WO1999042500A1 - Compositions polymeres derivees d'esters d'acide vinyl neo c9-c13 carboxylique - Google Patents

Compositions polymeres derivees d'esters d'acide vinyl neo c9-c13 carboxylique Download PDF

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Publication number
WO1999042500A1
WO1999042500A1 PCT/US1999/003921 US9903921W WO9942500A1 WO 1999042500 A1 WO1999042500 A1 WO 1999042500A1 US 9903921 W US9903921 W US 9903921W WO 9942500 A1 WO9942500 A1 WO 9942500A1
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WO
WIPO (PCT)
Prior art keywords
carboxylic acid
vinyl
acrylic
polymer
neo
Prior art date
Application number
PCT/US1999/003921
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English (en)
Inventor
Vijay Swarup
Peter S. Ellis
Henry Wu-Hsiang Yang
Oliver W. Smith
Thomas H. Henry
Original Assignee
Exxon Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Priority to US09/622,748 priority Critical patent/US6476136B1/en
Priority to AU27833/99A priority patent/AU2783399A/en
Publication of WO1999042500A1 publication Critical patent/WO1999042500A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/02—Esters of monocarboxylic acids
    • C08F18/04—Vinyl esters
    • C08F18/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms

Definitions

  • the present invention relates generally to compositions prepared by polymerizing vinyl neo C 9 - C 13 carboxylic acid esters.
  • Such compositions include latex compositions that are formed by polymerizing vinyl neo Cg - C- ⁇ 3 carboxylic acid esters with ethylenically unsaturated comoners such as acrylic acid esters and vinyl acetate.
  • the compositions of the present invention are particularly suitable for use in applications such as architectural (both interior and exterior), direct-to-metal and marine coatings and transportation maintenance applications.
  • VA/BA systems vinyl acrylic copolymer systems
  • VA/BA + BA/MMA systems vinyl acetate/butyl acrylate/vinyl ester systems
  • VA/BA/VE systems vinyl acetate/butyl acrylate/vinyl ester systems
  • these lower cost systems i.e., VA/BA + BA/MMA systems and VA/BA/VE systems, lack properties such as resistance to alkali hydrolysis, which is a highly desirable property for exterior paints. Therefore, there is a desire to develop a lower cost system with improved performance. 2
  • VA/BA systems vinyl acetate/butyl acrylate systems
  • VA ⁇ E systems vinyl acetate/vinyl ester systems
  • VA/BA systems and VA/VE systems that are currently available can be improved in the area of scrub and stain resistance, performance properties that are required for interior paints. Therefore, it is desirable to improve current VA/BA and VA/VE systems to obtain better performance such as scrub and stain resistance for interior coatings.
  • An object of the present invention is to modify a vinyl acrylic system to improve performance properties of exterior paints.
  • a second object of the present invention is to modify a vinyl acetate system to improve performance properties of interior paints and to use such a modified vinyl acetate system as a blended component with an all acrylic system for use in exterior paints.
  • a third object of the present invention is to modify all acrylic systems to improve performance properties for direct to metal coatings.
  • the present invention is directed to a polymer prepared by polymerizing a multi-isomer mixture of vinyl neo C 9 - C 13 carboxylic acid esters containing at least 25 wt% vinyl neo C 12 carboxylic acid ester, wherein the vinyl neo C 9 -C ⁇ 3 carboxylic acid is represented by the formula:
  • Figure 1 is a GC pattern for the vinyl neo C 9 -C 13 carboxylic acid ester mixture described herein;
  • Figure 2 is a GC pattern for the vinyl neo C 9 -C 12 carboxylic acid ester mixture used in the Examples;
  • FIG. 3 schematically illustrates alkali hydrolysis test results of colloid-stabilized latexes
  • FIG 4 schematically illustrates alkali hydrolysis test results of surfactant-stabilized latexes
  • Figure 5 schematically illustrates alkali hydrolysis test results of commercial latexes
  • Figure 6 illustrates the alkali hydrolysis test results of a VA/C12VE + BA/MMA system.
  • a vinyl neo carboxylic acid ester is a derivative of an acid having a neo structure, i.e., an acid having an ⁇ , ⁇ , ⁇ -trisubstituted carbon atom.
  • C12VE is a multi-isomer mixture of vinyl neo Cg
  • the C12VE typically comprises vinyl neo Cg carboxylic acid ester (neo Cg vinyl ester), vinyl neo C ⁇ 0 carboxylic acid ester (neo C 10 vinyl ester), vinyl neo Cn carboxylic acid ester (neo Cn vinyl ester), vinyl neo C ⁇ 2 carboxylic acid ester (vinyl C 2 vinyl ester), and vinyl neo C 13 carboxylic acid ester (neo
  • the vinyl neo Cg - C13 carboxylic acid esters may be represented by the formula:
  • Ri + R 2 + Rz 10 carbon atoms.
  • the C12VE can be prepared by a catalyzed reaction between a neo C 9 - C- I 3 carboxylic acid mixture and acetylene or vinyl acetate. Processes for the synthesis of vinyl ester are well known and disclosed in US
  • a polymer prepared from an ethylenically unsaturated comonomer, an acrylic comonomer, and the C12VE has improved water resistance and resistance to alkali hydrolysis properties.
  • a VA/BA system may be modified by the addition of C12VE to produce a VA/BA/C12VE system that has improved water resistance and resistance to alkali hydrolysis.
  • the polymer of the first embodiment is prepared from a monomeric mixture comprising from about 5 to 95 percent by weight of an ethylenically unsaturated comonomer, from about 5 to 75 percent by weight of an acrylic comonomer, and from about 5 to 75 percent by weight of the C12VE. More preferably, the polymer is prepared from a monomeric mixture comprising from about 30 to 90 percent by weight of an ethylenically unsaturated comonomer, from about 5 to 50 percent by weight an acrylic comonomer, and from about 10 to 50 percent by weight of the C12VE. Specific polymers are prepared from mixtures having monomeric ratios of ethylenically unsaturated comonomer/acrylic comonomer/C12VE of 63/27/10, 56/24/20 or 49/21/30.
  • Applicants have found that copolymers prepared from an ethylenically unsaturated comonomer and the C12VE may be incorporated into an interior paint formulation to impart improved scrub and stain resistance to the interior paint. Specifically, Applicants have found that the use of a C12VE to produce a VA/C12VE system results in improved scrub and stain resistance properties.
  • the copolymer of the second embodiment is prepared from a monomer mixture comprising from about 30 to 95 percent by weight of an ethylenically unsaturated comonomer and from about 5 to 70 percent by weight of the C12VE.
  • a preferred copolymer is prepared from a mixture having monomeric ratio of ethylenically unsaturated comonomer/C12VE of 85/15.
  • the copolymer prepared from an ethylenically unsaturated comonomer and the C12VE may be blended with an all acrylic polymer (i.e., a second polymer) to improve water resistance and resistance to hydrolytic stability.
  • a VA/C12VE system may be blended with all acrylic systems to produce a VA/C12VE+BA/MMA blend that may be used in exterior paints.
  • the first polymer of the third embodiment is prepared from a monomer mixture comprising from about 30 to 95 percent by weight of an ethylenically unsaturated comonomer and from about 5 to 70 percent by weight of the C12VE
  • the second polymer is prepared from a monomer mixture comprising from about 40 to 90 percent by weight of a first acrylic comonomer and from about 10 to 60 percent by weight of a second acrylic comonomer.
  • a preferred first polymer has a monomeric ratio of ethylenically unsaturated comonomer/C12VE of 85/15, while a preferred second polymer is 70/30.
  • the first and second polymers are blended in a ratio ranging from 99/1 to 1/99.
  • the multi-isomer mixture of vinyl neo carboxylic acid esters may be used to modify an all acrylic system prepared from acrylic comonomers to form a corrosion resistant composition.
  • the a multi-isomer mixture of vinyl neo carboxylic acid esters may be polymerized with acrylic comonomers to produce a BA/MMA/VE system for use in direct to metal coatings.
  • the latex of the fourth embodiment is prepared from a monomeric mixture comprising from 0 to 5 percent by weight acrylic acid, from about 10 to 60 percent by weight of a first acrylic comonomer, from about 10 to 80 percent of a second acrylic comonomer and from about 10 to 90 percent by weight of the vinyl neo carboxylic acid ester mixture.
  • a preferred latex has a monomeric ratio of 20/20/60.
  • the ethylenically unsaturated comonomer of the first, second and third embodiments is generally described as vinyl carboxylate comonomer and includes vinyl acetate.
  • the ethylenically unsaturated comonomer is selected from the group consisting of vinyl acetate, acrylic acid, methacrylic acid, an ester of acrylic acid, an ester of methacrylic acid, acrylonitrile, vinylidene chloride, styrene, methylstyrene, and a mixture thereof.
  • the acrylic comonomers of the first, third and fourth embodiments include alkyl (meth)acrylates and (meth)acrylic acid can also be advantageously used.
  • the present copolymers typically include a mixture of several different acrylic monomers including at least one (meth)acrylic acid monomer and one or more alkyl (meth)acrylate ester monomers.
  • the terms "(meth)acrylic” and “(meth)acrylate” in the context of the present invention refer to both acrylic and methacrylic derivatives.
  • alkyl (meth)acrylate ester monomers examples include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl 8
  • Preferred alkyl (meth)acrylate monomers include n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate.
  • suitable alpha, beta-ethylenically unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, crotonic acid, maleic acid, acid itaconic acid and the like, wherein (meth)acrylic acid is preferred.
  • Varying amounts of other free radical polymerizable monomers can be employed in the present copolymer including acrylonitrile, vinyl acetate, vinylidene chloride, styrene, methyl styrene, and the like. It should be noted that some commercially available acrylic monomers or monomer mixtures also include minor amounts of acrylonitrile, styrene, vinyl acetate, and the like.
  • the reaction of the selected acrylic monomers to form acrylic copolymers proceeds by emulsion polymerization which is a type of polymerization well known to the practitioners in the art.
  • the reaction mixture generally includes an initiator which may be any compound(s) or source for generating free radicals capable of initiating polymerization of the acrylic monomers, such as, for example, azo compounds, persulfates, redox couples and the like
  • the solids, in the form of a dispersed latex are allowed to cool to room temperature and the dispersed latex is usually separated from coagulum formed during polymerization by filtration.
  • the dispersed latex may be coated directly onto a substrate film or may be incorporated into a paint or coating formulation that is applied to a substrate film.
  • Suitable substrates include metal, glass, plastic, paper, cloth, wood, pressed wood, polymer film, woven fabric, nonwoven fabric, polyolefin, materials and the like.
  • metallic substrates in direct to metal application of the fourth embodiment include aluminum, copper and steel
  • examples of the plastic substrates include polyesters, polyolefins, polyethylene terephthlate, and the like.
  • the vinyl neo carboxylic acid ester mixture labeled "C12VE” in the following Examples is EXXARTM Neo 12 Vinyl Ester produced by Exxon Chemical Company.
  • the vinyl neo carboxylic acid ester labeled "C10VE” in Examples 1 , 2, 4, 5, 7 and 9 is EXXARTM Neo 10 Vinyl Ester produced by Exxon Chemical Company, which is a vinyl neo C 9-12 carboxylic acid ester mixture having 90% or more vinyl neo C ⁇ 0 carboxylic acid ester (neo C 10 vinyl ester) and the GC pattern shown in Figure 2.
  • Carrier Gas Helium
  • a colloid-stabilized (CS) latex recipe is given in Table 1.
  • the latex reactor system included a cylindrical kettle (1 liter) equipped with an inlet for nitrogen purge, condenser and mechanical stirrer. The system was connected to a Camille 2000 automated monomer feeding assembly. The reaction kettle was flushed with nitrogen for 30 minutes. A kettle charge, comprising a colloid, surfactant, initiator and deionized (Dl) water, was added to the kettle and the reaction mixture was purged with nitrogen for 30 minutes. The reaction mixture was stirred at a speed of 300 r.p.m. maintaining the temperature at 75°C. About 10% of the monomer mixture were added as an initial seed. After 30 minutes, the monomer mixture and the initiator solution were fed separately to the reaction zone.
  • Dl deionized
  • the addition time of the monomer mixture was 3 hours and that of the initiator solution was 3.5 h ours. After addition of the initiator solution was complete, the reaction mixture was post reacted for an additional 1 hour to ensure complete reaction. After determining the solids content of the latex, the reaction mixture was cooled and filtered through a fine filter to produce a stable latex. 11
  • Rhodocal DS-4 anionic surfactant 6.60
  • the surfactant-stabilized (SS) latexes were synthesized by a slightly modified procedure.
  • a pre emulsion solution is prepared by mixing the surfactant, monomers and Dl water with a high-speed stirrer at 500 r.p.m. for a period of 15 minutes. This pre emulsion solution replaces the monomer mixture of the colloid-stabilized procedure of Example 1 , Part A.
  • a detailed recipe is given in Table 2.
  • Rhodocal DS-4 anionic surfactant 3.60
  • Rhodocal DS-4 anionic surfactant
  • Latex samples prepared according to the colloid stabilized and surfactant stabilized latex preparation methods are described in Table 3.
  • the particle size of the latex samples described in Table 3 was measured using a Coulter N4MD sub-micron particle size analyzer. Minimum Filming Temperature (MFT) was determined using a Paul Gardner MPT Bar 90. These properties are shown in Tables 4 and 5.
  • MFT Minimum Filming Temperature
  • Amount (wt%) 10% 10% 20% 20% 30% 30%
  • a sample exterior flat house paint formulation is described in Table 6.
  • the latex used in an exterior paint formulation may be any of the latex samples described in Table 3. 15
  • Latex (53.5% solids) 31.44
  • Texanol ® (10 parts per hundred rubber based on % latex solids) was added to some of the colloid stabilized latex samples described in Table 3. The latex samples were vigorously shaken on vortex shaker and latex films of 4 mil wet film thickness were drawn on polypropylene panels using a draw down bar. The films were dried at room temperature for a week. The dried films were cut to about 7cm x 1.5cm specimens, weighed and 16
  • Colloid stabilized latexes generally performed better than the surfactant stabilized systems.
  • the performance of the surfactant stabilized systems may have suffered to some extent due to the presence of acrylic acid, which may have facilitated the hydrolysis of ester groups.
  • both absence of acrylic acid and presence of grafting at the cellulose sites of the colloid may have improved the overall hydrolytic stability of the colloid stabilized systems.
  • the trialkyl branching of the C12VE provides steric hindrance, which contributes to the alkali resistance and overall strength of polymer.
  • the steric hindrance of the vinyl neo C 9 - C- ⁇ 3 carboxylic acid esters deter the approach of alkali to the ester sites. This effect protects the ester groups from hydrolysis, thus improving their stability when exposed to environmentally harsh conditions.
  • the vinyl neo C 9 - C ⁇ 3 carboxylic acid esters can be used as protective monomers to provide shielding of the acetate groups from alkali attack and subsequent hydrolysis.
  • a latex for interior paints may be prepared according to the colloid stabilized latex preparation method described in Example 1 , using the VA/C12VE system of the present invention.
  • a sample interior paint formulation incorporating such a latex is described in Table 8.
  • Scrub resistance is a key property for interior paints.
  • the test used to measure scrub resistance involves subjecting paint that is coated on a substrate to abrasion, usually by rubbing a brush onto the substrate.
  • ASTM method number D2486-89 entitled "Scrub Resistance of Wall Paints,” was used for testing the scrub resistance of the coatings tested.
  • Scrub resistance properties of VA/C12VE system based interior paints vs. VA/C10VE system based interior paints and VA/BA system based interior paints at various PVC levels are shown in Table 9. The interior paints of Table 9 were prepared similarly to the sample paint formulation described in Table 8. 20
  • PVC Pigment Volume Concentration
  • the scrub test for Experiment No. 1 was conducted by coating a VA/C12VE system based interior paint onto two halves of a substrate. The two halves were subjected to abrasion that traversed the two halves until the paint in both halves had been worn through to the substrate. This procedure of coating/abrasion was repeated three times for a total of six VA/C12VE samples (each sample coated onto one half of a substrate). The number of cycles of abrasion for each of the six VA/C12VE samples was averaged to yield the numbers 1351.0, 387.0 and 236.0.
  • the coating/abrasion procedure was repeated three times for a total of six VA/C10VE samples (each sample coated onto one half of a substrate). The number of cycles of abrasion for each of the six
  • VA/C10VE samples was averaged to yield the numbers 1266.0, 395.0 and 21 1.0.
  • This procedure of coating/abrasion was repeated two times, each time alternating the position of the VA/C12VE and VA/C10VE systems on the halves of the substrate, for a total of two VA/C12VE and two VA/C10VE systems.
  • the number of cycles for abrasion for each of the two VA/C12VE and two VA/C10VE systems was averaged to yield the numbers set forth in Table 9.
  • interior paints prepared from a VA/C12VE system have unexpectedly improved scrub resistance compared to interior paints prepared from a VA/C10VE system or a VA/BA system.
  • VA/C12VE system is superior to that of a paint based on a VA/BA system. Improved porosity using a VA/C12VE system translates into improved stain resistance for interior paints, which is a key performance need in interior paints. 22
  • the VA/C12VE system described in Example 7 may be blended with an all acrylic system. Improved resistance to alkali hydrolysis is demonstrated for wet latexes prepared from VA/C12VE (having a ratio of 85/15) + BA/MMA blends compared to wet latex prepared from VA/BA (having a ratio of 80/20) + BA/MMA blends.
  • the blends according to the present invention approaches the resistance of an all acrylic system to alkali hydrolysis when blended in increasing ratios of VA/C12VE to BA/MMA.
  • VA/BA UCAR® 379G by Union Carbide
  • the all acrylic product is RHOPLEX MULTILOBE 200 by Rohm and Haas
  • VA/BA (80/20) is a VA/BA system having a monomeric ratio of 80/20.
  • Latex for direct to metal application may be synthesized similarly to the surfactant stabilized latex preparation described in Example 1.
  • Sample latexes having varying amounts of C10VE or C12VE are shown in Table 11. Corrosion testing was performed by preparing panels for corrosion testing using the wet latex along with 10 parts per hundred rubber Texanol® and 0.5 parts per hundred rubber urethane thickener (based on % solids), and 0.1% sodium nitrate solution to prevent flash rusting of the panels.
  • Latex films of 6 mil wet film thickness were drawn down on cold-rolled steel panels using a draw down bar. The panels were dried at room temperature for 4 h and then at 60°C for 2 days. Dried panels were scribed in the middle and placed in the salt fog chamber.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne généralement des compositions obtenues par polymérisation d'esters d'acide vinyl néo C9-C13 carboxylique. Ces compositions comprennent des compositions de latex formées par polymérisation d'esters d'acide vinyl néo C9-C13 carboxylique avec des comonomères non saturés ethyléniquement tels que des esters d'acide acrylique ou de l'acétate vinyl. Les compositions polymères selon la présente invention conviennent particulièrement bien comme revêtements (tant intérieurs qu'extérieurs) en architecture, applications directes sur des surfaces métalliques, revêtements marine ou revêtements d'entretien pour véhicules de transport.
PCT/US1999/003921 1998-02-23 1999-02-23 Compositions polymeres derivees d'esters d'acide vinyl neo c9-c13 carboxylique WO1999042500A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US09/622,748 US6476136B1 (en) 1999-02-23 1999-02-23 Polymer compositions derived from vinyl neo C9-C13 carboxylic acid esters
AU27833/99A AU2783399A (en) 1998-02-23 1999-02-23 Polymer compositions derived from vinyl neo c9-c13 carboxylic acid esters

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US7555498P 1998-02-23 1998-02-23
US60/075,554 1998-02-23
US9551998P 1998-08-06 1998-08-06
US60/095,519 1998-08-06
US9875698P 1998-09-01 1998-09-01
US60/098,756 1998-09-01
US11945399P 1999-02-10 1999-02-10
US60/119,453 1999-02-10

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001044378A1 (fr) * 1999-12-17 2001-06-21 Exxonmobil Chemical Patents Inc. Monomeres neoester de vinyle utilises dans des applications de durcissement par rayonnement
WO2006061139A1 (fr) * 2004-12-09 2006-06-15 Wacker Polymer Systems Gmbh & Co. Kg Poudre polymere hydrophobe redispersable dans l'eau
WO2010076006A2 (fr) 2008-12-29 2010-07-08 Celanese Emulsions Gmbh Copolymères de méthacrylate d'alkyle/acrylate d'alkyle utilisés en tant qu'encollage pour fibre de renforcement
EP3204551B1 (fr) 2014-10-06 2018-12-05 Ahlstrom-Munksjö Oyj Tissu en fibre et plaque de plâtre adaptée aux zones mouillées ou humides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993022353A1 (fr) * 1992-05-06 1993-11-11 Shell Internationale Research Maatschappij B.V. Polymeres et latex polymeres obtenus a partir d'esters vinyliques d'acides monocarboxyliques satures
WO1994014891A1 (fr) * 1992-12-18 1994-07-07 Exxon Chemical Patents Inc. Adhesifs acryliques contenant un ester de neo-acide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993022353A1 (fr) * 1992-05-06 1993-11-11 Shell Internationale Research Maatschappij B.V. Polymeres et latex polymeres obtenus a partir d'esters vinyliques d'acides monocarboxyliques satures
WO1994014891A1 (fr) * 1992-12-18 1994-07-07 Exxon Chemical Patents Inc. Adhesifs acryliques contenant un ester de neo-acide

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001044378A1 (fr) * 1999-12-17 2001-06-21 Exxonmobil Chemical Patents Inc. Monomeres neoester de vinyle utilises dans des applications de durcissement par rayonnement
WO2006061139A1 (fr) * 2004-12-09 2006-06-15 Wacker Polymer Systems Gmbh & Co. Kg Poudre polymere hydrophobe redispersable dans l'eau
KR100855574B1 (ko) * 2004-12-09 2008-09-03 와커 헤미 아게 수중에서 재분산될 수 있는 소수성화 중합체 분말
US7851521B2 (en) 2004-12-09 2010-12-14 Wacker Chemie Ag Hydrophobicizing water-redispersible polymer powder
WO2010076006A2 (fr) 2008-12-29 2010-07-08 Celanese Emulsions Gmbh Copolymères de méthacrylate d'alkyle/acrylate d'alkyle utilisés en tant qu'encollage pour fibre de renforcement
EP3204551B1 (fr) 2014-10-06 2018-12-05 Ahlstrom-Munksjö Oyj Tissu en fibre et plaque de plâtre adaptée aux zones mouillées ou humides
EP3312339B1 (fr) 2014-10-06 2020-01-01 Etex Building Performance International SAS Plaque de plâtre adaptée aux zones mouillées ou humides

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