RU2344148C2 - Cured coatings low permeable with respect to sulphurous gases - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: coating is made of polymer composition containing reaction product of multifunctional polyisobutylene with chain-terminal allylic groups and multifunctional polysiloxane with SiH links. Herewith daily diffusion rate of gas hydrogen sulphide, mercaptan through the membrane containing mentioned composition of thickness within approximately 10 to approximately 30 mils, at 50°C is smaller than approximately 0.0010 gram of hydrogen sulphide per one square meter of membrane. Multifunctional polyisobutylene with chain-terminal allylic groups, cross-linked with multipurpose polysiloxane with SiH links allows for composition more or less impenetrable with respect to gas sulphurous compounds, such as hydrogen sulphide, mercaptan that makes possible to produce protective coating for various finished product, particularly components of electronic devices, and method of protection of various finished products from specified gas sulphurous compounds.

EFFECT: production of composition more or less impenetrable with respect to gas sulphurous compounds.

12 cl

Description

FIELD OF TECHNOLOGY

This invention generally relates to polymer compositions, including two-component networks and multiblock copolymers containing polyisobutylene, suitable for use as coatings. More specifically, the present invention relates to the synthesis of various new compositions, including two-component networks and multiblock copolymers containing polyisobutylene, by linking multiple polyisobutylene polymer chains with siloxane compounds containing at least two SiH units suitable for use as coatings . Specifically, bicomponent networks that are synthesized by bonding multifunctional polyisobutylenes, preferably polyisobutylene with allyl terminal groups, multifunctional linear polysiloxanes, such as ditelechate linear polydimethylsiloxane with SiH end groups, can be coated onto the electronic devices by hydrosilylation. Similarly, multiblock copolymers can be synthesized by end-linking of bifunctional polyisobutylene with allyl end groups using bifunctional linear polysiloxanes with SiH end groups, such as polydimethylsiloxanes, by hydrosilylation. And yet other polymer networks containing polyisobutylene can be synthesized by linking multifunctional polyisobutylene, preferably diethylate polyisobutylene with allylic end groups, multifunctional compounds containing SiH units, preferably cyclosiloxanes, such as hexamethylhexahydrocyclosiloxane, as a result of hydrosilylation and coating.

BACKGROUND

With the discovery of live cationic polymerization, the synthesis of polyisobutylene (PIB) with controlled molecular weight and quantitative content of terminal functionality has become possible. Today it is known that polyisobutylene with terminal allyl groups as a result of hydrosilylation can be quantitatively linked at the end groups by molecules containing a SiH unit. This reaction results in the formation of a hydrolytically stable Si — C bond. However, until now, studies regarding the utility of quantifying the terminal functionality in polyisobutylene and the ability of PIBs with terminal allyl groups to form terminal groups with siloxane compounds as a result of hydrosilylation have focused on obtaining star-shaped polymers or star-shaped block copolymers. For example, US Pat. No. 5,663,245 teaches the synthesis and characterization of multibeam star-shaped polymers containing polyisobutylene rays emanating from a strictly defined siloxane core. Star-shaped block copolymers were obtained using block polyisobutylene polystyrene beams extending from a strictly defined siloxane core. Little research has been done (if any) on the usefulness of this synthesis reaction for producing nets, such as two-component nets, or multiblock copolymers.

The polymer nets of the present invention and, in particular, two-component nets (BCN) must be distinguished from the more conventional interpenetrating polymer nets (IPN). BCN is defined as an individual elastomeric network containing two chemically different covalently linked sequences; while IPN consists of two or more than two unrelated independent grids. The distinction made is significant in that the polymers in IPN are not chemically bonded, but instead, two independent networks are intertwined. Most of the two-component systems studied to date are IPN, with very few studies using BCN.

It should be understood that multiblock copolymers are similar to BCN in that they also contain two chemically different covalently linked sequences, but they are not crosslinked by the method in which BCNs are crosslinked. Instead, multiblock copolymers are linear blocks of at least two polymers, such as in the case of the present invention, polyisobutylene (-A-) and any of several bifunctional linear polysiloxanes (-B-), connected at the end groups with each other to form multiblock copolymers (-A-B-) n. That is, these block copolymers are synthesized differently than the “conventional” block copolymers, because the polymers (-A-) and (-B-) are formed before the binding at the end groups occurs. However, they are also not “two-component networks” as defined herein above, since they are not crosslinked and therefore elastomeric in nature and are soluble in various solvents. BCN has traditionally been required that two crosslinked components, at least theoretically, contribute to the physical and chemical characteristics of polymer networks. That is, the properties of a two-component grid will reflect the properties of the individual components. For example, two-component nets containing polyisobutylene and polysiloxane can be of considerable interest in the sense that polyisobutylene is known for its low cost, excellent mechanical properties, extremely low gas permeability and excellent resistance to environmental influences, hydrolysis and high temperature, while in contrast, siloxanes are relatively expensive, have poor mechanical properties, but are superior to others in relative High gas permeability, low surface energy and bi-compatibility.

SUMMARY OF THE INVENTION

The present invention provides a polymer composition of at least two chemically different components covalently bonded to each other, said composition being suitable for use as a coating. The present invention also provides a two-component network or multiblock copolymer with a strictly defined structure, containing multifunctional polyisobutylene and linear polysiloxane, such as polydimethylsiloxane, which are suitable for use as a coating. The present invention also provides a polymer composition that is elastomeric and therefore insoluble in solvents. The present invention further provides a method for synthesizing the bicomponent network mentioned above by end-binding of the bifunctional polyisobutylene to the allyl end groups of the multifunctional SiH end-group polydimethylsiloxane via hydrosilylation. The present invention further provides a method for synthesizing the multiblock copolymer mentioned above by end-linking of bifunctional polyisobutylene with allyl end groups by SiH-terminating bifunctional polydimethylsiloxane with hydrosilylation. The present invention further provides a method for synthesizing the polyisobutylene network mentioned above by end-linking of the dihelechelate polyisobutylene with allyl end groups (or another polyolefin with allyl end groups) by a compound containing SiH units such as hexamethylhexahydrocyclosiloxane and using hydrosilyl the resulting composition as a coating. At least one or more of the above objectives, together with their advantages compared to the prior art relating to polymer networks and multiblock copolymers, which will become apparent from the description that follows, are achieved by using the invention as described hereinafter in this document. In General, the present invention provides a composition containing the product of the hydrosilylation reaction in the form of many multifunctional polyisobutylenes with terminal allyl groups connected by many multifunctional siloxane compounds containing at least two SiH units. The present invention also provides a two-component network containing a hydrosilylation reaction product in the form of a plurality of multifunctional terminal allyl polyisobutylenes linked at the end groups by a plurality of diethylate linear polysiloxanes containing at least two SiH units, the two-component network having such chemical and physical properties which determine both polyisobutylene and polysiloxanes. The present invention further provides a multiblock copolymer containing a hydrosilylation reaction product in the form of a plurality of terminal allyl diethyl chelated polyisobutylenes linked at the end groups by a plurality of diethylated linear polysiloxanes containing up to two SiH units, while the multiblock copolymer has such chemical and physical properties which determine both polyisobutylene and polysiloxanes. And in addition to this, the present invention provides a polymer network containing a hydrosilylation reaction product in the form of a plurality of multifunctional allyl-terminated polyisobutylenes linked by a plurality of multifunctional siloxane compounds containing at least two SiH units. In addition, other objectives and aspects of the present invention can be realized by using a method for synthesizing a polymer network composition comprising binding a plurality of multifunctional polyisobutylenes to terminal allyl groups with a plurality of siloxane compounds containing at least two SiH units, by hydrosilylation, wherein said polymer the mesh is suitable for use as a coating.

The present invention provides a coating comprising a polymer composition which comprises a reaction product between a polyolefin and a siloxane or polysiloxane, wherein said coating is characterized by a low diffusion coefficient for hydrogen sulfide at 50 ° C, or alternatively a low diffusion coefficient for methyl mercaptan at 50 ° C, or low diffusion coefficient for both of them.

DETAILED DESCRIPTION OF THE INVENTION

The present invention primarily relates to the synthesis of polymer compositions, including two-component networks and multiblock copolymers containing multifunctional polyisobutylene and multifunctional compounds containing one or more SiH units. More specifically, the present invention seeks to take advantage of the well-known hydrosilylation reaction when carrying out end-linking between polyisobutylene with allyl end groups and molecules, such as siloxanes containing a SiH unit, in order to obtain new useful polymer compositions containing polyisobutylene or other polyolefins. You must understand that for the purposes of this invention, the term "polymer composition" refers to such compositions that contain two chemically different covalently linked sequences, such as, for example, polyisobutylene and polysiloxane, and includes two-component networks, multiblock copolymers and other related networks, proposed in the present invention.

Bicomponent networks including well-defined polyisobutylenes can be synthesized by end-linking between multifunctional polyisobutylene with allyl end groups and a strictly defined bifunctional linear polysiloxane with SiH end units as a result of hydrosilylation. The BCN data of the present invention are elastomeric and insoluble in solvents and appear to be of significant value to the elastomeric rubber industry.

In the same way, multiblock copolymers containing strictly defined polyisobutylenes and siloxanes can be synthesized by binding at the terminal groups of bifunctional polyisobutylene with terminal allyl groups by a bifunctional linear polysiloxane with SiH terminal units as a result of hydrosilylation. Then, when PIB and PDMS (polydimethylsiloxane) are used, the reaction scheme will result in multiblock PIB / PDMS copolymers as described in the scheme later in this document. In addition, it is also necessary to understand that where in the new composition the amount of polyisobutylene simply overwhelmingly exceeds the number of molecules containing SiH units, a synthesis of new polyisobutylene networks takes place. These polyisobutylene nets contain multifunctional, and preferably diethylate, polyisobutylenes with terminal allyl groups and a siloxane compound containing SiH units. More preferably, the polyisobutylene networks are synthesized by end-linking of the diethyl chelate polyisobutylene having terminal allyl groups by linear or cyclic hydridosiloxanes or hydrosilanes as a result of hydrosilylation. Such linear or cyclic hydridosiloxanes or hydrosilanes are well known in the art.

As a matter of fact, polyisobutylene networks with a strictly defined structure were synthesized by binding at the terminal groups of diethylate polyisobutylene characterized by a known number average molecular weight (Mn) containing SiH units of a cyclosiloxane compound with suitable functionality, namely, hexamethylhexane hydroxy reaction diethate PIB.

It must be understood that diethelic PIB and siloxane components are linked to each other. Accordingly, it is possible that if the siloxane component has sufficient molecular weight and dimensions, the network can form a two-component network. It is possible that the cyclosiloxane component will differ from the low molecular weight cyclic siloxanes (usually volatile), and if the siloxane component acquires sufficient molecular weight and size, then a network-like structure can form that will only swell instead of dissolving in solvents. To synthesize polymer compositions, multitechelate polyisobutylene with terminal allyl groups is initially synthesized, as is known in the art. PIBs with terminal allylic groups can be obtained by performing a "live" polymerization of isobutylene to achieve almost any length (and therefore practically any desired molecular weight), followed by quantitative terminal functionalization with the introduction of a terminal olefin group. Live polymerization of isobutylene can be induced to produce polyisobutylene with terminal chlorine atoms using the 2-chloro-2,4,4-trimethylpentane / TiCl4 initiating system in the presence of N, N-dimethylacetamide as an electron pair donor. A more detailed description of this technique is given in Electron Pair Donors in Carbocationic Polymerization, III. Carbonation Stabilization by External Electron Pair Donors in Isobutylene Polymerization ”Kaszas et al., J. Macromol. Sci., Chem., A26, 1099-1114 (1989). After completion of the polymerization, it is possible to carry out the allylation of “living” polyisobutylenes by neutralizing the active site in situ using an excess of allyltrimethylsilane to obtain PIB with terminal allylic groups. A more detailed description of this technique is provided by Elerctrofilic Substitution of Organosilicon Compounds II., Synthesis of Allyl-terminated Polyisobutylenes by Quantitative Alkylation of tert-Chloro-Polyisobutylenes with Allyltrimethylsilane, Wilczek et al., J. Polym. Sci .: Polym. Chem. 25, 3255-3265 (1987). After that, using H-NMR spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC), one can determine the characteristics of the resulting PIB with terminal allylic groups.

The compositions of the present invention are more fully described in US Pat. No. 6,050,051, thereby specifically incorporated herein by reference.

Siloxane polymers can be prepared independently of polyisobutylene. For example, SiH-terminated bifunctional polydimethylsiloxanes can be synthesized using acid-catalyzed equilibrium for cyclic tetramer D4 in the presence of the corresponding chain terminating agent, tetramethyldisiloxane. After that, you can get the characteristics of polysiloxanes using H-NMR spectroscopy and DSC. Where cyclosiloxane, such as hexahydrohexamethylcyclohexasiloxane, is desired, it can be obtained by hydrolysis of methyldichlorosilane, as is well known in the art and more specifically described in US Pat. No. 3,484,468, the disclosure of which is incorporated herein by reference. As used herein, the term “siloxane” includes monomeric or polymeric siloxane molecules containing one or more reactive units that will condense during the reaction with the olefinic terminal units of the ditelechelate polyolefins. This usually means that the siloxane units will have one or more, preferably two or more than two hydrogen atoms connected to silicon, for example silyl hydrides or hydridosiloxanes, described by the general formula:

M _a M ^H _b D _c D ^H _d T _e T ^H _f Q _g ,

where the various structural elements of the organosilicon compounds - M, D, T and Q - have the usual definitions:

M = R ¹ R ² R ³ SiO _1/2 ;

M ^H = HR ⁴ R ⁵ SiO _1/2 ;

D = R ⁶ R ⁷ SiO _2/2 ;

D ^H = HR ⁸ SiO _2/2 ;

T = R ⁹ SiO _3/2 ;

T ^H = HSiO _3/2 ; and

Q = SiO _4/2 ,

where each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} independently selected from the group consisting of monovalent hydrocarbon radicals with the number of carbon atoms in the range from one to sixty and monovalent organic radicals with the number of carbon atoms in the range from one to sixty, where the subscripts a, b, c, d, e, f and g are equal to zero or positive integers that satisfy the requirement that b + d + f≥1, preferably b + d + f≥2, more preferably b + d + f≥3, and most preferably b + d + f≥4. The phrase "monovalent organic radicals with the number of carbon atoms in the range from one to sixty" means any organic radical in which the carbon-carbon chain is interrupted by a heteroatom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus. As used herein, the term “siloxane” is broadly encompassing and includes functionalized and reactive siloxanes.

Since the dye chelate polyolefins used in the coatings of the present invention are reactive, they can be reacted to form terminal oxirane groups, i.e. terminal epoxy groups, and polymerized or crosslinked using the hydridosiloxanes described above, for example M _a M ^H _b D _c D ^H _d T _e T ^H _f Q _g .

Similarly, terminal olefin groups can be oxidized to form terminal carboxylic acid groups. After that, they can be condensed with silanol-containing molecules, for example, M _a M ^OH _b D _c D ^OH _d T _e T ^OH _f Q _g , where the standard definitions for the structure will be modified as follows:

M = R ¹ R ² R ³ SiO _1/2 ;

M ^OH = HOR ⁴ R ⁵ SiO _1/2 ;

D = R ⁶ R ⁷ SiO _2/2 ;

D ^OH = HOR ⁸ SiO _2/2 ;

T = R ⁹ SiO _3/2 ;

T ^OH = HOSiO _3/2 ; and

Q = SiO _4/2 ,

where each of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ^{9 are} independently selected from the group consisting of hydroxyl, monovalent hydrocarbon radicals with the number of carbon atoms in the range from one to sixty and monovalent organic radicals with the number of carbon atoms in the range from one to sixty, where the subscripts a, b, c, d, e, f and g are zero or positive integers satisfying the requirement that b + d + f≥ 1, preferably b + d + f≥2, more preferably b + d + f≥3, and most preferably b + d + f≥4. The phrase "monovalent organic radicals with the number of carbon atoms in the range from one to sixty" means any organic radical in which the carbon-carbon chain is interrupted by a heteroatom selected from the group consisting of oxygen, sulfur, nitrogen and phosphorus.

The coatings of the present invention can be obtained by reacting a diethyl chelate polyolefin, preferably polyisobutylene, and a suitably crosslinking hydridosiloxane under hydrosilylation conditions. Hydrosilylation is catalyzed using noble metals, preferably platinum, and many suitable compositions of such catalysts have been described. Many types of noble metal catalysts are known for this hydrosilylation reaction, and such catalysts can be used for the reaction in the present case. If optical transparency is required, catalysts that are soluble in the reaction medium are preferred catalysts. As for the noble metal, applicants define Ru, Rh, Pd, Os, Ir and Pt as the noble metals, and also include Ni in the definition of Ni due to its known hydrogenation activity. Preferably, the catalyst is a platinum compound, and the platinum compound can be selected from compounds represented by the formula (PtCl ₂ α-olefin), H (PtCl ₃ α-olefin), as described in US Pat. No. 3,195,601, incorporated herein by reference, or H ₂ PtCl ₆ . The olefin shown in the previous two formulas can refer to almost any type of olefin, but preferably it is alkenylene containing from 2 to 8 carbon atoms, cycloalkenylene containing from 5 to 7 carbon atoms, or styrene. Particular olefins used in the above formulas are ethylene, propylene, various isomers of butylene, octylene, cyclopentene, cyclohexene, cycloheptene and the like.

The next platinum-containing material used in the compositions of the present invention is the cyclopropane complex of platinum chloride described in US patent No. 3159662, incorporated herein by reference.

In addition, the platinum-containing material may be a complex formed from platinum chloride and up to 2 moles per gram of platinum of a representative selected from the class consisting of alcohols, ethers, aldehydes and mixtures of the above compounds, as described in US patent number 3220972, incorporated herein by reference.

Catalysts preferred for use with liquid injection compositions are described in US Pat. Nos. 3,715,334; 3,775,452 and 3,814,730 by Karstedt. Further information regarding the state of the art can be found in JL Spier, “Homogeneous Catalysis of Hydrosilation by Transition Metals, in Advances in Organometallic Chemistry , volume 17, pages 407 through 447, FGA Stone and R. West editors, published by the Academic Press (New York, 1979). Specialists in the relevant field can easily determine the effective amount of platinum catalyst. In general, an effective amount for hydrosilylation is in the range of about 0.1 to 50 ppm of the total organopolysiloxane composition and in all subranges within it.

The diethyl chelate polyolefins used in the coatings of the present invention can alternatively be reacted to form epoxidized terminal olefin groups, and the epoxidized diethyl chelate olefins can be reacted with hydridosiloxanes under acid catalysis to produce crosslinked polymers that can be used as coatings of the present inventions.

In order to obtain a high tensile strength value for the compositions of the present invention, it may be desirable to include a filler in the composition. Examples of many fillers that can be selected are titanium dioxide, lithopone, zinc oxide, zirconium silicate, silica gel, iron oxide, diatomaceous earth, calcium carbonate, colloidal silica, silica treated silica, precipitated silica, fiberglass, magnesium oxide , chromium oxide, zirconia, alumina, alpha quartz, calcined clay, asbestos, carbon, graphite, cork, cotton, synthetic fibers and the like.

Preferred fillers to be used in the composition of the present invention are either colloidal silicon dioxide or precipitated silica, the surface of which has been treated. In one surface treatment method, fumed silica or precipitated silica is exposed to cyclic organopolysiloxanes under conditions of heat supply and pressure. An additional method for treating fillers is one in which silica is exposed to siloxanes or silanes in the presence of an amine derivative.

A particularly preferred method for surface treatment of silica-based fillers is the use of methylsilane and silazane agents for surface treatment. Fillers based on colloidal or precipitated silicas subjected to surface treatment with methylsilanes or silazanes demonstrate the property of easy flowability, and, in addition, they do not increase the low viscosity values of the uncured liquid initial organosilicon composition. After curing, silica treated with silazane gives the cured elastomer an improved tear strength. Silazane treatments are described in US Pat. Nos. 3,635,743 and 3,847,848, incorporated herein by reference.

The filler is generally used with a concentration in the range of from about 5 to about 70 parts, preferably from 15 to 50 parts of the filler for every 100 parts by weight of the resulting crosslinked or net polymer. A preferred filler is colloidal silica treated with silazane, or a mixture of colloidal silica treated with silazane and precipitated silica treated with silazane. This latter mixture is particularly preferred when using a weight ratio between colloidal silica and precipitated silica in the range of from about 25/1 to about 1/1, and preferably from about 10/1 to about 5/1.

To increase the shelf life of a crosslinkable organopolysiloxane composition, it is possible to add a hydroxide-containing organopolysiloxane liquid. When a filler based on precipitated silica treated with silazane is present in the composition, in order to obtain an extended shelf life and provide improved recovery of the product from the mold in combination with a precipitated silica filler, it is possible to add hydroxy-containing organopolysiloxane liquids or resins. A suitable hydroxyl-containing organopolysiloxane liquid has a viscosity in the range of from about 5 to about 100 cP at 25 ° C, and preferably from about 20 to 50 cP. These fluids can be described by the formula

R _j (OH) _k SiO _{(4 - j - k) / 2} ,

where R is a monovalent hydrocarbon radical containing from one to forty carbon atoms, j may be in the range from 0 to about 3, preferably from 0.5 to about 2.0, k is in the range from 0.005 to about 2, and the sum j and k range from about 0.8 to about 3.0. The hydroxy substitution for organopolysiloxane liquid or resin is preferably hydroxy-terminated.

If it is desirable to obtain a cured composition, the two components — prepolymers based on PIB and siloxane — are mixed together in the presence of a noble metal hydrosilylation catalyst, any desired inhibitors, and the composition is cured. Depending on the chosen inhibitor, the composition can be cured by heat.

After the desired PIB and siloxane-based prepolymers have been prepared, allyl-terminated PIB precursor compounds can be crosslinked with well-defined siloxanes containing the desired amount of SiH functionality by hydrosilylation. In this operation, polyisobutylene can be dissolved in toluene (30 wt.%, PIB) and 1-ethynyl-1-cyclohexanol (Aldrich) can be added in order to slow down or suppress hydrosilylation, if necessary. It was found that the use of an inhibitor significantly reduces the amount of shrinkage during curing. In addition, inhibitors can enable the controlled initiation of a reaction between an allyl unit and a hydrosilyl unit, as described in US Pat. Nos. 5,506,289; 5,922,795; 5,928,564; 5,948,339; 6002039; 6015853 and 6034199, in their entirety are incorporated herein by reference. Thereafter, a 500 ppm H ₂ PtCl ₆ catalyst solution was added and the solution was stirred, poured into a Teflon mold, closed with a lid and placed in an oven at approximately 60 ° C for approximately 48 hours and at approximately 90 ° C for approximately 24 hours. After that, mesh patterns can be removed from the oven.

To confirm the effectiveness of hydrosilylation, it is possible to determine the amount of extractable components (sol fraction) after curing. Mesh samples are weighed, extracted (i.e., immersed in toluene, which is drained and replaced with a new one approximately every 8 hours) at room temperature for a period of time from about 48 to about 72 hours and their swelling is removed using a series of toluene / methanol mixtures. The concentration of the toluene / methanol mixture can be changed in increments of 10% approximately every 12-24 hours, starting from a ratio between toluene and methanol of approximately 90 to 10, and ending with 100% methanol. Samples of the nets can then be removed from the solvent and dried in a vacuum oven at approximately 60 ° C until a constant weight is achieved for approximately 3 days. The amount of sol can be obtained from the difference in weight for the mesh samples before and after extraction.

The compositions of the present invention are suitable for use as coatings to create impermeable barriers to vapor or gas that are impermeable to sulfur-containing compounds. Thus, the compositions of the present invention make it possible to use a method for producing a coated product, wherein said coated product is resistant to certain corrosive gases or vapors, for example sulfur-containing gases such as hydrogen sulfide, methyl mercaptan, sulfur dioxide, sulfur trioxide . Such a coating method or method results in a laminate comprising the coatings of the present invention and a substrate, wherein said substrate is a product that is desired to be protected, for example, an electronic device, a printed circuit board or a microcircuit.

Since the coatings of the present invention are particularly resistant or impervious to sulfur-containing gases, they are particularly suitable for protecting electronic device components in automobiles where silver used in electronic circuits of electronic device components will usually be reactive and corrode or corrode.

The word "impenetrable" can have several different meanings that determine the use case. As used herein, the word “impermeable” means the absence of measurable signs of oxide film or corrosion after a two-day exposure period when using 50 ppm (parts per million or parts per million, ppm) sulfur-containing compound, such as hydrogen sulfide or methyl mercaptan, at 50 ° C or higher temperature.

It must be understood that the preceding procedure results in the synthesis of multicomponent polymer compositions containing polyisobutylene. However, other olefins, for example methylpentene, propylene, can be polymerized by a process that results in allyl or olefin end groups. These materials can also be crosslinked by hydrosilylation to obtain polymer compositions that will be similar to those obtained from polyisobutylene. In order to demonstrate the practice of the invention, the following experiments were carried out. The following is only an illustration of the nature of the invention and should not be construed as limiting the scope of the invention. The scope of the invention is set forth in the claims below.

EXPERIMENTAL PART

The method of obtaining membranes or films for testing

Silicone based coating (solvent free)

1. A mold release agent was sprayed onto a clean glass surface.

2. The coating material was poured or dripped using a pipette onto the glass in the form of a line.

3. The coating material line was rolled using a rolling squeegee, for which the desired rolling thickness was set, varying in the range of 10-20 mils.

4. The glass was placed in an oven at 150 ° C for 15 minutes.

5. After that, the glass was removed from the oven and allowed it to cool to room temperature.

6. The cured coating was carefully peeled off the glass and cut into 5 ″ × 5 ″ squares.

PIB-based coating (when used as an ISOPAR solvent, boiling point ~ 100 ° С):

Steps 1, 2, 3 of the methodology were the same as in the above case of coatings on an organosilicon basis:

4. The glass was placed in an oven at 100 ° C for 1 hour.

5. The glass was removed from the oven and allowed to cool to room temperature.

The cured coating was carefully peeled off the glass and cut into 5 '' x 5 '' pieces.

Permeability Test Methodology

The film to be tested was cut into pieces with dimensions corresponding to the permeability test cell. The cell had a lower chamber into which a reference gas sample (H ₂ S or methyl mercaptan in nitrogen) was introduced, and an upper chamber for sampling during testing. As the reference gas sample penetrates through the membrane, passing from the bottom of the cell to the top, it will be trapped by purge gas and taken to the detector for quantitative analysis. The cell had an inlet and an outlet in order to ensure the continuity of the supply of the reference gas sample and the removal of gas taken as a sample at ambient pressures.

Permeability Test Procedure

The test film was cut into pieces with dimensions corresponding to the coating of the lower chamber of the 2-component permeability test cell. The lower chamber had a channel with inlet and outlet openings, so that the reference gas sample freely passed through the chamber without creating backpressure as a result. The reference gas sample was a mixture of 50 ppm H ₂ S or methyl mercaptan in nitrogen.

On the surface of the lower chamber there is a slotted groove. The groove contains an o-ring gasket. When the upper chamber is placed on the lower chamber, a film that covers the lower chamber and overlaps the annular sealing gasket forms a seal. The upper chamber is held in place when using the clamping device.

The upper chamber also has a channel with inlet and outlet openings. Nitrogen is blown through this channel at a flow rate of 45 cubic meters. cm / min As the reference gas sample (H ₂ S or methyl mercaptan) passed through the film, it was blown to the detector by a purge nitrogen stream.

When analyzing for the presence of H ₂ S, the purge gas was passed into an analyzer designed specifically for detecting H ₂ S at low levels. (Jerome-X631-0101 Gold Film Hydrogen Sulfide Analyzer manufactured by Arizona Instrument).

When analyzing the presence of methyl mercaptan, the purge gas was passed into a gas injection device, in which it was introduced into a Gas Chromatogram, including a PID, for quantitative measurements.

There are several ASTM methods that relate to the passage of liquids or gases through impermeable layers, but not specifically for this application. The reference method used was ASTM F739.

The liquid from the circulation bath was pumped through the channels in the cell in order to provide cooling or heating of the cell.

Test conditions

Cell temperature: 50 ° C.

The concentration of the reference gas sample: 50 ppm (vol.).

Total flow: 45 cubic meters. cm / min

Organosilicon membrane - the ability to diffuse transfer of hydrogen sulfide

Cell number 1 14 ± 2 mils thickness Reference gas sample: 50 ppm H ₂ S Temperature: 50 ° C Retention time amount amount (min) (ppm) g / m ² day Start 0 0.00 0.0000 2 0.43 0.0085 38 1,60 0,0315 99 1.70 0,0335 841 1.40 0,0276 901 1.70 0,0335 962 1.30 0,0256 1022 1.20 0,0237 1088 1,50 0,0296 1156 1,50 0,0296 1277 1.70 0,0335 1337 1.80 0,0355 1440 1,60 0,0315

Organosilicon membrane - the ability to diffuse transfer of hydrogen sulfide (continued)

Cell number 2 14 ± 2 mils thickness Reference gas sample: 50 ppm H ₂ S Temperature: 50 ° C Retention time amount amount (min (ppm) g / m ² day 0 0.00 0.0000 5 3.90 0,0769 68 3.70 0,0729 119 3.80 0,0749 871 3.70 0,0729 931 3.30 0.0650 1110 3.20 0.0631 1176 2.60 0,0531 1237 3.60 0,0710 1298 3.60 0,0710 1470 3.60 0,0710

Organosilicon membrane - methyl mercaptan diffusion transfer ability

Cell number 1 14 ± 2 mils thickness Reference gas sample: 50 ppm CH ₃ SH Temperature: 50 ° C Retention time amount amount (min) (ppm) g / m ² day Start 0 0.00 0.0000 one 0.00 0.0000 2 0.02 0,0006 four 0.06 0.0017 8 0.76 0.0210 16 1.30 0,0360 63 1.41 0,0390 124 1.37 0,0379 140 1,53 0.0423 184 1.31 0,0362 199 1.42 0,0393 244 1.33 0,0368 259 1.41 0,0390

Organosilicon membrane - methyl mercaptan diffusion transfer ability (continued)

Cell number 2 14 ± 2 mils thickness Reference gas sample: 50 ppm CH ₃ SH Temperature: 50 ° C Retention time amount amount (min) (ppm) g / m ² day 0 0.00 0.0000 four 0.06 0.0017 12 2.23 0,0617 34 2.65 0,0733 49 2.45 0,0678 94 2.60 0,0719 154 2,52 0,0697 214 2,51 0,0694 229 2.49 0,0689

Polyolefin (polyisobutylene) -siloxane membrane - the ability to diffuse transfer of hydrogen sulfide

Cell number 1 16 ± 2 mils thickness Reference gas sample: 50 ppm H ₂ S Temperature: 50 ° C Retention time amount amount (min) (ppm) g / m ² day 0 0,000 0.0000 60 0.001 0.0000 210 0,000 0.0000 1800 0,000 0.0000 1980 0.002 0.0000 2460 0.003 0.0001 2580 0.003 0.0001 2820 0.004 0.0001 3090 0.005 0.0001 3180 0.006 0.0001 4620 0.013 0,0003 5580 0.014 0,0003 5760 0.014 0,0003

Polyolefin (polyisobutylene) -siloxane membrane - the ability to diffuse transfer of hydrogen sulfide

Cell number 2 16 ± 2 mils thickness Reference gas sample: 50 ppm H ₂ S Temperature: 50 ° C Retention time amount amount (h) (ppm) g / m ² day 0 0,000 0.0000 thirty 0,000 0.0000 180 0,000 0.0000 1500 0,000 0.0000 2010 0.003 0.0001 2490 0.004 0.0001 2610 0.004 0.0001 2880 0.007 0.0001 3120 0.008 0,0002 3210 0.009 0,0002 4650 0.015 0,0003 5610 0.016 0,0003 5760 0.016 0,0003

Polyolefin (polyisobutylene) -siloxane membrane - diffusion transfer capacity of methyl mercaptan

Cell number 1 15 ± 2 mils thickness Reference gas sample: 50 ppm CH ₃ SH Temperature: 50 ° C Retention time amount amount (min) (ppm) g / m ² day 0 0.00 0.0000 60 0.00 0.0000 210 0.00 0.0000 1800 0.00 0.0000 1980 0.00 0.0000 2460 0.00 0.0000 2580 0.00 0.0000 2820 0.00 0.0000 3090 0.00 0.0000 3180 0.00 0.0000 4620 0.00 0.0000 5580 0.00 0.0000 5760 0.00 0.0000

Polyolefin (polyisobutylene) -siloxane membrane - diffusion transfer capacity of methyl mercaptan

Cell number 2 15 ± 2 mils thickness Reference gas sample: 50 ppm CH ₃ SH Temperature: 50 ° C Retention time amount amount (min) (ppm) g / m ² day 0 0.00 0.0000 thirty 0.00 0.0000 180 0.00 0.0000 1500 0.00 0.0000 2010 0.00 0.0000 2490 0.00 0.0000 2610 0.00 0.0000 2880 0.00 0.0000 3120 0.00 0.0000 3210 0.00 0.0000 4650 0.00 0.0000 5610 0.00 0.0000 5760 0.00 0.0000

These results demonstrate that membranes or films having a thickness in the range of about 10 mils to about 30 mils are characterized by transmission rates or diffusion rates of hydrogen sulfide of approximately 0.0003 g of hydrogen sulfide per square meter of membrane per day. These results also suggest that the films have more significant resistance to methyl mercaptan transfer; essentially no amount of methyl mercaptan passed through the membrane during the four-day test period (96 hours). Suitable transfer rates are approximately 0.0010 g or less of hydrogen sulfide per square meter of membrane per day, preferably the rate of approximately 0.0007 g or less of hydrogen sulfide per square meter of membranes per day, more preferably, the transmission rate is approximately 0, 0005 g or less of hydrogen sulfide per square meter of membrane per day, and most preferably, the transmission rate is about 0.0003 g or less of hydrogen sulfide per one square meter of membrane per day at 50 ° C. Suitable transfer rates are approximately 0.0010 g or less methyl mercaptan per square meter of membrane per day, preferably the transmission rate is approximately 0.0007 g or less methyl mercaptan per square meter of membrane per day, more preferably the transmission rate is approximately 0.0005 g either less methyl mercaptan per square meter of membrane per day, and most preferably the transmission rate is about 0.0003 g or less methyl mercaptan per one adratny meter of membrane per day at 50 ° C. Travel speed data can be used either individually or in combination to determine preferred operating parameters.

Claims (12)

1. A coating containing a polymer composition containing a reaction product between:
a) multifunctional polyisobutylene with terminal allyl groups and
b) multifunctional polysiloxane with SiH units,
however, the diffusion rate of gaseous hydrogen sulfide through a membrane containing the composition having a thickness in the range of about 10 to about 30 mils at 50 ° C. is less than about 0.0010 g of hydrogen sulfide per square meter of membrane per day. 2. The coating according to claim 1, where said diffusion rate is less than about 0.0005 g of hydrogen sulfide per square meter of membrane per day. 3. The coating according to claim 1, where said diffusion rate is less than about 0.0003 g of hydrogen sulfide per square meter of membrane per day. 4. A coating containing a polymer composition containing a reaction product between:
a) multifunctional polyisobutylene with terminal allyl groups and
b) multifunctional polysiloxane with SiH units,
wherein the diffusion rate of gaseous methyl mercaptan through a membrane containing said composition having a thickness in the range of about 10 to about 30 mils at 50 ° C. is less than about 0.0010 g of methyl mercaptan per square meter of membrane per day. 5. The coating of claim 4, wherein said diffusion rate is less than about 0.0005 g methyl mercaptan per square meter of membrane per day. 6. A coated product comprising a coating comprising a polymer composition comprising a reaction product between a) multifunctional polyisobutylene with terminal allyl groups and b) multifunctional polysiloxane with SiH units, wherein the diffusion rate of hydrogen sulfide gas through a membrane containing said composition having a thickness in the range of from about 10 to about 30 mils, at 50 ° C is less than about 0.0010 g of hydrogen sulfide per square meter of membrane per day ki. 7. The product according to claim 6, where the said diffusion rate is less than approximately 0.0005 g of hydrogen sulfide per square meter of membrane per day. 8. The product of claim 6, wherein said diffusion rate is less than about 0.0003 g of hydrogen sulfide per square meter of membrane per day. 9. A coated product containing a polymer composition containing a reaction product between a) multifunctional polyisobutylene with terminal allyl groups and b) multifunctional polysiloxane with SiH units, wherein the diffusion rate of gaseous methyl mercaptan through a membrane containing said composition having a thickness in the range from about 10 to about 30 mils, at 50 ° C. is less than about 0.0010 g methyl mercaptan per square meter of membrane per day. 10. The product of claim 9, wherein said diffusion rate is less than about 0.0005 g methyl mercaptan per square meter of membrane per day. 11. A method of protecting the product from the action of hydrogen sulfide, including a) obtaining a coating composition from a polymer composition containing the reaction product between a) multifunctional polyisobutylene with terminal allyl groups and b) multifunctional polysiloxane with SiH units, while the diffusion rate of gaseous hydrogen sulfide through the membrane containing said composition having a thickness in the range of from about 10 to about 30 mils at 50 ° C. is less than about 0.0010 g of sulfur a cost per square meter of membrane per day, and b) applying said coating composition to said article; and c) subsequent curing of said coating composition. 12. A method of protecting the product from the action of methyl mercaptan, comprising a) obtaining a coating composition from a polymer composition containing the reaction product between a) multifunctional polyisobutylene with terminal allyl groups and b) multifunctional polysiloxane with SiH units, while the diffusion rate of gaseous methyl mercaptan through the membrane containing said composition having a thickness in the range of from about 10 to about 30 mils at 50 ° C. is less than about 0.0010 g etilmerkaptana per square meter of membrane per day; b) applying said coating composition to said article; and c) subsequent curing of said coating composition.