DE1916489C - Process for making chlorinated co-telomers - Google Patents

Description

Carbon tetrachloride, used in the presence of an iron.

(II) - or iron (IJl) compound as a catalyst 15 The invention therefore relates to a method for

heated. Making chlorinated co-telomers from a

2. The method according to claim 1, characterized by marked vinyl monomers and chloroform or carbon, that the catalyst is a nonionic tetrachloride in the presence of iron salts and is Iron complex compound used. characterized in that one practically

3. The method according to claim I, characterized in that mixtures of Vm \! draws that the catalyst used is iron bromide chloride and vinylidene chloride or a binary or or ferric chloride is used. ternary mixture of vinyl chloride and / or vinylidene

4. The method according to claim 1 to 3, characterized in that chloride and a non-chlorinated, olefinically unmarked, that one uses an iron (III) compound saturated monomers as well as chloroform or dung and additionally a reducing agent 25 carbon tetrachloride in the presence of an iron I), which heats the iron (III) compound in the course or iron (III) compound as a catalyst, the telomerization into an iron (II! compound) The co-telomers prepared according to the invention convicted. are liquid or semi-solid substances with a medium

5. The method according to claim 3 and 4, characterized in molecular weight of generally 4 (X) to 3000 and characterized in that the iron salt contains 30 a chlorine content of 10 to 70%. You are special An inert soluble chloride useful as a plasticizer and plasticizer for the reaction mixture or adding bromide. synthetic resins and make them beyond that

6. The method according to claim 1 to 5, characterized in that it is fire-retardant due to its high chlorine content characterized in that the reaction mixture or self-extinguishing and non-flammable. You can an inert co-solvent is added. 35 as low or medium molecular weight copolymers are described whose polymer

chain ends each by one of chloroform or

Carbon tetrachloride-derived atomic groups are saturated.

The invention relates to a method for 40 The molar ratio of the monomers in the for

Manufacture of chlorinated co-telomers from a telomerization used mixtures depends on their

Vinyl monomers and chloroform or carbon- relative reactivity and can therefore

tetrachloride in the presence of iron salts as cata- fluctuate within wide limits. In practice

lyser. however, the preferred molar ratios are below

Will vinyl chloride in the presence of small amounts 45 1:10 to 10: 1 for binary mixtures. In the ternary of a non-polymerizable, aliphatic, low-level mixture, none of the monomers of molecular chlorohydrocarbon, for example carbon in a molar ratio of more than 6: 1, based on each material tetrachloride polymerized in an aqueous emulsion, of the other two monomers is present. The MoI-so is a polyvinyl chloride with a K value of chloroform or carbon tetrachloride about 28 to 30 in finely divided form (German 50 rid to the total amount of monomers can be 1: 1 patent specification 744 401). Individual monomers will be up to 1:10. A higher proportion of chloroform with chloroform or carbon tetrachloride in counter or carbon tetrachloride does not adversely affect the performance of a catalyst, especially an iron (III) reaction, but brings few advantages, or iron (II) salt, telomerized, this leads to this to non-chlorinated vinyl monomers which are suitable for the mixing of telomers in which the monomeric processes according to the invention are suitable, for. B. Acrylic and dimeric telomers can be present in considerable, even excess acid or methacrylic acid, their salts and their derivatives. Thus results such as acrylonitrile, acrylamide, alkyl acrylate ent-telomerization of vinyl chloride with carbon containing 4 to U carbon atoms, methacrylonitrile and tetrachloride in the presence of an iron chloride as alkyl methacrylate containing 5 to 12 carbon catalyst and under certain conditions a 60 atoms; in addition, fumaric acid or maleic reaction product in which the proportion of 1,1,1,3 acid, its salts and its organic derivatives, such as 3-pentachloropropane, can be up to 55%. Ahn- alkyl fumarates and alkyl maleates, which are no more than borne conditions- .. ^: n those cases in which contain 20 carbon atoms, styrene, butadiene, isobutadiene or styrene are used as monomeric reactants prene and maleic anhydride are used for telomerization ( Israeli 65 If one of the monomers used is a salt, so patent applications 16 079 and 16 080). it becomes in a molar ratio not more than 1:10,

It has now been shown, surprisingly, that, based on the remaining monomer (s), one

- as opposed to the known processes - applies.

The iron catalyst can either be an uncharged coordination compound, such as iron acetylacetonate or a salt, preferably a bromide or a chloride, which is either anhydrous or is preferably hydrated. Iron (IU) compounds are preferably used in the presence of a reducing agent, which they in the course of the telomerization converted into iron (II) compounds, e.g. B. Benzoin, acetaldehyde, isobutyraldehyde, benzaldehyde, Tin (H) chloride, acetoin, ammonia or ammo-ίο nium sulfite. The reducing agent can already be present at the start reaction or in the course of the Reaction to be added gradually. If, as indicated below, cosolvents are used, so could? some of these also serve as reducing agents. It can also be one of the comonomers act as reducing agents. The iron compound is preferably used in an amount of 0.05 to 10 mol percent, preferably 0.1 to 5 mol percent, based on the total monomers, are used.

A cosolvent is advantageously used so that the reaction mixture is consistently homogeneous; but this is not always necessary. There are no restrictions whatsoever with regard to the co-solvents. except that they must remain inert towards the reactants. Suitable solvents are z. B. methanol, ethanol, n-propanol, isopropanol, n-butanol, methylene chloride, dimethylformamide and Acetonitrile. If an alcohol is used as a co-solvent, it can also act as a reducing agent serve.

If the catalyst is an iron salt, its solubility in the reaction medium can be increased by adding a soluble, the reactants are increased to inert chloride or bromide, e.g. B. by an alkyl-substituted ammonium chloride or bromide or lithium chloride or bromide. This chloride or bromide is advantageously used in an amount of 0.05 to 4 mol, preferably 1 to 3 mol, per mol Iron salt added.

The invention will now be reviewed with reference to the following Examples explained in more detail

example 1

A homogeneous mixture of 14.5 g (0.15 mol) vinylidene chloride, 8.0 g (0.15 mol) acrylonitrile, 15.4 g (0.1 mol) carbon tetrachloride, 540 mg (2 mmol) FeCl ₃ x 6 H _ä O, 412 mg (3 mmol) of triethylammonium chloride, 424 mg (2 mmol) of benzoin and 5 cm ³ of acetonitrile was mm under a pressure of 0.2 in a glass vial sealed and heated for 4 hours at 110 C.

After cooling, the ampoule was opened and the reaction mixture with 1η-hydrochloric acid and then washed with water, dried over calcium chloride and heated in vacuo for 1 hour, final value 150 C / 0.2 mm, freed from carbon tetrachloride and unreacted monomers. There were 11.6 g of a co-telomer with an average molecular weight of 1570 and a chlorine content of 50.4 percent by weight receive. The molecular weight was determined by the isopiestic method (methode isopiestique), which corresponds best to the molecular weight range of the products obtained.

Example 2

Eleven experiments were carried out according to Example 1 with the difference that as one of the monomers 9.4 g (0.15 mol) of vinyl chloride were used and the comonomer, solvent, the amount of catalyst and the reaction conditions were varied. The changes in comparison with Example 1 and the test results are summarized in the following table.

Ver
search Comonomer solvent FeCl ₃ -OH ₂ O Tempe
rature R.
time Out
prey Cl Molecular
Weight G cm ³ mmol T Hours. G 2 Acrylonitrile, 8 CH ₂ Cl ₂ , 10 2 110 20th 7.5 43.5 510 3 Acrylonitrile, 8 - 1 82 20th 2.5 33 880 4th Acrylonitrile, 8 - 2 110 20th 9.0 42.5 760 5 Acrylonitrile, 8 CH ₃ CN, 5 I. 110 10 12.9 40 780 6th Acrylonitrile, 8 CH ₃ CN, 5 2 110 9 15.3 45 490 7th Ethyl acrylate, 15 (CH ₃ J ₄ CHOH, 10 1 82 20th 10.7 20th 1070 8th Ethyl acrylate, 15 (CH ₃ ) ₂ CHOH, 10 2 110 20th 14.4 30th 840 9 Ethyl acrylate, 15 CH ₃ CN, 10 2 110 18th 21.5 35 870 10 Ethyl acrylate, 15 CH ₃ CN, 10 1 110 6th 23.5 37 820 11th Acrylic acid, 10.8 CH ₃ CN, 5 2 110 8th 6.5 37.3 770 12th Vinylidene chloride, 14.6 CH ₁ CN, 10 2 110 1 17.2 70 2030

Example 3

A homogeneous mixture containing 12.9 g (0.15 mol) methyl acrylate, 9.4 g (0.15 mol) vinyl chloride, 12.0 g (0.1 mol) chloroform, 270 mg (1 mmol) FeCl ₃ x 6 H ₂ 0.206 mg (1.5 mmol) of triethylammonium chloride and 10 cm ^{3 of} ethanol was melted into a glass tube under a pressure of 0.2 mm Hg and ^{heated to 125 °} C. for 48 hours. The glass tube was then opened and the reaction mixture was worked up as in Example 1. The yield was 6.0 g of colorless co-telomer with an average molecular weight of 860 and a chlorine content of 22.3 percent by weight.

Example 4

A homogeneous mixture of 9.4 g (0.15 mol) of vinyl chloride, 4.85 g (0.05 mol) of vinylidene chloride, 6.4 g (0.05 mol) of n-butyl acrylate, 15.4 g (0.1 mol ) of carbon tetrachloride, 224 g (1 mmol) of FeCl ₂ .4H ₂ O, 206 mg (1.5 mmol) of triethylammonium chloride and 10 cm ³ of n-butanol was sealed in a glass tube and atif 20 hours 11O ° C heated. After cooling, the reaction product was worked up according to Example L. The yield was 10.3 g of a co-telomer with an average molecular weight of 1920 and a chlorine content of 47.3 percent by weight.

5 6

Example 5 Example 11

am a homogeneous mixture, containing 9.4 g (0.15 mol) experiment ί

Vinyl chloride, 5.2 g (0.05 mol) styrene, 4.3 g (0.05 mol) A homogeneous mixture of 19 g (0.3 mol) vinyl methyl acrylate, 15.4 g (0.1 mol) carbon tetrachloride , 5 chloride, 10 g (0.1 mol) ethyl acrylate, 20 g (0.13 mol) 224 mg (1 mmol) FeCl ₁ · 4 H ₂ O and 10 cm ³ methanol, carbon tetrachloride, 15 cm ^s ethanol, 360 mg was melted in a glass tube and _{heated to 125 ° C for 10 hours (1.3 mmol) FeCl 3} · 6 H ₈ O, 276 mg (1.3 mmol) ben. The reaction mixture was zoin and 175 mg of triethylammonium chloride was worked up as in Example 1. The yield was heated to 125 ° C for 30 minutes. After cooling, 8.4 g of a co-telomer with an average molecular weight and degassing of the unreacted vinyl chloride weight 675 and chlorine content 28.7 percent by weight. the reaction mixture was prepared as in Example 1

D- ία worked.

ts e ι s ρ ι e ι b. _{It WUR (j s m} p _{orm a} viscous liquid wedge 25 g

A homogeneous mixture of 14.5 g (0.15 mol) of co-telomer with a chlorine content of 36.7% and

Vinylidene chloride, 4.0 g (0.075 mole) acrylonitrile, 22.8 g 15 molecular weight 610 obtained.

(0.1 mole) di-n-butyl fumarate, 15.4 g carbon tetra-. ,

chloride, 270 mg (1 mmol) of FeCl ₃ · 6 HO and 15 cm ³ versucn ί

n-Butartol was melted into a glass ampoule. For comparison, two telomerizations were also used

and heated to 120 C for 15 hours. The reaction- only one monomer (Homotelomerisalion) after

mixture was worked up according to example 1. It is carried out according to the state of the art,

16.3 g of a co-telomer were kept with average a) Experiment 1 was with 25.2 g (0.4 mol) of vinyl

rem molecular weight 1630 and chlorine content 36.4 Chloride, but without ethyl acrylate, repeated,

weight percentage. A telomere of vinyl chloride and carbon

Example 7 obtained material tetrachloride, which fol-

The lower fractions resulted in:

tin homogeneous mixture of 19 g (0.3 mol) vinyl 4.8 g at 80 to 100 "C / 25 mm Hg,

chloride, 10 g (0.1 mol) ethyl acrylate, 17 g (0.13 mol) 10.2 g at 60 to 90 ° C / 0.1 mm Hg,

Chloroform, 15 cm ³ ethanol, 360 mg (1.3 mmol) 7.6 g distillation residue with molecular

FeCl ₃ · 6 H ₂ O and 275 mg (2 mmol) triethylammo weight 365 as well as

Nium chloride was obtained at 125 ° C. for 50 hours. 1.1 g of solid telomer were obtained.

heats and the reaction mixture according to Example 1 b) 7.75 g (0.08 mol) of vinylidene chloride and 4 g

worked up. There were 3.2 g of colorless co-telomer (0.026 mol) of carbon tetrachloride were with a

with a chlorine content of 25.9 percent by weight solution of 72 mg (0.26 mmol) FeCl ₃ · 6 H ₂ O, 55 mg

and a molecular weight of 790. (0.4 mmol) triethylammonium chloride and 55 mg

35 (0.26 mmol) benzoin ^{mixed in 3 cm 3} ethanol.

Example 8 The homogeneous solution was taken into a tube

melted at a pressure of 0.15 mg and 1 hour

Ls was heated to 125 C for a period of 20 g as in Example 7, however. During the implementation fell

(0.13 MoI) carbon tetrachloride in place of chlorine precipitates abundantly.

form worked. After heating at 125 ° C for 3 hours, the tube was cooled and opened and the reaction mixture according to Example 1 was spun onto the reaction mixture. The worked down. Yield: 3 g of colorless co-telomer, the impact was carefully washed with ethanol and Chlorine content 30.8%. Molecular weight 710th then dried. 2.4 g of homotelomer were obtained

Vinylidene chloride and carbon tetrachloride in the form

B e i s ρ i e 1 9 45 of a gray-tinged white powder that is between 170

and 190 ⁰ C melted.

Examples were with an additional 94 mg (1.3 mmol). The filtrate was evaporated in vacuo and

Isobutyraldehyde repeated and the reaction mixture dissolved the residue in methylene chloride. The solution

Heated to 125 ^° C. for 2 hours and then washed with 1 η hydrochloric acid and dried as in Example 1

worked up. Yield: 6.1 g of colorless co-telomer 50 and the solvent in vacuo at 50 ^G C

drawn with chlorine hall 36.7% and molecular weight 630. 0.25 g of residue was obtained.

. I _1n The same result was obtained with acetonitrile

Example IU instead of ethanol as a solvent for iron (lII) -

A homogeneous mixture of 6.3 g (0.1 mol) vinyl chloride. About 90% of the entire product was solid,

chloride, 28.8 g (0.2 mol) of dimethyl maleate, 4 g of 55. Comparing experiments 2a) and 2b) with

(0.02 mol) cadmium acrylate, 20 g (0.13 mol) carbon - Experiment 1, the following can be said:

fabric tetrachloride, 30 cm ³ ethanol, 360 mg (1.3 mmol) The homotelomerization of vinyl chloride under

FeCl ₃ · 6 H ₂ O, 275 mg (2 mmol) of triethylammonium- the conditions described give a mixture

chloride and 188 mg (2.6 mmol) isobutyraldehyde of telomers, about 68% of which are relatively volatile

was heated to 125 ° C. for 8 hours. 60 and 4.7% are solid and only 27.3% are viscous

After the reaction had ended, the excess product was present, the molecular weight of which was comparable

Vinyl chloride degassed and the residue in methylene has the lowest molecular weight of the invented

chloride dissolved. The solution was carefully mixed with a co-telomer according to the invention.

washed aqueous ammonium chloride solution and replacing 25% vinyl chloride by ethyl acrylate,

dried over calcium chloride. The solvent 65 thus becomes the beneficial results of Experiment 1

and the unconverted momomer were obtained.

evaporates; then 12 g of co-telomer were contained. The homotelomerization of vinylidene chloride gives

tend 38.5% chlorine and 2.7% Cd. a product that is approximately 90% solid.

Claims (1)

1 2 completely or predominantly polymeric Tdomere claims: obtained if a monomer mixture of vinyl chloride and / or vinylidene chloride and / or a 1. Process for the preparation of chlorinated non-chlorinated olefinically unsaturated monomers Co-telomers from a vinyl monomer and 5 in the presence of an iron compound as a catalyst Chloroform or carbon tetrachloride in counter- as well as chloroform or carbon tetrachloride War of iron salts, thereby marked telomerized. The new way of working enables draws that a practically homogeneous production of liquid or semi-solid Co-TeIo solution, containing mixtures of vinyl chloride containing up to 70% chlorine. The MoIe- . and vinylidene chloride or a binary or ter- iocular weight and consequently also the consistency näres mixture of vinyl chloride and / or vinyl is determined by the amount of iron compound used lidenchlorid and a non-chlorinated olefinic determined insofar as the molecular weight of the unsaturated monomers as well as chloroform or telomers, the lower the more iron catalyst