DE1443519A1 - Process for the preparation of partially perfluorinated or perfluorochlorinated, saturated or unsaturated organic compounds - Google Patents

Description

Process: -; for the production of partially perfluorinated.,.

perfluorochlorinated saturated or ψϊ ^ Ve rb incLUii & öja

Organic compounds containing one or more longer x-fluorocarbon or perfluorochlorocarbon chains; Wear. ,, are cvls sonierniittöl, non-flammable coolants and electrical insulating oils, hydraulic oils, lacquer, metal, plastic, or leather care agents, lianches can be used as surface-active compounds, ■ as lubricants, e.g. as additives to lubricating oils or Fats can be used to lower their interfacial tension. The evaporation rate of organic liquids and solids is often greatly reduced by these compounds, even if only slight sounds are mixed in. The sweating of "vVsielunachern- from plastics can in some cases also erode these substances- below suddenly. These compounds are also: .-. A valuable intermediate product, -2U for the production of surface-active- compounds. The unsaturated compounds in particular can be to modify textile casings, foils, artificial leather, Leaer and Lackobex surfaces by means of a superficial grafting reaction in order to improve their properties with regard to Selu-.utz &'braioungy"■3" j.sdurchlärisii: keit _w and •. "/ ■ etteri'estijköit ^ u spoil. Au & AO ^ -L'ijoup ^ rfluoralkan oder.-0 ^ -jW -diiod.perhalogena.lkan receives ..ian coveted intermediates for the construction of high polynes.

The present invention now describes a technically economical one Process, such compounds from unsaturated aliphatic, or alicyclic ouer with unsaturated side

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grouped., aromatic, organic compounds - '^; to obtain by:. """'""'",'"^;'

ilonojodperfluoralkane Jodperfluorchloralkane '' ''

αί, Φ-Diiodoperfluoroalkanes' ^, i ^ -diiodoperfluorochloroalkanes ^:

o £ -Iodine-i * i-hydrogen per fluoroalkane 0 (-iodine & i-h.ydrogenperf luorcliloralkane ot-iodine-itJ-ciilorperfluöralkane - _ "" "''" * "'

o (-Iodine - {*> - bromoperfluoroalkane """" oC-Iodine-Ä ^ -bromoperfluorochloroalkane 'iia mixture with the unsaturated,' organic compounds, "■ / ^: '

■ according to the invention, as a vapor, solution, or as a liquid

mixed, heated to temperatures between '2DQ C and 5CQ Ö in less than an hour, whereby, however,' preferably temperatures 'from 250 C'"'to 400 C, advantageously' at 1 atmosphere, at times" of more than -15 Minutes applied 'vrden.' For more inert olefins, such as ethylene, temperatures of more than 300 ° C are required. Less than 5 minutes' useful. At 'temperatures of' more than 100 ° C ver--; '' - the reaction runs in times of less "than a 'minute, ^ b"is'' too few secondsT The "therii-i'sche Adaxtion. von ^J Perf iuuTatLlcyi- · ■ iodiden is indeed already from Haszeldine" in Jbürn, Ghem. 5 "or ' 'Λ 93 "2 ' * 3483, but the high pressure applied and, above all, the 'long reaction time' led to increased education * Vön ^; '' 1: 2 educts which reduced the yield of the desired: 1 iddi- ~ "- " frion compounds to -a considerable proportion ". ins- 'especially at normal pressure and negative pressure and short reaction times contrary to the Le Chatelier's see "principle, surprising"

Completely. Especially the use of higher permeability doors and very short times, contrary to expectations, does not lead to '

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stronger elimination of iodine, rather the reaction proceeds smoothly and with fewer secondary reactions. Even with liormaldruck or vacuum, the space-time yield is much higher than with the previously described processes, those with long reaction times and under high. Pressure work. The use of lower pressures at or near atmospheric pressure allows exceptionally economical process management. Above all, compared to the previously known processes, there are no significant lengths of 1: 2 which reduce the yield Jodwasserstoffabspaltung · arise zusamaen with the iodine-containing reaction products of a katalytisciien hydrogenation and Jodwasserstoffabspaltung subjects so that laan, a uniform, iodine-free, saturated product obtained from two reaction products, which are often present in varying i.ienge, the calculated yield \, ill advantageous. Very is the application of erfineungsgemäßen method as easily be polymerized oils 1 ine, o'r.ne "horses polymer formation and with virtually no risk of explosion can be reacted quantitatively, without a dsr .Components in Loheru" must be applied excess.

This new process should be viewed as a continuous process often does not even require a closed loop system, u-_nn one of the return not noteworthy unconverted rerfluoralkyliodid- or olefin quantities, as in most

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Cases under the specified operating conditions very high "sales can be achieved even if the Feeaeaktionspartner in the Iviol ratio 1: 1 can be used. . . . "■

The process requires neither radiation nor catalysts. It is insensitive to minor impurities such as oxygen and water vapor. The reaction partners are according to the invention preferably continuously in a reactor vessel, or one Reactor cascade, but advantageously in a reaction tube, without ' or with fillers with slight overpressure or underpressure, advantageous implemented at lormaldrucic. It is essential that the Times are kept short according to the temperatures. Particularly It is advantageous that the process at normal pressure or Vacuum can be used because it is cheaper and more corrosion-resistant Material can be used, wo ^ arch the facility cost 'can be significantly reduced.

The high harvesting time yields allow an exceptionally economical one Procedures, however, are not expensive high pressure ·. pumps and systems, as before, required if one. the Reaction carried out in the vicinity of the normalaruck. The simple one continuous. Procedure by means of a flow pipe allows an automatic mode of operation, without complicated control devices. ~

As unsaturated reactants for the addition of mono- and diiodoperfluoroalkanes, or mono- and diiodoperhaloalkanes The following compounds and their homo- logs mainly come into play in question:

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Aliphatic homologues such as;

Ethylene, propene, 1-butene, 2-butene, isobutylene, 1-octene,

Cyclohexes
Aliphatic diolefins, such as:

Butadiene, isoprene, allene, cyclopentadiene, dicyclopentadiene,

Diallyl
Aliphatic ^ acetylenes, such as?

Acetylene, propyne, 1-butyne, 2-butyne, vinyl acetylene, octylacetylene Aliphatic ^ halogen olefins, such as:

Vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, i-fluoro-i-chloroethylene, vinylidene fluoride, 2-chlorobutadiene,

Allyl chloride, allyl thromide, ivLethallyl chloride Aromatic olefins, such as. eg:

Styrene, vinylnaphthalene, divinylbenzene olefins with a heterocyclic hydrocarbon residue, for example:

Vinylpiridine, vinylcarbazole, vinylpyrolidone Unsaturated mono- and dicarboxylic acids and their derivatives, such as

Acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, maleic anhydride, Dimethyl maleate, maleindinitrile, Acetylenedicarboxylic acid diaciditrile, acetylenic carboxylic acid methyl ester, Allyl cyanide, oleic acid methyl ester, acrylic acid, tetracyanoethylene, Cyclohexene-5,4-dicarboxylic anhydride, vinylidene

cyanide.
unsaturated alcohols and their derivatives, such as ζ ,, Β «:

Vinyl acetate, divinyl ether, vinyl ethyl ether, vinyl phenyl ether » Allyl alcohol, allyl acetate, ■ diallyl ether, methallyl acetate, 2-Buteii-1 ·, 4-dietetate, propargyl acetate ·, butynediol.

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Unsaturated ketones, such as s
Vinyl methyl ketone

Functional vinyl and allyl derivatives, such as, for example, vinylsulfonic acid, Ν, ΙΤ-dimethylvinylsulfonic acid, vinylphosphonic acid dichloride, vinylphosphonic acid dimethyl ester, methyl ester of vinyl boric acid. -

Unsaturated silicon compounds such as t

Vinyltrichlorosilane, vinyltrimethoxysilane, vinylmethyldichloro-

_: silane, vinylmethyl diethoxysilane, divinyldichlorosilane, 1,2,3,4-tetravinyl-1,2,3 »4-tetramethylcyklotetrasiloxane, octavinylcyclotetrasiloxane, yinyldimethylchlorosilane, yinyldimethylmethoxysilane, 1,2-divinyl-i, 1,2,2-tetramethyl, 1,2,2-tetravinyl-1,2-dimethyldisiloxane, 1-vinyl-5-chlorodecamethylpentasiloxane, yinyltrimethylsilane, bivinyldimethylsilane, polymethylvinylsiloxane, allyltrichlorosilane, allylmethyldichlorosilane, allyl dimethylchlorosilane.

Unsaturated stannans, such as:

Yinyltrichlorostannane, Allyldiniethylstannane, 1,2 -D ± v ± njl- 1,1, 2,2, -tetraniethyldistannoxane, allyltrichlorostannane.

Unsaturated organosulfur compounds, such as »

Diallyl sulfide, diallyl sulfoxide, divinyl sulfone, vinylmethyl • sulfone =.

Unsaturated amines and their derivatives, such as ζ.ΒΪ. » Allyldimethylamine, UjiT-diallylacetamide.

During this process, almost, exclusively 1 t i

- ■ "■■■■■■. ■. '■■. .-- - ■ -; ■ -": · ■ - ^ i ---' -M ^ -''..- '"" adducts , based on a double or triple bond. the

resulting products are often partially or completely through

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Secondary reaction deiodinated, partially unsaturated or saturated by secondary reaction. The reaction mixture is then mostly by suitable, hydrogenating decoding using hydrogen converted into the corresponding iodine-free, saturated compounds via platinum metal catalysts. Be in this way obtain high yields of iodine-free uniform substances which have exceptionally useful properties or represent valuable intermediates.

By using excess 1,2-diiodotetrafluoroethylene iui mixture with 1-propene obtained a reaction product, after gentle, catalytic hydrogenation 1-iodine-1,1,2,2-tetrafluoropentane supplies that after renewed conversion with acrylonitrile and subsequent, hydrogenating decoding to TJIP * '- tetrafluorocaprylic acid nitrile, which leads to the free Carboxylic acid saponified, a valuable starting product for production of perfluorocaprylic acid by 'El ek tr ο fluorination · according to patent application B 72 418 IV b / i2 ο represents.

The addition of long-chain perfluoroalk iodides to unsaturated ones Compounds of the type indicated above provide interfacial ■ 'active materials that reduce the interfacial tension between, oil and reduce air, water and air, oil and perfluoroalkanes. They are not biodegradable and therefore can be kept for a long time in water, which can be desirable to suppress evaporation losses.

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The lowering of the interfacial tension of normal, organic Compounds, such as oils, plastics, leveling agents, allows these compounds to be used as valuable emulsifier auxiliaries to use. For example, stains can form in footbed wax should be avoided when interacting with Sasaer. At 'Autolack-kon? · Serving wax will have an increased dirt-repellent effect and higher weather resistance achieved. Slit these substances treated films become adhesive-repellent and show in the In most cases, gas and aroma permeability are avoided. For this purpose, the consumption of substance is extremely low. With sf. Eh en ',' / axes or oil solutions in Frigen and chlorinated hydrocarbons Manufactured sprays allow the simple impregnation of textiles, which-thus become dirt- and water-repellent. Through the use of diunsaturated organic compounds oligomers and polymers can be prepared with diiodoperfluoroalkanes manufacture the raw materials for thernoplastics, thermosets ·, and Elastomers with valuable properties, such as non-flammability, Resistance to swelling, or very low freezing and embrittlement temperature form. . '"■ -.-

In almost all cases, the properties can be modified if instead of ivlono- or diiodoperfluoroalkanes, iono- or di-oligomers of i'rifluorochloroethylene or perfluoropropylene are used. Provided that, when using Li .ian j odperfluoral-kan or diun _u e s saturating Verbinö-Ungen not "l'eilumsatz to monoaddition compounds is interested, it is advantageous, both components in almost the same, the molar ratio

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to implement almost completely, which facilitates the work-up, liur in the event that one of the starting materials in the
Reaction temperature remains liquid, working under pressure is to share the correct mixing ratio with the
vapor component advantageous. But even in this case, a heterogeneous reaction in a packed column proceeds just as well at normal pressure. In all other cases, the pressureless reaction according to the invention or the superpressure reaction with short residence times offers great advantages which relate to the reduced expenditure on apparatus and control technology. Due to the low pressures and the short times, lifting reactions ζ.B * Formation of 1 t 2 adducts do not occur, which reduces the yield in the reaction under pressure. ■

The following limits, which are little influenced by pressure, are given as a favorable temperature and time range.

Reaction temperature reaction time advantageous
less than ⁰ O- less than 10 seconds 400 and above 30 seconds 20 seconds 350-400 3 minutes 40 seconds 500-550 10 mins 5 minutes 250-500 20 minutes 20 meows 200-25O 1 hour 45 minutes HO - 200 2 hours

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It is advantageous to proceed in such a way that both products, either one in a larger excess or in approximately equal molar proportions, are evaporated separately, the vapors are mixed well in a heat exchanger and brought to reaction temperature as quickly as possible? Gas mixture can flow through a reaction tube, a container, a container cascade, or a packed column at reaction temperature, whereupon the vapors are condensed by cooling. However, it is also entirely possible to carry out the reaction by means of a heating coil heated to over 250 ° C. in the vapors kept at a lower temperature if the higher-boiling reaction product separates out of the grass space by condensation. If one or both reactants remain liquid at the reaction temperature and you want to avoid the negative pressure necessary to produce a homogeneous gas phase, the reaction can also be carried out heterogeneously in a packed column, where vaporous reactants are brought into contact with the liquid reactant in cocurrent or countercurrent. Often, however, a slight overpressure of a few atmospheres is sufficient to prevent the occurrence of a gas phase when very high-boiling reactants are heated, so that one can work in a homogeneous, liquid phase. However, this has the disadvantage that, although heavy high-pressure apparatuses do not have to be used, pressure apparatuses, pumps and regulating devices which are omitted in the process at normal pressure are nonetheless necessary. - _L. Especially the use of glass, ceramics, or. Charcoal under pressure or negative pressure allows an exceptionally economical way of working, especially with regard to the iodine and hydrogen iodine produced, "so that as a rule one way of working

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One advantage of the process is that smaller amounts of oxygen, hydrogen and other impurities neither inhibit nor otherwise seriously interfere with the reaction Pressure, which also significantly lowers the investment costs. The possibility of reacting the products in a stoichiometric ratio with conversions of 90 - 98 ° F allows a direct, further use of the reaction product, which is usually obtained in quantitative yield, and the saving of an expensive recycle operation with rectification units, which makes the process highly economical will. In cases in which the reaction product is inconsistent due to the secondary reaction, e.g. by splitting off iodine, iodine or hydrogen iodide is usually split off immediately afterwards by known processes, or replaced by other halogens or as s only off and double bonds are hydrogenated. In this way, the yields of iodine-free end product are often extremely high and often exceed 90 %.

In general, in most cases the yields are higher than when the reaction is carried out in the liquid phase in the manner known hitherto under high pressure and a long reaction time. Many products can be only after this process befriedi _B implement end, although sometimes off aurch iodine or Jodwasserst from fission secondary reactions occur, the yields of desired products are still high enough to ivenn in comparison to siner previously "described the process -

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from a few hours to high pressure uninteresting low Yield "gets.

Eaten examples

Example 1 -. ■

Its glass tube spiral of 1.5 Ω length and now 6 inside diameter with 10 turns is kept at 590 ° C. by means of a salt bath. A gas stream of 47 cc / ain of ethylene, partially charged with 1-iodoperfluoroheptane vapor at 112 ° C., is passed through this reaction tube In this way passed through the glass spiral. The condensation was 17 sectinlon at a heating temperature of 370 ° C - 400 ° C. At the end of the tube, after throughput of 10 g of perfluorheptyl iodide, 10.5 g of an at-room temperature solidified axially Liquid can be obtained - which still contained 0.5 g of unused perfluoroalkylidide in addition to 3.65 g of 1-iodo-1,1-, 2,2-tetrahydropei ^ fluorononane. The ilus loot was $ 6.5 / <> · Greater iodine deposition did not occur. The 1 t 1 adduct obtained crystallizes in thin, fine, long blemishes on the surface of the reaction product and has a fat-like consistency with a great lubricating effect. It melts at about 35 C. The compound could be ^{distilled in vacuo at 20 mm u} g and 78 C. At normal pressure at 190 ° C.

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Example 2

1-Iodoperfluorodecane was added to ethylene as "in Example 1, but" at a reaction temperature of 29O C and a dwell time of about 2.5 minutes. The molar ratio of iodide to ethylene was set at 1: 5. The conversion was greater than S and the yield based on the perfluoroalkyl iodide used was over 95 % theoretical. The 1-iodo-1,1,2,2-tetrahydroperfluorododecane obtained, which "was solid at room temperature, could be distilled at 10 tm. Hg and 108 ° C.

Example 5

From 1-iodoperfluorobutane, 1-iodoperfluorohexane, 1-iodoperfluorooctane, the corresponding 1: 1 addition compounds are obtained, the yields were consistently above 90 °, the conversions between £ 85 and £ 95.

1 - iodine-1,1,2,2-tetrahydroperfluorhexane distilled "porridge 100 mm, 81 c

I-iodine-I ^^^ jtetrahvdroperfluorooctane "·», 45 am, 92 ° C

1-iodine-1,1,2,2, tetrahydroperfluorodecane "". 15 mm, 94 ° C

Example 4

1,6-Di iodoperf luorhexane was made up of the five facia molar ethylene quantities as a gas mixture at liormalciruck in a glass spiral 55Ο C and after a dwell time of JQ seconds at the Flowing through a column, held at this temperature, standing perpendicular to the plane and filled with slas beads, cooled again,

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whereupon the reaction product said goodbye. Of 26 g of 1,6-diiodoperfluorohexane was in this way 2.18 g of 1,8-Dijodr-i, 1,2,2-tetrahydroperfluoroktan Kp with _Q = 98 C corresponding to 8 fa yield and 26 g 1,1ü-diiodo- 3,3,4>4>5> 5 »6> 6-dodecafluorodecane which could be distilled at 118 C under a vacuum of ό mm Hg, obtained. The conversion to the diaddition compound was accordingly. 91 fo. If the monoaddition compound, which was obtained in a yield of 8%, is reacted again with the starting product, almost quantitative yields are obtained ... This product and its higher homologues are full. Intermediate products at dex Manufacture of plastic monomers and oligomer waxes.

Example 5 = ■ - - ■ ^

1-iodine-8-hydro _a enperfluorooctane. Was with the \ double molar_

itenge of acetylene passed as a gas mixture at a temperature of 39Ο C and a residence time of 20 seconds through a tube. Sales of more than 90 / ° were achieved. The. Capture.

1-iodine-1,1, 2,2,10-pentahydroperfluorodecane (jC "H. IC]? _O ) _Q H)

were 95 f ° of ... theory. The product could be distilled at 10 mm Hg and 77 C. - Be room temperature viar it is a solid one

Example 6 . ... ... ■. _ ■ ■. _; . ... - 'i-iodine'-ö-chloroperfluorohexane was combined with twice the stoichiometric amount of vinylidene oil. at 280 ° C. and a residence time of 60 seconds through a glass tube. There were obtained from 15 g of iodochloroperfluorohexane 17, i1, g of a dark-colored 7> tachs, which according to gas chromatography to -8jO fo from 1-J.od-i, Λ, 6-

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trichloro-2,2-dihydroperfluorohexane. This product is in strong acid or alkali to form 2,2-dihydro-8-chloroperfluorocaprylic acid saponifiable, which has surface-active properties.

Example 7

25 g of 1-iodoperfluorodecane were passed through a glass tube in gaseous form with twice the molar amount of vinyltrichlorosilane at 330 ° C. so that the residence time was 30 to 40 seconds. 32.1 g of crude product could "be obtained at the output of Beaktionsrohres by cooling a content of 1.6 g was 1-Jodperfluordecan detected in the product by Gaschroiaatogramm The conversion was 93i5 i * · In about 90;.. S yield was due to the fluorine silicon bound before _j and Camit was uirekt as impregnating agents used for textiles and paper. eans a solution of Beaktionsproduktes in carbon tetrachloride can be achieved by simple dipping or spraying water a textile fabric and impregnate oil repellent. the dirt-repellent effect is very _ö Ross'. it is better However, de to solve s Beaktionsprodukt by dropping in glycol or methanol, wherein (he pH is kept neutral by the addition of sodium hydroxide solution. Then, the resulting solution is reduced with hydrogen and active platinum carbon, or with üaHSO ,. this gives After washing the ethereal solution with H _? 0, an iodine-free fluorosilane of the formula:

\ OR

in yields of about 80 to 90 ^a ß> *

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This product in trichlorethylene solution, or the hydroxophylene fluorosilane compounds, which were obtained by conversion with glycol or triglycol, in glycol solution, can be applied to textiles, leather, paper and cellulose regenerate. Conveniently, heating the treated fabrics briefly Tempexaturen from 100 G to 150 ⁰ C, and so obtains a wash-resistant, highly effective oily soil and water-repellent impregnation. ■

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Claims (1)

- 17 claims 1 4 4 3 '5 Claim 1 Process for the production · of organic compounds that one or more tetrafluoroethylene and / or chlorotrifluoroethylene groups wear, characterized in that one mono- or diiodoperfluoroalkanes, cC-iodo-o-substituted perfluoroalkanes, Mono- or diiodoperhaloalkanes, with unsaturated, organic ones Compounds, individually or as a mixture or diluted with inert substances, for a short time to higher temperatures, preferably in continuous process at pressures less than 5 atmospheres heated. Claim 2 Method according to claim 1, characterized in that at Temperatures above 170 C with reaction times under two hours, advantageous at temperatures above 2.40 C and times below 30 Minutes, preferably at temperatures above 270 C and times of less than 10 minutes. Claim 3 Process according to Claims 1 and 2, characterized in that the reaction takes place at normal pressure or reduced pressure, preferably in the Gas phase is running. Claim 4 Method according to Claims 1 to 3 »characterized in that 1-Iodoperfluoroalkanes with a carbon chain with more than - 18 - 80 9807/0413 bad original 6 carbon atoms with ■ "unsaturated organic compounds implemented. ~ Claim 5 Method according to claim 1, characterized in that oCW diiodoperfluoroalkanes with unsaturated organic compounds implemented. Claim 6 ■ °. Method according to claim 1 and 2, characterized in that OL-iodine-65-hydrogen or o (r-iodine-6> -chloroperfluoroalkane implemented will. .......... Claim 7 ' Method according to claims 1 to 6, characterized in that as unsaturated compounds ethylene, acetylene, vinyl chloride, Vinylidene chloride, styrene, acrylonitrile, vinyltrichlorosilane, vinylmethyldichlorosilane and allyltrichlorosilane can be used. Claim 8 Method according to Claims 1 and 2, characterized in that at elevated pressure in a continuous procedure, preferably is worked in the liquid phase. Claim 9 Method according to Claims 1 to 6, characterized in that preferably at temperatures above 290 C and heating times less than 60 seconds of work is carried out » β 0-9 8-0-7 / 0 4 13 "." BATH