DE1008280B - Process for the production of liquid, oil or waxy, low molecular weight polymers containing carbon, fluorine and chlorine - Google Patents

Description

Organic substances, composed only or mainly of carbon and fluorine or carbon, chlorine and Are built up fluorine, are becoming increasingly important in technology. Among these substances are representatives of the most diverse molecular weights known, with all transitions between gaseous, liquid, oily, waxy and plastic-like conditions.

Various methods are known, according to which by polymerization reactions of e.g. B. trifluorochloroethylene such products are obtained. If you want to conduct the polymerization in such a way that low molecular weight oils, fats or waxes are obtained, so it is very difficult to obtain a desired boiling fraction preferentially. Furthermore, hereby the chain termination or chain transfer agent often introduces undesired elements in the form of end groups, the z. B. when installing hydrogen the use of the products obtained due to their thermal such as chemical instability and the difficulty of stabilization make it very difficult or even even to make impossible.

Another way to get the desired fluorochlorocarbon oils or waxes is there in that you can use higher molecular weight waxes or high molecular weight solid plastics, which are made from the elements Carbon, fluorine and chlorine are made up of low molecular weight by chemical or thermal breakdown Shares split. This ensures that the products obtained only consist of carbon, fluorine and Chlorine are built up and do not contain any alien end groups.

However, if this degradation is only carried out by heating of the polymer through, it is inevitable to work at higher temperatures. So in U.S. Patents 2,420,222 and 2,543,530 describe a process for heating polytrifluorochloroethylene described at temperatures of 400 to 650 °. The temperatures used bring now again with the disadvantage that very low molecular weight compounds are mainly obtained and of this again largely monomeric trifluorochloroethylene, as well as from those mentioned above Examples given in publications. For a technical production of fluorochlorocarbon oils This process would lead to the desired results because of the poor conversion Products out of the question, but for a regeneration of trifluorochloroethylene from no longer usable Polytrinuorchlorethylene.

It has now been found that the desired polymeric, fluorine and chlorine-containing, oil or Waohs-like polymers, the so-called fluorochlorocarbon oils or waxes, as the main product in the cracking of the corresponding high molecular weight pro-

Process for the production of liquid,
oil or waxy, carbon,

Containing fluorine and chlorine
low molecular weight polymers

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning,

Frankfurt / M.

Dr. Hans-Helmut Frey and Dr. Karl-Heinz Kahrs,

Frankfurt / M.-Unterliederbach,
have been named as inventors

Products, such as polytrifluorochloroethylene, are obtained when powdered metals or metal mixtures or inorganic metal salts or metal oxides of those metals which show changing valency are added to the perhaloethylene polymers and at a reaction temperature of 50 to 350 °, preferably ¹ SWeISe of 100 to 300 ° an applied vacuum ensures that the cracked products are discharged.

For the process, powders, salts and oxides come from rental metals with several valence levels into consideration. Examples include copper, cobalt, iron, manganese, bronze, brass in the form of powders, as well as the chlorides, sulphates and oxides of these metals.

Certain additives to polytrifluorochloroethylene in packaging have already been recommended, but only for the measure of better heat conduction; It was not known, however, that one could use the aforementioned Additions and cracking in a vacuum can carry out the reaction at lower temperatures, namely at temperatures from 50 to 350 °, preferably from 100 to 300 °. This achieves that by far most of the polymer is obtained as fluorochlorocarbon oils or waxes and only minor ones Amounts of monomers! Trifluorochlorethylene accrue.

The high yield of fluorochlorocarbon oils or waxes in the cracking of polytrifluorochloroethylene in a vacuum was all the more surprising than in the decomposition of polytetrafluoroethylene im Vacuum almost exclusively retained the monomer

709 5-9 / 419

as disclosed in U.S. Patent 2,406,153 is, and at a lower vacuum the yield of monomers! subsides. For reasons of analogy one would have in the cracking of polytrifluorochlorethylene should therefore expect mainly monomeric trifluorochloroethylene in a vacuum, instead of it especially in a vacuum the yield of monomers! depressed and the formation of fluorochlorocarbon oils or growing favored.

By varying the additives, the applied vacuum and the reaction temperature you have it in hand, preferring to work towards a specific faction. You get a very good one Vacuum as the main product a highly viscous oil to semi-solid wax and easily movable in a weak vacuum Oils.

The amount of additive can be kept within wide limits. For purely economic reasons For reasons, efforts will be made to add as few additives as possible. Generally one is sufficient Add 5 to 50% to achieve the desired effect, but, as I said, even smaller ones can be used or larger amounts are added.

It has also been found that when Co F _{3 is added,} colorless fluoic acid carbon oils or waxes are obtained. This is all the more surprising since other metal fruorides known as fluorine regulators, such as e.g. B. manganese trifluoride, do not lead to colorless products, but are about the _{same in action as CoF 2} , ie, more or less strongly discolored distillates are formed when carrying out the process according to the invention.

Another Λ ^ οίΐβίΐ of cracking with CoF ₃ is the residue-free decomposition of the polytrifluorochloroethylene, leaving behind pure CoF ₂ . When cracking with additives other than CoF ₃ , more or less large amounts of carbon always remain as residue, so that the metal powder, metal halide and oxide additives are contaminated and slagged and are difficult to work up for reuse. In contrast, the residue from cracking with CoF _{3 can} be isolated as a loose, pink powder that can be fluorinated _{again to Co F 3 without further work-up or purification.}

The chlorofluorocarbon oils produced by Co'Fg cracking or waxes are chemically and thermally stable, so that they can be stabilized by post-fluorination not applicable.

Naturally, it is very difficult to produce chemically uniform ones from these fluorochlorocarbon oils or waxes to isolate defined individuals, as a large number of chlorine compounds are present. The ratios are similar to those of petroleum. So you get a continuous boiling spectrum, beginning at room temperature under normal pressure up to 300 ° with a vacuum of 5 mm Hg.

Fractionation is made even more difficult by the instability of thermal stress during the distillation, during which halogen is split off.

You can cracking the polytrifluorochloroethylene carry out continuously or discontinuously, the additives before or during the Process can be mixed.

As a result of the preparation process and additionally during the distillation, these contain fluorocarbon oils or waxes one to several double bonds, which can be recognized qualitatively by the color from light yellow with a small number to the deepest brown-black with several double bonds can. The double bond content can be determined qualitatively by means of the hydrogenation iodine number. Due to their chemical instability, the chlorofluorocarbon oils or waxes are chemical conversions accessible, while otherwise namely the saturated fluorochlorocarbon oils or waxes precisely because of their chemical invulnerability distinguish themselves chemically very aggressive reagents and because of this their excellent Property of versatile application.

If you want to use the fluorochlorocarbon oils or waxes as such, you have to stabilize them. this is done by post-fluorination with metal fluorides or halogen fluorides, making them completely colorless and the hydrogenation iodine number drops to zero. The fluorochlorocarbon oils or waxes stabilized in this way can be used as plasticizers for polytrifluorochloroethylene, they are also of interest as high-quality lubricants for corrosive substances, as special transformer oils, heat and pump transfer fluids, as reaction media for chemical reactions and polymerizations.

For many technical purposes, the formation of unsaturated low molecular weight, at the same time fluorine, Products containing chlorine and carbon are valuable as they lead to further reactions, such as oxidation Fluorochlorocarboxylic acids, are more easily accessible. Such reaction products are particularly in the implementation of the present process with copper sulphate obtained, which should also be mentioned, that this reaction can advantageously also be carried out continuously, since there are no residues in the Implementation of the reaction arise.

example 1

In a stainless steel flask, 2000 parts by weight of Polytrifluorchiloräthylen with the NST value 300 (measure of the molecular weight, measurement in accordance with USA Patent Code 2 626 254), the 200 parts by weight of copper powder were admixed by applying electric heating to one Slowly heated vacuum of 10 mm Hg. At a temperature - of about 50 °, decomposition begins with fog formation. From around 100 °, yellow to yellow-brown colored oils begin to deposit in the template, in order to pass into a constant distillation in the temperature range from about 150 to 250 °. In order to exaggerate the last fractions of cracked products, the temperature must be selected at the end Increase it up to about 300 °.

In the original, 1245 parts by weight have increased. viscous fluorocarbon oil of yellow-brown color accumulated. 250 parts by weight remain in the flask gray residue that has been slagged into lumps by the charring products. The distillation of the raw material is difficult due to the thermal instability, since the elimination of halogen and the generation of a wide Ren double bond gases are created, which causes the vacuum and thus the boiling point to fluctuate sharply is subjected to distillation. The last part of the high-boiling fluorochlorocarbon oils Cracks to low levels during distillation, which also causes the boiling point to fluctuate sharply is subjected to distillation at the end. A carbonaceous residue remains. At a vacuum of 5 mm Hg, about 30% of the crude product is obtained up to 170 °, including that dissolved in the oil Gases. From 170 to 230 ° fall 22% and from 230 to

300 ° 36% fluorochlorocarbon oils. The rest consists of charred residue. The last high-boiling one Fraction is very viscous and already semi-solid. It is very dark in color and splits off halogen, such as can be recognized by the smell.

Example 2

When cracking 1000 parts by weight of polytrifluorochloroethylene of the NST value 300 in the mixture. with 100 parts by weight of copper (l) chloride for one At a temperature of 100 to 250 ° in a vacuum of 20 mm Hg in a glass flask, 500 parts by weight of fluorochlorocarbon oils are obtained. These boil in a vacuum of 5 mm Hg to 170 ° 25%, from 170 to 230 ° 21% and 230 to 300 ° 43% of the resulting crude product. A carbonaceous residue remains behind Slag.

Example 3

When adding 200 parts by weight of nickel chloride to 2000 parts by weight of polytrifluorochloroethylene with an NST value of 300 and cracking in the flask made of stainless steel at a temperature of 100 to 250 ° in a vacuum of 25 mm Hg 1530 parts by weight of liquid oils obtained, of which 60% in a vacuum of 5 mm Hg from 170 to 300 ° boil.

B e i s ρ i e 1 4

In a glass flask, a powdered mixture of 150 parts by weight of polytrifluorochloroethylene is dated NST value 300 in 15 parts by weight of iron (3) oxide at a vacuum of 50 mm Hg at temperatures starting with 100 ° and finally heated to 250 to 300 ° in order to distill off the last portions of liquid oils. 85 parts by weight of fluorochlorocarbon oils are obtained, 17% of which in vacuo of 5 mm Hg boil between 170 and 230 °.

Example 5

50 parts by weight of Polytrifluorohloräthylen of the NST value 300 are powdered with 25 parts by weight of cobalt trifluoride and mixed well. The mixture is heated in a glass flask at a vacuum of 10 mm Hg to temperatures of 100 to 250 °. 47.5 parts by weight of a white, semi-solid wax are obtained, 55% of which in a vacuum of Boil 5 mm Hg in the range of 230 to 300 °. Remain as residue. 22 parts by weight of a pink Powder, the analysis of which indicates cobalt difluoride. It can be used without further purification or Fluorine the work-up again to give cobalt trifluoride.

The distilled chlorofluorocarbon wax is chemically and thermally stable. It contains 50 to 51% fluorine, about 29% chlorine and about 20% carbon and is practically hydrogen free. It contains double bonds practically not at all, since it is completely colorless and the hydrogenation iodine value is extremely low.

Example 6

When cracking 1000 parts by weight of polytrifluorochloroethylene of NST value 300 and 500 parts by weight of cobalt trifluoride in a vacuum of 10 mm Hg at temperatures of 100 to 250 ° in one Pistons made of stainless steel are obtained 800 parts by weight of a white fluorochlorocarbon wax, of which 65% boil between 170 and 300 ° in a vacuum of 5 mm Hg. Stay in the flask 226 parts by weight of a pink powder that is fluorinated to cobalt trifluoride.

Example 7

On the other hand, 100 parts by weight of polytrifluorochloroethylene with an NST value of 300 with 50 parts by weight Manganese trifluoride in a glass flask at temperatures from 100 to 300 ° in a vacuum of 10 mm Hg cracked, 50 parts by weight of a dark yellow one. Obtain oil from which 40% of Boil 170 to 300 ° in a vacuum of 5 mm Hg. 43 parts by weight of a gray residue remain as a residue Powder composed mainly of manganese difluoride.

Comparison attempt

On the other hand, 100 parts by weight of polytrifluorochloroethylene of NST 300 in a glass flask at a vacuum of 6 mm Hg under the same Conditions, but without the addition of salts, as described in the above examples, cracked, so weak vapors occur only at an internal temperature of 270 °, which become stronger from 300 °, so that the vacuum drops to 15 mm Hg. The fluorochlorocarbon oil only begins to build up in the template from 350 ° to collect. The decomposition of the polytrifluorochloroethylene takes place in the temperature range from 350 to 450 ° stormy with a further decrease in the vacuum in front of you. After complete Decomposition 43 parts by weight of a yellow, highly viscous oil.

Example 8

10 parts by weight of anhydrous copper sulfate are mixed with 90 parts by weight of high-polymer polytrifluorochloroethylene mixed in the mortar.

The mixture is in the glass flask at weak Vacuum, 85 to 100 mm Hg, cracked. Cracking temperature 280 to 350 °. 65 parts of an oil-wax mixture fall in the process as a raw product. After fractionation, the following products are obtained:

fraction Kp. I mm consistency sales
(based on polytrifluorochloroethylene used) Molecular
weight A.
B.
C.
D.
E. 50 to 100 °
100 "150 °
150 "200 °
200 "250 °
250 "290 ° water-white liquid
yellow oil
yellow oil
vaseline-like
yellow wax 7 parts by weight, corresponding to 7%
8 "" 8%
9 "" 10%
19 "" 19%
17 "" 17% 470
510
770
890
1250 60 parts by weight, corresponding to 61%

7th chlorine carbon 8th Hydrogenation iodine number analysis fluorine 30.66%
30.13%
30.45% 20.12%
19.87%
19.15 o / _o hydrogen 122.8
92.2
not measured Fraction C
Group D
Group E 47.08%
46.81%
45.94% below 0.3%
below 0.3%
below 0.3%

Example 9

The procedure described in Example 8 is followed. Instead of the vacuum mentioned there, a

Vacuum of 9 mm of mercury applied. Broken down into io fractions:

in this way 85 parts by weight of crude product are obtained.

The oil-wax mixture obtained is in the following

fraction 50 · Ρ · 4 ΙΠΠ1 consistency sales Parts by weight, corresponding to 9% Molecular 100 (based on polytrifluorochloroethylene used) 10% weight A. 150 up to 100 ° colorless liquid 8th 11% 490 B. 200 "150 ° colorless liquid 9 18% 640 C. 250 "200 ° yellowish liquid 11 18% 745 D. 300 "250 ° vaseline-like 18th 13% 930 E. "300 ° yellow wax 18th Parts by weight, corresponding to 79% 1170 F. "350 ° brown wax 13th not measured 77

analysis fluorine chlorine carbon hydrogen Hydrogenation iodine number Fraction C
Group D 47.42 o / _o
48.00 o / _o 30.10%
29.89 o / _o 20.68%
20.59% below 0.3%
below 0.3% 116.0
92.0

Example 10 is in the glass flask at a vacuum of 9 mm Hg

50 parts by weight of anhydrous copper sulfate are cracked. Cracking temperature 280 to 350 °. Thereby

45 parts by weight of crude oil are obtained with 50 parts by weight of high-polymer polytrifluorene. At the frac-

chlorethylene mixed in the mortar. The following fractions are used for mixing:

fraction Kp. 23 mm
18 mm
17 mm
13 mm
18 mm , 34 to 100 °
, 100 "150 °
150 "200 °
200 "250 °
250 "310 ° consistency fluorine sales
(based on polytrifluorochloroethylene used) chlorine carbon hydrogen Molecular
weight A.
B.
C.
D.
E. colorless oil
light yellow oil
yellow oil
yellow oil
yellow oil 49.10%
48.34 o / _o 4 parts by weight, corresponding to 8%
7 "" 13%
7 "" 14%
9 "" 18%
14 "" 29o / _o 31.20%
29.80 o / ₀ 20.16 o / _o
20.55% below 0.3%
below 0.3% 450
500
640
800
1800 analysis 41 parts by weight, corresponding to 82% Hydrogen iodine number Fraction C
Group D 109.3
84.5

Example 11

30 parts by weight of anhydrous copper sulfate are combined with 70 parts by weight of high polymers in polytrifluorochloroethylene mixed in the mortar. The mixture is in the glass flask at a vacuum of

50 9 mm Hg cracked. Cracking temperature 280 to 350 °. 65 parts by weight of an oil-wax mixture are used obtained as a crude product. The following products result from fractionation:

fraction Kp 4 mm consistency sales
(based on polytrifluorochloroethylene used) Molecular
weight A.
B.
C.
D.
E. 38 to 100 °
100 "150 °
150 "200 °
200 "250 °
250 "315 ° colorless oil
light yellow oil
yellow oil
yellow oil
yellow wax 9.5 parts by weight, corresponding to 13.5%
8 "" 11%
12.5 "" 18 o / _o
15.5 "" 22 o _{/ o}
13.0 "" 18.5% 450
600
780
1020
1150 58.5 parts by weight, corresponding to 83.0%

analysis fluorine chlorine carbon hydrogen Hydrogenation iodine number Fraction C
Group D 48.70 o / _o
48.45% 30.20%
29.90 o / _o 20.82%
21.02 o / _o below 0.3%
below 0.3% 99.0
71.5

9 10

Example 12

5 parts by weight of anhydrous copper sulfate are cracked to 7 mm Hg. Craak temperature 280 to 350 °. with 95 parts by weight of high-polymer trifluorochloride * 74 parts by weight of an oil-wax ethylene fall mixed in the grater. The mixture mix on. After fractionation will be the following products are obtained in the glass flask at a vacuum of 5 to 5:

fraction Kp. consistency sales
(based on polytrifluorochloroethylene used) Molecular
weight B.
C.
D.
E.
F. 11 mm, 100 to 150 °
13 mm, 150 "200 °
15 mm, 200 "250 °
15 mm, 250 "300 °
5 mm, 300 "330 ° colorless oil
colorless oil
light yellow oil
yellow wax
yellow wax 3.5 parts by weight, corresponding to 3.7%
8.5 "" 9%
8.5 ■ "" 9 %
18 "" 19%
26 "" 27% 480
540
650
880
1050 64 parts by weight, corresponding to 67.7%

analysis fluorine Chlorine carbon hydrogen Hydrogenation iodine number Group D 48.24% 30.57% 20.21% below 0.3% 110.5

Example 13

30 parts by weight of anhydrous copper sulfate will be

The mixture is in the glass flask at

with 70 parts by weight of a copolymer from a vacuum of 9 mm of mercury. Trifluorochlorethylene and vinylidene fluoride mixed in the mortar (chlorine content of the copolymer
28.18%, corresponding to a molar ratio of trifluorochloroethylene to vinylidene fluoride 8: 1).

a cracking temperature of 280 to 350 °.

This results in 64 parts by weight of crude crack oil, the the following products result from fractionation:

fraction 12 mm,
10 mm,
10 mm,
9 mm,
9 mm, Kp. up to 100 °
"150 °
"200 °
"250 °
"275 ° consistency sales
(based on the polymer used) Parts by weight, corresponding to 14%
15%
15.7%
30%
"6% Molecular
weight A.
B.
C.
D.
E. 50
100
150
200
250 green-yellow oil
J) H
>> ti 10
10.5
11
21
4th Parts by weight, corresponding to 80.7% 420
650
830
1010
1100 56.5

analysis fluorine chlorine carbon hydrogen Hydrogenation iodine number Fraction C
Group D 49.40%
49.64% 27.50%
26.72% 22.81%
22.50% 0.84%
0.60% 82.8
56.4

Example 14

one

30 parts by weight of anhydrous copper sulfate were mixed with 70 parts by weight of a copolymer. The mixture is cracked in a glass flask at a vacuum of 7 mm Hg consisting of 98 percent by weight of trifluorochloride. Crack temperature ethylene and 2 percent by weight 1, 1, 1-trifluoropropene 280 to 350 °. 66 parts by weight of an oil (CF ₃ - CH = CH ₂ ), determined analytically, fall with the aid
of ultra-infrared recordings on pressed foils from the polymer, mixed in the Reilbschaik.

Wax mixture as a raw product. After fractionation the following products will be received:

fraction Kp., mm consistency 7.5
8th
11
15th
16.5 sales
(based on polymer) Molecular
weight A.
B.
C.
D.
E. 64 to
100 "
150 "
200 "
250 " 150 °
150 °
200 °
250 °
300 ° light oil
yellow oil
yellow oil
yellow oil
yellow wax 58.0 Parts by weight, corresponding to 10%
11%
16%
21%.
24% 423
594
813
1130
1130 Parts by weight, corresponding to 82%

analysis fluorine chlorine carbon hydrogen Hydrogenation iodine number Fraction C
Group D 48.85%
48.86% 29.17%
28.80%, 20.99%
20.88% below 0.3%
below 0.3% 106
88

709 509/419

Claims (3)

Patent claims: 1. Process for the production of liquid, oil or waxy, containing carbon, fluorine and chlorine low molecular weight polymers thermal decomposition of high molecular weight polymers consisting of carbon, fluorine and chlorine, characterized in that the decomposition of Perhalogenäthylenpolymeren under Addition of metal powders, inorganic metal salts or metal oxides of such metals, show the changing valence, performs in a vacuum at temperatures of about 50 to about 350 °. 2. The method according to claim 1, characterized in that the reaction is carried out at 100 to 300 ° performs. 3. The method according to claim 1 and 2, characterized in that there is ale additive cobalt trifluoride used. © 709 509/419 5.57