DE2160914C3 - Method of sealing leaks - Google Patents

Description

For sealing leaks, sealing measures are already in place has been proposed that consist of a liquid containing a polymeric curable compound exist. The liquid is filled into the vessel to be sealed and flows into the point to be sealed. According to US-PS 35 07 818, an aqueous dispersion of a cationic polychloroprene latex is used for this purpose described. A disadvantage of such sealing compounds, however, is that in many cases the kin leads 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 underground pipe systems or in leaks from pipes containing nitrogen or another protective gas contained 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 purged to remove any moisture and / or oxygen present therein. Hie: on will the sealing compound is introduced into the interior of the vessel under pressure in gaseous form.

The monomer which can be used in contact with air, HjO 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 In most cases, however, the sealant will contain both the volatile monomer and one volatilizable polymerization catalyst therefor.

The amount of the volatilizable catalyst charged with the monomer is at least one catalytic amount, d. H. an amount sufficient to induce polymerization of the monomer and maintain. This amount will vary according to the nature of the monomer and the catalyst as well the conditions in the vessel. The amount is usually more than 1% by weight of the monomer. A Excess catalyst material is not harmful, but can be uneconomical.

The volatilizable monomer can advantageously in a mixture with a gaseous carrier, which is opposite to the monomer and the catalyst is inert, are introduced.

If desired, the pipeline or the vessel first purged with an inert gas such as nitrogen before introducing the monomer or the monomer and the catalyst.

The components of the sealing measure in the volatile Condition can be added separately in controlled amounts into the vessel, whatever the Inergart is already under a suitable pressure.

So include! Yes method of the invention the Introduction of a normally gaseous or volatilizable monomer into an inert gas Carrier together with a volatilizable polymerization catalyst in a gas stream in a Pipeline, a vessel and the like is included. the Polymerization of the monomer will occur after leakage through the leak into the environment, which 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 have been supplied outside at the point of the leak, is conditional. The catalyst can also take the place of the Leaks before or during the introduction of the monomer by reacting a suitable volatile

Additive that reacts with certain components of the soil or with atmospheric agents, are formed. Thus, activating agents can 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. At the point of leakage, heat can also be generated by adding a suitable volatile material 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 located creates an intention.

The sealing method according to the invention is Particularly suitable for sealing leaks in underground pipelines, where the formation of the leaks at sealed connections or into the surrounding soil. In such cases there is a matrix available either in jute or in soil to absorb the monomeric crc. That way becomes a Polymcrisalionsstclle for achieving the desired tight seal.

Depending on the type of monomer and catalyst used, the monomer and the analyzer or the other components can either be added to the vessel afterwards. , nticr c -. «he can be introduced at the same time.

The Monomcrc and / or the catalyst; or be in the vessel is placed under a pressure sufficient to allow monomer vapors to escape from the leak into the umbilical well and about a space that is sufficient. to the To cause formation of a polymer which gives a tight seal at the location of the leak.

The Monomcrc are in a concentration introduced depending on the size and shape of the vessel and on the conditions of the environment depends. The concentration generally ranges from about 50 parts per million to about 10% by weight of the gas contained in the vessel or the inert carrier or deep carrier gas, if such is used. When the monomer is not gaseous but volatilizable. then it can be volatilized or in suitable organic solvents are dissolved. Such are / .. B. hydrocarbons, such as butane, hexane, heptane. Benzene and the like that are volatilize uniformly. It is also possible to carry out a dispensing in a carrier gas.

The organic monomers are preferably gaseous at room temperature and atmospheric pressure. It but monomers can also be used, which are volatilizable liquids that are used in Atmospheric pressure have relatively low boiling points or have such vapor pressures that they are in the temperature range from about 0 "C to about 100 ° C (the e.g. in underground pipelines) can be easily volatilized to concentrations of at least about 10 parts per million in the pipeline. But if the upper limit of the The temperature range concerned is higher, then the choice of volatilizable monomers expanded. In either case, the amount and volatility of the monomer must be in a sufficient concentration result in a tight seal in the vessel at room temperature and under the pressure conditions will result.

In the case of a gas pipeline, for example, the pressure in the pipeline can vary from about 0.33 kg / cm -1 to 7.03 kg / cm ^a or more.

Those which can be used according to the invention are volatilizable Organic monomers include both single-monomer systems that form homopolymers can and comonomer systems that form copolymers. It can be done according to general polymerization techniques and worked with the appropriate catalysts for the individual system will.

Although in the process of the invention any polymerizable volatilizable organic Monomers that can provide a tight seal may be used, but include those Sealing systems used advantageously one or more monomers from the following Groups:

1. Mono-ethylenically unsaturated hydrocarbons

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. Alkynylcstcr

12. Alkyl alcohols

13. Alkyl halides

14. Alkenyl ethers

15. Organo-silane compounds

Ib. Five-membered ring compounds containing a hetero-oxygen atom contain

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 nature of the monomer and ArI of the polymerization selected from the following groups:

1. Free radical catalysts

2. Mrtallorganischc compounds

3. Metal hydrides

4. Lewis acids

5. Alkaline earth compounds

6. Alkalis

7. Metal halides

8. Metal and metalloid alkoxides c

Monomers
Mono-ethylenically unsaturated hydrocarbons

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

Table I.

Mono-iithylenically unsaturated hydrocarbons

Mnnomeres

Kp C

Vapor pressure mm Mg

Ethylene
Propylene
I-butylene
2-butene (ice)
2-butene (trans)

Tetramethylethylene

Isobutylene

1-pentene

Styrene

α-methyl styrene

- 103.9

-47.8

-6.3

3.7

0.9

72-73

- 6.6
40
145.2

165

226.4 at 38 C 63 at 37.7 C

700 at -9 C "

Flash point 37.8 C (100 ° F)

1.9 at 20 C

are z. B. aluminum triethyl with titanium tetrachloride, Other catalysts of this type include triisobutyl aluminum and titanium tetrachloride or aluminum alkyl halides with vanadium halides or with titanium esters, like 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

Monomer

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 acid-reacting clays, and silica-alumina-composite kipers. The clays and the like can occur in the earth. Metal halides are x. B. Tin-IV-chloride and titanium-tetrachloride. Both substances are volatile. The halides ... J hydrides of boron are also good catalysts, with the inclusion of, for example, boron trichloride, bp 18 ° C, and boron trifluoride, a gas Kp IOL ⁰ C, diborane BiH ,,. a gas bp-92.5 ° C and pentaborane Β-, Η *. 48 ° C vapor pressure of 66 mm at 0 ⁰ C. The gas nature of the boron catalysts makes them particularly suitable when currents of polymerizable hydrocarbons and the gaseous catalyst are introduced under appropriate temperature and pressure conditions in a vessel for carrying out the inventive method.

Ethylene and propylene can also undergo low pressure polymerization using organometallic Ziegler-type catalysts die at near atmospheric pressure. Such catalysts Kp. C

v.mpldruck mm Mg

1,2-butadiene 18-19

3-methyl- 41
1,2-butadiene

1,3-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. polymerized to a homopolymer. However, both styrene and α-methylstyrene can also be polymerized using diborane gas as a catalyst. Likewise, styrene can be copolymerized with butadiene using diborane as a catalyst. Isoprene, which has a low boiling point of 34 ^° C. can be polymerized with aluminum or lithium alkyl type catalysts at moderate heat. If there is a small amount of moisture, the aluminum will react with it. whereby the required heat is supplied. Gaseous butadiene can mi <. polymerized with a catalyst of the "alfin" type in the presence of a solid surface. These catalysts are z. B. in Chapter 5 of the book by Raish and Schindler "Polymerization of Organometallic Compounds" described. In "Alfin" catalysis, the monomer molecules are absorbed and oriented before they enter the chain growth process.

Halo-alkenes
Examples are compiled in Table 3.

Table 3
Halo-alkenes

Monomer

Kp. (.

Vapor pressure mm Hg.

Allyl fluoride
2-fluoro-l. 3-butadiene
I-chloro-2-fluorine-; ethylene chloro-fluoride-iithylene

- 10 12

- 24

77 at 25 °. SOO at 100 °

! • 'ortsct / imi! 21 60914 8th 7th Monomer Vinylidene chloride Vapor pressure mm Hg Acelylene-diehlorid Kp. ( 599 at 25 ° 1,2-difluoroethylene 31.7 (cis form) (trans form) - Vinylidene fluoride 60.3 - Tralluoriithylene 47.5 - I-chloropropylene -84 - (ice cream) - 7 (.. 3 (trans) - 2-chloropropylene 32.8 - I lexa fluoro-1,3-butadiene 37.4 - Hexafluoropropylene 68.9 ° at 775 mm - 6.0 - - 29.4

The monomers listed above, ζ. Β. Chlorotrifluoroethylene can be polymerized in the gas phase using gaseous borohydride catalysts such as diborane or pentaborane. Vinylidene chloride can be polymerized with a borohydride catalyst ^{at 40 to 50 ° C. in 6 hours.}

Alkylene oxides

This group includes monomers such as ethylene oxide. Kp 10.73 ⁰ 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 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 CaCO) or SrCO), which can be found in many soils, as well as activated aluminum oxide or silicon oxide-aluminum oxide, which in turn can be introduced by way of liquid [iieiaiiorgaiiiscne riaiugemue and the like. One can also use combinations of acidic oxides such as alumina or silica-alumina with a metal alkyl compound. like boron tributyl. Zinc diet and cadmium diet work.

Alkylene carbonates

An example of this type of monomer is vinylene carbonate, which has a bp of 1o2 ^c 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 mm Hg at 20 ° C, 1-fluoro-acrylonitrile, Bp 43 to 48 ° C, and 1-MethylacrylnitriI. Bp 18 ° C. Acrylonitrile does not require a polymerization .is catalyst, rather, it polymerizes spontaneously under certain conditions, especially in the absence of oxygen or upon 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 one

Catalyst. Methacrylic acid. Kp I63 "C. Evaporated likewise rapidly and polymerizes when heated or in the presence of traces of HCl.

AI kin-carbon hydrogens

Monomeric vinyl acetylene is a dimer of acetylene. It Desitzt a Kp of 5 ⁰ C and at room temperature is a gas. It can be polymerized into a neoprene type elastomer using HCl as a catalyst.

Aldehydes

Examples of aldehyde monomers are aliphatic aldehydes, such as formaldehyde gas, boiling point -19.5 ° C. and acetaldehyde, b.p. 21 ° C. Examples of unsaturated aldehydes are acrolein, boiling point 52.5 ° C. Vapor pressure 214 mm Hg at 20 ° C. These monomers are all readily polymerizable, usually using free radical catalysts. Formaldehyde polymerizes rapidly in contact with a surface at temperatu- I CM UIItCI HdI U ClWd 71 / V ^, WUUCI ICSlC I UIJiII HI <_ g CL / 1 IVlCl. Examples of suitable catalysts are formic acid and HCl. SnCU, BF ₃ . Metal alkyl compound. such as cadmium dimethyl and finely divided sulfur.

Ketones

Acetone, bp 56.5 ° C, can be catalytically polymerized to form mesityl oxide. This represents an unsaturated one Ketone (isopropylidene acetone) with a boiling point of 130 ° C. a vapor pressure of 7.9 mm Hg at 20 ° C. The Mesityl oxide polymerizes to solid polymers in contact with air without specific catalysts.

Alkenyl ester

Examples of soiche monomers are methyl acrylate, bp 80 ° C, vapor pressure 68.2 mm Hg at 20 ⁰ C, ethyl acrylate, bp 99.6 ° C, vapor pressure 29.5 mm Hg bei'20 ° C, methyl methacrylate, bp 10 ] ⁰ C, flash point 29.4 ° C and ethyl methacrylate, bp 119 ° C, flash point 35.0 ° 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 includes vinyl esters, such as monomeric vinyl acetate. Kp 72J ⁰ C, vapor pressure 88.7 mm Hg at 20 ⁰ C, which polymerized and on light to a colorless mass vinyl formate Kp 46.6 ° C, vapor pressure 270 mm Hg at 20 ° C.

Alkenyl alcohols

An example is (70 ° F), the polymerized allyl alcohol, bp 96-97 ° C, flash point 21.1 ⁰ C on standing.

Alkenyl halides

The main monomers in this class are the vinyl halides, such as vinyl bromide. Bp I 5.8 ° C, vinyl chloride. Bp-13.37 ⁿ C. Vapor pressure 100, Tim Hg at -55.8 C "and vinyl fluoride. Bp -51 C. These monomers are generally homopolymeric with free radical catalysts such as methyl-ethyl-ketone-pemxide! Mcrt. They are in widely used to form copolymers with vinyl esters, such as vinyl acetate, which usually contain 3 to 30% of the ester, using similar catalysts.

Alkenyl ether

Examples of these monomers are Vinylbutylither, bp 94.3 ⁰ C. Vapor pressure 42mm Hg at 20 C and ⁿ Vinyläthyläther. Bp 35-36 "C, and vinyl isobutyl ether, bp 80 C. These monomers can be polymerized with boron halide catalysts such as boron trifluoride.

Orga no-silane compounds

Several organo-silanes act as monomers. You can either use one with or without a catalyst Enter into condensation polymerization. Thus, Vin l-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, Kp polymerized 64 to 66 ⁰ C. The using BFi or PFi as Nataiysator to a test polymers having a high molecular weight and a melting point above 100 ⁰ C.

Organometallic compounds

There are certain organometallic compounds that are capable of reacting with compounds to form solid polymeric adducts that 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 form a polymer of the structure [R ₃ Sn (CH ₂ CH ₂ R ') ,,], where R is lower alkyl and R' is phenyl. Similar polymers are obtained by reaction with monomeric acrylonitrile or with n-ocelene. (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 type of polymerization reaction and the properties of the Catalyst itself. Preferably the catalyst is a compound that works at room temperatures either is gaseous or which can easily be evaporated

The catalyst can be fed in at the same time as the monomer or even before or after it. In addition, the catalyst can be applied in such a way that it is for touch with the appearance of the monomers in place of the

ι Leaks available by the catalyst from a external source is introduced by means of a lance, or by placing it in the vessel in front of the monomer is introduced so that the earth or jute is pre-saturated at the leak point. The vessel is then rinsed

ίο 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.

I rcic radical catalysts

Various organic species fall into this class

Peroxides, such as acetylproxide. Methyl ether octone peroxide. l.auroylperox'd, tert. ßutyl hydroperoxide, cumene hy-

: u droperoxide. and certain nitriles such as NiA-azo-diisobutyronitrile.

Organometallic compounds

Many of these compounds are readily volatilizable. Examples are zinc alkyls, such as zinc diethyl, bp 118 ° (, vapor pressure 30 mm Hg at 27 "C and zinc-di-n-propyl, bp 160 ° C, vapor pressure 48 mm Hg at 10 ° C. Further examples are aluminum alkyls aluminum triethyl, bp 194 ^r C, and aluminum tri-IH methyl, Kp I3O ° C, aluminum alkyl hydrides, such as di-isrbutyl aluminum hydride and aluminum alkyl halides such as diethyl aluminum chloride, bp 208 ° C, vapor pressure 41 mm Hg at 12 "C. Also includes metal and metalloid alkoxides, such as silicates, titanates, ii-borates, phosphates and vanadates. Examples of these are ethyl silicate, isoporpyl titanate, methyl borate , Ethyl vanadate and the like.

Metal hydrides

Examples of this are borohydrides, such as diborane B> H ". a gas. Bp -92.5 ° C, and pentaborane B ₁ H * Bp 48 "C, uampiürucK oo mm tig at υ C.

Lewis acids

r »These include e.g. B. boron trifluoride. a gas, Kp -lOrCein.

Alkaline earth compounds

These are substances. which are found in the earth at the, o leakage, z. B. CaO, Ca (OH) ,, CaCO, and the Corresponding strontium compounds.

Alkalis

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

Phosphorus halides

Examples are: PCI ₁ , bp 76 ° C, POCU bp

mi 107 ° C, PF ₅ (gas), bp-84.6 ° C.

The released from the leak monomers or catalysts can with the oxygen or the Moisture that is adsorbed on the surface of the mineral particles or with organic materials in the

όί Earth or with groundwater or with trapped React air to initiate polymer growth or activate the catalyst or heat to Initiation of the polymerization to give.

It

In the event that the pipe is sunk in the ground, can be specific components of the earth, such as alkali carbonates, calcium and strontium salts etc. as Catalysts work. Occluded oxygen and trapped moisture also activate the ί conversion gen to the solid reaction products. These solid reaction products seal off existing leaks and bind the earth adjacent to the Ltcfc to form a fixed reinforcement matrix.

The invention is illustrated in the examples. m

H e i s ρ i c I I

A section of steel pipe 0.1 J in length. 0 1.9 cm; was provided with a 0.32 cm hole to prevent a leak / ti simulate. The test pipe was placed under 76.2 cm of clay-loam soil with a moisture content of 3% buried.

One end of the tube was connected to a valved feed line which was connected to a : <> source of dry nitrogen. This was done to flush moisture and oxygen out of the pipe. The nitrogen also served as an inert gas carrier for the caulking compound. The nitrogen line was with a heated vessel:. connected, which contained the liquid sealant. Pressure and flow meters and monitoring devices were also located in the feed line. The other end of the test tube was connected to an outlet line provided with a valve, 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:. Vessel, a slight excess of monomeric isoprene and aluminum triethyl was introduced into the nitrogen gas stream, so that a concentration of about 2000 ppm was achieved. At the point of leakage, the aluminum alkyl and the Moisture around. Whereby w heat was formed and water-

HClC ScUlllgUllgCII Clil.lill'l! WUIUCIl. Ο.ΙΛ ÜUI.-I uilÜMIgt

Aluminum alkyl then served as a catalyst for the isoprene polymerization, as a result of which the holes and the outer opening surface were sealed with a solid rubber plug.

Example 2

As in Example I, a stream of nitrogen was used, u Stream of ethylene oxide. Kp IO, 7 "C, introduced together with zinc diethyl as a catalyst. The concentration of the ethylene oxide was about 4000 ppm while that of the zinc diethyl was about 5000 ppm. To When the leak was reached, the zinc diet reacted with the moisture in the soil, creating heat was formed. The excess polymerized the ethylene oxide into a tight seal.

Example 3

As in Example I, a stream of tetrahydrofuran, bp 65 ° C ₁ at a concentration of 5000 ppm and of BFi at a concentration of 500 ppm was introduced into a nitrogen stream. In this way a viscous oily polymer was formed which plugged the openings of the pipe. If the pipe is surrounded by soil, then the tetrahydrofuran can be introduced into the conduit first and then allowed to flow through the corner opening to saturate the soil. The BFi can then be passed through the pipe together with the nitrogen gas, after which it polymerizes the tetrahydrofuran and saturates the soil, so that a seal in the opening and a solid reinforcement matrix of the surrounding soil is formed.

H e ι s \> ι «. ·! 4th

As in Example I, a current of A · ■ '\ Itutril. Kp 78 to 7TC, and of hydroperoxide (ratio 100 mol to 1 mole) with a concentration of 5000 ppm in nitrogen gas was formed in the pipe. Than the gas with the monomer was saturated, the pipe pressure was increased to 0.04 kg / cm- '. With these conditions and in contact with the surfaces of the pipe holes and the moisture was through a redox reaction a catalyst formed. The acrylonitrile polymerized into a solid polymer that plugged the leaks.

Example 5

As in Example I, 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. A seal made of solid polystyrene had formed at the leak points. Excess solid Polystyrene was then blown out of the tube.

Example 6

Like m BeiNpiiM i wuiu'l · u'a> Ruin for a siuin

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 monomeric styrene and monomeric butadiene each in a concentration of about 5000 ppm. together 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 included, characterized in that a) a catalytically effective amount of a polymerization catalyst at the site of the leak provides and that b) the vapor of a normally gaseous or volatilizable catalytically polymerizable organic monomers in the interior of the vessel with such Pressure introduces that monomer vapors can escape at the point of the leak, and this Maintains conditions until the leak is sealed by the formation of a polymer. 2. The method according to claim 1, characterized in that the catalyst from the outside to the Location 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 Introduces catalyst into the vessel in steam room at the same time. 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 Monoinercs a polymeric barcn unsaturated aliphatic aldehyde used. 7. The method according to any one of claims 1 to 5, characterized in that one is used as Mononicrcs a polymerizable polyethylenically unsaturated hydrocarbon is used. 8. The method according to claim 7, characterized in that that isoprene is used as the monomer and an aluminum-alkyl compound is used as the catalyst. 9. The method according to claim 8, characterized in that that as an aluminum-alkyl compound Aluminum triethyl used. 10. Careful procedure after an egg Claims, characterized in that you first the interior of the slope with an inert purges dry gas.