

Example 7

The results are compiled in the following table:

40

A reaction mixture containing 17,200 parts of vinyl perfluorobutyrate, 10.4 parts Dimanganese decacarbonyl and 240 parts carbon tetrachloride. This mixture was introduced into a polymerization vessel, which is then tightly closed or sealed and 24 hours was heated to 80 ° C for a long time. No removal precautions have been taken hit by air. At the end of this time the product was removed by evaporation of the unchanged monomer isolated giving a polymer yield of 40.3%.

Example 8

example

10
11
12th
13th
14th

solvent

water

toluene

Ethyl acetate

Tetrahydrofuran
Benzonitrile

Quantity (parts)

680 590 620 600 685

Polymer yield

»/ 0

84.6 31.1 33.0 74.2 43.7

Examples 15 and 16

The procedure of Examples 10-14 was repeated, but varying the source of halide became. No solvent was added, the amount of methyl methacrylate used however, methyl methacrylate was increased to 950 parts. The amount of halide used is in fl ll l

A reaction mixture containing 1000 parts of methacrylic acid, 15 parts of p-trichloromethylphenyltrichlorosilane and 1 part of dimanganese decacarbonyl was prepared. This mixture was compiled in the following table: a polymerization vessel was introduced, which then
tightly closed or sealed and for 2 hours
to 8O ⁰ C was heated. No operations or precautions have been taken to remove
Hit air. At the end of this time the pro 65
product isolated by evaporation of the unchanged monomer, with a yield of 13.0%
revealed.

at
game Halide lot
(TeUe) polymer
yield 15th
16 Benzotrichloride
chloroform 20th
22nd 91.4
64.8

Examples 17-20

The procedure of Examples 19 to 23 was repeated, but the monomer was varied, however, no solvent was used. The amount of monomer is shown in the table below. 24 parts of carbon tetrachloride were used.

at
game Monomer lot
(Parts) polymer
yield
%> 17th
18th
19th Vinyl pyridine
Methacrylic acid
Hydroxyethyl methacrylic
acid 1077
950
1085
1110 84.7
91.7
40.3
40.8 20th tert-butylaminoethyl
methacrylic acid

IO

ao

Comparative experiment

400 parts of styrene and 4 parts of triphenyl as were placed in a container equipped with a nitrogen blanket phosphine-nickel-tricarbonyl, 2100 parts of water, 15 parts of emulsifier and 2 parts of carbon tetrachloride brought in. After stirring for Va hour at 80 ° C. under nitrogen, the polymer became removed and dried. The yield was 95%.

The reaction was carried out in the presence of air using 3 parts of carbon tetrachloride repeated. After stirring for 1 hour, with free admission of air, the polymer yield was only 50%.

Claims (4)

Patent claims: 1. Process for the polymerization of free-radically polymerizable ethylenically unsaturated monomers in the presence of a transition metal carbonyl, an organic halogen compound and of atmospheric oxygen, characterized in that the transition metal carbonyl Dimanganese decacarbonyl or di-μ, μ-methylthio-diiron-hexacarbonyl used. 2. The method according to claim 1, characterized in that one uses the transition metal carbonyl in a concentration of 1 × 10 ^-5 to 5 × 10 ^-2 mol / l reaction mixture. 3. The method according to any one of claims 1 and 2, characterized in that as organic halogen compound one which has 2 or more on the same carbon atom has hanging chlorine or bromine atoms is used. 4. The method according to any one of claims 1 to 3, characterized in that the organic halogen compound is used in the reaction mixture in a concentration of 5 · 10 ^-3 to 2 · 10 ^-1 mol / l. 909534/410