JP2024504030A - Systems and methods for storing 1,1-disubstituted alkene compositions - Google Patents

Abstract

Disclosed are methods and systems for storing 1,1-disubstituted alkene compositions using storage containers. The storage container allows the 1,1-disubstituted alkene composition to exhibit a long shelf life and maintain reactivity. [Selection diagram] None

Description

Detailed description of the invention

[Technical field]
The present disclosure generally relates to systems and methods for storing and transporting 1,1-disubstituted alkene compositions.

[Background technology]
In some applications and products, polymerizable monomers are useful ingredients. For example, polymerizable monomers can be used in adhesives, coatings, sealants, moldings, films, articles, composite binders, and numerous other applications. 1,1-disubstituted alkene monomers are particularly suitable polymerizable monomers for such applications and exhibit excellent mechanical, physical and chemical properties. Additionally, 1,1-disubstituted alkene monomers may be readily polymerizable upon contact with various initiators and may exhibit favorable adhesive properties and cure times.

[Summary of the invention]
According to one embodiment, a method of handling a 1,1-disubstituted alkene composition includes providing a storage container and filling the storage container with a 1,1-disubstituted alkene composition. The storage container includes a barrier layer. The barrier layer reduces the water vapor transmission rate of the storage container.

According to another embodiment, a method of handling a 1,1-disubstituted alkene composition includes providing a storage container and filling the storage container with a 1,1-disubstituted alkene composition. The storage container is formed substantially entirely of plastic containing fluorine, nitrile, polyamide, or a composite of polyamides, or formed entirely of high density polyethylene or fluorinated high density polyethylene.

According to another embodiment, the container includes a storage container and a 1,1-disubstituted alkene composition stored in the storage container. The storage container includes a barrier layer. The barrier layer reduces the water vapor transmission rate of the storage container.

FIG. 1 shows a graph showing the amount of water absorbed over time in storage containers formed from various materials. FIG. 2 shows a graph showing the reactivity of DHMM and methylene malonate polyester (respectively) as a function of the amount of water absorbed in storage containers formed from various materials. FIG. 3 shows a graph showing the reactivity of DHMM and methylene malonate polyester (respectively) as a function of the amount of water absorbed in storage containers formed from various materials.

Description of embodiments

As used herein, 1,1-disubstituted alkene monomer refers to a monomer that has two carbonyl groups attached to the carbons on the alkenyl group and a hydrocarbyl group attached to each of the carbonyl groups. In such 1,1-disubstituted alkene monomers, the hydrocarbyl group can be attached directly to the carbonyl group forming a ketone or via an oxygen atom forming an ester.

As can be appreciated, 1,1-disubstituted alkene monomers exhibit several desirable properties in both monomeric and polymerized form. As monomers, 1,1-disubstituted alkene monomers are easily polymerizable and can be provided in optically clear solvent-free compositions. Monomers can be modified for specific applications by modification of the monomer size and structure (e.g., by modification of hydrocarbyl groups), by modification of the functional groups, and by forming monofunctional, difunctional, or polyfunctional monomers. can be adjusted accordingly.

In its polymerized form, 1,1-disubstituted alkene monomers exhibit excellent physical and chemical properties, including solvent and water resistance, and excellent strength and adhesive properties, among many other tunable properties. , and exhibits excellent optical properties.

Generally, 1,1-disubstituted alkene monomers can be polymerized by exposing the monomer to a suitable initiator or energy source. For example, 1,1-disubstituted alkene monomers can be anionically polymerized upon contact with a suitable anionic polymerization initiator or using a suitable free radical source (e.g., an activated thermal or photoinitiator). Can be free radically polymerized.

In order to improve the utility of compositions containing 1,1-disubstituted alkene monomers, it would be useful to provide systems and methods that can store and transport the monomers and extend the shelf life of the monomers. Dew. As can be appreciated, this eliminates the need to synthesize the monomer during or shortly before use, increasing the number of uses and users of 1,1-disubstituted alkene monomers.

In certain embodiments, the systems and methods described herein can improve the shelf life and storage of 1,1-disubstituted alkene compositions through the use of storage containers. The storage containers described herein include 1,1-disubstituted alkene monomers, or any composition containing 1,1-disubstituted alkene monomers alone or with other ingredients (both herein referred to as "1"). , 1-disubstituted alkene compositions) can generally be stored. For example, the storage containers described herein can be used to store and transport substantially pure 1,1-disubstituted alkene monomer, or one or more additional components, such as a deactivated initiator, It may be suitable for storing compositions that further contain stabilizers, fillers, etc. As used herein, substantially pure means about 85% or more, about 90% or more, about 95% or more, or about 99% or more pure.

As can be appreciated, 1,1-disubstituted alkene monomers can vary widely in structure. For example, 1,1-disubstituted alkene monomers can have various hydrocarbyl groups, various substituents or functional groups, and can be monofunctional, difunctional, or polyfunctional.

According to certain embodiments, suitable hydrocarbyl groups include at least straight-chain or branched alkyl groups, straight-chain or branched alkylalkenyl groups, straight-chain or branched alkynyl groups, cycloalkyl groups, alkyl-substituted cycloalkyl groups. , aryl, aralkyl and alkaryl groups. Additionally, suitable hydrocarbyl groups can also contain one or more heteroatoms in the backbone of the hydrocarbyl group.

In certain embodiments, suitable hydrocarbyl groups may also or alternatively be functionalized with substituents. Non-limiting examples of substituents may include one or more of halo, alkoxy, alkylthio, hydroxyl, nitro, cyano, azide, carboxy, acyloxy, and sulfonyl groups. In certain embodiments, substituents may be selected from one or more of halo, alkoxy, alkylthio, and hydroxyl groups. In certain embodiments, substituents may be selected from one or more of halo and alkoxy groups.

In certain embodiments, suitable hydrocarbyl groups can be C _1-20 hydrocarbyl groups. For example, a hydrocarbyl group can be functionalized with an ether group. Suitable ether groups may include, without limitation, ethoxy, propoxy and butoxy groups.

More specific preferred examples of hydrocarbyl groups include, in certain embodiments, C _1-15 straight or branched alkyl groups, C _1-15 straight or branched alkenyl groups, C _5-18 cycloalkyl groups. , C _6-24 alkyl-substituted cycloalkyl groups, C _4-18 aryl groups, C _4-20 aralkyl groups and C _4-20 alkaryl groups. In certain embodiments, the hydrocarbyl group is more preferably a C _1-8 straight or branched alkyl group, a C _5-12 cycloalkyl group, a C _6-12 alkyl-substituted cycloalkyl group, a C _4-18 aryl group. , a C _4-20 aralkyl group or a C _4-20 alkaryl group.

As used herein, alkaryl can include an alkyl group attached to an aryl group. Aralkyl can include an aryl group attached to an alkyl group. Aralkyl can also include alkylene-bridged aryl groups, such as diphenylmethyl or propyl groups. As used herein, aryl can include groups containing multiple aromatic rings. Cycloalkyl can include groups containing one or more rings, including bridged or fused rings. Alkyl-substituted cycloalkyls can include cycloalkyl groups having one or more alkyl groups attached to the cycloalkyl ring.

In certain embodiments, suitable alkyl groups may include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl and ethylhexyl. Similarly, examples of suitable cycloalkyl groups may include cyclohexyl and fenthyl, and examples of suitable alkyl substituents may include menthyl and isobornyl.

According to certain embodiments, suitable hydrocarbyl groups include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, ethylpentyl, hexyl, ethylhexyl, fenthyl, menthyl. and isobornyl groups.

In certain embodiments, illustrative examples of 1,1-disubstituted alkene compounds include methylene malonate compounds, methylene β-ketoester compounds, methylene β-diketone compounds, and any monofunctional, difunctional or Those monomers, oligomers or polymers that are multifunctional may be included. Compositions having one or more of such illustrative example compounds may be used as suitable compositions according to certain embodiments.

As can be appreciated, the 1,1-disubstituted alkene compounds can be monofunctional, difunctional or polyfunctional. As used herein, monofunctional monomer can refer to a monomer having a single addition polymerizable group. A difunctional monomer can refer to a monomer, oligomer, resin or polymer containing two addition polymerizable groups. A polyfunctional compound can refer to any monomer, oligomer, resin or polymer containing three or more addition polymerizable groups. In contrast to monofunctional compounds, difunctional and polyfunctional compounds can undergo additional crosslinking, chain extension, or both when polymerized. As can be appreciated, chain extension and crosslinking can provide enhanced functionality as well as improved durability, strength and longevity compared to monofunctional monomers.

によって示され、式中、各Ｘは、独立して、Ｏまたは直接結合であり得、Ｒ_１およびＲ_２は、同じであっても異なっていてもよく、ヒドロカルビル基をそれぞれ表すことができる。 Illustrative examples of monofunctional 1,1-disubstituted alkene compounds have the general formula I:

where each X can independently be O or a direct bond, and R ₁ and R ₂ can be the same or different and each can represent a hydrocarbyl group.

によって示され得、式中、各Ｘは、独立して、Ｏまたは直接結合であり得；Ｒ_３およびＲ_５は、同じであっても異なっていてもよく、ヒドロカルビル基をそれぞれ表すことができ；Ｒ_４は、ｎ＋１個の官能価を有するヒドロカルビル基であり得；ｎは、１以上の整数である。特定の実施形態では、ｎは３以下であり得；特定の実施形態では、ｎは２以下であり得るか、またはｎは、２～２０、もしくは４～７であり得る。 Illustrative examples of multifunctional monomers having multiple methylene groups linked by multifunctionalized hydrocarbyl groups have the general formula II:

where each X may independently be O or a direct bond; R ₃ and R ₅ may be the same or different and each represent a hydrocarbyl group. ; R ₄ may be a hydrocarbyl group having n+1 functionality; n is an integer greater than or equal to 1; In certain embodiments, n can be 3 or less; in certain embodiments, n can be 2 or less, or n can be 2-20, or 4-7.

Additional examples of multifunctional monomers having multiple methylene groups linked by difunctionalized hydrocarbyl groups (methylene malonate polyesters) have the general formula III:

where each X is an O bond; R ₆ and R ₈ may be the same or different and each represent a hydrocarbyl group; R ₇ is a diol; n is an integer of 1 or more. In certain embodiments, n can be 1 or more; in certain embodiments, n can be 2 or more, or n can be 1-100.

を有するメチレンマロネート化合物が挙げられ得、式中、Ｒ_９およびＲ_１０は、同じであっても異なっていてもよく、ヒドロカルビル基をそれぞれ表すことができる。例えば、メチレンマロネート化合物には、ジエチルメチレンマロネート（「ＤＥＭＭ」）、ジメチルメチレンマロネート（「ＤＭＭＭ」または「Ｄ３Ｍ」）、ヘキシルメチルメチレンマロネート（「ＨＭＭＭ」）、エチルエトキシエチルメチレンマロネート（「ＥＥＯＥＭＭ」）、フェンチルメチルメチレンマロネート（「ＦＭＭＭ」）、ジブチルメチレンマロネート（「ＤＢＭＭ」）、ジヘキシルメチレンマロネート（「ＤＨＭＭ」）、ジシクロヘキシルメチレンマロネート（「ＤＣＨＭＭ」）、ジ－ｎ－プロピルメチレンマロネート、ジ－イソプロピルメチレンマロネートおよびジベンジルメチレンマロネートが含まれ得る。さらに、特定の実施形態では、メチレンマロネート化合物とアセテート、ジアセテート、アルコール、ジオールおよびポリオールとの反応から形成される特定のエステル交換反応生成物を使用して、１，１－二置換アルケンマクロマーを形成することもできる。 According to certain embodiments, more specific examples of 1,1-disubstituted alkene compounds include general formula IV:

Mention may be made of methylene malonate compounds having the formula: wherein R ₉ and R ₁₀ may be the same or different and each represent a hydrocarbyl group. For example, methylene malonate compounds include diethyl methylene malonate ("DEMM"), dimethyl methylene malonate ("DMMM" or "D3M"), hexylmethyl methylene malonate ("HMMM"), ethyl ethoxyethyl methylene malonate (“EEOEMM”), Phentyl Methyl Methylene Malonate (“FMMM”), Dibutyl Methylene Malonate (“DBMM”), Dihexyl Methylene Malonate (“DHMM”), Dicyclohexyl Methylene Malonate (“DCHMM”), Di- N-propyl methylene malonate, di-isopropyl methylene malonate and dibenzyl methylene malonate may be included. Additionally, in certain embodiments, certain transesterification products formed from the reaction of methylene malonate compounds with acetates, diacetates, alcohols, diols, and polyols are used to produce 1,1-disubstituted alkene macromers. can also be formed.

によって表され得、式中、Ｒ_１１およびＲ_１２は、同じであっても異なっていてもよく、ヒドロカルビル基をそれぞれ表すことができる。 According to certain embodiments, examples of methylene beta ketoesters have the general formula V:

where R ₁₁ and R ₁₂ may be the same or different and each represent a hydrocarbyl group.

によって表され得、式中、Ｒ_１３およびＲ_１４は、同じであっても異なっていてもよく、ヒドロカルビル基をそれぞれ表すことができる。 According to certain embodiments, examples of methylene beta diketones have the general formula VI:

In the formula, R ₁₃ and R ₁₄ may be the same or different and each can represent a hydrocarbyl group.

Additional details and methods of preparing suitable 1,1-disubstituted alkene compounds and other suitable compositions are found in U.S. Pat. No. 8,609,885, U.S. Pat. 8,884,051 specification, US Patent No. 9,221,739 specification, US Patent No. 9,512,058 specification, US Patent No. 9,527,795 specification, International Publication No. 2013/ No. 059473, International Publication No. 2013/066629, and International Publication No. 2014/110388.

In certain embodiments, the 1,1-disubstituted alkene compound may also or additionally include a polyester macromer. As can be appreciated, compositions containing polyester macromers can undergo polymerization when exposed to basic initiators. Polyester macromers are disclosed in US Pat. No. 9,617,377 and US Pat. No. 9,745,413, each of which is incorporated herein by reference. Examples of suitable methylene malonate polyesters include transesterification and partial Michael addition products formed from the reaction of diethyl methylene malonate and 1,4-butanediol (hereinafter "methylene malonate polyesters"). It will be done.

As will be appreciated, the systems and methods described herein are capable of producing monomers by, for example, premature polymerization of the monomers or other chemical reactions between the 1,1-disubstituted alkene monomers and the storage vessel or surrounding environment. Long-term storage and transportation of 1,1-disubstituted alkene monomers can be facilitated without premature decomposition.

Generally, the storage containers described herein can be formed from materials that are non-reactive towards 1,1-disubstituted alkene monomers. As used herein, non-reactive means that the storage container material or the 1,1-disubstituted alkene composition does not substantially change either in appearance or weight when placed in contact with each other. It means that.

It has been discovered that the reactivity of plastics toward 1,1-disubstituted alkene monomers varies in part depending on the specific chemical nature of the 1,1-disubstituted alkene monomers. For example, monomers with relatively large hydrocarbyl groups, e.g., dicyclohexyl methylene malonate, which has a bulky ring structure, are more effective for certain plastics than similar methylene malonates with relatively small hydrocarbyl groups, e.g., diethyl methylene malonate. Low reactivity. In certain embodiments, the storage containers described herein can be designed to store and transport only certain 1,1-disubstituted alkene monomers. For example, storage containers for the storage and transportation of dicyclohexylmethylene malonate were not necessarily compatible with other 1,1-disubstituted alkene monomers such as diethylmethylene malonate or dihexylmethylene malonate. However, it can be formed from polypropylene or polymethylpentene.

However, as can be appreciated, it may be useful to construct the storage containers described herein from materials that are non-reactive with substantially all 1,1-disubstituted alkene monomers. Unmodified plastic materials that have been found to be substantially non-reactive towards 1,1-disubstituted alkene monomers include high density polyethylene ("HDPE"), polyethylene terephthalate ("PET") and Polyacrylonitrile (“PAN”) is generally included.

In certain embodiments, the storage containers described herein are alternatively formed from a reactive material, such as a reactive plastic, where the 1,1-disubstituted alkene monomer can be separated from the reactive material. can be done. For example, a storage container formed from polypropylene may be suitable for housing a non-reactive coating that contacts the 1,1-disubstituted alkene monomer.

In certain embodiments, examples of non-reactive coatings suitable for storage containers described herein may include non-reactive plastics, plastics with surface modification properties, and certain metals. For example, a storage container made from a laminated plastic with a 1,1-disubstituted alkene monomer and a PET or PAN layer in contact with another plastic such as polypropylene for strength may be a suitable storage container.

In certain embodiments, halogenation processes can be used to modify the surface of plastics. In certain embodiments, the plastic can be a substantially non-reactive plastic, such as HDPE, while in other embodiments, a reactive plastic can be modified. Modification of non-reactive plastics, such as HDPE, may be used to further improve the shelf life of 1,1-disubstituted alkene monomers, or in more harsh environments, such as temperatures above about 70°C, or high relative humidity (e.g. It may be useful to improve resistance to environments with relative humidity of about 75% or higher).

As can be appreciated, other surface modification treatments are also possible for the storage containers described herein. For example, an acrylamide or metal coating can be formed using known processes (eg, by surface activation followed by covalent bonding, sputtering or evaporation processes, iCVD processes, electroplating processes, etc.). In certain embodiments _, one of sulfur dioxide ( _SO2 ), methanesulfonic acid ("MSA"), trifluoromethanesulfonic acid ("TSA"), hydrochloric acid (HCl), and phosphoric acid ( _H3PO4 ) The above applications can be used to modify plastics. As can be appreciated, such compounds can suppress undesired surface initiation and reduce the amount of anionic polymerization. As can be appreciated, the formation of a non-reactive layer, in addition to improving the shelf life of the 1,1-disubstituted alkene monomer composition contained therein, is beneficial in lowering the cost of the storage container. It can be.

It has further been discovered that moisture, such as moisture present as atmospheric humidity, can impair the shelf life of 1,1-disubstituted alkene monomers. To improve shelf life, the storage containers described herein can include a barrier layer that prevents moisture migration through the storage container.

In certain embodiments, a barrier layer may be formed on one or more surfaces of the storage container. Alternatively, the storage container may be formed in part or in whole from a material that essentially prevents moisture migration. For example, storage containers formed from HDPE can withstand moisture migration without the formation of additional barrier layers. However, as can be appreciated, it may be useful in certain such embodiments for the storage container to include a barrier layer to further extend the shelf life of the 1,1-disubstituted monomer during storage. obtain. In certain embodiments, the barrier layer can be similar or substantially identical to the non-reactive coating. In certain such embodiments, the non-reactive coating can also function as a moisture barrier layer, and the storage container can include only a layer that acts as both a non-reactive coating and a moisture barrier layer.

In certain embodiments, the storage containers described herein contain 1,1-disubstituted alkene monomers that are exposed to harsh conditions (e.g., temperatures of about 50° C. to 70° C. or higher, and relative humidity of about 75% or higher). have a water vapor transmission rate sufficient to ensure that they remain reactive for at least about 60 days, at least about 90 days, or at least about 120 days even when exposed to can. In certain embodiments, the storage container has a storage capacity of about 5.4×10 ⁻³ (g-mm/cm ² /day) or less, such as about 5.7×10 ⁻⁴ (g-mm/cm ² /day). day), about 1×10 ⁻⁴ (g-mm/cm ² /day), about 5×10 ⁻⁵ (g-mm/cm ² /day), or less. In certain embodiments, the storage containers described herein exhibit such water vapor permeability (e.g., HDPE) or contain one or more non-reactive materials to achieve such water vapor permeability. It may be formed substantially entirely of a single material, including layers or moisture barrier layers.

As can be appreciated, it may also be useful to form storage containers that exhibit multiple properties. For example, halogenated layers to prevent swelling by certain 1,1-disubstituted alkene monomers, and/or undesired surface initiation, especially if acid stabilizers are not included in the 1,1-disubstituted alkene monomers. Storage vessels exhibiting a specific water vapor transmission rate are useful to maintain the reactivity of the 1,1-disubstituted alkene monomer while also including acid treatment to suppress the 1,1-disubstituted alkene monomer and/or reduce the amount of anionic polymerization. It can be.

Generally, the storage containers described herein can vary widely in size and shape. For example, the storage container can be sized to store small samples (e.g., about 10 mL to about 50 mL) or for long-term storage and bulk use (e.g., about 1 L to about 5 L or even more, e.g., It can be even larger for 1 cubic meter (1 m ³ ) or more). As can be appreciated, shelf life may vary depending on the size of the storage container, with larger sizes generally resulting in larger volume to surface area ratios.

As can be appreciated, the storage containers described herein may differ from previous storage containers known to store 1,1-disubstituted alkene compounds. For example, known storage vessels are often intended for use during the production of 1,1-disubstituted alkene compounds and for extended periods of time such as those contemplated by the storage vessels described herein. It was not intended to store monomer. Additionally, such previously known containers are often formed from laboratory glassware (e.g., borosilicate glass) or treated steel, and are also designed to be repeatedly sealed and transported. Not even designed. Other known storage containers include containers for cyanoacrylates. Such containers have not been evaluated and may not be suitable for 1,1-disubstituted alkene compositions, such as swelling of the storage container when filled with 1,1-disubstituted alkene compositions. or may impair the quality of the 1,1-disubstituted alkene composition due to changes in the viscosity of the composition due to premature polymerization or gelation.

The storage containers described herein may be formed generally as known in the art. For example, in certain embodiments, suitable storage containers may be formed by an injection molding process. In embodiments that include a non-reactive layer, the non-reactive layer may be formed after general molding and formation of the storage container.

In certain embodiments, a storage container may be filled by decanting the 1,1-disubstituted alkene composition into the storage container and then sealing the storage container. In certain embodiments, the storage container is filled under a dry atmosphere, e.g., an atmosphere having a relative humidity of about 50% or less, about 20% or less, about 10% or less, about 5% or less, or about 1% or less. obtain. By filling the storage container under a dry atmosphere, shelf life can be improved by minimizing hydrolysis of the 1,1-disubstituted alkene monomer.

Generally, the storage containers described herein may be sealed in any suitable manner. For example, small sample vials can be sealed by molding the storage container to a sealed end with heat and pressure. To open such small sample vials, the sealed end can be cut or punctured.

In certain embodiments, the storage container can include a disposable seal. The inclusion of a disposable seal allows the end user to know that the 1,1-disubstituted alkene monomer is not unnecessarily exposed to atmosphere or humidity. A sealing top can be placed over the disposable seal. As can be appreciated, in such embodiments the sealing top may be reactive to the 1,1-disubstituted alkene monomer since the disposable seal acts as a barrier.

In certain embodiments, the storage container can include a sealing top, such as a screw top. In such embodiments, the storage container lid may be formed from a non-reactive material or may include a non-reactive coating as previously described herein. As can be appreciated, such a storage container allows for long-term storage of the 1,1-disubstituted alkene monomer and can allow for multiple withdrawals of the monomer or composition.

As can be appreciated, the storage containers described herein can be modified in a variety of ways. For example, the storage container may be shaped and/or include additional packaging to facilitate handling and transportation in certain embodiments. For example, in certain embodiments, the storage container can include a handle.

In certain embodiments, the storage container can include thermal insulation. The insulation can enable the storage container to maintain a stable temperature when exposed to either high or low temperatures, such as those found during transportation. In certain embodiments, indicia can be included to identify the particular composition contained within the container, tare weight, or to enable direct storage or shipping of the storage container. For example, in certain embodiments, storage containers may comply with commercial and governmental regulations such that they can be shipped and transported directly by mail, courier, and freight services.

In certain embodiments, the storage container can be optically transparent to allow a user to visually assess the amount of composition contained therein. In other alternative embodiments, the storage container may be visually opaque to improve shelf life, such as in embodiments where a photoinitiator is present.

Generally, the methods and systems described herein can be used to improve the shelf life of 1,1-disubstituted alkene compositions. For example, in certain embodiments, systems and methods provide systems and methods that provide a 1,1-disubstituted alkene composition for about 3 months or more, about 6 It may be possible to have a shelf life of months or more, about 9 months or more, or even 12 months or more.

As can be appreciated, the systems and methods described herein can also be used to store compositions formed from 1,1-disubstituted alkene monomers and other ingredients. For example, in certain embodiments, the systems and methods described herein can be used to extend the shelf life of compositions that further include one or more additives. For example, the systems and methods may include, for example, one or more dyes, pigments, toughening agents, impact modifiers, rheology modifiers, plasticizers, natural or synthetic rubbers, fillers, reinforcing agents, thickeners, It may be used to store compositions further comprising opacifiers, inhibitors, fluorescent markers, thermal degradation reducers, heat resistance imparting agents, surfactants, wetting agents, conductivity synergists or stabilizers. For example, thickeners and plasticizers such as vinyl chloride terpolymer and dimethyl sebacate, respectively, can be used to modify the viscosity, elasticity, and robustness of the system. Additives can additionally or alternatively provide mechanical reinforcement to the polymerization system. Inclusion of such additives may be useful in providing a ready-to-use product or intermediate to the end user.

In certain embodiments, the systems and methods described herein can alternatively or additionally store a plurality of 1,1-disubstituted alkene monomers. For example, the systems and methods may be useful for compositions that include blends of multiple 1,1-disubstituted alkene monomers. Storage of blends of 1,1-disubstituted alkene monomers can provide additional benefits, such as in applications requiring blends of properties not possible when only a single 1,1-disubstituted alkene monomer is included. It can be used easily. Generally, in such embodiments, the systems and methods (eg, storage containers) may be compatible with each of the 1,1-disubstituted alkene monomers included in the blend. For example, a storage container for storing a blend of monomers comprising DEMM and DCHMM can be a storage container that can store either DEMM or DCHMM individually. However, as can be appreciated, certain compositions may exhibit combinatorial and/or synergistic effects and may be stored in storage containers in which each of the components cannot be stored individually. For example, a blend containing a large amount of DCHMM and a small amount of DEMM may be stored in a container that cannot store DEMM alone.

According to certain embodiments, the systems, methods and containers described herein can also include additional stabilizers to extend and improve the shelf life of the composition. One or more anionic polymerization inhibitors, for example, as a stabilizer package as disclosed in U.S. Pat. No. 8,609,885 and U.S. Pat. No. 8,884,051, each of which is incorporated by reference. , for example, liquid phase stabilizers (e.g., methanesulfonic acid ("MSA")), gas phase stabilizers (e.g., trifluoroacetic acid ("TFA")), or free radical stabilizers (e.g., 4-methoxyphenol, or monomethyl ether of hydroquinone ("MeHQ")), or dibutylhydroxytoluene ("BHT"). Additional free radical polymerization inhibitors are disclosed in US Pat. No. 6,458,956, incorporated herein by reference. Anionic polymerization stabilizers are generally electrophilic compounds that capture electrons from the composition or growing polymer chain. Anionic polymerization stabilizers can be used to terminate the propagation of additional polymer chains. Generally, only minimal amounts of stabilizer are required, and in certain embodiments, only about 1000 parts per million ("ppm") or less may be included. Certain embodiments may include a blend of multiple stabilizers, such as a blend of about 10 ppm MSA and 100 ppm MeHQ.

In certain embodiments, additional stabilizers can include antioxidants and acids. For example, between about 10 ppm and about 1% by weight of the 1,1-disubstituted alkene composition of a suitable antioxidant can be included in the 1,1-disubstituted alkene composition. In certain embodiments, suitable antioxidants may include hindered phenol derivatives and nitrogen-free thiol compounds. In certain embodiments, the hindered phenol derivative can be a primary antioxidant and the thiol compound can be a secondary antioxidant. In certain embodiments, suitable acids may include acids with an H ₀ of about 3 or less. In such embodiments, the acid may be included at a concentration between about 5 ppm or more and about 1% or less by weight of the 1,1-disubstituted alkene composition.

[Example]
Table 1 shows the results of evaluating the compatibility of various plastic materials with methylene malonate monomer. Compatibility was determined by immersing example test specimens formed from plastic sample containers in methylene malonate monomer and evaluating the change in sample weight. Each of the test pieces in the example had a width of 15 mm and a length of 60 mm. The specimens of each example were completely immersed in glass screw vials containing diethyl methylene malonate ("DEMM"), dihexyl methylene malonate ("DHMM") and dicyclohexyl methylene malonate ("DCHMM"). The sample vial was passivated with a solution of methanesulfonic acid ("MSA") in tetrahydrofuran ("THF"). The methylene malonate monomer included 2,000 parts per million ("ppm") of butylated hydroxytoluene ("BHT") stabilizer. Table 1 shows the stability results of the test pieces of the examples after being held at 70° C. for 4 days, 5 days, and 8 days. The plastics evaluated included high-density polyethylene (“HDPE”), fluorinated high-density polyethylene (“F-HDPE”), polypropylene (“PP”), polymethylpentene (“PMP”), and polystyrene (“PS”). , polycarbonate ("PC"), polyacrylonitrile ("PAN") and polyethylene terephthalate ("PET").

As shown in Table 1, Examples 2, 7 and 8, formed from fluorinated high density polyethylene, polyacrylonitrile and polyethylene terephthalate, respectively, demonstrated compatibility with each of the methylene malonate monomers. Examples 1, 3 and 4 (high density polyethylene, polypropylene and polymethylpentene) were not compatible with diethylmethylene malonate or dihexylmethylene malonate due to swelling, but showed compatibility with dicyclohexylmethylene malonate. Ta. Examples 5 and 6 (polystyrene and polycarbonate) were not compatible with any of the methylene malonate monomers because they either dissolved the specimen (polystyrene) or turned the surface of the specimen (polycarbonate) white.

HDPE containers were further evaluated by extending the test limits to 21 days and evaluating at 50°C and 70°C. The HDPE containers showed no visual change in appearance or weight after 21 days, suggesting that these materials are non-reactive and compatible with 1,1-disubstituted alkene monomers at temperatures below 50°C. It was done. At a temperature of 70° C., HDPE showed swelling, while F-HDPE showed better compatibility with 1,1-disubstituted alkene compositions.

In addition to the F-HDPE examples shown in Table 1, high density polyethylene surface coatings were further evaluated by modifying the inner surface of the HDPE sample container with a vapor deposited polyamide coating. The polyamide coated container was then filled with each of diethyl methylene malonate ("DEMM"), dihexyl methylene malonate ("DHMM") and dicyclohexyl methylene malonate ("DCHMM").

Sample vials with surface coatings showed no change in appearance or weight after evaluation at 50° C. and 70° C., suggesting the effectiveness of both the fluorinated surface and the polyamide coating as non-reactive coatings.

Table 2 shows the results of evaluating the moisture barrier of several examples to improve the shelf life of storage containers. Specifically, Table 2 shows that 50% of DHMM was added to a storage vessel formed from fluorinated high-density polyethylene (“F-HDPE”) and Unified Numbering System (“UNS”) S30400 austenitic stainless steel (SUS304 in Japan). Evaluate the impact of filling at °C. Example storage containers were filled, stored, opened, and reclosed under various relative humidity ("RH") conditions. Anion by counting the number of minutes it takes for 1 g of DHMM to harden and become non-flowing after mixing with 50 mg of 1 wt% ethyl 1-methyl-3-piperidine carboxylate in bis(2-ethylhexyl adipate) solvent. Polymerization reactivity was measured weekly.

Storage of DHMM under dry conditions at less than 1% relative humidity had no substantial effect on monomer reactivity, as shown by Examples 9 and 11. Under high humidity conditions (Examples 10 and 12), stainless steel performed better than F-HDPE in preventing hydrolysis reactions.

Additional testing of HDPE, PET, Baritainer® and aluminum storage containers was conducted over extended periods using a desiccant (anhydrous calcium chloride) to better understand water vapor transmission rates according to ASTM (D7709-12). went. These containers were used to evaluate changes in reactivity of dihexyl methylene malonate and methylene malonate polyester over time. Baritainer® is a multilayer plastic material known for its excellent oxygen barrier properties and includes HDPE and nylon layers. HDPE was purchased from Nalgene. The storage container was sealed in a dry air atmosphere using a torque according to ASTM standards (D7709) and stored in an oven set at 50° C. and 75% relative humidity. Table 3 shows the volumes of storage vessels evaluated and the volumes of samples used to evaluate water vapor transmission rates and reactivity.

The desiccant was weighed after the first day and every 7 days thereafter for 30 days to determine the water vapor transmission rate. Three replicates were performed for each storage container and the average weight was calculated to ensure statistical significance of the data. The results are shown in Table 4 and plotted in Figure 1. Daily water transfer (g/day) was determined by calculating the slope of the trend line using the least squares method. The calculated values are shown in Table 4.

Based on the results in Table 4 and using the surface area and thickness of each storage container evaluated, the following equation 1:
[Number 1]
WVTR (g-mm/cm ² /day) = water movement per day (g/day) x wall thickness (mm) / surface area (cm ² )
was used to generate water vapor transmission rate (“WVTR”).

The calculated WVTR is shown in Table 5. PET had a higher WVTR than either HDPE or Baritainer®. Since the WVTR should be immeasurably small in an aluminum container, it is theorized that the small amount of water absorbed by this container migrated through the plastic sealing top.

To determine the effect of storage container on anionic reactivity, three or four replicates were performed and stored for evaluation at 50°C and 75% relative humidity for 3 or 4 days and then for 7 days. , eliminating the need to open and then reseal the same container. Every 7 days, one container was removed for analysis and observation. For each observation, the storage vessel was emptied and an initiator was used to assess the anionic reactivity of the monomer.

Anionic reactivity testing of DHMM was performed by filling a 4 mL PP vial with 1 g of DHMM sample from the evaluated storage container and placing a magnetic stirring bar in the vial. While mixing using a stir bar at a speed of 500 revolutions per minute ("rpm"), add 0.025% 1,4-diazabicyclo[2.2.2]octane ("DABCO") solution in DEGDEE. The temperature of the reaction mixture was measured when 5 g had been deposited into the reaction mixture. A timer was started the moment the DABCO solution was added and continued until the observed temperature increase of the mixture exceeded 0.1° C./sec for 2 consecutive seconds. The measured time was recorded as an index of DHMM reactivity. Anionic reactivity testing of methylene malonate polyester was performed by adding 1 g of methylene malonate polyester sample from the evaluated storage container and 0.5 g of diethylene glycol diethyl ether ("DEGDEE") to a 4 mL polypropylene ("PP") vial. This was done by filling the vial with a stirring bar. The temperature of the reaction mixture was measured when 0.5 g of a 1% dimethylbenzylamine ("DMBA") solution in DEGDEE was deposited in the center of the reaction mixture while mixing using a stir bar at a speed of 500 rpm. A timer was started the moment the DMBA solution was added and continued until the observed temperature increase of the mixture exceeded 0.1° C./sec for 2 consecutive seconds. The time measured was recorded as an indicator of the reactivity of the methylene malonate polyester. The reactivity of the DHMM in each storage container over time is shown in Table 6, and the change in reactivity of the methylene malonate polyester is shown in Table 7.

As shown in Tables 6 and 7, substantial differences in reactivity changes were observed for the samples after storage in storage containers. Aluminum containers showed the least loss of reactivity over time, followed by HDPE, Baritainer®, and PET. The DHMM samples contained in PET containers did not react until day 21 and could not be cured by reactivity testing. These results provide evidence that as WVTR increases, a loss of reactivity occurs.

However, in contrast to the change in reactivity, the viscosity of DHMM did not change even within the PET container. The viscosity of the DHMM was 6.9 cP and 6.7 cP on the first day of the test (day 0) and on the day of the end of the test (day 21), respectively. This is a characteristic result of 1,1-disubstituted alkenes such as methylene malonate, and is different from other known anionically polymerizable compounds. As can be appreciated, most anionically polymerizable compounds, such as cyanoacrylates and isocyanates, rather exhibit a change in viscosity upon contact with water, as explained in US Patent No. 2003/0039781; Or it shows gelation due to early polymerization.

The amount of water absorbed (g) in the container when conducting the anionic reactivity test can be determined by the following formula: "Amount of water transferred per day (g/day) in Table 4" x "When performing the reactivity test Number of days visited (days).” The molar ratio of absorbed water to methylene malonate was used to determine the extent of loss of anionic polymerization reactivity due to hydrolysis. The correlation between water absorption/methylene malonate amount (g/g) and increase in DHMM reactivity time (seconds) is shown in FIG. 2 and Table 8, and for methylene malonate polyester is shown in FIG. 3 and Table 9.

By defining the tolerance limit for the increase in reaction time, the permissible amount of water/amount of methylene malonate (g/g) absorbed into the container during storage can be determined. According to FIG. 2, the relationship between the reactivity time (y, seconds) and the amount of water absorbed in the container/the amount of methylene malonate (x, g/g) can be determined by performing polynomial regression in the case of DHMM. It was determined as =60000000x ² +397944x+220 (Formula 1). A similar formula for methylene malonate polyester can be expressed as y=40000000x ² +17730x+109 (Equation 2) according to FIG.

This allowable amount of water/methylene malonate (W g/g) as well as the amount of methylene malonate filled in the container (M g), the wall thickness of the container (T mm), the surface area of the container (A cm ² ), and based on the required storage period (S days), equation 2:
[Number 2]
WVTR (g-mm/cm ² /day) = W (g/g) × M (g) × T (mm) / A (cm ² ) / S (day)
can be used to determine the acceptable WVTR (g-mm/cm ² /day).

As can be appreciated, increasing the curing time by more than 5 times is not acceptable for most applications. For example, coatings or molded articles made on the production line using 1,1-disubstituted alkenes will suffer from various problems if cure time is increased without compensating for changes in reactivity. Small differences in cure time can be compensated for by changing the line speed or by adding additional initiator to increase reaction rate and decrease cure time. However, excess initiator is required to compensate for the 5-fold increased reaction rate, and such amounts can adversely affect the quality of the coating film or molded article by causing yellowing or weathering problems. affect According to Equation 1, when 0.00095 (g/g) of water is absorbed per amount of DHMM in the container, the curing time of DHMM increases five times from 130 seconds to 650 seconds. According to Equation 2, when 0.0025 (g/g) of water is absorbed per amount of methylene malonate polyester in the container, the reactivity of methylene malonate polyester doubles from 80 seconds to 400 seconds. . Therefore, to avoid increasing the time to cure methylene malonate monomer or polyester by five times, the allowable water absorption/amount of methylene malonate in the container (W) should be reduced to 0.00095 (g/g). Can be set to . As can be appreciated, in some special applications it is not acceptable to more than double the reaction rate. According to Equation 1, when 0.000099 (g/g) of water is absorbed per amount of DHMM in the container, the reactivity of DHMM doubles from 130 seconds to 260 seconds. According to Equation 2, when 0.00093 (g/g) of water is absorbed per amount of methylene malonate polyester in the container, the reactivity of methylene malonate polyester doubles from 80 seconds to 160 seconds. . Therefore, in order to avoid doubling the reaction rate, the allowable amount of water absorption/amount of methylene malonate (W) in the container can be set to 0.000099 (g/g).

One of the most practical containers for shipping and storing reactive monomers such as methylene malonate is a plastic tote. The volume of a plastic tote is 1 m ³ and the entire volume of the plastic tote is usually filled with material. Considering that the density of DHMM is 1.03, the amount of methylene malonate (M) filled in the tote is assumed to be 1.03 x 10 ⁶ g. The wall thickness (T) of the tote is typically about 30 mm and the surface area (A) of the tote is 100 x 100 x 6 = 6 x 10 ⁴ cm ² . Water transfer rate can be measured according to ASTM (D7709-12) for given atmospheric conditions (temperature and relative humidity). For example, 50° C. and 75% RH may represent harsh conditions representing the hot and humid climate region that the 1,1-disubstituted alkene monomer may need to endure within the storage container. Assuming that the required shelf life (S) is 90 days for most applications, the acceptable WVTR (g-mm /cm ² /day) is 0.00095 (g/g) x 1.03 x 10 ⁶ (g) x 30 (mm)/6 x 10 ⁴ (cm ² )/90 (day) = 5.4 x 10 ⁻³ (g-mm/cm ² /day). Similarly, to avoid doubling the time to cure methylene malonate monomer or polyester, the acceptable WVTR (g-mm/cm ² /day) is 0.000099 (g/g) x Calculate as 1.03×10 ⁶ (g)×30 (mm)/6×10 ⁴ (cm ² )/90 (day) = 5.7×10 ⁻⁴ (g-mm/cm ² /day) Can be done.

[Exemplary Embodiment]
A1. providing a storage container with a barrier layer, the barrier layer reducing water vapor transmission rate of the storage container;
filling a storage container with a 1,1-disubstituted alkene composition;
A method of handling a 1,1-disubstituted alkene composition comprising:
A2. The 1,1-disubstituted alkene composition includes methylene malonate, methylene β-ketoester, methylene β-diketone, monofunctional, difunctional or polyfunctional monomers, oligomers or polymers thereof, and combinations thereof. A method according to term A1, comprising one or more of:
A3. The method according to paragraph A2, wherein the 1,1-disubstituted alkene composition comprises a dialkyl methylene malonate or methylene malonate polyester.
A4. A method according to any preceding paragraph, wherein the dialkyl methylene malonate comprises dihexyl methylene malonate.
A5. A method according to any preceding paragraph, wherein the barrier layer is formed from a material that is compatible with the 1,1-disubstituted alkene composition.
A6. The material compatible with the 1,1-disubstituted alkene composition comprises one or more of high density polyethylene, nitrile, polyamide, or a composite of polyamide, polyethylene terephthalate, polytetrafluoroethylene or metal. Method according to A5.
A7. The method according to paragraph A5 or paragraph A6, wherein the material comprises high density polyethylene.
A8. A method according to paragraph A7, wherein the material is modified by a halogenation process.
A9. The method according to paragraph A8, wherein the halogenation process comprises a fluorination process.
A10. The method according to paragraph A5, wherein the material comprises stainless steel or aluminum.
A11. The method according to any of paragraphs A5 to A10, wherein the barrier layer is an inner layer.
A12. The method according to any of Items A5 to A10, wherein the barrier layer is a surface layer.
A13. _The barrier layer comprises one or more of sulfur dioxide ( _SO2 ), methanesulfonic acid ("MSA"), trifluoromethanesulfonic acid ("TSA"), hydrochloric acid (HCl) and phosphoric acid ( _H3PO4 ). A method according to any previous section formed by application.
A14. A method according to any preceding paragraph, wherein the storage container exhibits a water vapor transmission rate of less than or equal to about 0.0054 g/cm ² /mm/day at a temperature of about 50° C. and a relative humidity of about 75%.
A15. A method according to any preceding paragraph, wherein the storage container exhibits a water vapor transmission rate of less than or equal to about 0.00057 g/cm ² /mm/day at a temperature of about 50° C. and a relative humidity of about 75%.
A16. A method according to any preceding paragraph, wherein the 1,1-disubstituted alkene composition exhibits a shelf life of about 3 months or more when the storage container is maintained at a temperature of about 50° C. and a relative humidity of about 75%. .
A17. The method according to paragraph A16, wherein the 1,1-disubstituted alkene composition substantially maintains one or more of viscosity and reactivity during shelf life.
A18. A method according to any preceding paragraph, wherein the 1,1-disubstituted alkene composition is charged at a relative humidity of about 50% or less.
A19. A method according to any preceding paragraph, wherein the 1,1-disubstituted alkene composition is charged at a relative humidity of about 10% or less.
A20. A method according to any preceding paragraph, wherein the 1,1-disubstituted alkene composition further comprises one or more antioxidants and acids.
A21. The method according to paragraph A20, wherein the one or more antioxidants comprise a primary antioxidant, and the 1,1-disubstituted alkene composition comprises between about 10 ppm or more and less than 1% by weight of the primary antioxidant.
A22. The method according to paragraph A21, wherein the primary antioxidant comprises a hindered phenol derivative.
A23. Item A20, wherein the one or more antioxidants further comprise a secondary antioxidant, and the 1,1-disubstituted alkene composition comprises between about 10 ppm or more and less than 1% by weight of the secondary antioxidant. -A method according to any of A22.
A24. The method according to item A23, wherein the secondary antioxidant contains a thiol and is substantially free of nitrogen.
A25. A method according to any of paragraphs A20-A24, wherein the 1,1-disubstituted alkene composition comprises between about 5 ppm or more and less than 1% by weight of acid.
A26. The method according to paragraph A25, wherein the acid has a H ₀ of about 3 or less.
A27. Any 1,1-disubstituted alkene composition comprises one or more of methanesulfonic acid ("MSA"), monomethyl ether of hydroquinone ("MeHQ"), and dibutylhydroxytoluene ("BHT") Method according to the previous section.
A28. Handling methods according to any preceding paragraph, including storage and shipping.
A29. A method according to any preceding paragraph, wherein the handling is carried out at a temperature of about 50°C or less.
A30. A method according to any preceding paragraph, wherein the storage container is substantially opaque to ultraviolet light.
A31. _The barrier layer contains one or more of sulfur dioxide ( _SO2 ), methanesulfonic acid ("MSA"), trifluoromethanesulfonic acid ("TSA"), hydrochloric acid (HCl), and phosphoric acid ( _H3PO4 ). The method according to any previous section applied.

B1. a storage container comprising a barrier layer, the barrier layer reducing water vapor transmission rate of the storage container;
a 1,1-disubstituted alkene composition stored in a storage container;
Container containing.
B2. The 1,1-disubstituted alkene composition includes methylene malonate, methylene β-ketoester, methylene β-diketone, monofunctional, difunctional or polyfunctional monomers, oligomers or polymers thereof, and combinations thereof. Containers according to term B1, containing one or more of:
B3. A container according to paragraph B2, wherein the 1,1-disubstituted alkene composition comprises a dialkyl methylene malonate or methylene malonate polyester.
B4. A container according to any preceding paragraph, wherein the dialkyl methylene malonate comprises dihexyl methylene malonate.
B5. A container according to any preceding clause, wherein the barrier layer is formed from a material that is compatible with the 1,1-disubstituted alkene composition.
B6. The material compatible with the 1,1-disubstituted alkene composition comprises one or more of high density polyethylene, nitrile, polyamide, or a composite of polyamide, polyethylene terephthalate, polytetrafluoroethylene or metal. Container according to B5.
B7. A container according to paragraph B5 or paragraph B6, wherein the material comprises high density polyethylene.
B8. Container according to item B7, in which the surface of the material has been modified by a halogenation process.
B9. Container according to paragraph B8, wherein the halogenation process comprises a fluorination process.
B10. Container according to item B5, wherein the material comprises stainless steel or aluminum.
B11. A container according to any of clauses B5 to B10, wherein the barrier layer is an inner layer.
B12. The container according to any of items B5 to B10, wherein the barrier layer is a surface layer.
B13. _The barrier layer comprises one or more of sulfur dioxide ( _SO2 ), methanesulfonic acid ("MSA"), trifluoromethanesulfonic acid ("TSA"), hydrochloric acid (HCl) and phosphoric acid ( _H3PO4 ). A container according to any preceding paragraph formed by application.
B14. A container according to any of the preceding clauses, wherein the storage container exhibits a water vapor transmission rate of about 0.0054 g/cm ² /mm/day or less at a temperature of about 50° C. and a relative humidity of about 75%.
B15. A container according to any of the preceding clauses, wherein the storage container exhibits a water vapor transmission rate of less than or equal to about 0.00057 g/cm ² /mm/day at a temperature of about 50° C. and a relative humidity of about 75%.
B16. A container according to any preceding paragraph, wherein the 1,1-disubstituted alkene composition exhibits a shelf life of about 3 months or more when the storage container is maintained at a temperature of about 50° C. and a relative humidity of about 75%. .
B17. A container according to paragraph B16, wherein the 1,1-disubstituted alkene composition substantially maintains one or more of viscosity and reactivity during its shelf life.
B18. A container according to any preceding paragraph, wherein the 1,1-disubstituted alkene composition is filled at a relative humidity of about 50% or less.
B19. A container according to any preceding paragraph, wherein the 1,1-disubstituted alkene composition is filled at a relative humidity of about 10% or less.
B20. A container according to any preceding paragraph, wherein the 1,1-disubstituted alkene composition further comprises one or more antioxidants and acids.
B21. The container according to paragraph B20, wherein the one or more antioxidants include a primary antioxidant, and the 1,1-disubstituted alkene composition includes between about 10 ppm or more and less than 1% by weight of the primary antioxidant.
B22. The container according to paragraph B21, wherein the primary antioxidant comprises a hindered phenol derivative.
B23. Item B20, wherein the one or more antioxidants further include a secondary antioxidant, and the 1,1-disubstituted alkene composition comprises between about 10 ppm or more and less than 1% by weight of the secondary antioxidant. ~A container according to any of B22.
B24. The container according to item B23, wherein the secondary antioxidant comprises a thiol and is substantially free of nitrogen.
B25. A container according to any of paragraphs B20-B24, wherein the 1,1-disubstituted alkene composition comprises between about 5 ppm or more and less than 1% by weight of acid.
B26. A container according to paragraph B25, wherein the acid has a H ₀ of about 3 or less.
B27. Any 1,1-disubstituted alkene composition comprises one or more of methanesulfonic acid ("MSA"), monomethyl ether of hydroquinone ("MeHQ"), and dibutylhydroxytoluene ("BHT") Containers according to the previous paragraph.
B28. Containers according to any of the preceding paragraphs, whose handling includes storage and shipping.
B29. A container according to any of the preceding clauses, wherein the handling is carried out at a temperature of about 50°C or less.
B30. A container according to any preceding clause, wherein the storage container is substantially opaque to ultraviolet light.
B31. A container according to any of the preceding clauses, wherein the storage container is formed entirely of said material.
B32. A container according to any preceding clause, wherein the storage container is sealed by a disposable seal.
B33. Container according to any preceding paragraph, wherein the storage container is sealed by a screw cap.
B34. A container according to any preceding clause, wherein the storage container is filled with dry air having a relative humidity of about 50% or less, about 20% or less, about 10% or less, about 5% or less, or about 1% or less.
B35. Diluting dry air having a relative humidity of about 50% or less, about 20% or less, about 10% or less, about 5% or less, or about 1% or less with an inert gas selected from nitrogen gas, helium gas, and argon gas A container according to any preceding paragraph, wherein the storage container is filled with a gas having an oxygen concentration of 5 to 21%, obtained by
B36. A container according to any preceding clause, wherein the storage container has a gas or liquid inlet and a gas or liquid outlet.
B37. Container according to paragraph B36, wherein the inlet and/or outlet comprises a valve.
B38. Container according to paragraph B36, wherein at least one of the outlets comprises a pipe leading to the lower part of the interior of the storage container so that the liquid can be discharged by the insertion of gas.
B39. A container according to paragraph B38, wherein the pipe is formed from a material that is compatible with the 1,1-disubstituted alkene composition.
B40. Preferably the 1,1-disubstituted alkene composition comprises no more than about 1000 ppm, more preferably no more than about 500 ppm, even more preferably no more than about 100 ppm of anionic polymerization inhibitor, based on the amount of 1,1-disubstituted alkene. , containers according to any preceding paragraph.
B41. Preferably the 1,1-disubstituted alkene composition comprises no more than about 5000 ppm, more preferably no more than about 2000 ppm, even more preferably no more than about 1000 ppm of a radical polymerization inhibitor, based on the amount of 1,1-disubstituted alkene. , containers according to any preceding paragraph.
B42. _The barrier layer contains one or more of sulfur dioxide ( _SO2 ), methanesulfonic acid ("MSA"), trifluoromethanesulfonic acid ("TSA"), hydrochloric acid (HCl), and phosphoric acid ( _H3PO4 ). Containers according to any preceding paragraphs, as applicable.

The dimensions and values disclosed herein are not to be understood as being strictly limited to the precise numerical values recited. Rather, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value.

Every maximum numerical limitation given throughout this specification is to be understood to include every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification includes every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification includes every narrower numerical range subsumed within such broader numerical range, as if each such narrower numerical range were expressly recited herein. Contains numerical ranges.

All documents cited herein, including any cross-referenced or related patents or applications, are herein incorporated by reference in their entirety unless expressly excluded or otherwise limited. Incorporated. Citation of any document indicates that it is prior art with respect to any invention disclosed or claimed herein, or that it alone or in conjunction with any other There is no admission that any such reference, in combination with any reference, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall control. shall be carried out.

The foregoing descriptions of embodiments and examples have been presented for purposes of illustration. It is not intended to be exhaustive or limited to the forms depicted. Many modifications are possible in light of the above teaching. Some of these modifications have been described and others will be understood by those skilled in the art. The embodiments were selected and described to illustrate various embodiments. It will be appreciated that the scope is not limited to the examples or embodiments described herein, but may be adapted to any number of applications and equivalent articles by those skilled in the art. Rather, the specification is intended to be defined in scope by the claims appended hereto.

It is to be understood that specific embodiments, features, structures or characteristics of the various embodiments may be interchanged, in whole or in part. Reference to a particular embodiment means that a particular aspect, feature, structure or property described in connection with a particular embodiment may be included in at least one aspect and may be exchanged with certain other embodiments. means. The appearances of the phrase "in a particular embodiment" in various places in this specification are not necessarily all referring to the same aspect, and that a particular embodiment is not necessarily mutually exclusive of other particular embodiments. It's not even a target. It is also to be understood that the steps of the methods described herein do not necessarily have to be performed in the order described, and the order of the steps of such methods is understood to be merely exemplary. Should. Similarly, such methods may include additional steps, and certain steps may be omitted or combined, consistent with certain embodiments.

Claims (43)

providing a storage container comprising a barrier layer, the barrier layer reducing water vapor transmission rate of the storage container;
filling the storage container with a 1,1-disubstituted alkene composition;
A method of handling a 1,1-disubstituted alkene composition comprising: The 1,1-disubstituted alkene composition may include methylene malonate, methylene β-ketoester, methylene β-diketone, monofunctional, difunctional or polyfunctional monomers, oligomers or polymers thereof, and combinations thereof. 2. The method of claim 1, comprising one or more of: 3. The method of claim 2, wherein the 1,1-disubstituted alkene composition comprises a dialkyl methylene malonate or methylene malonate polyester. 4. The method of claim 3, wherein the dialkyl methylene malonate comprises dihexyl methylene malonate. A method according to any one of claims 1 to 4, wherein the barrier layer is formed from a material that is compatible with the 1,1-disubstituted alkene composition. the material compatible with the 1,1-disubstituted alkene composition comprises one or more of high density polyethylene, nitrile, polyamide, or a composite of polyamide, polyethylene terephthalate, polytetrafluoroethylene or metal; The method according to claim 5. 7. A method according to claim 5 or claim 6, wherein the material comprises high density polyethylene. 8. The method of claim 7, wherein the material is modified by a halogenation process. 9. The method of claim 8, wherein the halogenation process comprises a fluorination process. 6. The method of claim 5, wherein the material comprises stainless steel or aluminum. A method according to any one of claims 5 to 10, wherein the barrier layer is an inner layer. A method according to any one of claims 5 to 10, wherein the barrier layer is a surface layer. _The barrier layer includes one or more of sulfur dioxide ( _SO2 ), methanesulfonic acid ("MSA"), trifluoromethanesulfonic acid ("TSA"), hydrochloric acid (HCl), and phosphoric acid ( _H3PO4 ). The method according to any one of claims 1 to 12, wherein the method is applied. 14. The storage container according to any one of claims 1-13, wherein the storage container exhibits a water vapor transmission rate of less than or equal to about 0.0054 g/ ^cm2 /mm/day at a temperature of about 50<0>C and a relative humidity of about 75%. Method described. 15. The storage container of claim 1, wherein the storage container exhibits a water vapor transmission rate of less than or equal to about 0.00057 g/cm ² /mm/day at a temperature of about 50° C. and a relative humidity of about 75%. Method described. Claims 1-15 wherein the 1,1-disubstituted alkene composition exhibits a shelf life of about 3 months or more when the storage container is maintained at a temperature of about 50°C and a relative humidity of about 75%. The method described in any one of the above. 17. The method of claim 16, wherein the 1,1-disubstituted alkene composition substantially maintains one or more of viscosity and reactivity during the shelf life. 18. The method of any one of claims 1-17, wherein the 1,1-disubstituted alkene composition is loaded at a relative humidity of about 50% or less. 19. The method of any one of claims 1-18, wherein the 1,1-disubstituted alkene composition is loaded at a relative humidity of about 10% or less. 20. The method of any one of claims 1-19, wherein the 1,1-disubstituted alkene composition further comprises one or more antioxidants and acids. 12. The one or more antioxidants comprises a primary antioxidant, and the 1,1-disubstituted alkene composition comprises between about 10 ppm or more and less than 1% by weight of the primary antioxidant. 20. The method described in 20. 22. The method of claim 21, wherein the primary antioxidant comprises a hindered phenol derivative. the one or more antioxidants further comprises a secondary antioxidant, and the 1,1-disubstituted alkene composition comprises between about 10 ppm or more and less than 1% by weight of the secondary antioxidant. , the method according to any one of claims 20 to 22. 24. The method of claim 23, wherein the secondary antioxidant comprises a thiol and is substantially free of nitrogen. 25. The method of any one of claims 20-24, wherein the 1,1-disubstituted alkene composition comprises between about 5 ppm or more and less than 1% by weight of the acid. 26. The method of claim 25, wherein the acid has a H ₀ of about 3 or less. Claims wherein the 1,1-disubstituted alkene composition comprises one or more of methanesulfonic acid ("MSA"), monomethyl ether of hydroquinone ("MeHQ"), and dibutylhydroxytoluene ("BHT") 27. The method according to any one of items 1 to 26. 28. A method according to any one of claims 1 to 27, wherein said handling includes storage and shipping. 29. A method according to any one of claims 1 to 28, wherein said handling is performed at a temperature of about 50°C or less. A method according to any one of claims 1 to 29, wherein the storage container is substantially opaque to ultraviolet radiation. a storage container comprising a barrier layer, the barrier layer reducing the water vapor transmission rate of the storage container;
a 1,1-disubstituted alkene composition stored in the storage container;
Container containing. 32. The container of claim 31, wherein the barrier layer is formed from a material that is compatible with the 1,1-disubstituted alkene composition. the material compatible with the 1,1-disubstituted alkene composition comprises one or more of high density polyethylene, nitrile, polyamide, or a composite of polyamide, polyethylene terephthalate, polytetrafluoroethylene or metal; 33. A container according to claim 32. 34. A container according to claim 32 or 33, wherein the material comprises high density polyethylene. 35. A container according to claim 34, wherein the surface of the material has been modified by a halogenation process. 36. The container of claim 35, wherein the halogenation process comprises a fluorination process. 33. The container of claim 32, wherein the material comprises stainless steel or aluminum. A container according to any one of claims 32 to 37, wherein the storage container is formed entirely from the material. 39. The container of any one of claims 31-38, wherein the 1,1-disubstituted alkene composition is filled into the storage container at a relative humidity of about 50% or less. 39. The container of any one of claims 31-38, wherein the 1,1-disubstituted alkene composition is filled into the storage container at a relative humidity of about 10% or less. A container according to any one of claims 31 to 40, wherein the storage container is substantially opaque to ultraviolet light. A container according to any one of claims 31 to 41, wherein the storage container is sealed by a disposable seal. Container according to any one of claims 31 to 41, wherein the storage container is sealed by a screw cap.

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