KR101151679B1 - Arc-extinguishing composition and articles manufatured therefrom - Google Patents

Abstract

The present invention provides an arc-blocking composition, such as melamine, and a method of erasing an arc by placing the composition along the passage of the arc to contact the arc. In one specific embodiment, the binder or at least one portion of the binder is a polymer comprising a functional group that binds to a binder included in the arc-erasing composition. The binder combines the polymer binder with the arc-erasing compound, such as melamine, to provide new and unpredictable physical strength and stability. In this embodiment, the molded composition comprising the arc-blocking composition bound to the binder maintains excellent arc-blocking ability while providing chemical stability and electrical insulation properties as well as unpredictable physical strength.

Arc elimination, arc blocking

Description

ARC-EXTINGUISHING COMPOSITION AND ARTICLES MANUFATURED THEREFROM}

The present invention relates to arc-quenching materials and articles made therefrom for high voltage electrical devices and to circuit safeguards which are preferably extinguished and destroyed under certain operating conditions, under certain operating conditions. (such as circuit interrupters). More specifically, the present invention relates to compositions for achieving arc-decaying and structural properties of devices such as circuit safety devices, high voltage fuses, circuit breakers, and separable cable connectors. .

In order to provide efficient circuit safety for circuit breakers, fuses, and similar devices, it is desirable to utilize arc-decaying materials or compositions that dissipate or inhibit arcing during electrical contact disconnect or fuse operation. Necessarily, the arc-decaying material must include features and characteristics sufficient for specific applications by efficiently extinguishing the arc through rapid evolution of the extinguishing gas. Of course, the released quenching gas should also be relatively electrical. In addition, it is also important that the arc-decaying material can be molded or made into articles and shapes having desirable structural properties, thermal stability, and environmental resistance to thermal cycling. .

In many circuit safety devices, it is typical to utilize a trailer / liner configuration as is well known in the art, wherein the arc is preferably between the trailer and the liner made from an arc-decaying composition. Drawn into annular space. The action of the gas produced by the trailer and / or liner on a confined arc tends to deionize the arc and force its clearing. Examples of trailer / liner configurations are described in US Pat. Description See bulletin 811-30. Similarly, in a high voltage fuse, which may also be characterized as a circuit safety device, a sleeve or liner is wrapped around the passage of the arc while the fuse is in operation, and the sleeve or liner is arc-cleared. It is characterized in that it is made from an arc-extinguishing material. Examples of fuses of this kind surrounded by an arc-erase sleeve or liner may be referred to US Pat. Nos. 3,629,767 and 4,307,369.

Representative arc-erasing materials and their properties are disclosed in US Pat. Nos. 3,582,586, 4,251,699, and 4,444,671. One composition of US Pat. No. 3,582,586 includes melamine and polyethylene. Although the composition is generally suitable for a variety of applications and exhibits desirable arc-decay properties, it is desirable for many applications to achieve compositions that exhibit improved mechanical and environmental resistance to thermal cycling while maintaining the desired arc-decay properties. Do.

One of the most efficient arc-blocking compounds used in the art for arc-decay is white crystalline powder with a melting point of 350 ° F. and its melting point and melamine subliming below it (C ₃ N ₆ H ₆ ). . Other related nitrogen-containing compounds are also recognized in the prior art as arc-decaying or arc-blocking compounds and are disclosed in US Pat. No. 2,526,448 by Amundson et al. Melamine and related compounds have good arc-blocking properties, but are extremely structurally weak and can be molded or deformed into a satisfactory structural shape except when combined with a suitable binder. Can't.

In order for the binder to be most efficient in the arc-decaying or arc-blocking composition, the binder must be volatilized or decomposed like melamine when an electric arc is present. However, the binder does not necessarily provide any arc-blocking or arc-erasing properties to the composition. Because in some cases the arc-blocking properties of the melamine included in the composition are sufficient for arc-blocking purposes. Therefore, the binder provides sufficient moldability primarily for melamine-containing compositions and provides sufficient physical strength, physical and chemical stability, and electrical insulation properties for the molded structure for structurally robust molded products. It is included for the purpose. The physical strength of the molded article is determined by its tensile strength, percent elongation, and the amount of energy required to break the molded structure, or impact strength. most obvious in impact strength.

Structural damage, such as cracks, has been found in conventional devices containing polyethylene as the main binder material, and the point of failure allows the air and other air spaces where the arc can be filled, thereby allowing the arc-blocking device to Such damage is unacceptable in the art as it significantly reduces the arc-blocking properties. Furthermore, failed arc scavenging compositions containing melamine mostly fail because the pressure wave by the arc physically destroys the composition before it has a chance to clear the arc. The arc-erasing composition described in the present invention erases the arc without physically breaking it. Thermoplastic polymeric binders have been found to be most useful in arc-blocking compositions based on melamine or similar compounds. This means that the amount of power required to sublimate melamine for the purpose of drawing the melamine into the center of the arc and generating a large volume of gas to purge the arc in a wide range of power conditions is smaller when electric arc is present. This is because the thermoplastic polymer binder volatilizes or decomposes even at low power conditions. Furthermore, the thermoplastic binder provides a composition having excellent molding properties, stability and electrical insulation properties.

Typical thermoplastic polymer resins known to be useful as binders in melamine-based arc-blocking compositions are polyethylene, polypropylene, polytetrafluoroethylene, acrylics, polystyrene, Cellulosics polyamides (nylons), polyacetals (DERLIN), polyphenylene oxides, blends such as ABS, and polyimides ). Binders such as thermosetting resins, epoxy resins, polyester resins, phenolic resins, and similar resins are known to be useful as binders in arc-blocking compositions. Also, melamine-based, such as butyl compounds, isoprene-based compounds, neoprene-based compounds and other synthetic elastomers Rubber-like materials, which are elastomeric in arc-blocking compositions, are known to be included as part of the binder.

In U.S. Patent No. 4,975,551 of the applicant, it consists of a polymer containing a carboxylic acid group, in particular two different monomers, at least one of which is like an ethylene acrylic acid copolymer A binder has been disclosed comprising a copolymer containing a carboxylic moiety. As disclosed, the carboxylic acid functionalities of the binder provide amines, thiols, alcohols, halogens to provide the composition with increased physical strength and safety. interacts with arc-eliminating compounds having carboxylic acid-active sites such as halogens, and similar sites. The molded composition comprising the arc-blocking compound and the binder maintains good arc-blocking ability, chemical stability and electrical insulation properties as well as increased physical strength.

Briefly, the present invention provides a new and improved arc scavenging composition comprising a new and improved binder for a composition containing an arc-blocking compound such as melamine, and disposing the composition along the passage of the arc to contact the arc. Thereby providing a method of eliminating an arc. In one embodiment according to the invention, the binder, or at least a portion of the binder, is a polymer comprising a functional group that binds to a binder included in the arc-erasing composition. The binder may be a polymer that is compatible with the binder, and the polymer binder is bonded to the arc-erasing compound such as melamine to provide new and unpredictable physical strength and safety to the arc-erasing compound It includes a functional group that binds to.

In other embodiments of the arc-erasing composition and article described herein, the melamine or other arc-erasing compound, when introduced into the composition in finely ground form, provides unpredictable good results, Improved results are provided by incorporating a plasticizer into the polymeric binder.

At least three embodiments of the arc-decaying material and article are described herein and each provides an improved mechanical property and / or arc-clearing result, each embodiment separately or in combination with one or two of the other embodiments. . Each of the three independent embodiments may be included in the materials and articles described herein, or any two or three of the embodiments may be combined in the more advanced materials and articles mentioned herein.

Briefly described, the three embodiments are as follows.

(1) the arc interacting simultaneously with the arc-erasing material and the polymeric binder mechanically and / or chemically to improve the mechanical and / or the arc-erasing properties of the compositions and articles described herein Mix the binder in the erasure composition.

(2) A plasticizer (eg caprolactam for nylon base polymer) is mixed into the arc-erasing composition for the base binder polymer. This is to improve elongation and other mechanical properties, in particular to reduce the brittleness of the arc-clearing composition.

(3) The finely ground arc-decaying material is mixed into the arc-erasing composition. Preferably, the arc-decaying material is melamine, guanidine, guanidine acetate, guanidine carbonate, 1,3-diphenylguanidine, cyan Cyanurate, melamine cyanurate, hydantoin, allantoin, urea, urea phosphate, benzoguanidine, dithioammelide ), Ammeline, halogenated cyanuric halide, and combinations thereof. According to the present embodiment, the arc-decaying material has at least 90% by weight of the particles, wherein the particles have a particle size of less than 200 μm, preferably less than 150 μm, more preferably less than 100 μm. And, more preferably, have a particle size distribution smaller than 50 μm. In order to take full advantage of this embodiment, the arc-decaying particles at least within 95% by weight should have a particle size of less than 50 μm.

The arc-decaying compositions described herein are suitable for deionizing and extinguishing high voltage electrical arcs. The composition comprises an effective amount of arc-erasing material such as melamine, and includes arc-erasing properties and tensile strength, elongation, environmental resistance to thermal cycling, and It contains a sufficient amount of binding polymer to achieve a desirable combination of similar structural properties. Additionally, the composition may include additives, fillers or fibrous materials for various applications and applications of the composition.

The composition mixes the components using dry blending, roll mill, extrusion and / or other plastic compounding techniques to obtain molding resin compositions. This makes it uniform. The molding composition is then molded into articles of the desired shape by injection molding, extrusion, and similar plastic processing techniques. In a preferred composition, for example, in order to form a trailer for a safety device, a nylon base polymer binder is mixed with melamine and anhydride-functional coupling agent to form melamine, nylon, and the anhydride- Coupling and / or miscibility between functional binders achieve the desired arc-clearing and mechanical properties.

In other embodiments as mentioned above, the composition comprises a non-functionalized base polymeric binder with or without a binder, and finely ground arc-erasing material and / or It contains a plasticizer for the base polymer binder.

According to one aspect of the composition, article and method described herein, the present invention comprises an arc-clearing compound, such as melamine, in an efficient ratio, and a binder-interaction such as ethylene maleic anhydride polymer. There is provided a new and improved arc-dissipating composition consisting of a polymeric binder comprising a coupling agent-interactive moieties and a suitable binder. The binder may chemically and / or mechanically combine the arc-erasing compound with the binder, and the arc-erasing compound with the polymeric binder to have desirable environmental resistance to improved strength and thermal cycling. .

According to another aspect of the composition, article and method described herein, the present invention exhibits desirable properties at least on the order of the electrical arc-erasing properties exhibited in the arc-erasing compositions and articles that were conventionally possible when molded, It provides a new and improved arc-clearing composition with improved mechanical properties.

According to another aspect of the composition, article and method described herein, the present invention provides a new and improved arc-erasing composition comprising an arc-blocking compound and a polymeric binder. The binder is a copolymer formed from a polymer or two other monomers, and includes a binder reactor or a coupling agent reactive groups or moieties for bonding the binder to the arc-blocking compound through a binder.

According to another aspect of the composition, article and method described in the present invention, the present invention comprises an arc-erasing compound having at least one site in response to a coupling agent-contained functional group; Or a new and improved arc-erasing composition comprising a polymeric binder material comprising a plurality of reactive coupling agent contained functional moieties. The binder material causes the arc-erasing compound and the polymeric binder to chemically bond with a binder when the composition is molded under heat and pressure so that the shaped composition has new and unpredictable physical strength.

According to another aspect of the composition, article and method described herein, the invention provides an arc-blocking compound and an amine-activity having at least one active amine site in its molecule, such as melamine Thermoplastic resin binder materials containing moieties and binder-active moieties; It provides a new and improved arc-blocking composition comprising a suitable binder together to bind the arc-blocking compound to the polymeric binder through the binder.

According to the composition, article and the other side of the method described in the present invention, the present invention is new and unpredictable in terms of molding and physical strength, such as tensile strength, elongation and resistance to thermal cycling and resistance to cracking It provides new and improved arc-blocking compositions that not only provide properties but also provide sufficient and good arc-blocking properties.

Although not mentioned and described above with reference to the contents of the present invention, the contents and advantages of the present invention will become apparent when referring to the detailed description of the preferred embodiments described below with reference to the drawings.

1 is a bar graph showing the mechanical toughness characteristics of the arc-erasing compositions of Table 1 compared to the case of DERIN 500.

2 and 3 are bar graphs showing the weight change by water and nitric acid of the arc-erasing compositions of Table 1 compared to the case of DELIN 500.

4 is a bar graph showing the particle size distribution of standard grade and fine grade melamine.

5 is a conceptual diagram illustrating a fuse sleeve or liner made from an arc-erasing composition in accordance with one embodiment of the present invention.

FIG. 6 is a side view of a portion of the sleeve or liner of FIG. 5 surrounding the fuse, taken away. FIG.

According to one embodiment of the composition, article, and method described herein, a binder-active functional group in which the arc-erasing composition bonds to a binder, such as an anhydride group. It has been found that when including a binder containing a functional group, the physical and thermal properties of the arc-clearing composition can be improved unpredictably. Such binders include arc-clearing compounds with available reactive sites such as amine groups; Compounds containing one or more of the available hydroxyl groups, epoxy groups and / or aziridine groups; Or particularly efficient when used with one or more available thiol groups with available carboxylic acid-reactive sulphur atoms, but with other arc-erasing compounds It is also effective when used together. The polymeric binder having one or more binder-active functional groups described in the present invention, and the active binder are melamine or benzoguanamine, dithioammelide, ammeline, And other similar arc-clearing compounds such as halogenated cyanuric halides.

The functionalized, binder-active polymeric binder does not need to form 100% of the binder material used in the arc-erasing composition, but in small amounts by 0.5 to 20% by weight relative to the binder material used in known arc-erasing compositions. Improved good results were seen when functionalized binders were included. The non-reacted (non-functional) portion of the binder and the polymeric binder must be sufficiently miscible to form a uniform composition when the composition is melted.

Suitable polymeric binders having one or more coupling-agent reactive functional groups include anhydrides, carbonyls, hydroxyls, carboxyl, amines, amides (amide), ether, lactam, lactone, epoxy, ester, sulfate, sulfonate, sulfinate, sulfamate at least one functional group selected from the group consisting of sulfamate, phosphate, phosphonate, and phosphinate; Or thermoplastic and thermosetting polymers having an aromatic ring capable of covalently or ionic bonding to the binder. Preferably, the binder is an anhydride, carbonyl group, carboxyl group, hydroxyl group, amine, amide (particularly any kind of nylon), ether, and as part of a ring structure or as an extension coupling agent. -reactive functional group) characterized in that it comprises at least one functional group selected from the group consisting of aromatic rings having an active group. Examples of suitable polymeric binders containing such binder-active functional groups include polypropylene, nylon 4/6, nylon 6/6, nylon 6, nylon 11, nylon 6/12, high-impact nylon, minerals. Mineral-filled nylon, polycarbonate, polystyrene, acrylonitrile butadiene styrene, polysulfone, polybutylene terphthalate, polyethylene terphthalate (polyethylene terphthalate), polyphenylene sulfide, polyester thermoplastic elastomer, polyetherimide, styrenic thermoplastic elastomer, olefinic thermoplastic elastomer thermoplastic elastomer, polyurethane thermoplastic, polyphenylene jade Polyphenylene oxide, polyetheretherketone, phenylene ether copolymer, polycarbonate / acrylonitrile butadiene styrene, polyarylether ketone ), Polyetherketoneetherketoneketone, polyphthalamide, and polyletherketoneketone and blends of two or more of the above polymers. Other suitable base resins include perfluoroalkoxy, ethylene tetrafluoroethylene, and polyvinylidene fluoride.

The functionalized binder used in one embodiment of the arc-blocking composition can be used in a wide variety of amounts as is well known in the art with the arc-blocking or arc-erasing compounds such as melamine, and the present invention It can be a combination of several kinds of other thermosetting and / or thermoplastic binder materials that are well known in the art. The functionalized binder is generally included in approximately at least 10%, preferably approximately at least 20%, relative to the total weight of the arc-blocking composition. The most optimal results aimed at molding, physical and chemical stability and strength, arc-blocking properties and insulating properties are when the functionalized binder is included in the range of about 15 to 50% by weight of the arc-blocking composition. It is preferably achieved when it is in the range of approximately 20 to 40% relative to the total weight of the article and the molded molded arc-interrupting composition.

The binder used in the coupling agent embodiment for bonding the arc-erasing compound to the functionalized polymeric binder is preferably active to provide covalent bonds to both the arc-erasing compound and the polymeric binder. Monomers or polymer compounds containing reactive functional groups. However, the attractive force acting between the binder and / or the arc-erasing compound and / or the polymeric binder may cause electrostatic complexing, ion complexing, chelation, hydrogen bonding. any mechanism selected from the group consisting of bonding, ion-dipole, dipole / dipole, Van Der Waals forces, and combinations thereof. Preferred binders are polymers, for example terpolymers having anhydride functional groups for reacting with the preferred melamine arc-erasing compounds. For example, ethylene / ethyl acrylate / maleic anhydride terpolymer coupling agent, such as Rotader 4720 from Atopina Chemicals Corporation, In order to bind the melamine and the nylon binder (for example, nylon 6), it may react with the nitrogen atom of the melamine and the nitrogen atom of the nylon binder. The non-functional portion of the rotder binder is compatible with the nylon (eg nylon 6) polymeric binder. Other examples of suitable binders are organosilanes, organofunctional silylating agents, in particular the organosilanes are amino, epoxy, acrylate, n-mercapto (n-). mercapto) and vinyl functionality. The vinyl functional group is (3-acryloxypropyl) trimethoxysilane ((3-Acryloxypropyl) trimethoxysilane); N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (N- (2-Aminoethyl) -3-aminopropyltrimethoxysilane); 3-aminopropyltriethoxysilane; 3-aminopropyltrimethoxysilane; 3-Isocyanatopropyltriethoxysilane; (3-Glycidoxypropyl) trimethoxysilane; 3-mercaptopropyltrimethoxysilane; And vinyltrimethoxysilane.

Preferred binders are functionalized polyolefins, for example polyethylene or polypropylene functionalized with one or more reactive functionalities. The reaction functional group provides a reactivity or electrostatic bond between the arc-erasing material and the polymeric binder. The binder comprises glycidyl methacrylate (GMA) and / or maleic anhydride (MAH) functional groups for better compatibility with polyester, polyamide and / or polyolefin polymeric binders. do. Most preferred binders are functionalized polyolefins, in particular terpolymers of ethylene or propylene (PE or PP) with ethyl acrylate (EA) and maleic anhydride (MAH) or from 6.5 to 30% by weight of EA, from 0.3 to 3.1% by weight MAH or GMA, the remaining 66.9 to 93.2% by weight is glycidyl methacrylate with PE or PP, preferably polyethylene. Terpolymers containing the MAH are sold under the trade name Rotader from Atofina Chemicals. Other suitable binders are terpolymers of PE or PP and MAH and n-butyl acrylate (Lotader grades 2210, 3210, 4210 and 3410); Ethylene / butane copolymer (elastic polymer) grafted with maleic anhydride (MAH), approximately 0.25% by weight MAH sold by Dow Plastics as AMPLIFY GR 208 functional polymer To 1% by weight of a copolymer comprising; Titanate quarternary ammonium compounds sold by KEN-REACT ^® water soluble chelate Titanate Quats and KEN-REACT ^® LICA ^® by KENRICH petrochemicals; KEN-REACT ^® NZ ^® neoalkoxy Zirconates and Quats; KEN-REACT ^® KZ ^® Cycloheteroatom Zirconates; KEN-REACT ^® KA Reluminates; CAPOW ^® KR ^® and L ^® Series titanic acid binder powders; Styrene / maleic anhydride copolymers; Epoxy modified polyolefins, in particular ethylene having 3 to 8% by weight of GMA, methyl acrylate (MA) sold from Atopina Chemicals as Rotader AX8840, Rotader AX8900 and Rotader AX8930 from 0 to approximately 24 to 25% Terpolymers of / methyl acrylate / glycidyl methacrylate (E-MA-GMA) or copolymers of ethylene and glycidyl methacrylate (E-GMA); A copolymer of ethylene (E / MAA) and / or propylene (P / MAA) with methacrylic acid (MAA), wherein the MAA acid group is a metal, for example lithium, sodium, or zinc, iron ( DuPont SURLYN ^® 9320W) the copolymer partially neutralized with a; Polyolefins grafted with maleic anhydride of any kind; Polyolefins grafted with any kind of styrene / acrylonitrile; Copolymers grafted with polypropylene / polymethylmethacrylate sold by INTERLOY ^™ W1095H1 from Crompton Corporation; Or the like.

The arc-blocking compound, such as melamine, included in the composition described herein, is included in the composition in a normal amount, as is well known in the art, and generally it is about the total weight of the arc-blocking composition. Amount from 5% to about 90%, preferably from about 10% to about 70%, even more preferably from about 20% to about 50% by weight of the composition. Excellent results are achieved with the arc-blocking compound and the binder material when the weight ratio of the arc-blocking compound to the polymeric binder is within the ratio range of 4 to 1 to 1 to 1. Optimal results are achieved when the weight ratio of the arc-blocking compound and the polymeric binder material is included in the composition in a ratio of 2 to 1 to 3 to 1.

In an embodiment of the binder described herein, of the total polymeric binder included in the arc-blocking composition, the functional group-containing polymer or copolymer comprises an amount sufficient to enhance the tensile strength of the molded composition It should preferably be included so that the tensile strength increases by at least 10% by the addition of the functional group-containing binder.

For example, a representative prior art arc-blocking composition comprises melamine in a polyethylene binder, wherein the weight ratio of melamine to the polyethylene binder is 3 to 1 and its tensile strength is 1133 psi. By replacing only 5% of a binder-interacting functionalized polymeric binder, such as ethylene / maleic anhydride, with polyethylene with a suitable binder for the functionalized polymer and the melamine, the tensile strength is Increase by more than 10%. By completely removing the polyethylene and replacing 100% of ethylene / maleic anhydride with the binder material for melamine, the tensile strength is increased to 1677 psi, or nearly 50%. An improvement in physical strength is achieved by including the functional group-containing binder material, and a binder-active binder therewith, wherein the functional group-containing binder in the composition is from about 0.5% to 100% by weight of the binder present in the composition. Achievement is achieved by substitution up to%.

In the binder embodiments described herein, in order to achieve full advantage, the binder material used with the arc-blocking compound should include the functional group-containing polymer or copolymer described in the present invention, the content of which Is about 2% to 100% by weight relative to the total weight of the polymeric binder contained in the composition, preferably about 50% to about 100% by weight. The remaining percentage of binder material is polyolefin such as polyethylene and / or polypropylene; As polyfluorinated resins, for example, polytetrafluoroethylene, acrylic resins, polyfluorinated resins such as polyamides such as nylon, and epoxy resins, polyester resins, phenolic resins, and the like Any other suitable binder, including thermoplastics, can be any kind of binder as long as it is an efficient binder for molding and arc-erasing properties. Various elastomeric materials may also be included to enhance the stretching properties of the molded composition, and such elastomers include butyl-based and / or isoprene-based and / or neoprene- There are neoprene-based synthetic elastomers.

In the above binder embodiments described herein, the binder of the present invention was not capable of molding into the desired shape while exhibiting structural properties, thermal stability, and environmental resistance to thermal cycling with conventionally known arc-decaying compositions. This is possible and can be usefully used with any kind of arc-blocking compound to provide an arc-decaying composition. A very unpredictable improvement in structural (mechanical) properties is achieved by the binder embodiment, when the arc-blocking compound has one or more active sites, wherein the active site is one or more. It chemically reacts with the reactive moieties of a coupling agent and also chemically with the functional binder described herein. For example, melamine (C ₆ N ₆ H ₆ ) is three equally capable of chemically bonding (including ionic and / or covalent bonds) with the extending functional moieties of the vinyl / maleic anhydride binder. Include three equally spaced reactive primary amine moieties. The anhydride group acts as a binder for the melamine, achieving new and unpredictable tensile strength, elongation and resistance to thermal cycling while maintaining good arc-erasing properties.

In a preferred embodiment of the invention, the proportion of functional group-containing monomers used to form the functional binder polymer or copolymer, such as when copolymerizing ethylene with maleic anhydride or similar, for example, provides sufficient activity. For very wide range. For example, an anhydride moiety in the copolymer having chemical bonds (including ionic and / or covalent bonds) at one, two or all three active amine sites extending from the melamine vinyl structure. By this method, when a functional group-containing polymer is used at least as part of the binder in the preparation of the arc-decaying composition, chemical bonding of the compound-binder in various ways for different properties can be provided.

In the binder embodiments described herein, in general, the content of the functional group-containing monomer polymerized or copolymerized with the second monomer in the formation of the copolymer is approximately relative to the total weight of the polymerizable monomer. 0.5% to approximately 80%. The second monomer is approximately 20% to 95% by weight of the total weight of both monomers. Such copolymers, including varying amounts of maleic anhydride monomers, such as ethylene / maleic anhydride copolymers made by Atofina, are readily available. The copolymer binder, sold under the trade name LODATER 4720 by Atopina, provides arc-decaying compositions having very good structural properties, thermal stability and environmental resistance to thermal cycling. For example, other functionalized polymers and copolymers that have some anhydride percentage as the coupling agent-reactive moieties can be used, and when used as a bound binder in arc-decaying compositions Similar structural improvements should be provided.

In the binder embodiments described herein, the active site in the arc-decaying composition is functionalized by the polymeric binder to achieve new and unpredictable tensile strength, elongation, and resistance to cracking that could not be achieved in the prior art. It has been theorized that it is chemically bonded (ionically and / or covalently) with wealth. In addition to the reactive amine groups extending from melamine arc-quenching compounds, other arc-decaying compounds may also include an active site. Other arc-decaying compounds include benzoguanamine having a pair of extending reactive amine groups; Thio substituted organic arc-quenching compounds such as dithioammelide; Ammeline; And halogenated compounds such as cyanuric chloride. Each of these compounds is capable of generating a large volume of arc-erasing gas under an environment where an electric arc is applied. Each of these compounds can be selected from the group consisting of the binder-active binder to achieve new and unpredictable structural, mechanical and physical properties in the arc-erasing or arc-blocking composition; And / or finely ground forms of the arc-erasing compound; And / or in combination with the plasticizers for the polymeric binders, may be usefully employed in accordance with the compositions, materials, and articles described herein.

In accordance with the binder embodiments described herein, an active, arc-extinguishing compound, such as melamine, may be incorporated into the active functional group at one or more of the active compound sites. by reacting with the functionalized polymeric binders described in the present invention, it is theorized that they form chemical bonds (ion and / or covalent bonds).

Similarly, any kind having active epoxy groups, aziridine groups, thiol groups, hydroxyl groups, halogen groups, and pseudo-active sites The arc-clearing compound of also has chemical bonds (ion and / or covalent bonds) with active functional groups from the polymeric binders used in the compositions described herein to provide new and unpredictable structural properties, thermal stability, and thermal cycling resistance. Can be included).

The molecular weight of the active, functionalized polymeric binder can have a wide range of values, and according to the compositions, articles and methods of the present invention, the average molecular weight with very good physical properties, thermal stability and resistance to thermal cycling Values can range from as low as approximately 250 to as high as 500,000 or more. The average molecular weight of the polymeric binder is preferably about 1,000 to about 100,000, more preferably about 1,000 to about 50,000.

For additional insulation, strength, and / or arc-erasing properties, other materials that may be added to the compositions and articles of the present invention are generally added from about 0.1% to about 10%, respectively, relative to the total weight of the composition. Fiber additives include glass, inorganic fibers and organic fibers such as polyacrylonitrile, polyamide, and polyester fibers. Fillers may include, for example, cellulosic materials, calcium carbonate, metal oxides, comminuted polymers, carbon black, and natural and synthetic silica materials.

Figure 6 is an arc-erasing material molded or extruded from the arc-erasing composition of the present invention and produced (molded or extruded) in the form of an annular fuse sheath or liner 10. An example of the specific use of The fuse sheath or liner 10 surrounds a fuse 12 disposed within the fuse tube 14. These fuses 12 serve to block both low and high levels of fault current. At low morning currents, if the sheath 10 does not explode or rupture, it remains entirely, and the arc between both electrodes elongates entirely within the fuse tube 14. The elongated arc interacts with the arc-erasing material of the sheath 10 to release an arc-extinguishing gas. If a sufficient amount of arc-erasing gas is released from the sheath and the pressure of the gas in the sheath remains sufficiently high even when the current is zero, the presence of arc-erasing gas may cause re-ignition of the arc. There will be sufficient dielectric strength to prevent. The fuse 12 may also be used to block high morning currents. In high morning flows the sheath usually ruptures, and the clearing of the arc, which is formed between the two electrodes of the fuse, is mainly due to the release of arc-erasing gas from the bore of the fuse tube 14.

Data ( DATA )

Various compositions were prepared and tested as shown in Tables 1-7 to show the unexpected structural properties achieved in the embodiments described herein and in the claims when compared to other arc-erasing compositions.

Arc-Erase Composition Toughness Numbers Material / Toughness Measurement
(Material / Toughness Measurement) Elongation (%) Unnotched Izod Impact Strength (ftlbs / in) Derlin 15-30 24-40 X-Material * 0.55 0.25 TX-Material ** 3.9 3.2 70% nylon / 30% melamine 2.9 2.8

* 70% melamine / 30% nylon

** 72% melamine / 28% EAA

material %, 6 kinds of nylon
(Type Nylon 6) %, Kind of melamine
(Type Melamine) %, Binder
(Coupling Agent) 6.1 50 (note 1) 30, fine 20 (3) 6.2 50 (note 1) 30, normal 20 (3) 6.6 50 (note 2) 30, normal 20 (3)

Note 1: This nylon 6 was impact modified and plasticized with 4-8% of Caprolactam (the monomer used to make nylon 6).

Note 2: This nylon 6 is impact deformed, but without plasticizer.

Note 3: The binder is Lotader 4720 (Atofina), 30% ethyl acrylate, 0.3% maleic anhydride (functional group) and the rest is ethylene.

Note 4: Both materials 6.1 and 6.2 have a rubbery feel. Material 6.6 is less rubbery and has increased stiffness (increased modulus). It is clear from this data that caprolactam is an efficient material that gives toughness (compared to 6.2 and 6.6), and fine melamine is also an efficient material that gives enhanced toughness (compared to 6.1 and 6.2). However, the greatest effect comes from the coupling agent / impact modifier. The increase in toughness can be seen to improve dramatically over what appears to be from the X-material to the TX-material. This is also evident in the type of material in which toughness and stiffness are in harmony.

Note 5: Material 6.1 has also proved to be an arc-extinguishing material (AEM) better than Dullin. In addition, material 6.1 may be used at higher temperatures than X or TX.

For electrical testing, the samples were molded from arc compressor parts and slat-shaped parts. The results of the molding are shown in the following data. Next, these parts were assembled into Arc Compressor Assemblies using fabrication parts to complete the assembly.

Test procedure ( TEST PROCEDURES )

Three types of tests were performed: mechanical, environmental, and electrical.

Mechanical testing ( Mechanical Test ):

Tensile tests were performed to ASTM D 638, respectively. Elongation was measured from crosshead movement. Unnotched Izod impact testing was performed in accordance with ASTM D 4812, respectively. Since the nylon 6 is hygroscopic, the samples were tested in a dry as molded (DAM) state and at the same time in a controlled state. The results of previous experiments on the Derlin 500 were used for comparison.

Environmental testing ( Environmental Test ):

Most of the flex bar materials (width 1 / 2˝ and 1 / 8˝ and length 5˝) were immersed in distilled water for 7 days in a solution containing 10% nitric acid in a volume ratio for environmental testing. By miscalculation, the first three days were in a 7% solution. By not immersing the sample completely, an air / solution interface is created, showing a tendency to accelerate chemical attack. Nylon 6 was hygroscopic, so it was performed under conditions of 100% distilled water. The effects on weight and width were recorded.

Electrical test Electrical Test ):

Electrical tests were performed. Initially, a high voltage test with a nominal circuit of cutoff test, 25 kV, and 400 A was prepared. Travel record and timing shots were performed first, then the switch was opened and closed, then the arcing time was opened and the pre-strike time was closed. Recorded.

For this test, samples were placed in a Mini-Rupter switch. A steel (unpainted) ground plane was placed in front of the mini-buster and 8 inches from the end of the mini-rupter blade in open conditions. Voltage was applied to the mini-rupter strut and the ground plane, frame, and adjacent phases were grounded. Barrier boards were not used in the switch. The results are shown in the graph of FIG. Composition 6.1 was the first tested arc-erasing material equal to or above Dulin's toughness level. Composition 6.1 also showed rubber-like properties.

Environmental testing ( Environmental Test ):

The results of the environmental tests are shown in FIG. 2 (weight change) and FIG. 3 (size change). A positive change means an increase in weight or size, and a negative change means a loss in weight or size.

Both 6.1 and F.1 compositions provided much better resistance to nitric acid than dullin. 6.1 and F.1 showed yellowing by surface attack, but there was no loss of material. The reduced sample showed severe corrosion at the water surface, which looked like the reduced sample from the Swamp.

It can be seen that nylon 6 material increased by 1.6% in both weight and size due to water absorption.

Electrical test Electrical Test ):

The test results at 25 kV, 400 A (nominal) for the 6.1 composition are shown in Table 3. The arcing times for the 6.1 material were surprisingly better than the acetal control material (DERLIN). 6.1 In tests involving restrikes on materials, this restraint caused the compressor to be so flexible that hot gases escaped.

Compressor, Electrical Result, 25 kV, 400 A Trace number
(Trace #) Voltage
(kV) electric current
(A) Closing Pre-Strike (ms) Open arc time
(Opening Arc Time) (ms) Video, id note 29 24.6 382 3.6 6.1 30 24.2 381 14 31 24.5 389 3.4 32 24.4 375 19 33 24.7 387 1.5 34 24.9 383 13.2 9 35 25.6 400 4.9 10 36 24.8 378 13.9 11 37 25.4 392 2.1 12 38 24.6 385 13.5 13 39 24.5 399 One 14 40 24.9 383 16.8 15 restrike, clear n / a n / a n / a n / a No data 44 n / a 382 12.8 17 Restrike, no clear

material Elongation
(Elongation,%) Unnotched Izod Impact Strength (ftlbs / in) Coefficient
(Modulus, ksi) 70% nylon / 30% melamine
(Control) 2.9 2.8 na TX-Material
(Control) 3.9 3.2 na 6.1 36.7 No Break (1) 50 6.2 20.5 No Break (1) 60 6.6 9.46 No Break (1) 137

Note 1: The material is folded under the blade without breaking.

(material folds under blade without breaking)

Material 6.1 and material 6.2 both have a rubber-like feel. Material 6.6 has less rubbery properties than 6.1 and 6.2, and has greater stiffness or increased modulus. It is clear from this data that caprolactam is an efficient material that gives toughness (compared to 6.2 and 6.6), and fine melamine is also an efficient material that gives enhanced toughness (compared to 6.1 and 6.2). However, the greatest effect comes from the coupling agent / impact modifier. The increase in toughness can be seen to improve dramatically over what appears to be from the X-material to the TX-material. This is also evident in the type of material in which toughness and stiffness are in harmony.

Material 6.1 has also proven to be an arc-extinguishing material (AEM) better than Derlin. In addition, material 6.1 may be used at higher temperatures than X or TX.

AEM weight change material % Change by water % Change due to nitric acid F.1 (melamine and acrylic binder) 0.87 -0.42 6.1 1.70 2.12 Derlin 500 0.41 -20.07

AEM size change material % Change by water % Change due to nitric acid F.1 (melamine and acrylic binder) 1.43 0.00 6.1 1.63 0.61 Derlin 500 0.10 -12.34

According to a second embodiment of the arc-erasing composition, article, and method described in the present invention, when the arc-erasing compound is supplied in a finely pulverized form (see Tables 2 and 4), a molded arc- The scavenging composition exhibits unexpectedly increased toughness, and particularly increased elongation, thereby preventing the destruction of the molded article.

According to the second embodiment, when the arc-erasing compound is supplied in a finely pulverized form, the particle size distribution of the compound is at least 90% by weight and up to 100% of the particles have a particle size of approximately Smaller than 200 μm. Preferably the particles within at least 90% by weight have a particle size of less than approximately 100 μm, and more preferably, the particles within at least 99% by weight of the arc-erasing compound particles have a particle size of less than about 100 μm. small. In order to achieve the full advantage of the second embodiment of the compositions, articles and methods described herein, at least 90% by weight of the arc-erasing compound particles and up to 100% of the particles have a particle size of It should be smaller than 50 μm. A good increase in elongation of the molded arc-erasing apparatus is achieved with finely ground melamine obtained from DSM. The melamine is Melamine Grade 003, also sold for other purposes and the particle size distribution is as follows: 40 μm below 99 wt%; 30 μm below 90 wt%; 15 μm below 50 wt%; And 5 μm below 10% by weight.

According to a third embodiment of the composition, article and method described in the present invention, by including a plasticizer in the composition for the binder polymer, structural properties are increased without sacrificing the arc-erasing properties of the molded article. Turned out.

In order to determine which plasticizer is suitable for a particular polymeric binder, as is well known in the art, miscible plasticizers should have a solubility parameter (δ) suitable for the particular polymeric binder. One method of determining the solubility parameter (δ) is according to ASTM Designation D-3132-84 (reapproved in 1990). The solubility parameter (δ) of the plasticizer for the polymeric binder should be as similar as possible to the value of the solubility parameter (δ) of the polymeric binder. For example, some preferred polyamide (nylon) polymeric binders have the value of the solubility parameter (δ) as follows.

Δ of binder
(δ for binder) Preferred δ of the Plasticizer
(Preferred δ for plasticizer) δ of ε-caprolactam
(δ for ε-caprolactam) Nylon 6: δ = 12.83 11.5-14.0
12.7 Nylon 8: δ = 12.7 11.5-14.0 Nylon 11: δ = 11.065 10-13 Nylon 12: δ = 10.72 9-13 Nylon 6/6: δ = 12.95-13.6 11.5-14.0 Nylon 6/10: δ = 11.86 11-14

The polyester polymer binder has a value of the solubility parameter δ in the range of approximately 9.5 to 12. Maleic anhydride has a δ of approximately 13.6. Adipate plasticizers have relatively low solubility parameters but are suitable for plasticizing amines. Epoxy has a δ of approximately 9-11 and an ether of approximately 7.5-11. Ketones have a δ of approximately 8.4 to 10; Lactones are approximately 10-14; Maleates are approximately 8.5-10; Phenols are approximately 9.5-13; Phosphates are approximately 7.5-10; Phosphonates are approximately 8-10. The above is a general guideline, and the solubility parameters of polymers (polymer binders) and compatible solvents (plasticizers) for the polymer binder are, for example, specific interactions and miscibility of the polymer mixture: miscible. A Practical Guide to Prediction & Design of Polymer Mixtures, Michael M. Specific Interactions and the Miscibility of Polymer Blends: Practical Guides for Predicting & Designing Miscible Polymer Mixtures, Michael M. Coleman, et al., Lancaster, Pa. USA; Technomic Pub. Co., 1991 ) And C. M. Hansen, J. Paint Technol., 1967.39.104 (C.M. Hansen, J. Paint Technol., 1967.39.104).

In general, any type of monomer used to form the polymeric binder can be used as a plasticizer for the polymeric binder (eg, to plasticize nylon 6, as described in the third (plasticizer) example of the present invention). using ε-caprolactam). In order to achieve a homogeneous mixture when the arc-erasing composition is melted during the arc forming process, the plasticizer must be compatible with the polymeric binder. If the plasticizer is not sufficiently miscible with the polymeric binder, when melted the plasticizer does not form a uniform composition when it is separated from the binder or melted together with the arc-erasing compound and other components of the composition.

The data in Table 7 is the result of comparing the elongation of molded articles comprising DSM melamine grade 003 and molded articles comprising standard grade melamine. Compositions with and without plasticizers are also shown in Table 7. The comparison of finely ground melamine and standard grade melamine is shown in FIG. 4.

In Table 7, activity with an AEM-containing composition comprising (1) 70% nylon / 30% melamine and (2) 72% melamine / 28% ethylene acrylic acid (EAA), one of the materials of Applicant's US Pat. No. 4,975,551. Compare compositions comprising polymeric binders containing functional parts (ethylene / maleic anhydride copolymer) and binders for active binders (LOTADER 4720-30% ethylene acrylate / 0.3% maleic anhydride / 69.7% ethylene copolymer) .

The present invention provides an arc-blocking composition, such as melamine, and a method of erasing an arc by placing the composition along the passage of the arc to contact the arc. The composition comprises an arc-blocking compound, a binder, and a binder and maintains excellent arc-blocking ability while providing not only excellent physical strength but also chemical stability and electrical insulation properties.

Claims (31)

An arc-extinguishing compound; A polymeric binder for the arc-extinguishing compound; And 2 to 100% by weight of a binder (coupling agent) for connecting the arc-erasing compound with the polymer binder, based on the total weight of the binder, The binder may be a monomer or a polymer having anhydride functionality; Organosilanes; Organofunctional silylating agents having amino, epoxy, acrylate, n-mercapto or vinyl functionality; Polyolefins functionalized with one or more reactive functionalities that provide covalent bonds or electrostatic attraction to the arc-erasing compound and the polymeric binder; Monomers or polymers including glycidyl methacrylate or maleic anhydride functional groups; Functionalized polyolefins; Terpolymers of ethylacrylate, maleic anhydride and polyolefin; Terpolymers of ethyl acrylate and glycidyl methacrylate with polyolefins; Terpolymers of maleic anhydride and n-butyl acrylate and polyolefins; Copolymers in which maleic anhydride is grafted to a copolymer of ethylene and butane (ethylene / butane); Titanate quarternary ammonium compounds; Neoalkoxy zirconates; Quarternary ammonium zirconates; Cycloheteroatom zirconates; Aluminate; Styrene and maleic anhydride copolymers; Epoxy modified polyolefins; Terpolymers of ethylene / methylacrylate / glycidylmethacrylate of ethylene, methylacrylate, and glycidyl methacrylate; Copolymers of ethylene and glycidyl methacrylate; Copolymers of ethylene and partially neutralized methacrylic acid; Copolymers of propylene and partially neutralized methacrylic acid; Maleic anhydride grafted polyolefins; Styrene / acrylonitrite grafted polyolefins grafted with styrene and acrylonitrile; And polypropylene / polymethylmethacrylate grafted copolymers. . The method of claim 1, The polymer binder may be anhydride, hydroxyl, carbonyl, carboxyl, amine, amide, ether, lactam, lactone. , Epoxy, ester, sulfate, sulfonate, sulfinate, sulfamate, phosphate, phosphonate, phosphinate (phosphinate), and a combination comprising a functional (functionality) selected from the group consisting of (arc). 3. The method of claim 2, Wherein said polymeric binder comprises a functional group selected from the group consisting of anhydrides, carbonyl groups, carboxyl groups, hydroxyl groups, amines, amides, ethers, esters, and combinations thereof. The method of claim 3, The binder is an arc-erasing composition, characterized in that it comprises a polyamide (polyamide). 5. The method of claim 4, The polyamide is nylon. The method of claim 5, Wherein said nylon is selected from the group consisting of nylon 4/6, nylon 6, nylon 6/6, nylon 11 and nylon 6/12. The method of claim 1, The arc-clearing compound is melamine, guanidine, guanidine acetate, guanidine carbonate, 1,3-diphenylguanidine, cyanurate ), Melamine cyanurate, hydantoin, allantoin, urea, urea phosphate, benzoguanidine, dithioammelide, amelin (ammeline), halogenated cyanuric halide, and arc-clearing composition, characterized in that selected from the group consisting of a combination thereof. The method of claim 7, wherein Wherein said arc-erasing compound is selected from the group consisting of melamine, benzoguanidine, dithioamelide, amelin, halogenated cyanuric acid, and combinations thereof. 9. The method of claim 8, Wherein said arc-erasing compound is melamine. 10. The method of claim 9, Wherein the melamine particles within at least 90% by weight of the melamine particles have a particle size of less than 200 μm. The method of claim 10, Wherein said melamine particles within at least 90% by weight of the melamine particles have a particle size of less than 100 μm. 12. The method of claim 11, Wherein said melamine particles within at least 90% by weight of the melamine particles have a particle size of less than 50 μm. The method of claim 1, The binder is an arc-erasing composition, characterized in that 50 to 100% by weight in the composition relative to the total weight of the binder. The method of claim 1, The binder may include a titanate quarternary ammonium compound; Neoalkoxy zirconates; Quarternary ammonium zirconates; Cycloheteroatom zirconates; And aluminate. The method of claim 1, The binder may be a monomer or a polymer having anhydride functionality; Organosilanes; Organofunctional silylating agents having amino, epoxy, acrylate, n-mercapto or vinyl functionality; Polyolefins functionalized with one or more reactive functionalities that provide covalent bonds or electrostatic attraction to the arc-erasing compound and the polymeric binder; Monomers or polymers including glycidyl methacrylate or maleic anhydride functional groups; Functionalized polyolefins; Terpolymers of ethylacrylate, maleic anhydride and polyolefin; Terpolymers of ethyl acrylate and glycidyl methacrylate with polyolefins; Terpolymers of maleic anhydride and n-butyl acrylate and polyolefins; Copolymers in which maleic anhydride is grafted to a copolymer of ethylene and butane (ethylene / butane); Styrene and maleic anhydride copolymers; Epoxy modified polyolefins; Terpolymers of ethylene / methylacrylate / glycidylmethacrylate of ethylene, methylacrylate, and glycidyl methacrylate; Copolymers of ethylene and glycidyl methacrylate; Copolymers of ethylene and partially neutralized methacrylic acid; Copolymers of propylene and partially neutralized methacrylic acid; Maleic anhydride grafted polyolefins; Styrene / acrylonitrite grafted polyolefins grafted with styrene and acrylonitrile; And polypropylene / polymethylmethacrylate grafted copolymers. The method according to any one of claims 1 to 15, Arc-clearing composition, characterized in that it further comprises a plasticizer (compatible plasticizer) compatible with the polymeric binder. An arc-erasing sheath surrounding an electrical fuse, wherein the sheath is formed from the composition of claim 1. An arc-erasing sheath surrounding an electrical fuse, wherein the sheath is formed from the composition of claim 16. An arc-erasing sheath surrounding an electrical fuse, wherein the sheath is formed from the composition of any one of claims 2-15. delete delete delete delete delete delete delete delete delete delete delete delete

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