DE2160914B2 - Method of sealing leaks - Google Patents

Description

To seal leaks, sealing means have already been proposed, which consist of a one polymeric curable compound-containing liquid exist. The liquid is in the to be sealed The vessel is filled and flows into the area to be sealed. According to US-PS 35 07 818 is a for this purpose aqueous dispersion of a cationic polychloroprene latex described. A disadvantage of such sealing compounds, however, is that in many cases the introduction a liquid is not very useful and that considerable difficulties may arise, e.g. B. to remove the excess sealing liquid. In particular for sealing leaks in pipes suggests a need for a simple and reliable method of sealing.

The invention is defined in the claims

The method according to the invention is particularly suitable for sealing very small leaks in

ίο underground pipe systems or in leaks from Lines that contain nitrogen or another protective gas under pressure.

According to a preferred embodiment of the invention, the interior of the vessel is advantageously initially with a dry, non-reactive gas such as nitrogen, helium, argon or dry natural gas rinsed to remove the moisture contained therein and / or remove the oxygen present. Thereupon the sealing compound is taken into the interior of the vessel

jii introduced pressure in gaseous form.

A monomer which is capable of coming into contact with air, H2O, can be used as a monomer or to polymerize under alkaline or acidic conditions as they exist at the location of the leak. In

In this case, no additional polymerization catalyst needs to be added to the monomer. In the however, in most cases the sealant will contain both the volatilizable monomer and one volatilizable polymerization catalyst therefor.

jo The amount of that introduced with the monomer The volatilizable catalyst is at least a catalytic amount; H. an amount that is enough to induce and maintain the polymerization of the monomer. This amount varies accordingly

r> the nature of the monomer and the catalyst as well the conditions in the vessel. The amount is usually greater than 1% by weight of the monomer. A Excess catalyst material is not harmful, but can be uneconomical.

The volatilizable monomer can advantageously be introduced as a mixture with a gaseous carrier which is inert towards the monomer and the catalyst.
If desired, the pipeline or the vessel

4 "> must first be purged with an inert gas, such as nitrogen, before adding the monomer or monomers and introduces the catalyst.

The components of the sealing compound in the volatilized state can get. Innt in controlled

be added in quantities to the vessel in which the Inergart is already under a suitable pressure.

Thus, the method of the invention comprises the introduction of a normally gaseous or mixed

r> volatile monomers in a gaseous inert carrier together with a volatilizable polymerization catalyst into a gas stream contained in a pipeline, vessel, and the like. the Polymerization of the monomer is after

M) leakage through the leak into the environment that the Atmosphere or soil, activated, which is caused by the action of moisture, oxygen, the alkalinity or acidity of the soil or other agents that may be present or that of

h> have been fed to the outside of the leak, The catalyst can also be used at the point of leakage before or during the introduction of the monomer by implementing a suitable volatile

Additive that reacts with certain components of the soil or with atmospheric agents, are formed. Activating agents can thus be supplied to the site of the leak by a stream injected from a suitable agent or catalyst through a hollow tube or lance.

In addition, heat and / or moisture can be supplied inside or outside the leakage point be by passing a stream of water vapor or hot gas through a hollow lance in the place of the Injected leaks. Heat can also be built up at the point of the leak by using a suitable duct Additive with moisture, oxygen and / or other means of the soil or the atmosphere is reacted, the reaction being exothermic or by an external electric field electromagnetic induction takes place. In this way, in the pipeline or in the vessel itself as well as in the surrounding external environment in which the vessel can be found creates an intention

The sealing method according to the invention is particularly useful for sealing leaks in underground Pipelines suitable where leakage occurs in joints sealed with jute or in the surrounding areas Soil is made into it.In such cases, a matrix of either jute or soil is available around the To absorb monomers. In this way, a polymerization site for the achievement of the desired solid seal generated

Depending on the type of monomer used and the catalyst used, the monomers and the catalyst or the other components either sequentially or simultaneously in the vessel to be introduced.

The monomer and / or the catalyst are introduced into the vessel under a pressure that sufficient to prevent monomer vapors from escaping from the leak into the environment and for a period of time that is sufficient to allow the To cause the formation of a polymer which gives a tight seal at the location of the leak

The monomers are introduced in a concentration which depends on the size and shape of the Vessel and depends on the conditions of the environment The concentration ranges in general from about 50 parts per million to about 10% by weight of the gas or inert gas contained in the vessel Carrier or the carrier gas, if one is used. If the monomer is not gaseous, but is volatilizable then it can be volatilized or dissolved in suitable organic solvents. Such are z. B. hydrocarbons such as butane, hexane, heptane, benzene and the like, which volatilize uniformly. It is also possible to carry out a dispersion in a carrier gas.

The organic monomers are preferably gaseous at room temperature and atmospheric pressure. However, monomers can also be used which are volatilizable liquids which have relatively low boiling points at atmospheric pressure or which have vapor pressures such that they ^{easily volatilize in the temperature range from about 0} ° C. to about 100 ^° C. (which is present, for example, in underground pipelines) can be made to give concentrations of at least about 10 parts per million in the pipeline. If, however, the upper limit of the relevant temperature range is higher, then the choice of volatilizable monomers is expanded.In any case, the amount and volatility of the monomer must result in a concentration sufficient to produce a tight seal ϊ at room temperature and under the pressure conditions in the vessel will.

In the case of a gas pipeline, for example, the pressure in the pipeline can vary from about 0.33 kg / cm ² to 7.03 kg / cm ² or more.
The usable according to the invention ve., - volatile-

organic monomers include both single-monomer systems, which can form homopolymers and comonomer systems which form copolymers. It can according to the general polymerization techniques and using the appropriate ones

is catalysts for the individual system are being worked.

Although in the method of the invention all any polymerizable volatilizable organic monomers can be used which have a can result in a solid seal, but advantageously comprise the sealing systems used one or more monomers from the following groups:

1. Mono-ethylenically unsaturated hydrocarbons ^r 'fe

2. Polyethylene unsaturated hydrocarbons

3. Halo-alkenes

4. Alkylene oxides and epoxides
5. alkylene carbonates

6. Alkenyl nitriles

7. alkanecarboxylic acids

8. Alkyne hydrocarbons

9. Aldehydes
10. Ketones

11. Alkenyl ester

12. Alkenyl alcohols

13. Alkenyl halides

14. Alkenyl ether

15. Organo-silane compounds

16. Five-membered ring compounds containing a heterooxygen atom

17. Organometallic compounds

18. Oligomers of the above monomers

When used with the volatilizable monomer, a suitable volatilizable polymerization catalyst is used, then this catalyst is used depending on the type of polymer and the type of polymerization in selected from the following groups:

1. Free radical catalysts

2. Organometallic compounds

3. Metal hydrides

4. Lewis acids

"5. Alkaline earth compounds

6. Alkalis

7. Metal halides

8. Metal and metalloid alkoxides

Monomers

Mono-ethylenically unsaturated hydrocarbons

These compounds include gaseous or volatile liquid hydrocarbons, the alkenes can be bi with a single double bond. Such are z. B. gaseous or volatile olefins. Examples of such olefins are shown in Table 1.

Table 1

Mono-ethylenically unsaturated hydrocarbons

Monomer

Kp C

Vapor pressure mm Hg

Ethylene

Propylene

1-butylene

2-butene (ice)

2-butene (trans)

Tetramethyl -

ethylene

Isobutylene

1-pentene

Styrene

ff-methylstyrene

-103.9

-47.8

-6.3

3.7

0.9

72-73

-6.6

145.2

165

226.4 at 38 C.
63 at 37.7 C.

700 at -9 C

Flash point 37.8 C
(100 ⁰ F)

1.9 at 20 C

The polymerisation of the alkenes can either be a true polymerisation to a homopolymer or a co-polymerisation. In the latter z. B. used in the production of ethylene-propylene terpolymer elastomers complex mixtures of alkanes, alkenes, alkadienes and others. Of the gaseous olefins, isobutylene is catalytically polymerized the fastest, with butyl rubber being formed. The catalysts are usually permanent substances such as acids or their anhydrides or metal halides. Examples of acids are sulfuric acid, phosphoric acid, hydrogen fluoride and acidic clays and silica-alumina composite bodies. The clays and the like can occur in the earth. Metal halides are e.g. B. Tin-IV-chloride and titanium-tetrachloride. Both substances are volatile. The halides and hydrides of boron are also good catalysts, with the inclusion of, for example, boron trichloride, bp 18 ° C and ₁ of boron trifluoride, a gas Kp IOL ⁰ C, diborane B2Hf> a gas Kp 92.5 ^O C and pentaborane B ₅ H ₉ 48 ⁰ C, vapor pressure 66 mm at 0 ⁰ C. the gas nature of the boron catalysts makes them particularly suitable when currents are introduced the polymerizable hydrocarbons and the gaseous catalyst under suitable temperature and pressure conditions in a vessel for carrying out the method according to the invention .

Ethylene and propylene can also be a low-pressure polymerization using organometallic catalysts of the Ziegler type at almost Enter atmospheric pressure. Such catalysts are e.g. aluminum triethyl with litanteirachlorid. Other catalysts of this type include triisobutyl aluminum and titanium tetrachloride or aluminum alkyl halides with vanadium halides or with titanium esters, such as diethyl aluminum chloride with vanadium oxychloride or isopropyl titanate.

Polyethylene unsaturated
Hydrocarbons

This group includes gaseous or volatile hydrocarbons with multiple Ethylenic unsaturation. Examples are conjugated hydrocarbons such as butadiene and its Derivatives as well as divinylbenzene, alkenylstyrenes, isoprene and the like. Examples are given in Table 2:

Table 2

Polyethylene unsaturated hydrocarbons

Monaneres

Kp. C

Vapor pressure mm Hg

1,2-butadiene 18-19

3-M ethyl- 41
^2l 1,2-butadiene

1. "-Butadiene -4.4

Isoprene (2-methyl- 34
1,3-butadiene)

«) Divinylbenzene 199.5

Flash point 76.7 C

Styrene is usually made using a free radical catalyst such as benzoyl peroxide. to polymerized a homopolymer. Both styrene and α-methylstyrene can, however, also under Use of diborane gas as a catalyst to be polymerized. Likewise, styrene can with butadiene copolymerized using diborane as a catalyst. Isoprene, which is a low one Boiling point of 34 ° C can be done with aluminum or lithium alkyl type catalysts at moderate heat are polymerized. If there is a small amount of moisture, it will settle Aluminum with it. whereby the required heat is supplied. Gaseous butadiene can with a Catalyst of the "Alfin" type in Gegenwar *, a fixed one Surface to be polymerized. These catalysts are z. B. in chapter 5 of the book by Raish and Schindler "Polymerization of Organometallic Compounds". With the »Alfin« catalysis the monomer molecules absorbed and oriented before they enter the chain growth process.

Halo-alkenes
Examples are listed in Table 3.

Table 3
Halo-alkenes

Monomer

Kp. (

Vapor pressure mm Hg

Allyl fluoride
2-fluoro-1,3-butadiene
l-chloro-2-fluoroethylene
Chlorine fluoride-iithylene

-10

-24
- 27.9

77 at 25 °, 500 at 100 °

lortsel / ιιημ 21 60914 8th 7th Monomer Vinylidene chloride Vapor pressure mm Hg Acetylene dichloride Kp. ( 599 at 25 ° 1,2-difluoroethylene 31.7 (cis form) (trans form) Vinylidene fluoride 60.3 - Tetrafluoroethylene 47.5 I-chloropropylene 84 - (ice cream) 76.3 (trans) 2-chloropropylene 32.8 - I Ό vyfliinr-I ^ -Hiit: irlipn 37.4 Hexafluoropropylene 68.9 ° at 775 mm - ftf) 29.4

The above-mentioned monomers, / .. B. chlorotrifluoroethylene, can be polymerized in the gas phase using gaseous borohydride caialyzers, such as diborane or pentaborane. Vinylidene chloride can be polymerized in 6 hours at 40 to 50 ^° C. with a borohydride catalyst.

Alkylene oxides

This group includes monomers such as ethylene oxide, bp 10.73 "C and propylene oxide, bp 33.9 ° C., vapor pressure 445 mm Hg at 20 ° C. The polymerization catalyst can be an alkali or an alkaline earth metal oxide such as CaO, SrO or be a heavy metal oxide such as ZnO, which can be introduced via volatile organometallic compounds or which is found in the soil. Metal halides such as SnCU are also suitable. Other catalysts include alkaline earth carbonates such as CaCOi or SrCO _1, which are found in many layers , as well as activated aluminum oxide or silicon oxide-aluminum oxide, which in turn can be introduced by way of liquid organometallic halides and the like. Combinations of acidic oxides such as aluminum oxide or silicon oxide-aluminum oxide with a metal alkyl compound such as boron tributyl, zinc diethyl and cadmium diethyl can also be used work.

Alkylene carbonates

An example of this type of monomer is vinylene carbonate, which has a bp of 162 ^; C and which can be polymerized with a free radical catalyst such as 1-propane-azo-methane in about 18 hours at room temperatures and pressures.

Alkenyl nitriles

Examples of this type of monomer are acrylonitrile, bp 77.3 ° C, vapor pressure 83 mmHg at 20 ⁰ C, 1-fluoro-acryI-nitrile, bp 43 to 48 ^C and C. l-methylacrylonitrile, bp 18 ° C. Acrylonitrile does not require a polymerization catalyst, but polymerizes spontaneously under certain conditions, especially in the absence of oxygen or on exposure to visible light or in the presence of alkalis.

Alkene carboxylic acids

Acrylic acid, boiling point 141 ° C., evaporates quickly and polymerizes in the presence of oxygen without a catalyst. Methacrylic acid. Bp I63 ° C. evaporates also rapidly and polymerizes when heated or in the presence of traces of HCl.

Alkyne hydrocarbons

Monomeric vinyl acetylene is a dimer of acetylene It has a Kp of 5'C and is at Room temperature a gas. It can be made into a neoprene-type elastomer using HCl as the Catalyst are polymerized.

Aldehydes

Examples of aldehyde monomers are aliphatic aldehydes, such as formaldehyde gas, bp -19.5 ° C, and acetaldehyde, bp 21 ° C. Examples of unsaturated aldehydes are acrolein. B.p. 52.5 ° C, vapor pressure 214 mm Hg at 20 ⁰ C. These monomers are usually all free using free radical catalysts readily polymerizable. Formaldehyde polymerized rapidly in contact with a surface at tempera ren where ^{f (-'te} polymers fabric are! Below about 90 C. ^c. Examples of suitable catalysts sine formic acid. HCl. SnCl. BF _first metal alkyl compound such as cadmium-dimethyl and finely divided Sulfur.

Ketones

Acetone. Bp 56.5 ¹ C, can be catalytically polymerized to mesityl oxide. This represents an unsaturated ketone (acetone-isopropylidene) with a Kp from 130 ⁰ C a vapor pressure of 7.9 mm Hg at 2O ⁰ C represents. .Jas mesityl oxide polymerized in contact with air without specific catalysts to solid polymers.

Alkenyl ester

Examples of such monomers are methyl acrylate, bp 80 ⁰ C, vapor pressure 68.2 mm Hg at 20 ⁰ C, ethyl acrylate, bp 99.6 ° C, vapor pressure 29.5 mm Hg at 20 ° C, methyl methacrylate, bp 101 ° C, flash point 29.4 ° C and ethyl methacrylate, bp 119 ° C, flash point 35.0 ⁰ C

These liquid substances polymerize rapidly in the presence of light, heat or catalysts of the free radical type, such as methyl ethyl ketone peroxide.

This group also Vinylester, such as vinyl acetate monomer, bp 72.5 ° C drop, vapor pressure 88.7 mm Hg at 20 ⁼ C, the polymerized at the light to a colorless mass, and vinyl formate. Bp 46.6 ° C, vapor pressure 270 mm Hg at 20 ° C.

Alkenyl alcohols

An example of this is allyl alcohol, bp 96 to 97 ° C, flash point 21.1 ° C (70 ⁰ F), which polymerizes when left to stand.

Alkenyl halides

The main monomers of this class are the vinyl halides, such as vinyl bromide, bp 15.8 "C, vinyl chloride, bp -13.37 ° C, vapor pressure 100 mm Hg at -55.8" C and vinyl fluoride. Kp -51 ⁰ C These monomers are generally homopolymerized with free radical catalysts, such as methyl ethyl ketone peroxide. They are widely used to form copolymers with vinyl esters, such as vinyl acetate, which usually contain 3 to 30 percent of the ester. Similar catalysts are used here.

Alkenyl ether

Examples of these monomers are vinyl butyl ether, bp 94.3 C. Vapor pressure 42 mm Hg at 20 ° C. and Vinyl ethyl ether, bp 35-36 "C. And vinyl isobutyl ether, Bp 80 "C. These monomers can be used with boron halide catalysts. how boron trifluoride can be polymerized.

Organosilane compounds

Several organo-silanes act as monomers. You can either use one with or without a catalyst Enter into condensation polymerization. Thus, vinyl triacetoxysilane can with moisture and without one catalyst form a polymer. Also dimethyl diethoxy silane polymerizes into a rubbery solid with moisture and acid or a basic catalyst. Propyl-trimethoxy-silane polymerized also with moisture and ammonia as a catalyst to a solid.

Five-membered ring compounds, the one
Contain hetero-oxygen atom

An example is tetrahydrofuran, bp 64 to 66 ° C, which polymerized using BFj or PFi as a catalyst to form a solid polymer having a high molecular weight and a melting point above 100 ⁰ C.

Organometallic compounds

There are certain organometallic compounds which are capable of reacting with compounds to form solid polymeric adducts which contain ethylenic unsaturations. So z. B. Organotin hydrides react with CC unsaturated monomers to form organotin polymers. Thus z. B. a trialkyltin hydride with styrene to a polymer of the structure [R ₃ Sn (CH ₂ CH ₂ R ¹ Jn] T um, where R is lower alkyl and R 'is phenyl. Similar polymers are obtained by reaction with monomeric acrylonitrile or with n-octene (AJ. Leusink et al, "Synthesis of Group IV Organometallic Polymers and Related Compounds" (1965) US DepL Comm. Clearing House, AD 69554).

As already stated, the polymerization catalyst introduced with the monomer depends on the monomer itself, the nature of the Polymerization reaction and the properties of the catalyst itself. Preferably the catalyst is a compound that is either gaseous at room temperature or that can easily be vaporized

The catalyst can be used simultaneously with the monome

ren or even before or after. In addition, the catalyst can be used in such a Way to be applied that he for the contact with the appearance of the monomers in the place of the > Leaks are available by introducing the catalyst from an external source through a lance, or by placing it in the vessel in front of the monomer, so that the soil or the jute is presaturated. The vessel is then rinsed in and charged with the monomer.

These classes of catalysts will now be discussed briefly to illustrate the invention. However, this is not intended to make any restriction.

Free radical catalysts

Various organic species fall into this class

Peroxides, such as acetyl peroxide, methyl ethyl ketone peroxide, Lauroyl peroxide. tert. Butyl hydroperoxide, cumene hy-

.'η droperoxide, and certain nitriles, such as Λ, Λ-azo-diisobutyronitrile.

Organometallic compounds

Many of these compounds are readily volatilizable. Examples are zinc alkyls such as diethylzinc, bp 118, vapor pressure 30 mmHg at 27 ° C and zinc di-n-propyl, bp 160 ⁰ C, vapor pressure, ° C 48 mm Hg at 1O ⁰ C. Further examples of aluminum alkyls, such as aluminum triethyl, bp 194 ° C, and aluminum-trii "methyl, bp 130 ⁰ C ₁ aluminum alkyl hydrides, such as di-isobutyl-aluminum hydride and aluminum alkyl halides such as diethyl aluminum chloride, bp 208 ⁰ C, vapor pressure 41 mm Hg at 12 ⁰ C. Also includes metal and metalloid alkoxides, such as silicates, titanates, borates, phosphates and vanadates. Examples of these are ethyl silicate, isoporpyl titanate, Methyl borate, ethyl vanadate and the like.

Metal hydrides

Examples include boron hydrides, such as diborane B) H ₆ , tin gas. Kp -92.5 ⁰ C, and pentaborane B ₅ H ,, Kp ·· 3 ° C. Vapor pressure 66 mm Hg at 0 ° C.

Lewis acids

4 "i These include e.g. boron trifluoride, a gas, bp -101 ° C.

Alkaline earth compounds

These are solids that can be found in the earth at the leakage point, e.g. B. CaO, Ca (OH) ₂ , CaCO ₃ and the corresponding strontium compounds.

Alkalis

In some polymerizations, alkalis can be used as ο; Catalysts, e.g. B. ammonia gas, sodium carbonate and the like can be used.

Phosphorus halides

Examples are: PCI ₃ , bp 76 ° C, POCl ₃ , bp

bo 107 ° C, PF ₅ (gas), bp- 84.6 ° C.

The released from the leak monomers or catalysts can react with the oxygen or the moisture are adorbiert on the surface of the mineral or organic materials in the soil or ground water, or air trapped to initiate the Polyrnerwachstum or the catalyst to activate or give heat to initiate the polymerization.

In the event that the pipe is sunk in the earth, specific components of the earth, such as Alkali carbonates, calcium and strontium salts etc. act as catalysts. Also occluded oxygen and Trapped moisture activate the conversion-> gen to the solid reaction products. These solid reaction products seal existing leaks and bind the soil adjacent to the leak, forming a solid reinforcement matrix.

The invention is illustrated in the examples. ι ο

example 1

A section of steel pipe 0.13 m long, 0 1.9 cm; was provided with a 0.32 cm hole to prevent a leak -, simulate. The test pipe was placed under 76.2 cm of clay loam with a moisture content of 6.3% buried.

One end of the tube was connected to a valved feed line, soft with a _> <> Source of dry nitrogen was connected. This was done to keep moisture out of the pipe and Flush out oxygen. The nitrogen also served as an inert gas carrier for the caulking compound. the The nitrogen line was connected to a heated vessel containing the liquid sealing compound. Pressure and flow meters and monitoring devices were also located in the feed line. That the other end of the test tube was connected to a valved outlet pipe, jo which was connected to a pressure measuring device and a pressure recording device. The test tube was first purged with a stream of dry nitrogen gas to remove oxygen and moisture. The room temperature was 20.0 to 24.4 ° C. In the π The vessel was made of monomeric isoprene and aluminum triethyl introduced in slight excess into the nitrogen gas stream, so that a concentration of about 2000 ppm was achieved. At the point of leakage, the aluminum alkyl reacted with the moisture, causing jo Heat was generated and anhydrous conditions were maintained at the leak point. The excess Aluminum alkyl then served as a catalyst for isoprene polymerization, creating the holes and the outer opening area with a solid rubber stopper 4-, has been sealed.

Example 2

As in Example 1 was a stream of ethylene oxide, boiling point 10.7 ° C, together with a stream of nitrogen Zinc diethyl introduced as a catalyst. The concentration of ethylene oxide was about 4000 ppm during that of the zinc diet was about 5000 ppm. After the leak was reached, the zinc diet settled with it the moisture in the soil, creating heat. The excess polymerized that Ethylene oxide to form a tight seal.

Example 3

As in Example 1, a stream of tetrahydrofuran, boiling point 65 ° C, in a concentration of 5000 ppm and of BF3 at a concentration of 500 ppm in a nitrogen stream. In this way a viscous oily polymer formed, which plugged the openings of the pipe. When the pipe is from Earth, then the tetrahydrofuran can first be introduced into the pipe and then through flow through the leak opening to saturate the earth. Then the BFi together with the Nitrogen gas can be passed through the tube, which polymerizes the tetrahydrofuran after exiting and the earth saturates, leaving a seal in the opening and a solid reinforcement matrix of the surrounding soil is formed.

Example 4

As in Example i, a stream of acrylonitrile, boiling point 78 to 79 ° C., and of hydroperoxide (ratio 100 mol to 1 mol) with a concentration of 5000 ppm in nitrogen gas was formed in the tube. When the gas became saturated with the monomer, the pipe pressure was increased to 0.04 kg / cm ² . Under these conditions and in contact with the surfaces of the pipe holes and the moisture, a catalyst was formed by a redox reaction. The acrylonitrile polymerized into a solid polymer that plugged the leaks.

Example 5

As in Example 1, the tube was charged with a stream of nitrogen gas containing monomeric styrene in at a concentration of 5000 ppm and diborane at a concentration of 50 ppm. The stream was maintained for about 15 hours at atmospheric pressure. At the leakage points, a seal had come from made of solid polystyrene. Excess solid polystyrene was then blown out of the tube.

Example 6

As in Example 1, the pipe was with er.em stream charged by nitrogen gas, the monomeric methyl methacrylate acrylonitrile at a concentration of 5000 ppm and butylborine at a concentration of 50 ppm. After about 15 hours they were Holes have been sealed with solid polymethyl methacrylate.

Example 7

As in Example 1, the tube was charged with a stream of nitrogen gas equal to equimolar parts monomers! Styrene and monomers! Butadiene each in a concentration of about 5000 ppm with diborane in a concentration of about 5% by weight of the total added monomers. To A solid stopper made of the copolymer had formed at the leak points for 12 hours.

Claims (10)

Patent claims: 1. Method for sealing leaks in vessels and the like which contain flowable media contain, characterized in that a) a catalytically effective amount of one Polymerization catalyst provides at the point of the leak and that b) the vapor of a normally gaseous or volatilizable catalytically polymerizable organic monomers introduces into the interior of the vessel with such a pressure that at the site of the leak Monomer vapors can escape, and these conditions are maintained until through formation of a Polymer the leak is sealed 1 method according to claim 1, characterized in that that one brings the catalyst from the outside to the place of the leak. 3. The method according to claim 1, characterized in that the catalyst and the Introduces monomers sequentially into the interior of the vessel 4. The method according to claim 1, characterized in that the monomer and the Simultaneously introduces catalyst into the vessel in vapor form 5. The method according to any one of the preceding claims, characterized in that the Monomers in admixture with a stream of a carrier gas which is opposite to the monomers and the catalyst is inert, introduces. 6. The method according to any one of the preceding claims, characterized in that as Monomer uses a polymerizable unsaturated aliphatic aldehyde. 7. The method according to any one of claims 1 to 5, characterized in that the monomer a polymerizable polyethylenically unsaturated hydrocarbon is used. 8. The method according to claim 7, characterized in that there is isoprene as the monomer and as Catalyst used an aluminum alkyl compound. 9. The method according to claim 8, characterized in that the aluminum-alkyl compound Aluminum triethyl used. 10. The method according to any one of the preceding claims, characterized in that one first flush the inside of the vessel with an inert dry gas.