KR102328456B1 - Process for the protection against corrosion of an article in a wet environment and composition therefore - Google Patents

Abstract

The present invention provides a method comprising the steps of: (a) applying a layer of a corrosion protection composition comprising (i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less and (ii) a water absorbing filler onto the surface of an article; , and (b) applying a mechanical protective layer on top of the corrosion protection composition layer, wherein the article is in a humid environment.
The invention also relates to a tape comprising a corrosion protection composition and a layer comprising the corrosion protection composition according to the invention.
The invention also relates to an article comprising (a) a layer of a corrosion protection composition according to the invention on the surface of the article, and (b) a mechanical protective layer protecting said layer of the composition.

Description

PROCESS FOR THE PROTECTION AGAINST CORROSION OF AN ARTICLE IN A WET ENVIRONMENT AND COMPOSITION THEREFORE

The present invention relates to a method for protecting an article in which the article is in a humid environment. The present invention relates in particular to the protection of articles against corrosion in wet environments, in particular in oil or gas pipes or lines and risers of oil drilling and production rigs and pits.

For example, articles in wet environments such as sweating pipelines, submerged oil lines or pipes, gas lines or pipes, and risers of drilling and production rigs or rigs can be placed on, at and below the water line. corrode or deteriorate. These articles are subject to deterioration or damage from salt water, corrosive contamination, cycles of wetting and drying, cycles of freezing and thawing, and electrolysis. In addition, erosion, marine organisms, mechanical impact, water content and wear can even cause premature failure of properly designed articles. Accordingly, there is a need to protect these articles from damage or deterioration.

Corrosion is not only a problem with metal articles in wet environments, but also concrete articles, for example, can be damaged by corrosion. Concrete can absorb water from a humid environment, causing corrosion of the (metal) reinforcing factors present in the concrete.

The anticorrosive treatment that has been carried out so far uses a quasi-manual technique. The most widely practiced method actually consists in using the service of a driver to manually coat the parts to be treated with, for example, paint, resin or mastic under several or tens of meters of water. Such techniques, implemented under difficult conditions, are very costly, risky, and often unsatisfactory in their effectiveness.

In addition to the adverse effects due to corrosion, eroded articles are subjected to the consequences of various mechanical pressures, such as, for example, gravity, repeated impacts of waves, pressures of ocean currents or traction in marinas. Offshore drilling and rigs, particularly risers, are relatively sensitive structures in this respect, both due to their structure and their exposure to natural factors.

It is known from the prior art that methods of anti-corrosion protection of structures in marine environments and/or partially or wholly submerged structures, wherein the encasing is used with a corrosion inhibiting material such as a curable polymer composition. References include, for example, US 4892410, US 5049005, US 5226751 and US 5591265, all of which are incorporated herein by reference.

US 4892410 describes a jacket configuration in which a two-component curable polymer composition is injected, after which the polymer composition is cured. The polymer composition may be, for example, an epoxy resin.

US 5049005 describes a device for protecting a branch girder joint against corrosion, the device comprising, for example, an elastomeric material such as an epoxy resin or polyurethane.

US 5226751 describes a method for drying a pile by placing a jacket around a pile and then injecting air and preheating gas into the pile. In a subsequent step, the jacket is filled with expanded closed cell foam formed from liquid chemicals or epoxy resins.

US 5591265 describes a formwork comprising an elongated member, preferably tubular, in which a cured resin material is injected between an annular space existing between the metal article to be protected and the wall of the formwork.

A disadvantage of the methods as described in US 4892410, US 5049005, US 5226751 and US 5591265 is that the cured rigid polymer composition is used and generally has poor adhesion properties to the surface of metal articles. Moreover, such hardened, rigid polymer compositions provide a rigid seal that can fracture or tear under the influence of mechanical pressure, such as, for example, wave action. Another disadvantage of these materials is that volatile solvents are required when these materials are applied, which solvents are not known to be environmentally friendly. Also, after application of these materials, the solvents evaporate, thus forming a micro-porous seal that is at least permeable to corrosive substances such as salts, water and moisture. Also, while hardened, rigid polymers are important for easy removal when repairs, replacements or overhauls are to be performed, they are not easily removed from the metal article. Numerous methods are known in the art that can be used to protect against corrosion or other types of damage.

EP 1644433, incorporated by reference, describes an improved non-polar, non-thermosetting fluid polymer composition. However, although this improved composition can be used under humid conditions, condensation of water may not occur on the surface of the article to be protected during application of the composition.

EP 751198, incorporated by reference, describes a non-polar, non-thermosetting fluid polymer composition that can be used to protect against corrosion of underground metal articles in contact with moisture. Polymers comprising polyisobutene and/or poly(oxydimethylsilylene) having a viscosity of 60000 to 120000 cSt (60 to 1200 Pa.s) at 20° C. are advantageously used. The preparation may contain one or more fillers. The preparation may also contain one or more products obtained directly from petroleum, such as, for example, bitumen products and paraffinic products such as, for example, petroleum gels and waxes. The non-polar, non-thermosetting, fluid polymer composition can be used to protect risers, steel components and pipelines of oil drilling platforms submerged in seawater. However, during application of the composition, the surface needs to be essentially dry in order to achieve sufficient adhesion of the composition to the surface of a riser, steel component or pipeline.

EP 826817, incorporated by reference, describes a belt-like covering for sealing coverings of structures. The covering includes a base and a kneadable material such as a paste. Kneadable materials may include non-polar, non-curing liquid polymers such as, for example, petroleum products such as tarry, bituminous, petrolatumic and rubbery materials. Preferably, a polymer comprising polyisobutene and/or poly(oxydimethylsilylene) having a viscosity of 60000 to 120000 cSt (60 to 1200 Pa.s) at 20°C is used. The preparation may include one or more fillers. The preparation may also include one or more products obtained directly or indirectly from petroleum, such as, for example, bituminous products, eg, paraffinic products such as petroleum gels and waxes. The covering may be used in offshore industry, but during application of the covering the surface of the structure must be essentially dry in order to achieve sufficient adhesion of the covering to the surface of the structure.

A composition known in the art for corrosion protection of fully submerged articles is STOPAQ ^® Subsea Compound sold by Stopaq Oil & Gas Services BV. ^{STOPAQ ®} Subsea Compound containing wax, mineral oil and bentonite can be applied to the surface of an article while the article is submerged.

A disadvantage of the Subsea Compound is that it has insufficient working scope for specific applications. The operating temperature of the Subsea Compound is in the range of about -20°C to about 35°C, but a maximum operating temperature of about 45°C can be achieved under certain conditions. At temperatures above about 45[deg.] C., the composition may be more liquid and will come off the surface without sufficiently adhering to the surface of the article. Also, at temperatures above 45° C., phase separation can occur, where the mineral oil begins to separate from the majority of the product. Due to the relatively low maximum performance temperature, Subsea Compound is not suitable for the protection of non-submerged articles such as, for example, parts of partially submerged articles located above the water level, or sweating pipelines. Consequently, two different corrosion protection compositions are needed to be used against partially submerged articles: Subsea Compound for protection of submerged parts (i.e. sub-water-level parts) and another composition for parts positioned above water level.

Several compositions comprising polyisobutene, fillers and plasticizers are known in the art as waterproofing compositions.

For example, US 4558875, incorporated by reference, contains 10-40% by weight of a rubber containing polyisobutylene as a main component, 10-20% by weight of silicate, 10-60% by weight of bentonite and 10-40% by weight of a plasticizer. and wherein said silicate and bentonite act as fillers. The polyisobutylene preferably has a viscosity of about 840,000-2,220,000 g mol ^-1 Staudinger molecular weight of 70000-130000 M _{S V} M corresponding to the average molecular weight (viscosity average molecular weight M _V is the relation M _V = 0.0233 (M _S ) is by ^1.56 to be calculated from a Staudinger molecular weight M _S, for example, see references incorporated by reference ExxonMobil product brochure "Vistanex Polyisobutylene Properties &Application", 2003). ^{Preferred polyisobutenes are Vistanex ®} L-80, Vistanex ^® L-100 and Vistanex ^® L-140 having a viscosity average molecular weight of about 750,000-2,350,000 g mol ^{-1 .} The plasticizer may be, for example, a mineral oil softener, a vegetable oil softener, a fat, an oil, a paraffin derivative, and the like. The waterproofing composition can be extruded, for example, into an elongated waterproofing agent that can be inserted into a joint gap and waterproofed in the gap. No mention is made of corrosion inhibition in US 4558875.

US 5663230, incorporated by reference, discloses a waterproofing composition that exhibits controlled swelling or volume expansion when submerged in water. An exemplary waterproofing composition comprises about 10-30% by weight of an elastomeric blend, about 15-30% by weight filler, about 20-40% by weight plasticizer, and about 25-35% by weight water expandable bentonite clay. The elastomeric blend comprises 50-60 wt% thermoplastic elastomer (TPE), 10-20 wt% crosslinked butyl rubber and 20-40 wt% polyisobutene. The elastomeric blend present in the waterproof composition at about 10-30 wt% preferably comprises about 30 wt% polyisobutene. Preference is given to polyisobutene homopolymers having a molecular weight of about 10,700-11,900 (Staudinger), which corresponds to a viscosity average molecular weight of about 44,000-53,000 g mol ^-1 , such as Vistanex ^{® LM polyisobutene.} Examples of the plasticizer include, for example, process oils such as petroleum aromatic naphthenic oil, naphthenic aromatic oil, naphthenic paraffinic oil and paraffinic oil. A waterproofing composition comprising 6.10-6.24% by weight of polyisobutene is disclosed. US 5663230 makes no mention of corrosion inhibition.

There is a need in the art for materials that can be applied in humid environments and that protect articles against corrosion with a wide range of operating temperatures. There is also a need for a material that is easy to apply to the article to be protected and which can be applied while the article is in the humid environment. Preferably, the material can be applied in a humid environment without requiring extensive pretreatment of the article to be protected.

the present invention

(a) (i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less and (ii) a water absorbing filler

applying on the surface of the article a layer of a corrosion protection composition comprising:

(b) applying a mechanical protection layer on top of the corrosion protection composition layer;

A method for protecting an article from corrosion, comprising: the article being in a wet environment.

The present invention also relates to a method for protecting an article against corrosion according to the present invention, wherein in step (a) a tape is applied on the surface of the article, wherein the tape (i) has a glass transition temperature of -20°C or less an amorphous polymer composition comprising an amorphous polymer having; and (ii) a layer of a corrosion protection composition comprising a water absorbing filler.

The present invention also relates to a tape comprising a layer comprising (i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less and (ii) a corrosion protection composition comprising a water absorbing filler. .

In addition, the present invention provides (i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20 °C or less; and (ii) a water absorbing filler, wherein the composition comprises 20-80% by weight of the amorphous polymer composition, based on the total weight of the composition, and wherein the amorphous polymer is 1,000-150,000 g mol ^- and a composition having a number average molecular weight M _n ^{in the range of 1.}

Also, the present invention

(a) an amorphous polymer composition comprising (i) an amorphous polymer having a glass transition temperature of -20°C or less on the surface of the article; and (ii) a water absorbing filler

A corrosion protection composition layer comprising a, and

(b) a mechanical protective layer protecting the corrosion protection composition layer

It relates to articles containing

As used in this specification and claims, the verb "to comprise" and its verb conjugations means that, in its non-limiting sense, items following the word are included, but not specifically excluded items. used as

Also, reference to an element by the indefinite article "a or an" indicates the possibility that more than one element is present, unless the context clearly requires that one is and only one element be present. do not exclude Thus, the indefinite article “a” generally means “at least one.”

The term "polymer" is meant to include homopolymers and copolymers.

The term “copolymer” is meant to include polymers comprising two or more different monomers.

The term “poly-alkene” is used herein in very general terms and refers to a polymer comprising at least one alkene monomer.

In general, when referring to an amorphous polymer comprising an isobutene monomer as a main component and optionally further monomers such as 1-butene, 2-butene and/or butadiene, the skilled person will use the term "polyisobutene" in the general use in a way These amorphous polymers have similar properties, particularly in terms of glass transition temperature and surface tension. Depending on the desired purity of the polyisobutene, they can be prepared by various methods (cf. Ullmanns "Encyklopadie der technischen Chemie", 4th Ed., Vol. 19, pp. 216-223, 1980 and Vol. 13, pp. 621-623, 1977). , all incorporated by reference). According to its common customary usage, the term "polyisobutene" means at least about 50% by weight, at least about 75% by weight, at least about 90% by weight or at least about 95% by weight, calculated relative to the total weight of polyisobutene. % of isobutene monomers, and monomers _{selected from the group consisting of C 2} -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene, and mixtures thereof, in an amount equal to or less than about 50%, less than about 25%, or less than about 10% by weight. % or less or about 5% by weight or less. Likewise, according to its common customary usage, the term “polyisobutene” includes polybutene and polymers such as essentially non-crosslinked butyl rubber as described below. In the present invention, the term "polyisobutene" is used for isobutene polymers as defined above.

In the present invention, the term "polyisobutene homopolymer" means, for example, from polyisobutene with a lower isobutene monomer content as described above, and from polybutene and butyl rubber as described below, with a very high isopartum content. Used to distinguish polyisobutenes with ten monomer content. Thus, as used herein, the term "polyisobutene homopolymer" refers to a polymer consisting essentially of isobutene monomers, i.e. greater than about 98% by weight of isobutene by weight of isobutene based on the total weight of the polymer and not more than 100%, preferably preferably about 99-100%, more preferably about 99.5-100%, more preferably about 99.7-100%, especially about 99.9-100%.

As used herein, the term "polybutene" will be obtained from the oil refining process, a polymer prepared from the fraction - - C ₄ (C ₄ containing the butadiene to 1-butene, 2-butene, isobutene and, optionally, such as a fraction) call it

As used herein, the term "butyl rubber" refers to a polymer consisting of about 95-98% by weight isobutene and about 2-5% by weight isoprene, based on the total weight of the polymer.

amorphous polymer

According to the invention, the amorphous polymer is preferably a hydrocarbon polymer. The hydrocarbon polymer is optionally (partially) halogenated, preferably with bromine, chlorine or fluorine. The hydrocarbon polymer is preferably essentially non-vulcanized (uncrosslinked) so that its cold flow properties are optimized. The amorphous polymer may be a blend of two or more different amorphous polymers.

_{It is preferred that the amorphous polymer has a number average molecular weight M n} in the range of about 500-1,000,000, more preferably about 1,000-800,000, more preferably about 1,000-600,000, more preferably about 1,500-300,000, and particularly about 2,000-150,000. . The molecular weight distribution M _w /M _n of the amorphous polymer is preferably from 1 to about 10, more preferably from 1 to about 5, more preferably from 1 to about 4, and most preferably from about 1.5 to about 3.5. The number average molecular weight and molecular weight distribution can be determined, for example, by gel permeation chromatography (GPC) as is well known in the art.

According to the present invention, the amorphous polymer has a glass transition temperature Tg of less than about -20°C, preferably less than about -40°C, more preferably less than about -50°C, and most preferably less than about -60°C. It is also preferred that the amorphous polymer has a surface tension of less than about 50 mN/m at 20°C, preferably less than about 40 mN/m at 20°C. The glass transition temperature or glass transition temperatures can be measured by differential scanning calorimetry (DSC) as is well known in the art. In addition, surface tension is determined by methods known in the art ( cf. S. Wu, J. Colloid. Interface. Sci. 31 , 153, 1969 ; DG LeGrand, GL Gaines, Jr., J. Colloid. Interface Sci. 31 , 162, 1969 ; all incorporated by reference).

Preferably, the amorphous polymer is a poly-alkene. Preferred monomers for preparing the amorphous polymer are those _{selected from the group consisting of C 2} -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene and mixtures thereof, wherein the alkene and/or alkadiene is optionally one or more bromine, chlorine Or it may be substituted with a fluorine atom. The alkene may be an α-alkene or an internal alkene. The diene may be conjugated or unconjugated.

Preferably, C ₂ -C ₁₂ alkene is ethene, propene, 1-butene, 2-butene, isobutene (2-methyl propene), 1-pentene, 1-hexene, 2-methyl-1-pentene, 4 -methyl-1-pentene, 1-octene and mixtures thereof.

Preferably, the C ₄ -C ₁₂ alkadiene is butadiene, isoprene (2-methyl-1,3-butadiene), 2,4-dimethyl butadiene, penta-1,3-diene, 3-methyl-1,3-penta Diene, 2,4-hexadiene, 2-neopentyl-1,3-butadiene, 2-methyl-1,5-hexadiene, 2,5-dimethyl-2,4-hexadiene, 2-methyl-1, 4-pentadiene, 2-methyl-1,6-heptadiene, cyclopentadiene, methyl cyclopentadiene, cyclohexadiene, 1-vinyl-cyclohexadiene, norbornadiene, 5-ethylidene-2-norbornene , divinylbenzene, dicyclopentadiene, 1,4-hexadiene, 5-vinyl-2-norbornene and mixtures thereof.

Amorphous polymers having a glass transition temperature of less than about −20° C. are well known in the art, see, for example, Kirk-Othmer, Encyclopedia of Chemical Technology (4 ^th Ed., Vol. 8, pp. 905-1093, 1993). , and 4 ^th Ed, Vol. 9, pp. 1-37, 1994 ), and in the Polymer Handbook (3 ^rd Ed., J. Bandrup, EH Immergut (Eds.), 1989) , all of which are incorporated by reference. to be incorporated The polymer handbook provides a number of examples of amorphous polymers having a glass transition temperature of less than about -20°C: (non-vulcanized) butyl rubber at about -71°C, poly(1-hexene at about -58°C) ) (prepared by Ziegler-Natta catalysis; cf. ref. 1072: J. Bourdariat, R. Isnard, J. Odin, J. Polym. Sci., Polym. Phys. Ed. 11 , 1817-1828, 1973 ) (p. VI/213), about -24 ° C. isotactic poly(1-butene) ( cf. eg, RW Warfield, R. Brown, J. Polym. Sci. A-2 5 , 791, 1967 ) (p. VI/213), and poly at about -73°C. (Isobutene) (p. VI/214). It should be noted that some of these polymers can sometimes be (partially) crystalline, which often depends on the catalyst composition and treatment conditions used in the polymerization process. For example, EP 300.638 A2, which is incorporated by reference, describes a process for the preparation of high crystallinity poly(1-butene). However, it can be expected that, for example, certain polyisobutenes, certain polybutenes or certain butyl rubbers may have different glass transition temperatures than those listed in the polymer handbook. Atactic polypropenes have a glass transition temperature of about -20°C ( cf. U. Gaur, B. Wunderlich, J. Phys. Chem. Ref. Data 10 , 1052-1063, 1981 , incorporated by reference). .

Amorphous polymers having a surface tension of less than about 50 mN/m at 20° C. are also well known in the art. ^{The Polymer Handbook (3 rd} Ed., J. Bandrup, EH Immergut (Eds.), 1989 ), which is incorporated by reference, provides various examples of such amorphous polymers: polyisobutene (M _n =2300): 20 33.6 mN/m at °C; atactic polypropene: 29.4 mN/m at 20°C; Branched polyethene (M _n =7000): 35.3 mN/m at 20°C; ethene propene copolymer (Mw in the range of about 15,000-63,000; propene content in the range of about 34-60 mol %): 30.7-33.8 mN/m at 20°C; Poly(4-methyl-1-pentene): 25 mN/m at 20°C. It should be noted that the surface tension is essentially independent of the molecular weight for molecular weights above about 2000, and the surface tension thus reaches within about 1 mN/m of its value at an unlimited molecular weight.

According to a preferred embodiment of the present invention, the amorphous polymer is preferably

(a) about 50.0-98% by weight of isobutene and about 2-50.0% by weight, based on the total weight of the polymer, of isobutene and other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene, or mixtures thereof; polymer;

(b) a polymer comprising about 98-100 weight percent isobutene, based on the total weight of the polymer;

(c) about 50.0-99.9% by weight of propene and about 0.1-50.0% by weight, based on the total weight of the polymer, of propene and other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene, or mixtures thereof; a polymer comprising 100% by weight of propene;

(d) a polymer comprising about 0.1-50.0% by weight of ethene and about 50.0-99.9% by weight of ethene and other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadienes, or mixtures thereof, based on the total weight of the polymer;

(e) about 0.1-50.0% by weight of 2-methyl-1-pentene and, based on the total weight of the polymer, a C ₂ -C ₁₂ alkene other than 2-methyl-1-pentene, a C ₄ -C ₁₂ alkadiene or its a polymer comprising about 50.0-99.9% by weight of the mixture, or about 100% by weight of 2-methyl-1-pentene; and

(f) mixtures of (a), (b), (c), (d) and/or (e)

is selected from the group consisting of

Examples for group (a) include "polyisobutene", "polybutene" and "butyl rubber". Examples for group (b) include "polyisobutene homopolymer". Examples for group (c) include ethene-propene elastomers, EPDM elastomers and atactic polypropenes. Examples for group (d) include ethene butene copolymers. Examples for group (e) include homopolymers of 2-methyl-1-pentene.

According to a more preferred embodiment of the present invention, the amorphous polymer is polyisobutene, polybutene, butyl rubber, atactic polypropene, copolymer of propene and propene with other C ₂ -C ₁₂ alkenes (and optionally dienes) , ethene and C ₂ -C ₁₂ alkenes other than ethene (and optionally dienes), and mixtures thereof. According to a more preferred embodiment of the present invention, the amorphous polymer is ethene-propene copolymer, ethene-butene copolymer, ethene-propene-butene trimer, ethene-propene-diene copolymer, polyisobutene, polybutene, butyl rubber, atactic polypropene and mixtures thereof. More preferably, the amorphous polymer is selected from the group consisting of polyisobutene, polybutene, butyl rubber, atactic polypropene and mixtures thereof. More preferably, the amorphous polymer is selected from the group consisting of (a), (b) and mixtures thereof, wherein (a) and (b) are polymers as defined above. More preferably, the amorphous polymer is selected from the group consisting of polyisobutene, polybutene, butyl rubber and mixtures thereof. More preferably, the amorphous polymer is polyisobutene, preferably the polyisobutene is a polyisobutene homopolymer. All of these polymers have a glass transition temperature of less than about -20°C, as described above.

Polybutene also preferably has a number average molecular weight M _n of about 500-20,000, more preferably about 1,300-20,000, a molecular weight distribution of about 1.5-3, ^{a density of about 0.90-0.98 g/cm 3} and 100 according to ASTM D 445. A kinematic viscosity of approximately 200-100,000 cSt (mm ² .s ^-1 ) at °C (e.g., data from Saybolt Universal Seconds used in Ineos datasheet September 2008 in mm ^{2 according to ASTM D 2161} can be converted to .s ^{-1 ).} Suitable polybutenes are, for example, several Indopol grades available from Ineos (UK), several polybutene grades available from Kermat (Belgium), several Nisseki polybutene grades available from JX Nippon Oil & Energy, and Kothari Petrochemicals (India). ) includes several KVIS grades available from For example, Indopol H-300 has a glass transition temperature (DSC) of about -66.9°C, a number average molecular weight M _n (GPC) of about 1300, a molecular weight distribution (GPC) of about 1.65, and a density of ^{about 0.904 g/cm 3} and a kinematic viscosity of about 605-655 cSt at 100°C. Indopol H-18000 has a number average molecular weight M _n (GPC) of about 6000, a molecular weight distribution (GPC) of about 1.70, ^{a density of about 0.921 g/cm 3} and a kinematic viscosity of about 36000-45000 cSt at 100° C. (Ineos Datasys September 2008). KVIS 30 has a molecular weight M _n (GPC) of about 1250-1350, a kinematic viscosity of about 600-697 cSt and a density of ^{about 0.8910-0.910 g/cm 3 .}

The butyl rubber preferably has a Mooney viscosity ML 1 + 8 (ASTM D 1646; 125° C.) of about 25-75 and an unsaturation level of about 1.0-3.0 mol %. ^{Suitable materials are Exxon TM} Butyl Rubber with a density of 0.92 g/cm ^{3 and} a density of 0.92 g/cm ³ , with a Mooney viscosity of 51±5 ML 1 + 8 (ASTM D 1646; 125° C.) and 1.75±0.20 mol%. Lanxess Butyl 101-3 with unsaturation.

Poly(2-methyl-1-pentene) preferably has a melt index of about 1-250 g/min (ASTM D 1236, 260° C., 5 kg), a softening point of about 160-200° C. (Vicat, ASTM D 1525) and 25° C. has a density of about 0.82-0.95 g/cm ^{3 at} Amorphous poly(2-methyl-1-pentene) with low glass transition temperature is described, for example, in Haiyang Gao, Xiaofang Liu, Ying Tang, Jin Pan and Qing Wu, Polym. Chem. 2(6) , 1398-1403, 2011,.

The ethene-propene copolymer, ethene-butene copolymer and ethene-propene-butene trimer preferably have a Brookfield viscosity (sometimes referred to as melt viscosity) of about 300-200,000 mPa.s at 190°C according to ASTM D 3236. has Suitable products include certain Eastoflex grades available from Eastman Chemical Company, Rextac ^® grades from ^{Rextac LLC and Vestoplast ®} grades from Evonik. The ethene-propene copolymer Eastoflex 1045, for example, has a Brookfield viscosity (ASTM D3236) of about 4500 mPa.s and a glass transition temperature of -22° C., while Eastoflex E1003 has a Brookfield viscosity of about 300 mPa.s. (ASTM 3236) and a glass transition temperature of -33° C. ( cf. Eastman brochure “Eastoflex ^™ - amorphous polyolefins”, 2009 ). Other examples are Brookfield of Vestoplast ^® 703 and a glass transition of about 120000 mPa.s at a temperature of about -27 and 190 ℃ ℃ in glass transition temperature and 190 ℃ of about -28 ℃ having a Brookfield viscosity of about 2700 mPa.s Vestoplast ^® 792 with viscosity (Evonik brochure "Vestoplast ^® - Amorphous Poly-alpha-olefins"). In these amorphous propene copolymers and trimers, the amount of propene is preferably at least about 50% by weight, preferably about 70-98% by weight, based on the total weight of the atactic propene copolymer.

The atactic polypropene has a Brookfield viscosity of about 200-10000 mPa.s at 190°C according to ASTM D 3236. Suitable products include Polytac ^TM grades from Crowley Chemical Company and Rextac ^® grades from Rextac LLC. For example, Polytac ^TM grades have Brookfield viscosities in the range of about 500-2500 mPa.s at 190°C, and Rextac ^® 2104, 2115 and 2180 Brookfields of 400, 1500 and 8000 mPa.s at 190°C, respectively. has a viscosity.

The polyisobutene preferably has a number average molecular weight M _n in the range of about 500-1,000,000, more preferably about 1000-800,000. _{In a preferred embodiment, the polyisobutene has a number average molecular weight M n} in the range of about 1000-600,000, more preferably about 1000-300,000, more preferably about 1500-180,000, and especially about 2000-150,000. The molecular weight distribution M _w /M _n of the polyisobutene is preferably from 1 to about 10, more preferably from 1 to about 5, more preferably from 1 to about 4, and most preferably from about 1.5 to about 3.5.

The number average molecular weight M _n of polyisobutene is determined, for example, by GPC for low molecular weights up to about 100,000. For higher number average molecular weights, they _{are measured by viscometry (Studinger Index J O} , formerly known as intrinsic viscosity), where the Staudinger Index is an Ubbelohde viscometer (for flow time measurement, dilute polymer solution is used) using the equation ) is calculated from the flow time at 20 °C through capillary 1 of:

_sp / c (1 + 0.31 x

_sp) [cm³/g]J _o =

_sp / c (1 + 0.31 x

_sp ) [cm ³ /g]

_sp = (t/t_o) - 1

_sp = (t/t _o ) - 1

where t is the flow time of the Hagenbach-Couette corrected solution, T _O is the flow time of the Hagenbach-Couette corrected solvent (eg isooctane), and c is the concentration if the _{solution is in g/cm 3 .} Then, the number average molecular weight M _n and the viscosity average molecular weight M _v are calculated as follows:

References include the BASF brochure "Glissopal ^® 1000, 1300 and 2300" (December 2005), the BASF brochure "Oppanol ^® Type B" (B10-B15) (January 2009) and the BASF brochure "Oppanol ^® Type B" ( B10-B80) (January 2009), all of which are incorporated herein by reference.

The polyisobutene used in the composition according to the invention preferably has a Staudinger Index J _O of ^{about 1-1500 cm 3} /g, preferably about 2-1000 cm ^{3 /g, measured at 20°C.} In a preferred embodiment, the polyisobutene has a Staudinger Index J _O ^{of about 1-500 cm 3} /g, preferably about 2-300 cm ³ /g, and more preferably about 3-150 cm ³ /g.

The polyisobutene more preferably has a surface tension of less than about 40 mN/m as measured at 20°C. The density of polyisobutene is preferably about 0.86-0.98 g/cm ³ .

Polyisobutene can be prepared in a variety of ways. The polymerization can be carried out in a single step process or in a multistep process. The polymerization is carried out in the liquid phase using a Lewis acid as catalyst, preferably using a boron trifluoride complex catalyst, optionally in the presence of a co-catalyst. Such processes are well known in the art.

Preferred polyisobutenes are those of the Glissopal and Oppanol grades, in particular of the Oppanol grade, which are commercially available from BASF, in particular those of the Oppanol B type. Other preferred polyisobutenes are commercially available from Nippon Oil, particularly those of the Tetrax grade. Such polyisobutenes are classified herein as "polyisobutene homopolymers", ie polymers comprising at least about 98% by weight of isobutene, based on the total weight of the polymer.

Amorphous polymer composition

The amorphous polymer composition according to the present invention preferably comprises an amorphous polymer or a mixture of two or more amorphous polymers. This amorphous polymer is as described above.

According to the present invention, the amorphous polymer composition comprises, based on the total weight of the amorphous polymer composition, about 50-100% by weight of polyisobutene, more preferably a polyisobutene homopolymer, and about 0-50% by weight of other amorphous polymers. and wherein the other amorphous polymer is preferably selected from the group consisting of amorphous polymers (a) - (f) as described above.

More preferably, the other amorphous polymer is polybutene, polyisobutene, butyl rubber, ethene-propene copolymer, ethene-butene copolymer, ethane-propene-butene trimer, amorphous propene copolymer, atactic poly propene, poly(2-methyl-1-pentene) and mixtures thereof. These polymers have a glass transition temperature of less than about -20°C, as described above.

More preferably, the amorphous polymer comprises about 70-100 weight percent polyisobutene, preferably a polyisobutene homopolymer, and about 0-30 weight percent other amorphous polymer, based on the total weight of the amorphous polymer composition. More preferably, the amorphous polymer composition comprises about 90-100 wt% polyisobutene, preferably a polyisobutene homopolymer, and about 0-10 wt% other amorphous polymer, based on the total weight of the amorphous polymer composition. More preferably, the amorphous polymer composition comprises about 100% by weight of polyisobutene, preferably a polyisobutene homopolymer.

Accordingly, the present invention relates to an amorphous polymer composition comprising about 75-95% by weight of polyisobutene, preferably a polyisobutene homopolymer, and about 5-25% by weight of another amorphous polymer, based on the total weight of the amorphous polymer composition. it's about The present invention also relates to an amorphous polymer composition comprising about 80-90% by weight of polyisobutene and/or polyisobutene homopolymer and about 10-20% by weight of another amorphous polymer, based on the total weight of the amorphous polymer composition. will be.

corrosion protection composition

A corrosion protection composition according to the present invention comprises (i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of less than -20°C and (ii) a water-absorbing filler. The amorphous polymer composition (i) and the amorphous polymer are as described in detail above. The water-absorbing filler (ii) is described in more detail below.

Preferably, the corrosion protection composition comprises about 20-80%, more preferably about 20-70%, more preferably about 25-60% and most of the amorphous polymer composition (i) by weight, based on the total weight of the composition. Preferably about 30-50% by weight. Preferred embodiments of the amorphous polymer and the amorphous polymer composition are as described above.

In a more preferred embodiment, the amorphous polymer has a number average molecular weight M in the range of about 500-1,000,000, more preferably about 1,000-800,000, more preferably about 1,000-600,000, more preferably about 1,500-300,000, and particularly about 2,000-150,000. _{have n} .

Accordingly, in a preferred embodiment, the present invention

(i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less, and

(ii) water-absorbing filler

wherein the composition comprises 20-80% by weight of an amorphous polymer composition based on the total weight of the composition, and wherein the amorphous polymer has a number average molecular weight M _n in the range of 1,000-150,000 g mol-1. to the composition.

The corrosion protection composition preferably comprises about 20-80% by weight of the water-absorbing filler (ii) based on the total weight of the composition.

In a preferred embodiment, the amorphous polymer is selected from the group of polymers consisting of (a) - (f) as defined above. In a more preferred embodiment, the amorphous polymer is selected from the group consisting of (a), (b) and mixtures thereof.

In a preferred embodiment, the corrosion protection composition further comprises a plasticizer (iii) selected from the group consisting of waxes, mineral oils and mixtures thereof. The plasticizer (iii) is described in more detail below.

Corrosion protection compositions, as described below, include, for example, additional filler materials and/or antioxidants, surface tension modifiers, for example pH modifiers such as potahume or sodium hydroxide (KOH or NaOH), It may further include one or more other additives such as colorants, pigments, and the like. In a preferred embodiment, the corrosion protection composition further comprises a surface tension modifier (iv). Examples of surface tension modifiers include anionic surfactants such as fatty acids (eg, tall lactic acid), cationic surfactants, amphoteric ionic surfactants, and non-ionic surfactants. Preferably, the surface tension modifier is about 0.1-20 wt%, more preferably about 0.1-15 wt%, more preferably about 0.3-10 wt%, and most preferably about 0.5-5 wt%, based on the total weight of the composition. % is present.

In another preferred embodiment, the corrosion protection composition according to the invention also comprises an antioxidant (v). The antioxidant (v) is described in more detail below.

In a preferred embodiment, the corrosion protection composition according to the present invention comprises, based on the total weight of the composition, about 20-79% by weight of an amorphous polymer composition (i), about 20-60% by weight of a water-absorbing filler (ii) and a wax, mineral oil and about 1-20% by weight of a plasticizer (iii) selected from the group consisting of mixtures thereof. In another preferred embodiment, the corrosion protection composition according to the present invention comprises, based on the total weight of the composition, about 25-75% by weight of an amorphous polymer composition (i), about 22-60% by weight of a water-absorbing filler (ii) and a wax; about 3-15% by weight of a plasticizer (iii) selected from the group consisting of mineral oil and mixtures thereof.

In a preferred embodiment, the corrosion protection composition according to the present invention comprises, based on the total weight of the composition, about 20-78.9% by weight of an amorphous polymer composition (i), about 20-45% by weight of a water-absorbing filler (ii), wax, mineral oil and about 1-20% by weight of a plasticizer (iii) selected from the group consisting of mixtures thereof, and about 0.1-15% by weight of one or more surface tension modifiers (iv). In another preferred embodiment, the corrosion protection composition according to the present invention comprises, based on the total weight of the composition, about 20-78.9% by weight of an amorphous polymer composition (i), about 20-50% by weight of a water-absorbing filler (ii), a wax; about 1-15% by weight of a plasticizer (iii) selected from the group consisting of mineral oil and mixtures thereof, and about 0.1-15% by weight of one or more surface tension modifiers (iv). In another preferred embodiment, the corrosion protection composition according to the present invention comprises, based on the total weight of the composition, about 20-72.9% by weight of an amorphous polymer composition (i), about 24-50% by weight of a water-absorbing filler (ii), a wax, about 3-15% by weight of a plasticizer (iii) selected from the group consisting of mineral oil and mixtures thereof, and about 0.1-15% by weight of one or more surface tension modifiers (iv).

Preferably, the corrosion protection composition according to the present invention comprises, based on the total weight of the composition, about 20-50% by weight of an amorphous polymer composition (i) having a glass transition temperature of -20°C or less, and a water-absorbing filler (ii) about 20-40% by weight, plasticizer (iii) about 1-20% by weight, surface tension modifier (iv) about 0.1-15% by weight, and antioxidant (v) about 0.05-5% by weight. Preferably, the sum of components (i), (ii), (iii), (iv) and (v) is 100% by weight. However, when the sum is not 100% by weight, it will be clear to the person skilled in the art that the composition comprises additional components such as, for example, additional filler materials, additives, and the like.

Accordingly, the composition optionally further comprises one or more additives (vi), and/or one or more additional fillers (vii). When one or more additives (vi) are present, each of the one or more additives is present in an amount of about 0.01-10% by weight, preferably about 0.05-5% by weight, based on the total weight of the composition. When one or more additional fillers (vii) are present, the total amount of the one or more additional fillers is about 25-45% by weight based on the total weight of the composition. Preferably, the sum of components (i), (ii), (iii), (iv), (v) and (vi) and/or (vii) is 100% by weight. However, if the sum is not 100% by weight, it will be clear to the person skilled in the art that the composition comprises additional ingredients.

When at least one additive (vI) is present, the at least one additive is selected from the group consisting of colorants and pH adjusting agents. Additional fillers (vii) are described in more detail below.

In another preferred embodiment, the corrosion protection composition comprises, based on the total weight of the corrosion protection composition, about 20-80% by weight of the amorphous polymer composition (i), about 20-80% by weight of a water-absorbing filler (ii) and an additional filler (vii) ) about 0% by weight. More preferably, the composition comprises, based on the total weight of the corrosion protection composition, about 20-70% by weight of an amorphous polymer composition (i), about 22-60% by weight of a water-absorbing filler (ii) and about 22-60% by weight of an additional filler (vii) 8-58% by weight. More preferably, the composition comprises, based on the total weight of the corrosion protection composition, about 25-60% by weight of the amorphous polymer composition (i), about 24-50% by weight of a water-absorbing filler (ii) and about 24-50% by weight of an additional filler (vii) 16-51% by weight. Most preferably the composition comprises, based on the total weight of the corrosion protection composition, about 30-50% by weight of the amorphous polymer composition (i), about 25-40% by weight of a water-absorbing filler (ii) and about 25% by weight of an additional filler (vii) -45% by weight.

An important property of the corrosion protection composition according to the invention is its ability to absorb water. The corrosion protection composition can absorb sufficient water from the surface of the article in a short time (ie, seconds/minutes to hours) in the humid environment to be protected so that the corrosion protection composition can quickly adhere to the surface of the article.

The water-absorption of the corrosion protection composition according to the present invention is based on an immersion method based on ASTM Standard D 570-98 (2005), "Standard Test Method for Water Absorption of Plastics", incorporated by reference, as shown in the following examples. is detected by Thus, water-absorption is the amount of water absorbed relative to the mass of the corrosion protection composition in a specified amount of time, expressed in weight percent.

Preferably, the corrosion protection composition according to the present invention is about 1-30% by weight, more preferably about 1.5-25% by weight, more preferably about 2-20% by weight, more preferably about 2.5-15% by weight, and most It preferably has a water-absorption in the range of about 3-10% by weight.

However, if the thickness of the layer of the corrosion protection composition according to the invention exceeds a certain maximum thickness, the water-absorption of the layer of the corrosion protection composition no longer depends on the mass of the corrosion protection composition, but on the surface area of the layer. Accordingly, the water-absorption is preferably expressed in terms of the amount of water absorbed relative to the surface area of the layer of the corrosion protection composition in a certain amount of time, ie the water-absorption in g/m ² . ^{The water-absorption (g/m 2} ) of the corrosion protection composition according to the invention is also detected by an immersion method based on ASTM standard D 570-98 (2005) and is described below and in the Examples.

Water-in the detection of the absorbance, to the water, as shown in-absorbency (g / m ² absorbency (g / m ^2), the water indicated by the water grams absorbed per square meter of the corrosion protective composition layer shown in ), care must be taken to ensure that the corrosion protection composition layer has a thickness greater than the maximum thickness above, thus eliminating the influence of layer thickness on ^{water-absorption (g/m 2 ).}

If the water-absorption (g/m ² ) of the corrosion protection composition is too low, the composition absorbs sufficient water from the surface of the article to be protected in a short time so that the corrosion protection composition can adhere to the surface of the article quickly enough. Can not. Accordingly, the water-absorption (g/m ² ) of the corrosion protection composition according to the present invention is preferably at least about 100 g/m ² , more preferably at least about 300 g/m ² , more preferably at least about 450 g/m ² or more, more preferably at least about 600 g/m ² , more preferably at least about 750 g/m ² , and most preferably at least about 900 g/m ² .

However, if the water-absorption (g/m ² ) of the corrosion protection composition is too high, the composition becomes weaker, loses its concentration, and can be separated from the surface too easily. Accordingly, preferably the water-absorption (g/m ² ) of the corrosion protection composition according to the present invention is about 10,000 g/m ² or less, preferably about 9,000 g/m ² or less, more preferably about 7,500 g/m ^{2 or less.} or less, more preferably about 6,000 g/m ² or less, more preferably about 4,500 g/m ² or less, and most preferably about 3,000 g/m ² or less.

Preferably, the corrosion protection composition according to the present invention is about 100-10,000 g/m ² , preferably about 300-9,000 g/m ² , more preferably about 450-7,500 g/m ² , more preferably 600-6,000 g /m ² , more preferably in the range of about 750-4,500 g/m ² , and most preferably in the range of about 900-3,000 g/m ² .

As described above, and as described in more detail in the Examples, water-absorption (in wt. %) and water absorbance (g/m ² ) were measured using dilution water at a temperature of 23±1° C. and 72 Immersion of time is detected by an immersion method based on ASTM standard D 570-98 (2005). As described in the examples, the determination of the water-absorption (g/m ² ), w _A (g/m ² ) of the corrosion protection composition according to the invention is:

(1) Weighing a cup having a known depth and known diameter within the range of 15-25 mm (circular surface) or a known length and width (rectangular or square surface) within the range of 30-50 mm to obtain mass A;

(2) completely filling the plastic cup with the composition, avoiding air ingress, and leveling the surface;

(3) weighing the filled cup to obtain mass B;

(4) placing the filled cup in a container of dilution water maintained at a temperature of 23±1° C. and immersing the cup completely;

(5) placing the cup in a climate cabinet and maintaining the water temperature at 23 ± 1°C for 72 hours;

(6) removing the cup from the container after 72 hours, drying the surface thereof, and weighing the dried cup to obtain mass C; and

Calculating, as to the absorbency (g / m ²⁾ - water are indicated as (7) g / m ²

includes

One of the advantages of the corrosion protection composition according to the invention is that it has an improved setting for the article to be protected, including improved deformability. In addition, the composition according to the present invention has very good adhesion, ie, very good adhesion to the surface of the article, even when the surface is wet. Moreover, the composition according to the invention has a very high adhesion tack. ^{For example, compared with the STOPAQ ®} Subsea Compound known in the prior art, not only the adhesion of the composition according to the present invention to the surface to be protected is improved, but also due to the improved adhesive tack of the composition, Optimum adhesion to the skin is achieved in a faster time, especially at lower temperatures.

The composition according to the invention does not set, retains its flexibility, is essentially impermeable to water, moisture salts, etc., and is densely porous. An additional and very important feature of the corrosion protection composition of the present invention is that if the protective layer of the composition is mechanically deformed to a relatively small extent, for example by the action of waves, the damage is such that the flowability and/or the composition of the present invention Alternatively, due to the viscoelastic properties, it is automatically restored in a relatively short time. That is, the composition has self-healing properties, and any deformation or damage caused by mechanical deformation or other pressure will recover as a result of the flow of the composition into the hole or cavity. In conclusion, the protective layer comprising the composition according to the present invention is not only smooth when applied, but also disappears in time even when marks, engravings, dents, cavities, etc. are caused by mechanical force, and the smooth surface of the protective layer can be reproduced. will be. Because of these flow properties, any protective layer comprising the composition according to the invention does not tear or break and does not form internal stresses. Likewise, the unevenness in the surface of the article is completely filled or covered with the corrosion protection composition according to the invention, whereas materials according to the prior art often present problems in this environment. The flowable and/or viscoelastic properties of the composition according to the invention also indicate that it has no pot life, whereas the protective coatings and curing resins known in the prior art are required to be applied within a certain period of time.

For example, if the composition according to the invention is ^{compared to the STOPAQ ®} Subsea Compound known in the prior art, the composition according to the invention not only inhibits water from reaching the surface to be protected, but also between said surface and the layer of the corrosion protection composition. Due to the fact of minimizing the voids present in the surface, an improved protection against corrosion is obtained.

Another advantage of the corrosion protection composition according to the present invention is high chemical stability and resistance over a wide pH-range, and there is essentially no cathodic delamination or undercreep corrosion (eg due to under-film migration of water). .

In addition, the compositions according to the present invention have very good thermal stability, from about -20°C to about 60°C, preferably from about -25°C to about -65°C, more preferably from about -30°C to about 70°C, and most Preferably, it can be used within the operating temperature range of about -50°C to about 80°C. When an article is partially immersed, for example, on the riser of an oil rig platform, the temperature above the water surface is generally different from the temperature below the water surface. Due to the wide operating temperature range of the corrosion protection composition according to the invention, it is now possible to use the same corrosion protection composition both on the part of the article located below the water surface and on the part above the water surface.

There are additional important advantages of the corrosion protection composition according to the invention. Most protective systems require the use of a primer prior to application of these systems to articles to provide sufficient adhesion, particularly in humid environments. In the case of using the composition according to the present invention, the use of a primer is unnecessary, which means that the composition can be applied in a shorter period of time so that the operation cost can be lower.

For example, a problem that arises when prior art coating systems are applied is that air bubbles can form during coating, which can easily burst open, thus causing pinholes and poor protection in the coating layer. The inventors have found that when the composition of the present invention is used, any air bubbles present between the surface of the article and the protective layer of the composition according to the invention do not migrate within the protective layer of the composition, and move away from the surface of the article. . Where the article comes into contact with salt, for example seawater, salt crystals form on the surface of the metal article, eg requiring thorough cleaning before a coating system is applied to the surface. do. In contrast, the composition according to the invention encapsulates salt crystals, and removal of these crystals is not required. The necessity for salt crystals to be removed in prior art protection systems is that these crystals are hygroscopic and absorb water and thus penetrate the protective layer. As a result, the salt crystals expand and thus crack in the protective layer, which in turn leads to a deteriorated protection against corrosion. In practice, such salt crystals cause serious problems in the operation of articles, so that the protection systems of the prior art need to be replaced regularly. However, the composition according to the invention does not suffer from this problem and is therefore significantly more economical to the end user.

Articles protected by the composition according to the invention can be easily inspected, since the protective layer of the composition according to the invention can be easily removed, and can be reapplied after inspection. Most materials according to the art are significantly more difficult to remove. Moreover, since it is clear to the person skilled in the art that a cured system applied in an uncured state cannot be reapplied, if removed, before the material is reapplied as in the prior art, possibly all, of the metal article. The surface needs to be thoroughly cleaned. Consequently, the protective layer of the composition according to the invention is also more easily tested.

filler

The corrosion protection composition according to the invention comprises a water-absorbing filler (ii). A water-absorbing filler is defined as a material that is capable of absorbing water and is suitable for use as a filler material.

The water-absorbing filler may comprise two or more water-absorbing fillers and may have organic and/or inorganic properties. The water-absorbing filler may include an intumescent filler, ie, a filler that expands when wetted. The water-absorption of a filler is defined as the amount of water absorbed in relation to the dry mass of the filler in a specified amount of time. Water-absorption (w _A ) is expressed as the ratio of the mass of water absorbed by the dry filler specimen (m _wg ) to the dry mass of the filler specimen (m _{d ) at a particular time.} Water-absorption is expressed by multiplying the ratio by the mass (in wt. %).

The water-absorption capacity of the filler is detected according to the method described in the standard NEN-EN-ISO 10769:2011, which is incorporated by reference. The standard relates to a method for detecting the water absorption of bentonite. However, the same method is applied in the present invention for the detection of the water-absorbency of various fillers. According to NEN-EN-ISO 10769:2011, the water-absorption of the water-absorbing filler is measured at ambient temperature, and the duration of the test is 24 hours.

In a preferred embodiment, the water-absorbing filler is at least about 1 wt%, preferably at least about 2 wt%, more preferably at least about 3 wt%, more preferably at least about 5 wt%, more preferably at least about 10 wt%; more preferably at least about 15 wt%, more preferably at least about 20 wt%, more preferably at least about 25 wt% and more preferably at least about 30 wt% water-absorption. In another preferred embodiment, the water-absorbing filler has a water-absorption of at least about 20% by weight, more preferably at least about 25% by weight, and more preferably at least about 30% by weight. More preferably, the water-absorbency of the water-absorbing filler is at least about 40% by weight, at least about 50% by weight, or at least about 70% by weight. More preferably, the water-absorption of the water-absorbing filler is at least about 100% by weight. Most preferably, the water-absorbency of the water-absorbing filler is at least about 150% by weight, or at least about 200% by weight. The amount of water-absorbing filler present in the composition depends, inter alia, on the water-absorbing degree w _{A of the filler.} When a water-absorbing filler having a lower water-absorption is applied to the corrosion protection composition, in order to ensure sufficient water-absorption of the corrosion protection composition, the amount of said filler in the composition is generally a higher water-absorption capacity. It is higher than in the case where the filler having the above is applied.

The water-absorption capacity of the filler depends, inter alia, on the specific surface, particle size and surface activity of the filler.

For example, calcium carbonate (CaCO ₃ ) is not a water-absorbing filler according to the definition of a water-absorbing filler as described herein.

A wide range of various water-absorbing fillers are known in the art, examples of which are silica, calcium oxide, for example, several clay minerals such as vermiculite and green clay, and polyacrylamide, such as polymethylacrylate, for example. water-absorbing polymers such as Water-absorbing polymers are known in the art and described, for example, in “Modern Superabsorbent Polymer Technology” (FL Buchholtz and AT Graham, Wiley VCH, 1998, pp. 71-103), which is incorporated herein by reference. described in detail.

In a preferred embodiment, the water-absorbing filler comprises mineral clay. Clay minerals are hydrous phyllosilicates, ie, hydrosilicates of aluminum (Al), magnesium (Mg), potassium (K) or iron (Fe), and other less abundant elements. Clay minerals are known in the art, and see, for example, Kirk-Othmer, "Encylopedia of Chemical Technology" (4 ^th Ed., John Wiley & Sons, New York 1993, Volume 6, pp. 383), which is incorporated by reference. -423) in more detail. Examples of clay minerals include vermiculite, kaolinite, and smectites such as montmorillonite and bentonite. In another preferred embodiment, the water-absorbing filler comprises montmorillonite clay and/or bentonite clay, in particular bentonite clay. Clay minerals are, for example, sodium bentonite clay, sodium montmorillonite clay, potassium bentonite clay, potassium montmorillonite clay, calcium bentonite clay, calcium montmorillonite clay, aluminum bentonite clay, aluminum montmorillonite clay , a combination of two or more bentonite clays, a combination of two or more montmorillonite clays, or a combination of one or more bentonite clays and one or more montmorillonite clays. In addition, the bentonite clay and/or montmorillonite clay may include a surface-modified bentonite clay. Preferably, the mineral clay comprises bentonite clay, more preferably sodium bentonite clay.

For example, as measured by NEN-EN-ISO 10769:2011, sodium bentonite (Cebogel) has a water absorption within the range of about 330-400 wt%, and kaolin (speswhite) has a water absorption within the range of about 20-30 wt% It has water absorption.

In a preferred embodiment, the water-absorbing filler comprises a filler that binds to water by a chemical reaction, such as, for example, cement. In another preferred embodiment, the water-absorbing filler comprises cement, preferably hydraulic cement. Hydraulic cement is a cement that hardens due to reaction with water. Examples of hydraulic cements are Portland cement and Portland cement blends (eg, Portland blast furnace cement or Portland fly ash cement), supersulfated cements, calcium aluminate cements and calcium sulfoaluminate cements.

In another preferred embodiment, the water-absorbing filler comprises silicon dioxide. In another preferred embodiment, the water-absorbing filler comprises both silicon dioxide and a filler that binds to water by a chemical reaction.

Preferably, the corrosion protection composition according to the present invention is about 20-80% by weight, more preferably about 22-60% by weight, more preferably about 24-50% by weight and most preferably about 20-80% by weight, based on the total weight of the corrosion protection composition. water-absorbing fillers in an amount of 25-40% by weight.

Apart from the one or more water-absorbing fillers, the composition may optionally include one or more additional fillers, which may have organic or inorganic properties. The one or more additional fillers comprise about 0-60% by weight, preferably about 8-58% by weight, more preferably about 16-51% by weight, and most preferably about 25-45% by weight, based on the total weight of the corrosion protection composition. % may be present.

The total amount of fillers present in the corrosion protection composition, ie the total amount of the at least one water-absorbing filler plus the optional at least one additional filler, is 20-80% by weight, preferably based on the total weight of the corrosion protection composition. 30-80% by weight, more preferably 40-75% by weight and most preferably 50-70% by weight.

Accordingly, the corrosion protection composition according to the present invention preferably contains about 20-80% by weight of water-absorbing filler and about 0% by weight of additional filler, more preferably about 20% by weight of water-absorbing filler, based on the total weight of the corrosion protection composition. 22-60 wt% and about 8-58 wt% additional filler, more preferably about 24-50 wt% water-absorbing filler and about 16-51 wt% additional filler, and most preferably about 25 wt% water-absorbing filler -60% by weight and about 25-45% by weight of additional fillers.

Fillers of organic nature are, for example, cellulose, polystyrene, polyvinyl chloride, polyethene, polypropene, polyisoprene, rubber, polyamide and polyester. Among these examples, polyethene and polypropene may also be present in the amorphous polymer composition that is part of the corrosion protection composition. However, when these polymers are applied as filler materials, for example, the glass transition temperature or molecular weight specified for an amorphous polymer composition does not necessarily have to be met. For example, syndiotactic polypropenes having a glass transition temperature higher than -20°C can be used as fillers.

Examples of inorganic fillers include, for example, inorganic minerals such as calcium carbonate, calcium sulfate, aluminum hydroxide, aluminum oxide, magnesium oxide, silicon dioxide, titanium dioxide, finely divided quartz, glass, talc, slate and kaolin, salts and / or oxide.

plasticizer

In a preferred embodiment, the corrosion protection composition according to the invention further comprises a plasticizer, said plasticizer preferably selected from the group consisting of waxes, mineral oils and mixtures thereof. The wax may be a petroleum derived wax, a vegetable or animal wax, or a synthetic wax such as, for example, polyethylene wax or Fischer-Tropsch wax. Waxes are well known in the art and are described, for example, in Kirk-Othmer, " Encyclopedia of Chemical Technology" (4 ^th Ed. 1998 , volume 25, p. 614-626).

In a preferred embodiment, the wax comprises petroleum wax. Petroleum wax is defined as any wax derived from petroleum. A significant fraction of petroleum consists of these waxes, which can be refined by vacuum distillation. Petroleum derived waxes are hydrocarbons, usually hydrocarbons comprising mixtures _{of C 20} -C _{40 alkanes.} The wax may include saturated n- and i -alkanes, cycloalkanes (naphthenes) and alkyl- and naphthene-substituted aromatics.

Examples of petroleum derived waxes are paraffin wax, semi-microcrystalline wax and microcrystalline wax. Paraffin wax mainly contains n -alkanes. Microcrystalline waxes contain, in addition to n -alkanes, a significant proportion of branched and cyclic saturated hydrocarbons. Semi-microcrystalline waxes contain more branched and cyclic compounds than paraffin waxes. As is known to those skilled in the art, the exact composition of a petroleum derived wax can vary greatly depending on the composition of the petroleum derived therefrom. In a preferred embodiment, the composition comprises microcrystalline wax.

In another preferred embodiment, the composition comprises mineral oil. Mineral oil is primarily defined as a mixture of hydrocarbons having more than 25 carbon atoms, also known as petroleum jelly, paraffin jelly, white petrolatum, soft paraffin or petrolatum. In another preferred embodiment, the composition comprises a wax, preferably a mixture of microcrystalline wax and mineral oil.

In a preferred embodiment, the composition comprises, based on the total weight of the composition, about 1-25%, more preferably about 1-20%, more preferably about 2-15% and most preferably about 1-25% by weight of plasticizer (iii) 3-10% by weight.

antioxidant

According to a preferred embodiment, the corrosion protection composition according to the invention further comprises an antioxidant (v). The antioxidant may be a primary antioxidant, a secondary antioxidant, a multifunctional antioxidant (ie, an antioxidant with combined primary and secondary antioxidant functions) or a lactone. In addition, the antioxidant may include a combination of two or more antioxidants.

The optional one or more antioxidants are about 0.05-5% by weight, preferably about 0.1-4% by weight, more preferably about 0.2-3% by weight and most preferably about 0.3-2% by weight, based on the total weight of the composition. may be present in the amount of

According to the present invention, the primary antioxidant is preferably selected from the group consisting of hindered phenolic compounds, hindered alkylthiomethylphenol or arylthiomethylphenol compounds, and secondary aromatic amines. Such compounds are well known in the art and include sterically hindered phenolic compounds 2,6-di-t-butyl-4-methylphenol, Irganox ^® 1330, Irganox ^® 1010, Irganox ^® 1098, Irganox ^® 1076, Irganox ^® 245, Irganox ^® 259, Irganox ^® 1035, Irganox ^® 2246, Irganox ^® 3114 and Irganox ^® 3125, sterically hindered alkylthiomethylphenols Irganox ^® 1520, i.e. 2,4-di-octylthiomethyl-6-methyl phenol, and for example For example, secondary aromatic antioxidants comprising (polymerized) 1,2-dihydro-2,2,4-trimethylquinoline such as ^{Agerite ® MA.}

According to the present invention, the secondary antioxidant is preferably selected from the group consisting of phosphites and thio-esters. Suitable secondary antioxidants include, for example, Irgafos ^® 168, Irgafos ^® 12 and Irgafos ^® P-EPQ (all phosphites), and Lowinox ^® TBM-6, BNX ^® DLTDP (CAS No. 123-28-4) and Morstille 18 DSTDP (all thio-esters).

The multifunctional antioxidant preferably comprises both primary and secondary antioxidant functions. Examples of multifunctional antioxidants are Irganox ^® L 115 and Irganox ^® 565.

An example of a lactone that can be used as an antioxidant is Irganox ^® HP-136.

According to the present invention, the composition preferably comprises a primary antioxidant, wherein the primary antioxidant is preferably selected from the group consisting of hindered phenolic compounds and secondary aromatic amines, most preferably hindered phenols. compound is selected from the group consisting of.

According to the invention, the composition preferably comprises a secondary antioxidant, wherein the secondary antioxidant is preferably selected from the group consisting of phosphites.

According to a more preferred embodiment, the composition comprises a combination of a primary antioxidant and a secondary antioxidant, preferably a combination of a primary antioxidant and a synergistic secondary antioxidant. A suitable combination is Irganox ^® 1010 and Irganox ^® 168.

According to a more preferred embodiment, the composition comprises a combination of a primary antioxidant, a secondary antioxidant and a lactone. In another preferred embodiment, the lactone is Irganox ^® HP-136.

Further examples of primary antioxidants, secondary antioxidants, multifunctional antioxidants and lactones are described, for example, in WO 2005/005528, incorporated by reference.

process

The invention also relates to a method for protecting an article against corrosion in which a layer of a corrosion protection composition according to the invention is applied to the surface of the article. The article is in a humid environment during application of the layer of the corrosion protection composition.

Therefore, the present invention

(a) on the surface of the article;

(i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less, and

(ii) water-absorbing filler

applying a layer of a corrosion protection composition comprising:

(b) applying a mechanical protective layer on top of the corrosion protection composition layer;

A method of protecting an article against corrosion, wherein the article is in a humid environment.

The corrosion protection composition according to the invention has been described in detail above.

Accordingly, the present invention relates to a method for protecting an article against corrosion, wherein the article is present in a humid environment during step (a) of the process, ie during application of the layer of the corrosion protection composition to the surface of the article. The corrosion protection composition layer may be applied to the entire surface of the article or to a portion of the surface.

Due to the improved setting of the corrosion protection composition according to the invention on the article to be protected, including improved deformability, very good adhesion tack and very good adhesion to the surface of the article, the process is carried out in which the article is in a humid environment. It can be carried out in the water, ie in a splash zone or the like. According to "Corrosion Control of Steel-Fixed Offshore Platforms Associated with Petroleum Production" (NACE Standard RP 0176-03, NACE International, Houston, 2003), which is incorporated herein by reference, the "splash zone" is defined as areas (eg, on offshore platforms) where the effects of tides, waves, wind and seawater alternately come and go; Surfaces wetted only during major storms are excluded from this area.

The invention relates in particular to the protection against corrosion of said articles. Consequently, it is preferred that the article consists essentially of metal, in particular steel or concrete. Alternatively, the surface of the article may consist essentially of metal, in particular steel, or concrete, while the interior of the article may comprise other materials. The method according to the invention is particularly suitable for oil or gas lines or pipes and oil drilling and for the protection against corrosion of risers of production rigs and mining rigs. However, the method according to the invention also protects the article against external mechanical influences, such as vibrations and shocks, for example caused by the action of waves.

The article to be protected by the method according to the invention is in a humid environment, for example a marine environment. Here, an article existing in a humid environment is defined as an article in which the surface of the article or a part thereof is wetted or moistened, that is, water is present on the surface of the article or a part thereof, or the surface of the article is located in water.

The article may be, for example, a submerged oil or gas pipeline, a riser in a drilling or production rig or pit, or an article located (partially) above the water but located in a so-called splash zone that can be wetted by waves or tidal action, etc. It can be completely or partially submerged in water. In one embodiment of the method according to the invention, the article in the wet environment is a submerged article, for example an oil or gas pipe or line located in water. In another embodiment of the present invention, the article in a wet environment is a partially submerged article, such as, for example, risers of oil drilling and production rigs and mining rigs located at sea or oil pipes or lines located partially underwater. . In another embodiment of the present invention, the article in the wet environment is the article located in the splash zone.

Alternatively, the article may be in a humid environment due to condensation of water from the environment on the surface of the article, such that water is present on the surface of the article or a portion thereof. An example of such an article is a sweating pipeline, ie a pipeline in which water is present on its surface due to condensation from the environment, or a gutter. In another embodiment of the method according to the invention, the article in the wet environment is a sweating pipeline or gutter.

The first step (a) of the method according to the invention comprises applying a layer of a corrosion protection composition according to the invention on the surface of the article which is present in a humid environment. In other words, the corrosion protection composition layer is applied to the surface while the surface or part thereof is wet or moistened, i.e., during the performance of step (a) of the method, water is absorbed onto the surface of the article or part thereof. exist on the

Contrary to methods known from the prior art, the corrosion protection composition according to the invention can be applied directly onto the wet surface of the article.

Thus, the method according to the invention can be carried out on an article without the need to separate the article from the wet environment, if the article is actually placed in a wet environment. The method can even be performed underwater to protect submerged articles. It is not essential that the surface of the article be dried prior to application of the composition according to the invention in step (a) of the method. In addition, large-scale pretreatment of the surface of the article is generally not required in the process according to the invention.

For example, when a submerged article is to be protected, in methods known in the art, it is often necessary to form a casing around the article and remove the water present in the casing. Subsequently, the surface of the article often has to undergo a thorough pretreatment, for example by sand blasting, in order to prepare the surface of the article. These time-consuming and costly steps are not required in the process according to the invention, requiring minimal surface treatment or no surface pretreatment at all.

The second step (b) of the method according to the invention comprises applying a compressible, flexible mechanical protective layer. A mechanical protective layer is applied on top of the layer of the corrosion protection composition according to the invention and completely covers the layer. Application of the mechanical protective layer “on top of” the layer of the corrosion protection composition is located on the side of the corrosion protection composition layer opposite from the side of the corrosion protection composition layer in which the mechanical protection layer is in contact with the surface of the article to be protected. means to do In one embodiment, the mechanical protection layer is in direct contact with the corrosion protection composition layer. In another embodiment, an additional intermittent layer may be present between the corrosion protection composition layer and the mechanical protection layer. The function of the mechanical protective layer is to protect the composition layer according to the invention applied in step (a) of the method. In addition, the mechanical protection layer ultimately minimizes the voids present under the corrosion protection layer, enables a self-healing effect by generating a pre-stress in the material, and prevents deterioration of the composition over time. Prevents the corrosion protection composition from excessive exposure to water that can result.

The term "mechanical protective layer" refers to a layer that protects the underlying layer or layers from external influences. The mechanical protective layer can be applied, for example, in the form of a tape. Examples of mechanical protective layers include polymeric (multilayer) films comprising, for example, polyethene, polypropene, polyvinyl chloride, polyester, epoxide, polyurethane or aramid. In addition, the polymer film may be laminated with reinforcing fibers such as, for example, glass fibers or carbon fibers. A suitable protective layer is provided, for example, by a high shear tape. High shear tapes are well known in the art and are described, for example, in US 5,817,413 and US 6,033,776, incorporated by reference.

A self-healing action can be obtained when the mechanical protective layer is applied with stress to a substrate comprising a protective layer of the composition according to the invention, or when the mechanical protective layer is contracted around a substrate, for example a pipe, , whereby defects in the protective layer are repaired after a sufficient time has elapsed. The protective layer then applies a continuous stress on the composition layer according to the invention. If the protective layer has suffered minimal damage, this stress ensures the flow of the composition according to the invention towards the damaged area, covering any exposed surface of the underlying substrate.

An example of a suitable mechanical protective layer is a glass fiber reinforced polyurea layer. This protective layer serves as a rigid mechanical reinforcement of the layer of the corrosion protection composition and protects the layer against impacts and indentations from, for example, driftwood, boat landings, and the like. In a preferred embodiment, a watertight layer is applied over the mechanical protection layer. In another preferred embodiment, the mechanical protection layer itself is a watertight layer. In another preferred embodiment, two different layers are applied on top of the corrosion protection composition layer, wherein the first layer, ie the layer in direct contact with the corrosion protection composition layer, is a flexible tape, and the second layer, ie said The layer in direct contact with the fusible tape is an additional rigid mechanical layer, for example glass fiber reinforced polyurea.

Furthermore, step (a) of the method according to the invention can be carried out by application of a tape to the surface of the article, said tape comprising a layer of the corrosion protection composition according to the invention.

Accordingly, the present invention also relates to a method according to the present invention, wherein in step (a) a tape is applied onto the surface of an article, wherein said tape (i) comprises an amorphous polymer having a glass transition temperature of -20°C or less. A method according to the invention comprising a layer comprising an amorphous polymer composition and (ii) a corrosion protection composition according to the invention comprising a water-absorbing filler. The corrosion protection composition according to the invention has been described in detail above.

A mechanical protective layer for protecting the composition layer according to the present invention may be included in the tape. In this case, step (b) of the method according to the invention is also carried out by application of said tape on the surface of the article, so that steps (a) and (b) of the method according to the invention are in this case are executed at the same time

tape

The invention also relates to a tape for protecting articles against corrosion, wherein the tape comprises a layer comprising a corrosion protection composition according to the invention. The corrosion protection composition is described in detail above. Therefore, the present invention

(i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less, and

(ii) water-absorbing filler

A tape comprising a layer comprising a corrosion protection composition comprising:

In a preferred embodiment of the tape according to the invention, the amorphous polymer is

(a) about 50.0-98% by weight of isobutene and about 2-50.0% by weight, based on the total weight of the polymer, of isobutene and other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene, or mixtures thereof polymers;

(b) a polymer comprising about 98-100 weight percent isobutene, based on the total weight of the polymer;

(c) about 50.0-99.9% by weight of propene and about 0.1-50.0% by weight of a C ₂ -C ₁₂ alkene other than propene, a C ₄ -C ₁₂ alkadiene, or a mixture thereof, based on the total weight of the polymer; or a polymer comprising about 100% by weight propene;

(d) a polymer comprising about 0.1-50.0% by weight of ethene and about 50.0-99.9% by weight of ethene and other C ₂ -C ₁₂ alkene, C ₄ -C ₁₂ alkadiene, or mixtures thereof, based on the total weight of the polymer. ;

(e) about 0.1-50.0% by weight of 2-methyl-1-pentene and about 50.0-99.9% by weight of 2-methyl-1-pentene and other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene, or mixtures thereof , or a polymer comprising about 100% by weight of 2-methyl-1-pentene; and

(f) mixtures of (a), (b), (c), (d) and/or (e)

is selected from the group consisting of

In another preferred embodiment of the tape according to the present invention, the amorphous polymer is selected from the group consisting of (a) and (b), and mixtures thereof.

In another preferred embodiment of the tape according to the invention, the amorphous polymer has a number average molecular weight M _n in the range of 1,000-150,000 g/mol.

In another preferred embodiment of the tape according to the invention, the corrosion protection composition further comprises a plasticizer (iii) selected from the group consisting of waxes, mineral oils and mixtures thereof.

The tape may be applied to the article to be protected while the article is in a humid environment. In other words, the tape can be applied to the surface of the article while the surface or part thereof is wet or moistened, ie, water is present on the surface of the article or part thereof during application of the tape. It is not necessary to dry the surface of the article prior to application of the tape. That is, the tape can be applied directly to a (partially) submerged article, to an article in a splash zone or to an article having a wet surface due to condensation of moisture on the surface of the article, such as, for example, a sweating pipeline. can Extensive pretreatment of the surface of the article to be protected is generally not necessary. Since the composition layer according to the invention can be easily deformed, the tape can be easily applied to the article to be protected against corrosion. Moreover, after application, the tape can also be easily removed. Although some residues remain on the surface of the metal article due to the cohesive failure, these residues can be easily removed by scraping. Moreover, the tape according to the present invention can be suitably used to restore damaged or corroded metal articles already provided with some protective materials according to the prior art, provided that the surface of the metal article has been cleaned to the level of St-2 according to ISO standard 8501-1. have. Consequently, as mentioned above, the tape has self-healing properties due to the flow and/or viscoelastic properties of the layer of the corrosion protection composition according to the present invention.

Preferably, the tape comprises an additional layer (b) which will protect layer (a). In particular, during transport, this protective layer (b) prevents the adhesive layers of the tape from adhering to each other as the tape can be easily wound on a bobbin, spool or other suitable means.

Therefore, the present invention also

(a) (i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less, and

(ii) water absorption filler

a first layer comprising a corrosion protection composition comprising; and

(b) a second layer protecting layer (a)

It relates to a tape comprising a.

Layer (b) may, for example, have the function of a release liner, which is removed from the tape during application of the tape. Layer (b) may then comprise any material suitable for a release liner, such as, for example, paper, a C ₂ -C _{20 alkene polymer or copolymer, and the like.}

Alternatively, layer (b) may comprise, for example, a polyvinyl chloride film having a siliconized outer surface. When such layer (b) is present, the presence of an additional release liner is unnecessary. In addition, said layer serves as a separation layer to increase the ease of application and as a layer which allows for proper adhesion of a subsequently applied mechanical protective layer.

In a particular embodiment, the tape comprises a further layer (c), wherein layer (c) is preferably one or more _{polymers of C 2} -C ₂₀ α-alkenes and/or alkadiene, as described in more detail below. or a film comprising a copolymer, polyvinyl chloride (PVC), polyurethane, or non-woven polyester fabric.

If layer (c) is present, it is located on the side of layer (a) different from the side on which layer (b) is located. That is, the order of the layers in the tape is (b) - (a) - (c), where layer (a) is located between (b) and (c). Accordingly, the present invention also

(a) (i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less, and

(ii) water absorption filler

a first layer comprising a corrosion protection composition comprising;

(b) a second layer protecting layer (a); and

(c) a layer comprising a film comprising a polymer or copolymer of one or more C ₂ -C ₂₀ α-alkenes and/or alkadiene, polyvinyl chloride (PVC), polyurethane, or non-woven polyester fabric.

It relates to a tape comprising a.

Layer (c) serves as a separation layer to increase the ease of application and as a layer which allows for proper adhesion of a subsequently applied mechanical protective layer.

Moreover, the tape preferably comprises component (d) embedded in layer (a), said component (d) preferably having a woven, knitted or spool-knitted structure capable of deformation in two orthogonal directions. and a reinforcing net-like structure with The reinforcing mesh structure is as well known in the art, for example, from polyester, or from polyolefins, such as fibers made from, for example, ethane homopolymers or copolymers or propene homopolymers or copolymers. It can be made from fibers. Also, the present invention

(a) (i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less, and

(ii) water absorption filler

a first layer comprising a corrosion protection composition comprising;

(b) a second layer protecting layer (a);

(c) optionally, _{a layer comprising a film comprising a polymer or copolymer of one or more C 2} -C ₂₀ α-alkenes and/or dialkenes, polyvinyl chloride (PVC), polyurethane, or non-woven polyester fabric. ; and

(d) reinforcing mesh structure embedded in layer (a)

It relates to a tape comprising a.

Thus, in the tape, the layers are located in the order (b) - [(a)+(d)]. If said layer (c) is present, the order of the layers in the tape is accordingly (b) - [(a) + (d)] - (c).

Layer (c) of the tape preferably comprises a film comprising one or more _{polymers or copolymers of C 2} -C ₂₀ α-alkenes and/or dialkenes, polyvinyl chloride (PVC), polyurethane, or non-woven polyester fabric. include Examples of such polymers and copolymers are EP(D)M elastomers, ethylene homopolymers, ethylene-α-alkene copolymers, propylene homopolymers and propylene-α-alkene copolymers, in particular propylene-ethylene copolymers, which It may contain high amounts of propylene, such as, for example, greater than or equal to 80% by weight, based on the total weight of the polymer, or low amounts of propylene, such as, for example, less than 20% by weight, based on the total weight of the copolymer. . When the copolymer is an ethylene copolymer in a preferred embodiment of the present invention, the C ₂ -C ₂₀ α-alkene is preferably a C ₃ -C ₁₂ α-alkene, in particular a C ₃ -C ₈ α-alkene. Examples of suitable α-alkenes are propene, 1-butene, 1-hexene and 1-octene. The ethylene copolymer preferably comprises 0.1-30% by weight of α-alkenes, in particular 0.1-20% by weight of α-alkenes. The density of the ethylene homopolymer or copolymer (measured according to ASTM D 1248) is preferably 0.800-0.975 g/cm ³ , in particular 0.850-0.950 g/cm ³ . The melt index (measured according to ASTM D 1248) of the ethylene homopolymer or copolymer is preferably 0.1-50 g/min, in particular 0.2-20 g/min. Layer (c) of the tape preferably comprises one or more of the following polymers: low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), ethene propene copolymer, ethene propene diene copolymer. According to a preferred embodiment of the present invention, layer (c) of the tape comprises LDPE, HDPE or LLDPE or a combination thereof. More preferably, the materials used for layer (c) are prepared in a metallocene catalyzed polymerization process.

Obviously, layer (c) may comprise one or more layers, for example a multilayer film comprising an LLDPE outer layer and an HDPE inner layer. Such multilayer films are well known in the art.

Layer (c) may further comprise other additives such as pigments and fillers.

The tape according to the present invention preferably has a total thickness of about 1-20 mm, more preferably about 1-15 mm, more preferably about 1-10 mm and most preferably about 1-7 mm. The width of the tape may obviously be adjusted as desired or suitably, but is preferably about 2.0-100.0 cm, more preferably about 2.5-75.0 cm, more preferably about 3.0-70.0 cm, more preferably about 4.0-65.0 cm and most Preferably about 5.0-60.0 cm. Also, the length of the tape can obviously be adjusted as desired or suitably. For example, a tape having a length of several meters may be wound around a bobbin or spool prior to use. However, the tape may also be in the form of a sheet. The length and width of the sheet can obviously be adjusted as desired or suitably.

The thickness of layer (c) is preferably about 10-500 μm, more preferably about 20-300 μm.

The invention also relates to a method of protecting an article against corrosion, comprising the step of applying a tape according to the invention to a surface of an article, said article being in a humid environment. The tape according to the invention is described in detail above.

The invention also relates to a method for producing a tape for the protection of articles against corrosion, wherein the composition according to the invention as defined above is laminated onto a film, said film preferably having the above definition for layer (c) of said tape. as described above, including films comprising a polymer or copolymer of one or more C ₂ -C ₂₀ α-alkenes and/or alkadiene, polyvinyl chloride (PVC), polyurethane, or non-woven polyester fabric. It relates to a method of manufacturing a protective tape for an article.

After the lamination step, the surface of the layer (a) which is not in contact with the layer (c) is preferably protected by a layer (b), wherein the layer (b) is made of, for example, an alkene polymer or copolymer, paper or the like. It may be any suitable material comprising

Optionally, component (d) is present embedded in layer (a) as defined above.

After the tape is manufactured, it is preferably wound around a bobbin or spool or similar suitable means so that it can be easily transported to the area or location where it is to be used.

Finally, we have found that when using tapes known in the art, significant stiff windings in the overlap region do not come into intimate contact, resulting in occlusion of water in the overlap region between different windings. It has been noted that corrosion (“spiral corrosion”) occurs. However, due to the fluidity and/or viscoelastic properties of the layer (a) when using the tape according to the invention, this problem does not arise.

protective article

The invention also relates to an article obtainable by the method according to the invention. Therefore, the present invention also

(a) on the surface of the article;

(i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less, and

(ii) water absorption filler

A corrosion protection composition layer comprising a, and

(b) a mechanical protective layer that protects the composition layer

It relates to articles containing

The corrosion protection composition is described in detail above.

The article may optionally include additional layers. In a preferred embodiment, the article further comprises a watertight layer. In another preferred embodiment, the mechanical protective layer (b) is itself a watertight layer.

A mechanical protective layer (b) is applied on top of the layer of the corrosion protective layer (a) and completely covers it. A suitable protective layer is provided, for example, by high shear tapes well known in the art. High shear tapes are described in US 5,817,413 and US 6,033,776, both incorporated by reference.

A layer of a corrosion protection composition according to the present invention may be included in the tape according to the present invention. The mechanical protective layer (b) can be applied individually to the article, or alternatively, the mechanical protective layer (b) can also be incorporated into the tape. The invention also relates to an article comprising the tape according to the invention. In the article, the surface of the article is covered by the tape. The tape is described in detail above.

In a preferred embodiment, the article consists essentially of metal, in particular of steel or concrete. Alternatively, the surface of the article may consist essentially of metal, in particular steel or concrete, while the interior of the article may comprise other materials. The article may be, for example, a tubular article such as a gas or oil pipe or line. The article may also be a riser, a pillar foundation or, for example, a wharf of a bridge, a buttress foundation of a dam, a concrete wall, etc. in oil drilling or production rigs or rigs.

Example

composition

Several compositions according to the invention (see Table 1) were prepared by mixing the ingredients in a paddle mixer at 90°C.

corrosion protection composition composition A B C Oppanol B10 25.0 31.0 37.5 sodium bentonite 25.3 31.0 49.6 microwax 6.0 - 5.0 mineral oil 12.0 12.4 7.5 CaCO ₃ 24.3 16.5 - Aerosil - 1.45 - portland cement 7.0 7.1 - Irgafos 168 0.20 0.19 0.20 Irganox 1010 0.20 0.19 0.20

Adhesion Adhesion was tested according to the peel-strength test as described in ISO 21809-3 (2008) Annex D. The requirements in ISO 21809-3 Amendment 1 Table 41 were used. Peel strength was measured, after which the specimens were inspected for occurrence of cohesive failure (the desired property), absence of interfacial failure and residual film on the substrate. The results are summarized in Table 2.

Cathode Stripping

Cathodic peel (CD) was tested according to ISO 21809-3 (2008) Annex F. The requirements in ISO 21809-3 Amendment 1 Table 41 were used. The results are summarized in Table 2.

Drip resistance

Drip resistance was tested according to ISO 21809-3 (2008) Annex J at various elevated temperatures. The results are summarized in Table 2.

Adhesive, cathodic peel and drip resistance composition A B C adhesive
- Peel strength max (N/mm)
- Destruction mechanism
- film remaining on the substrate

0.10
adhesive
you
0.08
adhesive
you
0.35
adhesive
you CD exam
- Peel (mm)
- self-healing

20
radish
0
you
11
radish Drip resistance (℃) 80 80 65

The results shown in Table 2 show that the corrosion protection composition according to the present invention exhibits excellent adhesion and excellent drip resistance.

Water-absorbency of corrosion protection compositions

The water-absorption properties of the corrosion protection compositions are detected using a method according to ASTM D570 adapted for corrosion protection compositions according to the present invention.

Weigh a plastic cup with a surface (curved surface) or a known length and width (rectangular or square surface) with a known depth within the range of 15-25 mm and a known diameter within the range of 30-50 mm (mass A). A cup having a depth of 20 mm and a curved surface of 44 mm diameter was used here. The cup was completely filled with the corrosion protection composition to avoid air ingress. The surface is leveled using a putty knife. Weigh the cup filled with the corrosion protection composition (mass B).

Subsequently, this filled cup is placed in a container with distilled water maintained at a temperature of 23 ± 1 °C. The filled cup must be completely immersed. Then, the container containing the cup is placed in a climate cabinet, and the water temperature is maintained at 23±1° C. for 72 hours. After 72 hours of immersion, the cup is removed from the container, its surface is dried with tissue paper, and the dried cup is weighed (mass C).

The water-absorption, expressed in % by weight, is calculated as follows:

The water-absorption (g/m ² ) is calculated as follows:

As is known to those skilled in the art, the method of calculating the surface of the cup depends on the shape of the surface. A circle surface is πr ² , where r is the radius of the circle, and a square or rectangular surface is l*w, where l is the length and w is the width of the surface.

Water-absorbency (g / m ²⁾ the surface that the depth of the cup is used to measure greater than the minimum depth as described above, whereby the water to be measured according-absorbency (g / m ²⁾ is the water-absorbency (g /m ² ) will be independent of the mass (BA) of the corrosion protection composition used.

Polyisobutene 30.8% by weight, water-absorbing filler (sodium bentonite, Cebogel Premium) 25.3% by weight, mineral oil (Vara 4800) 4.9% by weight, Aerosil 1.5% by weight, finely divided quartz (silica powder) 30.5% by weight, Portlandhuttencement CEMII/S Water of a composition according to the invention comprising 32.5% by weight of R 3.1% by weight, 2.9% by weight of surfactant (Dmex), 0.50% by weight of antioxidants (0.25% of Irgafos 168 and 0.25% of Irganox 1010) and 0.31% by weight of pigment green -Absorbance (g/m ² ), W _A (g/m ² ) was measured according to the method described above. ^{The water-absorption (g/m 2} ) of this composition measured after 72 hours immersion in distilled water at 23±1° C. was 2354 g/m ² .

Claims (11)

(a) (i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less, wherein the amorphous polymer has a number average molecular weight M _n in the ^{range of 1,000-150,000 g mol -1 .} , and
(ii) a water-absorbing filler having a water-absorption of at least 20% by weight as measured according to the method described in the standard NEN-EN-ISO 10769:2011
applying on the surface of the article a layer of a corrosion protection composition comprising:
(b) applying a mechanical protection layer on top of the corrosion protection composition layer;
wherein the article is in a wet environment, and wherein the article in a wet environment is an article in which water is present on the surface of or a portion of the article, or is submerged or partially submerged in water. It is defined as a submerged article,
wherein the composition has a water-absorbency w _A (g/m ² ) of at ^{least 600 g/m 2} , wherein w _A (g/m ² ) is
(1) Weighing a surface having a depth and diameter within the range of 15-25 mm or a cup having a length and width within the range of 30-50 mm to obtain a mass A;
(2) completely filling the plastic cup with the composition, avoiding air ingress, and leveling the surface;
(3) weighing the filled cup to obtain mass B;
(4) placing the filled cup in a container of dilution water maintained at a temperature of 23±1° C. and immersing the cup completely;
(5) placing the cup in a climate cabinet and maintaining the water temperature at 23 ± 1°C for 72 hours;
(6) removing the cup from the container after 72 hours, drying the surface thereof, and weighing the dried cup to obtain mass C; and
(7) calculating the water-absorbency expressed in ^{g/m 2 as follows}

is measured by, and
wherein the water-absorbing filler comprises a filler that binds to water by a chemical reaction, or is selected from sodium bentonite clay, sodium montmorillonite clay, or a combination thereof;
Methods of protection against corrosion of goods.
According to claim 1,
amorphous polymer
(a) a polymer comprising 50.0-98% by weight of isobutene and 2-50.0% by weight, based on the total weight of the polymer, of isobutene and other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene or mixtures thereof;
(b) a polymer comprising greater than 98 weight percent isobutene and up to 100 weight percent, based on the total weight of the polymer;
(c) 50.0-99.9% by weight of propene and 0.1-50.0% by weight, based on the total weight of the polymer, of propene and other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene or mixtures thereof, or propene 100 polymer comprising weight percent;
(d) a polymer comprising 0.1-50.0% by weight of ethene and 50.0-99.9% by weight of ethene and other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadienes or mixtures thereof, based on the total weight of the polymer;
(e) 0.1-50.0% by weight of 2-methyl-1-pentene and, based on the total weight of the polymer, 2-methyl-1-pentene with other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene or mixtures thereof 50.0-99.9% by weight of a polymer comprising 100% by weight of 2-methyl-1-pentene; and
(f) at least two of (a), (b), (c), (d) and (e);
A method of protecting an article against corrosion, selected from the group consisting of
3. The method of claim 2,
wherein the amorphous polymer is selected from the group consisting of one or more of (a) and (b).
4. The method according to any one of claims 1 to 3,
In step (a) a tape is applied onto a surface of an article, wherein the tape comprises the layer of the corrosion protection composition.
4. The method according to any one of claims 1 to 3,
wherein the corrosion protection composition further comprises a plasticizer (iii) selected from the group consisting of waxes, mineral oils and mixtures thereof.
A composition for protection against corrosion of an article in a humid environment in which water is present on the surface of or a portion of the article, or an article submerged or partially submerged in water, said composition comprising:
(i) an amorphous polymer composition comprising an amorphous polymer having a glass transition temperature of -20°C or less, and
(ii) a water-absorbing filler having a water-absorption of at least 20% by weight as measured according to the method described in the standard NEN-EN-ISO 10769:2011
wherein the composition comprises 20-80% by weight of the amorphous polymer composition based on the total weight of the composition, and wherein the amorphous polymer has a number average molecular weight in the range ^{of 1,000-150,000 g mol -1} has M _n ,
wherein the composition has a water-absorbency w _A (g/m ² ) of at ^{least 600 g/m 2} , wherein w _A (g/m ² ) is
(1) Weighing a surface having a depth and diameter within the range of 15-25 mm or a cup having a length and width within the range of 30-50 mm to obtain a mass A;
(2) completely filling the plastic cup with the composition, avoiding air ingress, and leveling the surface;
(3) weighing the filled cup to obtain mass B;
(4) placing the filled cup in a container of dilution water maintained at a temperature of 23±1° C. and immersing the cup completely;
(5) placing the cup in a climate cabinet and maintaining the water temperature at 23 ± 1°C for 72 hours;
(6) removing the cup from the container after 72 hours, drying the surface thereof, and weighing the dried cup to obtain mass C; and
(7) calculating the water-absorbency w _A ^{expressed in g/m 2 as follows}

is measured by, and
wherein the water-absorbing filler comprises a filler that binds to water by a chemical reaction, or is selected from sodium bentonite clay, sodium montmorillonite clay, or a combination thereof.
7. The method of claim 6,
amorphous polymer
(a) a polymer comprising 50.0-98% by weight of isobutene and 2-50.0% by weight, based on the total weight of the polymer, of isobutene and other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene or mixtures thereof;
(b) a polymer comprising 98-100% by weight of isobutene, based on the total weight of the polymer;
(c) 50.0-99.9% by weight of propene and 0.1-50.0% by weight, based on the total weight of the polymer, of propene and other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene or mixtures thereof, or propene 100 polymer comprising weight percent;
(d) a polymer comprising 0.1-50.0% by weight of ethene and 50.0-99.9% by weight of ethene and other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadienes or mixtures thereof, based on the total weight of the polymer;
(e) 0.1-50.0% by weight of 2-methyl-1-pentene and, based on the total weight of the polymer, 2-methyl-1-pentene with other C ₂ -C ₁₂ alkenes, C ₄ -C ₁₂ alkadiene or mixtures thereof 50.0-99.9% by weight of a polymer comprising 100% by weight of 2-methyl-1-pentene; and
(f) at least two of (a), (b), (c), (d) and (e);
A composition selected from the group consisting of.
7. The method of claim 6,
wherein the amorphous polymer is selected from the group consisting of one or more of (a) and (b).
7. The method of claim 6,
wherein the composition further comprises a plasticizer (iii) selected from the group consisting of waxes, mineral oils and mixtures thereof.
A tape comprising a layer comprising the corrosion protection composition according to claim 6 .
(a) a layer of the corrosion protection composition according to any one of claims 6 to 9 on the surface of the article, and
(b) a mechanical protective layer protecting the layer of the corrosion protection composition;
An article comprising