TWI475052B - Oligomeric phosphonates and compositions including the same - Google Patents

Description

Oligophosphonate and composition comprising the same Cross-references to relevant applications:

The present application claims priority to U.S. Provisional Patent Application Serial No. 61/426,341, filed on Dec. 22, 2010, the disclosure of which is incorporated herein by reference. Co-oligomers (phosphonates) and co-oligomers (phosphonate carbonates) are herein incorporated by reference in their entirety.

Government interest: not applicable

Parties to the joint research agreement: not applicable

Incorporate by reference on CD-ROM: Not applicable

Field of invention

This invention relates to oligomeric phosphonates and compositions comprising the oligomeric phosphonates.

A current state of the art process for providing flame retardancy of polymers is the use of additives such as brominated compounds or compounds comprising aluminum and/or phosphorus. The use of the additive and polymer can have deleterious effects on the processing characteristics and/or mechanical properties of the article from which it is made. In addition, these compounds are somewhat toxic and can be leached into the environment over time, making them less desirable to use. In some countries, certain brominated additives have been phased out due to environmental concerns.

Summary of invention

Specific examples include an oligomeric phosphonate-containing composition wherein from about 60% to about 100% of the total oligomeric phosphonate has two or more reactive end groups. In other embodiments, from about 75% to about 99% of the total oligomeric phosphonate There are two or more reactive end groups. In certain embodiments, the reactive end group can be, for example, an epoxy group, a vinyl group, a vinyl ester, an isopropenyl group, an isocyanate, or a combination thereof, and in certain embodiments, the total oligomeric phosphonate From about 80% to about 100% can have two or more hydroxyl end groups. In various embodiments, the oligomeric phosphonate or a portion thereof can include an oligomeric phosphonate, a random co-oligo (phosphonate), a block co-oligomer (phosphonate), a random co-oligo Poly(phosphonate carbonate), block co-oligomer (phosphonate carbonate) or a combination thereof. In certain embodiments, the oligomeric phosphonate can include a linear oligomeric phosphonate, a branched oligomeric phosphonate, or a combination thereof, and in other embodiments, the oligomeric phosphonate can further include a height Branched oligomeric phosphonates. In certain embodiments, the oligomeric phosphonate can have a number average molecular weight of from about 500 grams per mole to about 5000 grams per mole, or in other embodiments, the phosphonate can have a number average molecular weight of about 1500. G/mole to about 3000 g/mole.

In certain embodiments, the oligomeric phosphonate can include units derived from bisphenol, or in particular embodiments, units derived from bisphenol A. In other embodiments, the oligomeric phosphonate or portion thereof can comprise a unit of formula I: Wherein the Ar-based aromatic group and the -O-Ar-O- system are derived from resorcinol, hydroquinone or bisphenol; the R-based C _1-20 alkyl group, the C _2-20 olefin, the C _2-20 alkyne, C _5-20 cycloalkyl or C _6-20 aryl; and n is an integer from 1 to about 10. In this specific example, -O-Ar-O- can be derived from bisphenol A, bisphenol F, 4,4'-bisphenol, phenolphthalein, 4,4'-thiodiphenol, 4,4'-fluorenyl Diphenol, 3,3,5-trimethylcyclohexyl diol or a combination thereof.

Some specific examples are directed to an oligomeric phosphonate comprising from about 60% to 100% of the total oligomeric phosphonate having two or more reactive end groups; a polymer composition with at least one polymer . In other embodiments, from about 75% to about 99% of the total oligomeric phosphonate has two or more reactive end groups. In certain embodiments, the reactive end group can be, for example, an epoxy group, a vinyl group, a vinyl ester, an isopropenyl group, an isocyanate, or a combination thereof, and in certain embodiments, the total oligomeric phosphonate From about 80% to about 100% can have two or more hydroxyl end groups. In various embodiments, the oligomeric phosphonate or a portion thereof can include an oligomeric phosphonate, a random co-oligo (phosphonate), a block co-oligomer (phosphonate), a random co-oligo Poly(phosphonate carbonate), block co-oligomer (phosphonate carbonate) or a combination thereof. In certain embodiments, the oligomeric phosphonate can include a linear oligomeric phosphonate, a branched oligomeric phosphonate, or a combination thereof, and in other embodiments, the oligomeric phosphonate can further include a height Branched oligomeric phosphonates. In certain embodiments, the oligomeric phosphonate can have a number average molecular weight of from about 500 grams per mole to about 5000 grams per mole, or in other embodiments, the phosphonate can have a number average molecular weight of about 1500.克/莫耳至约3000 Gram/mole. The polymer composition of claim 10, wherein the oligomeric phosphonate comprises a unit derived from bisphenol.

In certain embodiments, the oligomeric phosphonate can include units derived from bisphenol, or in particular embodiments, units derived from bisphenol A. In other embodiments, the oligomeric phosphonate or portion thereof can comprise a unit of formula I: Wherein the Ar-based aromatic group and the -O-Ar-O- system are derived from resorcinol, hydroquinone or bisphenol; the R-based C _1-20 alkyl group, the C _2-20 olefin, the C _2-20 alkyne, C _5-20 cycloalkyl or C _6-20 aryl; and n is an integer from 1 to about 10. In this specific example, -O-Ar-O- can be derived from bisphenol A, bisphenol F, 4,4'-bisphenol, phenolphthalein, 4,4'-thiodiphenol, 4,4'-fluorenyl Diphenol, 3,3,5-trimethylcyclohexyl diol or a combination thereof.

Polymers of various specific examples may include polycarbonates, epoxides, epoxy-derived polymers, polyepoxides, benzo Classes, polyacrylates, polyacrylonitriles, polyesters, poly(ethylene terephthalate), poly(propylene terephthalate), poly(butylene phthalate), unsaturated polyester, poly Indoleamine, polystyrene, high impact polystyrene, polyurea, polyurethanes, polyphosphonates, polyphosphonates, poly(acrylonitrile butadiene styrene), polyphthalamide Amine, polyarylate, poly(aryl ether), polyethylene, polypropylene, polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride, bismaleimide polymerization The polymer, polyanhydride, liquid crystal polymer, cellulosic polymer, or combinations thereof, and in some embodiments, the polymer can be an epoxy or polyurea. In some embodiments, the polymer composition may further comprise, for example, a filler, a shredded or continuous glass fiber, a metal fiber, an organic fiber, an arylamine fiber, a carbon fiber, a carbon nanofiber or a ceramic fiber, and an interfacial activity. Agents, organic adhesives, polymer adhesives, crosslinkers, coupling agents, diluents, anti-pigmentation agents, fluorinated polyolefins, polyfluorenes, lubricants, mold release agents, neodymium tetrastearate Tetraol ester, nucleating agent, antistatic agent, conductive carbon black, carbon nanotube, organic antistatic agent, polyalkylene ether, alkyl sulfonate, perfluorosulfonic acid, perfluorobutane sulfinic acid Potassium salt, polyamine-containing polymer, catalyst, colorant, ink, dye, antioxidant, stabilizer, metal phosphinate, melamine cyanurate, melamine derivative, flame retardant or combination thereof .

Other specific examples are directed to a method for preparing an oligomeric phosphonate comprising combining a phosphonate monomer with a comonomer to produce a monomer mixture comprising a molar excess of comon; heating The monomer mixture; adding a polymerization catalyst to the monomer mixture to produce a reaction mixture; and maintaining a polymerization temperature. In certain embodiments, the phosphonate monomer can be a monomer of formula XIV: Wherein each of R ⁶ and each R ^{7 is} independently hydrogen or C ₁ -C ₄ alkyl; y and yy are each independently an integer from 1 to 5; and R is C ₁ -C ₄ alkyl or C ₅ -C ₁₀ aryl. In a particular embodiment, the phosphonate monomer can be, for example, diphenylmethylphosphonic acid, oxymethyldiphenoxyphosphine, or a combination thereof. In other embodiments, the comonomer may be, for example, resorcinol, hydroquinone, bisphenol A, bisphenol F, and 4,4'-bisphenol, phenolphthalein, 4,4'-thiodiphenol, 4, 4'-nonyldiphenol, 3,3,5-trimethylcyclohexyl diol or a combination thereof. In certain embodiments, the polymeric catalyst can be tetraphenylphosphonium and its derivatives with associated anions such as tetraaryl borohydrides, halides, or substituted or unsubstituted phenate groups. And, in some embodiments, the catalyst can be phenyltetraphenylphosphonium. Some embodiments of the method can include heating the monomer mixture and the polymerization catalyst under reduced pressure. The reaction mixture can be heated at a temperature of from about 100 ° C to about 350 ° C, and in some embodiments, a temperature within this range can be maintained throughout the process. Still other specific examples include a method of stopping heating when the phenol is stopped. In certain embodiments, the monomer mixture can include an oligocarbonate, a carbonate monomer, an oligoester, an ester monomer, or a combination thereof, and in a particular embodiment, the carbonate monomer can be carbonic acid Diphenyl ester, 4-tributylphenyl-phenyl carbonate, di-(4-tributylphenyl) carbonate, biphenyl-4-yl-phenyl carbonate, di-(biphenyl) 4-yl)ester, 4-(1-methyl-1-phenylethyl)-phenyl-phenyl carbonate, di-[4-(1-methyl-1-phenylethyl)-benzene carbonate Alkyl ester or a combination thereof.

Further specific examples include a method for preparing an oligomeric phosphonate comprising providing an oligomeric phosphonate having a hydroxyl group at one end, an oligomeric phosphonate which binds to the majority of the terminal hydroxyl group, and an effective amount Epichlorohydrin, and maintaining the reaction conditions to produce an oligomeric phosphonate having a majority of epoxy groups at one end. In various embodiments, the oligomeric phosphonate having the majority of the terminal hydroxyl groups may include an oligomeric phosphonate, a random co-oligo (phosphonate), a block co-oligomer (phosphonate), Random co-oligomer (phosphonate carbonate), block co-oligomer (phosphonate carbonate) or a combination thereof. In certain embodiments, the oligomeric phosphonate can include a linear oligomeric phosphonate, a branched oligomeric phosphonate, or a combination thereof, and in particular embodiments, the oligomeric phosphonate can include a height Branched oligomeric phosphonates.

Still a further specific example includes an oligomer-containing phosphonate, wherein from about 60% to about 100% of the total oligomeric phosphonate has two or more reactive end groups; a polymer composition with an engineering polymer . In other embodiments, from about 75% to about 99% of the total oligomeric phosphonate has two or more reactive end groups. In certain embodiments, the reactive end group can be, for example, an epoxy group, a vinyl group, a vinyl ester, an isopropenyl group, an isocyanate, or a combination thereof, and in certain embodiments, the total oligomeric phosphonate From about 80% to about 100% can have two or more hydroxyl end groups. In various embodiments, the oligomeric phosphonate or a portion thereof can include an oligomeric phosphonate, a random co-oligomer (phosphonate), a block Co-oligomers (phosphonates), random co-oligomers (phosphonate carbonates), block co-oligomers (phosphonate carbonates), or combinations thereof. In certain embodiments, the oligomeric phosphonate can include a linear oligomeric phosphonate, a branched oligomeric phosphonate, or a combination thereof, and in other embodiments, the oligomeric phosphonate can further include a height Branched oligomeric phosphonates.

The polymer composition can include engineering polymers such as, but not limited to, polycarbonates, epoxides, epoxy derived polymers, polyepoxides, benzoses Classes, polyacrylates, polyacrylonitriles, polyesters, poly(ethylene terephthalate), poly(propylene terephthalate), poly(butylene phthalate), unsaturated polyester, poly Indoleamine, polystyrene, high impact polystyrene, polyurea, polyurethanes, polyphosphonates, polyphosphonates, poly(acrylonitrile butadiene styrene), polyphthalamide Amine, polyarylate, poly(aryl ether), polyethylene, polypropylene, polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride, bismaleimide polymerization , polyanhydride, liquid crystal polymer, cellulose polymer or a combination thereof. In some embodiments, the polymer composition may further comprise a filler, a shredded or continuous glass fiber, a metal fiber, an organic fiber, an arylamine fiber, a carbon fiber, a carbon nanofiber or a ceramic fiber, a surfactant. , organic adhesives, polymer adhesives, crosslinkers, thinners, coupling agents, anti-pigmentation agents, fluorinated polyolefins, polyfluorenes, lubricants, mold release agents, neopentyl tetrastearate Alcohol ester, nucleating agent, antistatic agent, conductive carbon black, carbon nanotube, organic antistatic agent, polyalkylene ether, alkyl sulfonate, perfluorosulfonic acid, potassium perfluorobutane sulfinate Salts, polyamine-containing polymers, catalysts, colorants, inks, dyes, antioxidants, stabilizers, metal phosphinates, melamine cyanurates, melamine derivatives, flame retardants, or combinations thereof.

Still other specific examples include articles of manufacture containing oligomeric phosphonates wherein from about 60% to about 100% of the total oligomeric phosphonate has two or more reactive end groups. In other embodiments, from about 75% to about 99% of the total oligomeric phosphonate has two or more reactive end groups. In certain embodiments, the reactive end group can be, for example, an epoxy group, a vinyl group, a vinyl ester, an isopropenyl group, an isocyanate, or a combination thereof, and in certain embodiments, the total oligomeric phosphonate From about 80% to about 100% can have two or more hydroxyl end groups. In various embodiments, the oligomeric phosphonate or a portion thereof can include an oligomeric phosphonate, a random co-oligo (phosphonate), a block co-oligomer (phosphonate), a random co-oligo Poly(phosphonate carbonate), block co-oligomer (phosphonate carbonate) or a combination thereof. In certain embodiments, the oligomeric phosphonate can include a linear oligomeric phosphonate, a branched oligomeric phosphonate, or a combination thereof, and in other embodiments, the oligomeric phosphonate can further include a height Branched oligomeric phosphonates.

In various embodiments, the article of manufacture can be, for example, a coating on a plastic, metal, ceramic or wood product, free-standing films, fibers, foams, molded articles, fibers Reinforced composites, support parts, electrical components, electrical connectors, printed circuit laminates, covers, secondary components and components, televisions, computers, laptops, printers, cellular phones, video game consoles, a DVD player, a stereo, a digital music player, a portable video recorder, and a touch screen, and in some embodiments, the article can be used in electrical components, electrical connectors, printed wiring boards, Printed circuit board, TV, computer, laptop light and electricity Brain, printer, photocopier, scanner, cellular mobile phone, video game console, DVD player, stereo, digital music player, portable video recorder or touch screen laminate or fiber Reinforced complex.

Detailed description

The above summary of the present invention is not intended to describe each illustrative embodiment or every possible implementation of the invention. The following detailed description specifically illustrates these specific examples.

Before describing the present compositions and methods, it is to be understood that they are not limited to the particular compositions, methods, or rules described, as these may vary. It is also to be understood that the terms used in the description are only for the purpose of describing particular examples or specific examples and are not intended to limit the scope of the invention.

It must also be noted that, as used herein and in the appended claims, the <RTI ID=0.0> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; All process and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art, unless otherwise defined. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosed embodiments, the preferred methods, devices, and materials are now described.

"Optional" or "optionally" means that the subsequently described event or detail may or may not occur, and that the description includes examples of the occurrence of the event and examples of non-occurrence.

By "substantially not" is meant that in certain embodiments, the events described subsequently may occur at most less than about 10% of the time, or the components described thereafter may be less than about the total composition. 10%; and in other embodiments, up to about 5%; and in still other embodiments, up to about 1%.

As used herein, the term "carbonate" provides its usual meaning, for example, carbonic acid includes a salt of a divalent, negative CO group or an ester of this acid uncharged. "Diaryl carbonate" is a carbonate having at least two aryl groups bonded to a CO group, and the most preferred embodiment of the diaryl carbonate is diphenyl carbonate, but the definition of the diaryl carbonate is not Limited to this particular embodiment.

The term "aromatic dihydroxide" means any aromatic compound comprising at least two linked hydroxy substituents. Examples of "aromatic hydroxides" include, but are not limited to, benzenediols such as hydroquinone and any bisphenol or bisphenol containing compound.

The term "alkyl" or "alkyl group" refers to a branched or unbranched hydrocarbon or group of 1 to 20 carbon atoms such as, but not limited to, methyl, ethyl, n-propyl, isopropyl. Base, n-butyl, isobutyl, tert-butyl, octyl, decyl, tetradecyl, hexadecyl, nonylalkyl, tetradecyl and the like. "Cycloalkyl" or "cycloalkyl group" is a branched or unbranched hydrocarbon in which all or some of the carbon is arranged in a ring, such as, but not limited to, cyclopentyl, cyclohexyl, methylcyclohexyl and Its similar group. The term "short-chain alkyl" includes alkyl groups of 1 to 10 carbon atoms.

The term "aryl" or "aryl group" refers to a monovalent aromatic hydrocarbon group or group consisting of one or more conjugated rings wherein at least one ring is aromatic in nature. The aryl group may include, but is not limited to, a phenyl, naphthyl, biphenyl ring system and Similar group. The aryl group may be unsubstituted or substituted with a variety of substituents including, but not limited to, alkyl, alkenyl, halo, benzyl, alkyl or aromatic ethers, nitro, cyano and the like. Its combination.

"Substituent" refers to a molecular group that replaces hydrogen in a compound and may include, but is not limited to, trifluoromethyl, nitro, cyano, C ₁ -C ₂₀ alkyl, aromatic or aryl, halo (F, Cl, Br, I), C ₁ -C ₂₀ alkyl ether, C ₁ -C ₂₀ alkyl ester, benzyl halide, benzyl ether, aromatic or aryl ether, hydroxyl, alkoxy, amine A group, an alkylamino group (-NHR'), a dialkylamino group (-NR'R") or other group which does not interfere with the formation of a diaryl ester of an alkylphosphonic acid.

As defined herein, an "aryl alcohol" or "aryl alcohol group" is an aryl group having a hydroxyl (OH) substituent on the aryl ring. Non-limiting examples of such aryl alcohols are phenol, naphthol and the like. A wide variety of aryl alcohols can be used in the specific examples of the invention and are commercially available.

The term "alkanol" or "alkanol group" refers to a compound that is an alkyl group containing from 1 to 20 carbon atoms or more and having at least one hydroxyl substituent. Examples of alkanols include, but are not limited to, methanol, ethanol, 1- and 2-propanol, 1,1-dimethylethanol, hexanol, octanol, and the like. The alkanol group may be optionally substituted with a substituent as described above.

The term "enol" or "enol group" refers to a compound that is an olefin containing from 2 to 20 carbon atoms or more and having at least one hydroxyl substituent. The hydroxyl group can be arranged in any heterogeneous configuration (shun or reverse). The enol may be further substituted with one or more substituents as described above, and in certain embodiments of the invention, may be substituted for the alkanol. Enols are known to those skilled in the art and many are readily commercially available.

As used herein, the terms "flame retardant", "flame resistance", "fire retardant" or "refractory" mean that the composition has a limiting oxygen index (LOI) of at least 27. "Flame retardant", "flame resistance", "fire retardant" or "fire resistance" may also be tested by measuring the post-combustion time according to the UL test (subject 94). In this test, based on the results obtained from ten test samples, the test materials were classified into UL-94 V-0, UL-94 V-1 and UL-94 V-2. Simply put, the criteria for each of these UL-94-V-classes are as follows:

UL-94 V-0: The total flame burn of each sample after removal of the ignition flame should not exceed 10 seconds and the total flame burn of 5 samples should not exceed 50 seconds. There should be no test sample that will release the drip that will ignite the degreased cotton.

UL-94 V-1: The total flame burn of each sample after removal of the ignition flame should not exceed 30 seconds and the total flame burn of 5 samples should not exceed 250 seconds. There should be no test sample that will release any drops that will ignite the degreased cotton.

UL-94 V-2: The total flame burn of each sample after removal of the ignition flame should not exceed 30 seconds and the total flame burn of 5 samples should not exceed 250 seconds. The test sample releases the burning particles which ignite the degreased cotton.

Fire resistance can also be tested by measuring the post-combustion time. These test methods provide a laboratory test procedure for measuring and comparing the surface flammability of a material when exposed to a specified level of radiant heat to measure the surface flammability of the material when exposed to fire. The test is performed using a small sample (to the extent that the material or combination can typically be evaluated). The rate at which the flame travels along the surface depends on the physical and thermal properties of the material, product or combination under test, the method and orientation of the sample, the type and extent of fire or heat exposure, the availability of air, And the nature of the surrounding paddock. Variations in the measured fire-test-response characteristics cannot always be predicted by or from this test if different test conditions or end-use conditions are changed. Therefore, the results are only reasonable for the fire test exposure conditions described in this procedure.

A current state of the art process for providing flame retardancy of polymers is the use of additives such as brominated compounds or compounds comprising aluminum and/or phosphorus. The use of the additive and polymer can have deleterious effects on the processing characteristics and/or mechanical properties of the article from which it is made. In addition, these compounds are somewhat toxic and can be leached into the environment over time, making them less desirable to use. In some countries, certain brominated additives have been phased out due to environmental concerns.

As used herein, "molecular weight" can be determined by relative viscosity (η _rel ) and/or gel permeation chromatography (GPC). The "relative viscosity" of a polymer is measured by dissolving a known amount of polymer in a solvent and comparing the time it takes for the solution to pass through a specially designed capillary (viscometer) at a fixed temperature. Relative viscosity is a measure of the molecular weight of a polymer. It is also well known that relative viscosity reduction is a sign of reduced molecular weight, while molecular weight reduction results in loss of mechanical properties such as strength and toughness. GPC provides information on the molecular weight and molecular weight distribution of the polymer. It is known that the molecular weight distribution of polymers is important for properties such as thermal oxidative stability (due to different end group amounts), toughness, melt flow and fire resistance, for example, low molecular weight polymers drop more when burned.

As used herein, the term "toughness" is intended to indicate the ability of the material to resist breaking or breaking when pressurized or impacted. Available in a variety of standards The quasi-chemical test determines the toughness of the material. In general, toughness is qualitatively determined using a film or a shaped sample.

As used herein, the phrase "low viscosity when shearing", "shear thinning" or the like is intended to indicate when the material melts and accepts shear forces (such as it encounters certain types of blends). The viscosity is reduced when the melt is forced through the die or body having a similar orifice. The shear thinning behavior can be transferred to the blend of materials. Thus, for example, the blend of highly branched oligomeric phosphonates or co-oligo(phosphonate carbonate) and thermoplastics can have shear thinning, however the thermoplastic alone or thermoplastic can be linear or small Branched oligomeric phosphonates or blends of co-oligomers (phosphonate carbonates) do not. Shear thinning can be measured using standardized methods such as Shear Thinning Index (STI). STI represents the ratio of the viscosity at low rpm shear to the viscosity at high rpm (typically about ten times lower than the low speed). For example, low shear can be 1 rpm and high shear can be 10 rpm. The higher the STI value, the greater the shear thinning of the material.

Specific examples of the invention are directed to reactive oligomeric phosphonates, random or block co-oligomers (phosphonates), and random or block co-oligomers (phosphonate carbonates) for the manufacture of these a method of polyphosphonate, a polymer composition comprising the oligomeric phosphonate and another monomer, oligomer or polymer, a method for preparing the composition, a manufactured article comprising the oligomeric phosphonate And articles of manufacture comprising the polymer composition. In various embodiments, the reactive oligomeric phosphonate, random or block co-oligo (phosphonate) and co-oligo (phosphonate carbonate) can include reactive end groups such as, for example, Hydroxy end group, epoxy end group, isocyanate end group, vinyl end group, vinyl ester end group, isopropyl Alkenyl end groups, and the like, and combinations thereof. In certain embodiments, the reactive end group can allow the oligomeric phosphonate to chemically react with other monomers, oligomers, or polymers in the polymer composition, resulting in cross-linking or chain extension or a combination thereof. . For example, the reactive end group (such as a hydroxyl end group, an epoxy end group, a vinyl end group, a vinyl ester end group, an isopropenyl end group or an isocyanate end group) can be combined with, for example, but not limited to, an alcohol, Carboxylic acid and its salts, anhydrides, mercapto chlorides, epoxy compounds, aldehydes, ketones, amines, thiols, Grignard reagents, vinyl, acetylene groups and sodium hydroxide, acid and salt functional groups reaction. When a monomer, oligomer or polymer comprising these functional groups is oligomerized with a hydroxyl end group, an epoxy end group, a vinyl end group, a vinyl ester end group, an isopropenyl end group or an isocyanate end group When the phosphonate is combined, crosslinking or chain extension or a combination of both may occur. Thus, the reactive oligomeric phosphonate, random or block co-oligo (phosphonate) and random or block co-oligomer (phosphonate carbonate) can impart flame resistance without detracting from the The mechanical properties of the base polymer of the polymer composition.

The oligomeric phosphonates of this specific example may be linear or branched, and in certain embodiments, the oligomeric phosphonates may be highly branched. Generally, the concentration of the reactive end groups (based on the total number of terminals of the oligomeric phosphonate) can be high. For example, the oligomeric phosphonate can have from about 80% to 100%, from about 85% to about 99%, or from about 90% to about 98%, by weight of the total number of reactive end groups of the terminal. In other embodiments, more than 90% of the total terminal of the oligomeric phosphonate may have reactive end groups. For other specific examples of branched or highly branched oligomeric phosphonates, the percentage of reactive end groups may range from about 50% to 100%, from about 75% to about 95%, or from about 80% of the total number of terminals. % to about 90%, And in certain embodiments, more than 80% of the total terminal of the branched or highly branched oligomeric phosphonate may have reactive end groups.

For the sake of simplicity, the terms "oligophosphonate", "phosphonate oligomer" and the like are to be interpreted as referring to any of the types of oligomers described herein, including oligomeric phosphines. Acid esters, random or block co-oligomers (phosphonates) and random or block co-oligomers (phosphonate carbonates). The oligomers comprised by these terms may be linear, smallly branched (referred to as a relatively small number of branches, for example, from 1 to about 5 branches per oligo) or highly branched (referred to as a relatively high number). Branches, for example, greater than 5). While individual oligomer types can be recited in certain exemplary embodiments, any of the oligomeric phosphonates described herein can be used in this exemplary embodiment. For example, the exemplary description "using an oligomeric phosphonate" can be said to be a linear, small amount of branched or highly branched oligomeric phosphonate, which can be an oligomeric phosphonate, random or block co-oligomer (phosphine) An acid ester), and a random or block co-oligo(phosphonate carbonate) type oligomeric phosphonate.

Specific examples of the invention are not limited to oligomeric phosphonate, co-oligo (phosphonate) or co-oligo (phosphonate carbonate) versions, and in certain embodiments, the oligomeric phosphonates, Oligomers (phosphonates) or co-oligomers (phosphonate carbonates) can be found in U.S. Patent Nos. 6,861,499, 7, 816, 486, 7, 645, 850 and 7, 838, 604, and U.S. Publication No. 2009/0032770, each of which is incorporated herein by reference. The structure described and claimed in this document is incorporated herein. Briefly, the oligomer may comprise a repeating unit derived from a diaryl alkylphosphonate or a diaryl arylphosphonate. For example, in certain embodiments, the phosphonate oligomer comprises a structural unit as illustrated by Formula I: Wherein the Ar-based aromatic group and -O-Ar-O- may be derived from a dihydroxy compound having one or more selectively substituted aryl rings such as, but not limited to, resorcinols, hydroquinones And bisphenols such as bisphenol A, bisphenol F and 4,4'-bisphenol, phenolphthalein, 4,4'-thiodiphenol, 4,4'-nonyldiphenol, 3,3,5-three Methylcyclohexyl diol, or a combination of these; R system C _1-20 alkyl, C _2-20 olefin, C _2-20 alkyne, C _5-20 cycloalkyl or C _6-20 aryl; n is an integer from 1 to about 20, 1 to about 10 or 2 to about 5, or any integer between these ranges.

In other embodiments, the co-oligomer (phosphonate carbonate) or co-oligomer (phosphonate) may each have a structure such as, but not limited to, those of formula II and III: And combinations thereof, wherein each of Ar, Ar ¹ and Ar ² is independently an aromatic group and -O-Ar-O- may be derived from a dihydroxy compound having one or more selectively substituted aryl rings, Such as (but not limited to) resorcinols, hydroquinones and bisphenols such as bisphenol A, bisphenol F and 4,4'-bisphenol, phenolphthalein, 4,4'-thiodiphenol, 4, 4'-nonyldiphenol, 3,3,5-trimethylcyclohexyl diol, or a combination of these; R-based C _1-20 alkyl, C _2-20 olefin, C _2-20 alkyne, C _{5-20cycloalkyl} or C _6-20 aryl; R ¹ and R ² are aliphatic or aromatic hydrocarbons; and m, n and p may each be the same or different, and may each independently be from 1 to about 20, An integer from 1 to about 10, or from 2 to about 5, or any integer between these ranges. In some embodiments, m, n, and p are each about equal to and typically greater than 5 or less than 15.

As indicated by the term "random", a plurality of specific examples of "random co-oligomer (phosphonate carbonate)" or "random co-oligo (phosphonate)" monomers are randomly incorporated. In the polymer chain, the oligomeric phosphonate chain may thus comprise alternating phosphonates and carbonate or ester monomers or short fragments, wherein several phosphonate or carbonate monoester systems are supported by aromatic Hydroxide linkage. The length of such fragments can vary within the respective random co-oligomer (phosphonate carbonate) or co-oligo (phosphonate).

In a particular embodiment, the Ar, Ar ¹ and Ar ² may be bisphenol A and R may be methyl, providing oligomeric phosphonates having reactive end groups, including random and block co-oligomers ( Phosphonate carbonates) and co-oligomers (phosphonates). This compound may have a structure such as, but not limited to, a structure of the formula IV, V and IV: And combinations thereof, wherein m, n, p are each and R ¹ and R ^{2 are} as defined above. The co-oligomer (phosphonate) or co-oligomer (phosphonate carbonate) may be a block co-oligomer (phosphonate), block co-oligomer (phosphonate carbonate), wherein m, n And p each is greater than about 1, and the copolymer comprises a distinguishable repeat phosphonate and carbonate block or phosphonate and ester block. In other embodiments, the oligomeric co-oligomer (phosphonate) or co-oligomer (phosphonate carbonate) can be a random copolymer, wherein m, n, and p can each vary and can be An integer from 1 to about 20, 1 to about 10, or 2 to about 5, wherein the sum of m, n and p is an integer from 1 to about 20, 1 to about 10 or 2 to about 5, or between these ranges Any integer.

Special consideration is given to co-oligomers (phosphonates), co-oligomers (phosphonate carbonates), block co-oligomers (phosphonates) and block co-oligomers (phosphonate carbonates), not intended to be theoretically Limitations, oligomers comprising carbonate components (whether carbonate blocks or randomly aligned carbonate monomers) can provide improved toughness over oligomers derived from phosphonates alone. The co-oligomer can also provide a higher glass transition temperature ( _Tg ) than the phosphonate oligomer and better thermal stability.

Some specific examples of co-oligomers (phosphonate carbonates) may be from at least 20 mole % of a diaryl alkylphosphonate or a selectively substituted diaryl aryl phosphonate, one or more carbonic acid An aryl ester and one or more aromatic dihydroxides, wherein the molar percentage of the high purity alkylphosphonic acid diaryl ester is based on the total amount of the transesterification component (ie, the total alkylphosphonic acid diaryl) The ester and total diaryl carbonate are based on. Likewise, certain embodiments of the co-oligomer (phosphonate) may be from at least 20 mole % of a diaryl alkylphosphonate or a selectively substituted alkyl aryl phosphonate, one or more An aryl ester, and one or more aromatic dihydroxides, wherein the molar percentage of the high purity alkylphosphonic acid diaryl ester is The total amount of ester-based components is based on the basis.

The phosphonate and carbonate content of the oligomeric phosphonate, random or block co-oligomer (phosphonate carbonate) and co-oligo (phosphonate) may vary among specific examples, and specific examples are not It is limited to the phosphonate and/or carbonate content or the range of the phosphonate and/or carbonate content. For example, in certain embodiments, the co-oligomer (phosphonate carbonate) or co-oligomer (phosphonate) can have a phosphorus content of from about 1% to about 12% by weight of the total oligomer, and In other embodiments, the phosphorus content can range from about 2% to about 10% by weight of the total oligomer.

In some embodiments, the molecular weight (weight average molecular weight, such as by gel) of the oligomeric phosphonate, random or block co-oligomer (phosphonate) and co-oligo (phosphonate carbonate) Osmotic chromatography, based on polystyrene correction, can range from about 500 grams per mole to about 18,000 grams per mole, or any value within this range. In other embodiments, the molecular weight range can range from about 1500 grams per mole to about 15,000 grams per mole, from about 3000 grams per mole to about 10,000 grams per mole, or any value within these ranges. In still other embodiments, the molecular weight can range from about 700 grams per mole to about 9000 grams per mole, from about 1000 grams per mole to about 8,000 grams per mole, from about 3000 grams per mole to about 4000 grams. / Moore, or any value within these ranges.

The highly branched oligomers of various embodiments have a highly branched structure and a high degree of functional group (i.e., chemical reactivity). The branched structure of this highly branched oligomer produces a high concentration of terminal groups (one at the end of almost every branch), which may include reactive functional groups such as hydroxyl end groups, epoxy end groups, Vinyl end groups, vinyl ester end groups, isopropenyl end groups, isocyanate end groups, and the like. In some specific examples, the highly branched widow The polymer can have a unique combination of chemical and physical properties (when compared to linear oligomeric phosphonates). For example, a high degree of branching prevents crystallization and is less likely to provide chain entanglement, such that the highly branched oligomers have solubility and low solution viscosity and melt viscosity (especially when sheared) in organic solvents.

In certain embodiments, the highly branched oligomers can include branches that are not perfectly (ie, absolutely regular) aligned. For example, different branches on a single highly branched oligomer can have different lengths, functional group compositions, and the like, and combinations thereof. Thus, in certain embodiments, the highly branched oligomers of the present invention can have a broad molecular weight distribution. In other embodiments, the highly branched oligomers of the invention are perfectly branched (including nearly identical branches) and have a monodisperse molecular weight distribution.

The degree of branching of the highly branched oligomer of the present invention can be defined as the number average component of the branching group per molecule, that is, the terminal group plus the branched monomer unit to the terminal group, the branched monomer unit, and The ratio of the total number of linear monomer units. For linear oligomers, the degree of branching (as defined by the number average component of the branching group per molecule) is zero, and for ideal dendrimers, the degree of branching is one. The highly branched oligomer can have a degree of branching between the linear oligomer and the desired dendrimer. For example, the degree of branching of the highly branched oligomers can be from about 0.05 to about 1, from about 0.25 to about 0.75, or from about 0.3 to about 0.6, and in certain embodiments, the highly branched oligomer can have about The number average component of the branching group of 0.5.

The highly branched oligomers of the invention can generally be represented by the structure of formula VII below: Wherein B is a number of highly branched oligomers and w-system branches, v is an integer not zero, and L is a linking group and an F-based reactive group.

The linking group (L) can be any moiety that is chemically compatible with the monomers of the above oligomeric phosphonates, co-oligomers (phosphonates) or co-oligo(phosphonate carbonates). For example, in certain embodiments, L can be any unit derived from an aryl or heteroaryl group, including a single aryl group, a diaryl group, a triaryl group, a tetraaryl group, and the like. In other embodiments, L can be a covalent bond that directly links the functional group (F) to the highly branched oligomer, and in yet other embodiments, L can be a C ₁ -C ₁₀ alkyl group, C ₂ a -C ₁₀ olefin or a C ₂ -C ₁₀ alkyne which may or may not be branched.

The linking group (L) allows one or more functional groups (F) to be attached to each of the branch terminals of the highly branched oligomer. In some embodiments, each of the branching terminals can have an attached linking group, and in other embodiments, one or more of the branching terminals of the highly branched oligomer (B) can have no Attached link group. The branching terminal of this unattached linking group can be terminated using a hydroxyl or phenolic group bound to the monomeric unit of the highly branched oligomer. For a branching terminal comprising a linking group (L), each linking group may have from 0 to 5 or more bonded functional groups. Thus, in certain embodiments, one or more of the linking groups of the reactive highly branched oligomer may have no attached functional groups such that the branching ends associated with the linking group are substantially unreactive. In other embodiments, one or more linking groups of the reactive highly branched oligomer may have one or more attached functional groups that provide potential for reaction with other monomers, oligomers or polymers. Branch terminal, and in its In its specific embodiment, one or more linking groups of the reactive highly branched oligomer may have a plurality of attached functional groups. For example, two aryl groups associated with a triaryl group can include a monofunctional group (F) and a third aryl group that attaches the linking group to a highly branched polymer or oligomer. The functional group (F) may vary among specific examples and may be any chemical moiety capable of reacting with other chemical moieties. Non-limiting examples of such functional groups (F) include hydroxyl groups, carboxylic acids, amines, cyanate esters, isocyanates, epoxy groups, glycidyl ethers, vinyl groups, and the like, and combinations thereof. The reactive highly branched oligomers of the present invention are reactive with a variety of functional groups such as epoxides, anhydrides, activated halides, carboxylic acids, carboxylates, isocyanates, aldehydes, vinyls, acetylenes, and decanes. . These groups may be present on another monomer, oligomer or polymer used in the preparation of the polymer composition.

The highly branched oligomer portion (B) of the general structure shown above may be any phosphonate-containing highly branched oligomer. For example, in certain embodiments, the highly branched oligomer can comprise a repeating unit derived from an alkyl or aryl phosphonic acid diaryl ester, and in certain embodiments, the highly branched oligomer can have Structure including the unit of formula I: Wherein the Ar-based aromatic group and -O-Ar-O- may be derived from a compound having one or more selectively substituted aryl rings such as, but not limited to, resorcinols, hydroquinones and Phenols such as bisphenol A, bisphenol F and 4,4'-bisphenol, phenolphthalein, 4,4'-thiodiphenol, 4,4'-nonyldiphenol, 3,3,5-trimethyl Cyclohexyl diol, or a combination of these; R system C _1-20 alkyl, C _2-20 olefin, C _2-20 alkyne, C _5-20 cycloalkyl or C _6-20 aryl; An integer from 1 to about 20, 1 to about 10, or 2 to about 5, or any integer between these ranges.

The highly branched oligomer (B) of this specific example may further include a unit derived from a branching agent or a polyfunctional aryl group, a polyfunctional diaryl group, a polyfunctional triaryl group, a polyfunctional tetraaryl group or the like. . In certain embodiments, the unit derived from the branching agent can be derived, for example, from a polyfunctional acid, a polyfunctional diol, or an acid/diol mixture. In other embodiments, the highly branched oligomeric phosphonate may have a derivative derived from a tri- or tetrahydroxy aromatic compound or a triaryl or tetraaryl phosphate, a triaryl or tetraaryl carbonate or a triaryl or tetraaryl a unit of a base ester or a combination thereof, such as, but not limited to, symmetrical trimellitic acid, pyromellitic acid, trimellitic anhydride, pyrogallic anhydride, trimethylolpropane, dimethyl hydroxy citrate, new Pentaerythritol, and the like and combinations thereof. This branching agent provides a branching point within the highly branched oligomeric phosphonate. In a particular embodiment, the branching agent can be a triaryl phosphate such as, for example, those of formula VIII: Wherein each of R ³ , R ⁴ and R ⁵ may independently be hydrogen, C ₁ -C ₄ alkyl; and p, q and r are each independently an integer of from 1 to 5.

The number of branches (w) may be directly proportional to the number of units derived from the branching agent and may be any integer from about 2 to about 20. In some embodiments, n can be an integer greater than 3, greater than 5, or greater than 10, or any within these ranges What is the value; and in other embodiments, n can be from about 5 to about 20, from about 5 to about 15, from about 5 to about 10, or any value between these ranges.

Some specific examples of reactive highly branched phosphonates can have the following structure, wherein B is a formula IX or formula X: Wherein Ar ³ and Ar ⁴ are each independently an aromatic group, and -O-Ar ³ -O- and -O-Ar ⁴ -O- may be derived from an aryl ring having one or more selectively substituted groups. Dihydroxy compounds such as, but not limited to, resorcinols, hydroquinones and bisphenols such as bisphenol A, bisphenol F, and 4,4'-bisphenol, phenolphthalein, 4,4'- Thiophenol, 4,4'-nonyldiphenol, 3,3,5-trimethylcyclohexyl diol, or a combination of these; L ¹ and L ² are each independently a covalent bond or an aryl group Or a heteroaryl group, including a single aryl group, a diaryl group, a triaryl group, a tetraaryl group or the like; R may be a C _1-20 alkyl group, a C _2-20 olefin, a C _2-20 alkyne, a C _5-20 a cycloalkyl or C _6-20 aryl group; z is an integer from 1 to about 20, 1 to about 10, or 2 to about 5, or any integer between these ranges; and w ¹ and w ² are each independently Grounds 1 to 5. X can be derived from any of the above-mentioned branching agents. In certain embodiments, the X in each B can be the same molecule, such that the branches having the structure of Formula VII and Formula VII can extend from the same Branching Agent (X) molecule. In a particular embodiment, X can be a triaryl phosphate of formula VIII as described above. In other embodiments, two or more Xs may be linked as illustrated in Formula XI, Formula XII, or Formula XIIII:

Wherein B ¹ and B ² are each independently a highly branched polymer as described above; X ¹ and X ² are each independently a branching agent as described above; each of Ar ⁵ and Ar ^{6 is} independently The aryl group, and -O-Ar ⁵ -O- and -O-Ar ⁶ -O- may be derived from a dihydroxy compound having one or more selectively substituted aryl rings, such as (but not limited to) Resorcinols, hydroquinones and bisphenols such as bisphenol A, bisphenol F and 4,4'-bisphenol, phenolphthalein, 4,4'-thiodiphenol, 4,4'-fluorenyl Diphenol, 3,3,5-trimethylcyclohexyl diol, or a combination of these; each R is as defined above; and s is an integer from 1 to about 20, 1 to about 10, or 2 to about 5. Or any integer between them. In various embodiments, the individual reactive highly branched oligomers can have a moiety of any of the oligomers of Formula I, and VIII to XIII. Thus, specific examples include reactive highly branched oligomers having any combination of the formulas provided above. In other embodiments, the reactive highly branched oligomer can consist essentially of one or both of the structures presented above. For example, the highly branched oligomer can be composed of two units derived from a branching agent (X) which are linked by a structure of formula XI to a branch of formula IX, or the highly branched oligomer can be tri- or Four branching agent compositions (which are linked by the structures of Formulas XI and XIII to the branches of Structural Formula IX). Of course, as discussed above, any combination of formulae is possible and may be present in a single reactive highly branched oligomer.

An exemplary representation of the reactive highly branched oligomers of the invention is provided below: Wherein the Ar is an aryl or heteroaryl group, the R system is a C ₁ -C ₄ alkyl group or an aryl group, and the R' is an alkyl group or an aromatic group derived from a branching agent.

In certain embodiments, the molecular weight (weight average molecular weight, such as borrowed) of the highly branched oligomeric phosphonate, random or block co-oligo (phosphonate) and co-oligo (phosphonate carbonate) Determined by gel permeation chromatography, based on polystyrene correction, may range from about 500 grams per mole to about 18,000 grams per mole, or any value within this range. In other embodiments, the molecular weight range can range from about 1500 grams per mole to about 15,000 grams per mole, from about 3000 grams per mole to about 10,000 grams per mole, or any value within these ranges. In still other embodiments, the molecular weight can range from about 700 grams per mole to about 9000 grams per mole, from about 1000 grams per mole to about 8,000 grams per mole, from about 3000 grams per mole to about 4000 grams. / Moore, or any value within these ranges.

The highly branched oligomeric phosphonate, random or block co-oligo (phosphonate carbonate) and co-oligo (phosphonate) phosphonate and carbonate content can vary in specific examples, and Specific examples are not limited to the phosphonate and/or carbonate content, or the range of the phosphonate and/or carbonate content. For example, in certain embodiments, the co-oligomer (phosphonate carbonate) or co-oligomer (phosphonate) can have from about 2% to about 12%, from 2% to about the total oligomer. 10% by weight, or less than 10% by weight of phosphorus.

A plurality of specific examples of reactive highly branched oligomers can have more than about 40% or more than about 50% of reactive end groups, based on the total number of terminal ends, as by known titration methods Decide. In certain embodiments, the reactive highly branched oligomer can have more than about 75% or more than 90% of reactive end groups, based on the total number of terminal ends, as determined by titration. . In further embodiments, the reactive highly branched oligomer can have from about 40% to about 98% of reactive end groups, from about 50% to about 95% of reactive end groups, or from about 60% to about 90%. The end group of % is based on the total number of branch terminals. As discussed above, the individual branch terminals can have more than one reactive end group. Thus, in certain embodiments, the reactive highly branched oligomer can have more than 100% reactive end groups. As discussed above, the term "reactive end group" is used to describe any chemical moiety that is capable of reacting with other chemical moieties at the branching end. A large number of reactive functional groups are known in the art and are encompassed by the present invention. In a particular embodiment, the reactive end group can be a hydroxyl, epoxy, vinyl or isocyanate group.

Without wishing to be bound by theory, the reactive highly branched oligomers of the present invention may have a low melt viscosity when sheared (as compared to linear oligomeric phosphonates) due to their highly branched nature. Thus, the reactive highly branched oligomers described herein can be blended with monomers, oligomers, and polymers without reducing the melt process capability. Thus, a plurality of specific examples of highly branched oligomeric phosphonates provide better meltability and improved processing. In addition, the reactive highly branched oligomers of the present invention can have higher molecular weights and provide greater reactivity, increase cross-linking of polymer compositions, and improve their toughness over the use of linear oligomeric phosphonates. A similar composition was prepared. In some specific examples The reactive highly branched oligomers of the present invention can be used in thermoplastics as reactive or non-reactive additives to improve shear thinning. For example, highly branched oligomers can be prepared to have no or very little reactive end groups which can be used to modify shear thinning without reacting or crosslinking the polymer to which the oligomer has been added.

A number of specific examples of oligomeric phosphonates, including linear and highly branched oligomeric phosphonates, can have high molecular weight and/or narrow molecular weight distribution (ie, low polydispersity). For example, in certain embodiments, the oligomeric phosphonate can have a weight average molecular weight (Mw) from about 1,000 grams per mole to about 18,000 grams per mole (as determined by η _rel or GPC), and in other specifics. In an example, the oligomeric phosphonate can have a Mw of from about 1,000 to about 15,000 grams per mole (as determined by η _rel or GPC). In this particular example, the number average molecular weight (Mn) can range from about 1,000 grams per mole to about 10,000 grams per mole, or from about 1,000 grams per mole to about 5,000 grams per mole; and in certain embodiments Wherein Mn can be greater than about 1,200 grams per mole. In certain embodiments, the narrow molecular weight distribution (i.e., Mw/Mn) of the oligomeric phosphonate can range from about 1 to about 7, and in other embodiments from about 1 to about 5. In still other embodiments, the co-oligomer (phosphonate carbonate) can have a relative viscosity (η _rel ) of from about 1.01 to about 1.20. Without wishing to be bound by theory, the relatively high molecular weight and narrow molecular weight distribution of the oligomeric phosphonates of the present invention may confer an excellent combination of properties. For example, the oligophosphonate of this specific example is extremely flame retardant and has excellent hydrolytic stability and can be imparted on a polymer bonded to the oligomeric phosphonate to produce such features as those described below. Polymer composition. Moreover, the oligomeric phosphonates of this specific example typically have excellent combinations of processing characteristics including, for example, good thermal and mechanical properties.

Some specific examples are directed to methods for making the oligomeric phosphonates of the present invention. Linear oligos such as those described above can generally be prepared by the methods described in U.S. Patent Nos. 6,861,499, 7, 816, 486, 7, 645, 850 and 7, 838, 604, and U.S. Publication No. 2009/0032, 770, incorporated herein by reference. In certain embodiments, the polymerization time can be reduced to reduce the number of monomer units incorporated into the oligomer. In other embodiments, a monomer unit having a molar excess of a hydroxyl functional group (such as, for example, an aromatic dihydroxy compound, a dihydric phenol or a bisphenol) may be provided in the reaction mixture to increase the linear oligomerization. The possibility that the two ends of the substance contain a hydroxyl end group.

Other specific examples are directed to methods for making reactive highly branched oligomers. For example, in various embodiments, a mixture of monomers (such as, for example, phosphonates and comonomers) can be provided; in the case of co-oligomers (phosphonate carbonates), phosphonates, Monomers and carbonate monomers or oligomers; or in the case of co-oligomers (phosphonates), the phosphonates and co-monomers can be combined with ester monomers or oligomers to prepare reactive height fractions Branch oligomers. The reaction mixture can include monomer mixtures (such as those described above), branching agents, catalysts, and various solvents and co-agents. In certain embodiments, the method can include the step of heating the reaction mixture; and in other embodiments, the method can include applying a vacuum to the reaction mixture during heating to remove volatile by-products of the reaction.

In certain embodiments, the components of the monomer mixture can vary among specific examples and can depend on the type of oligomer or co-oligomer to be synthesized. For example, some specific examples include phosphonate monomers such as diaryl phosphonates or diaryl phosphonates. The phosphonate monomer can have any structure and, in certain embodiments, can be of formula XIV: Wherein each R ⁶ and each R ⁷ may each independently be hydrogen, C ₁ -C ₄ alkyl; y and yy are each independently an integer from 1 to 5; and R may be C _1-20 alkyl , C _2-20 olefin, C _2-20 alkyne, C _5-20 cycloalkyl or C _6-20 aryl. In certain embodiments, the diaryl phosphonate can be diphenyl methylphosphonate (DPP) or oxidized methyl diphenoxy phosphine.

Without wishing to be bound by theory, in the preparation of the oligomeric phosphonates of the invention, high purity alkyl phosphinate diaryl esters or selectively substituted alkyl phosphonic acid diaryl esters are used, and in particular embodiments High purity DPP can provide improved properties over similar polymers or oligomers as described in the prior art. The phrase "high purity" with reference to a diaryl aryl phosphonate or a selectively substituted alkyl phosphinate and DPP is described as less than about 0.15% by weight total acidic component, less than about 0.10 weight. %, and in some embodiments, less than about 0.05% by weight. Such acidic components are known in the art and can include, but are not limited to, phosphoric acid, phosphonic acid, methylphosphonic acid, and monophenyl methylphosphonate. Since the alkyl phosphinate diaryl ester, the selectively substituted alkylphosphonic acid diaryl ester or DPP used in the preparation of the random copolymer of the present invention includes a low degree of this acidic component, these high purity are used. The oligomeric phosphonates produced by the phosphonate monomers can include a significant reduction in the extent of the acidic component contaminants. In certain embodiments, the oligophosphonate of this particular example may not substantially comprise an acidic component contaminant, and in other embodiments, the oligophosphonate of this particular example may comprise, for example, less than about 0.15 % by weight of total acidic components, less than about 0.10 % by weight, and in certain embodiments, less than about 0.05% by weight.

The comonomer can be any monomer, oligomer or polymer that is capable of reacting with the above phosphonate monomers in a polymerization reaction. For example, in certain embodiments, the comonomer can be an aromatic dihydroxy compound, a dihydric phenol, a bisphenol, and the like, or a combination thereof. Specific examples of such compounds include, but are not limited to, resorcinols, hydroquinones, and bisphenols such as bisphenol A, bisphenol F, and 4,4'-bisphenol, phenolphthalein, 4,4' - thiodiphenol, 4,4'-nonyl diol, 3,3,5-trimethylcyclohexyl diol. Any such compounds or combinations of such compounds can be used in the methods of the specific examples.

In a specific example comprising a carbonate monomer, the carbonate monomer can be any difunctional carbonate known in the art or a combination thereof. In certain embodiments, the carbonate monomer can be a diaryl carbonate monomer such as, but not limited to, diphenyl carbonate, 4-tributylphenyl-phenyl carbonate, di-(4) -Tris-butylphenyl)ester, biphenyl-4-yl-phenyl carbonate, di-(biphenyl-4-yl) carbonate, 4-(1-methyl-1-phenylethyl carbonate) -Phenyl-phenyl ester, di-[4-(1-methyl-1-phenylethyl)-phenyl]carbonate, and analogs thereof, and combinations thereof. In certain embodiments, the carbonate monomer can be diphenyl carbonate.

The branching agents used in the methods of the various specific examples may vary and may be included in the respective components or may be generated in situ by the action of the polymerization catalyst and the dihydroxy compound. For example, a branching agent can be topically dispersed from a dihydroxy compound by splitting or Fries recombination. Without intending to be limited by theory, a portion of the bisphenol A in the reaction mixture such as those described above may naturally undergo a reaction which increases the number of reactive hydroxyl groups (extended from the bisphenol A molecule), and the bisphenol A molecule acts as Branching agent. Bisphenol A and other similar aromatic dihydroxy groups Compounds may be referred to as "cleavable" dihydroxy compounds because they can carry out these reactions to topically branch species under polycondensation conditions.

In certain embodiments, the branching agent can be a polyfunctional acid, a polyfunctional diol, or an acid/diol mixture. In other embodiments, the highly branched oligomeric phosphonate may have a derivative derived from a tri- or tetrahydroxy aromatic compound or a triaryl or tetraaryl phosphate, a triaryl or tetraaryl carbonate or a triaryl or tetraaryl a unit of a base ester, or a combination thereof, such as, but not limited to, symmetrical trimellitic acid, pyroghuric acid, trimellitic anhydride, pyrogallanoic anhydride, trimethylolpropane, dimethyl hydroxy citrate, Neopentyl alcohol, and analogs thereof, and combinations thereof. This branching agent provides a branching point within the highly branched oligomeric phosphonate.

In a particular embodiment, the branching agent can be a triaryl phosphate such as, for example, those of formula VIII: Wherein each of R ³ , R ⁴ and R ⁵ may independently be hydrogen, C ₁ -C ₄ alkyl; and p, q and r are each independently an integer of from 1 to 5. In various embodiments, the branching agent can be 1,1,1-tris(4-hydroxyphenyl)ethane, triaryl phosphate, tri- and tetra-functional carbonates or esters, and the like. And combinations thereof; and in certain exemplary embodiments, the branching agent can be triphenyl phosphate. In certain embodiments, the trihydroxy and tetrahydroxy compounds used to prepare the specific examples of the oligomeric phosphonates can include, but are not limited to, phloroglucinol, 4,6-dimethyl-2,4,6 -tris-(4-hydroxyphenyl)-2-heptene, 4,6-dimethyl-2,4,6-tris-(4-hydroxyphenyl)-heptane, 1,3,5-three -(4-hydroxyphenyl)-benzene, 1,1,1-tris-(4-hydroxyphenyl)-ethane, tris-(4-hydroxyphenyl)-phenylmethane, 2,2-dual- [4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane, 2,4-bis-(4-hydroxyphenyl)isopropylphenol, 2,6-bis-(2'-hydroxyl -5'-methylbenzyl)-4-methylphenol 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenol)-propane, tetra-(4-hydroxyphenyl)methane, Tetra-[4-(4-hydroxyphenylisopropyl)phenoxy]-methane, 1,4-bis-(4,4"-dihydroxytriphenylmethyl)-benzene, and analogs thereof Combinations and mixtures thereof.

The branched dose added to the reaction (whether the branching agent is combined with other monomers prior to heating, added after heating has begun, or both) can be similar and can vary among specific examples. In various embodiments, the branching agent can provide an amount of from about 0.5 mole percent or from about 1 mole percent to up to about 10 mole percent or more. For example, in some embodiments, the total branching agent provided can be 1% or more, 2% or more, 3% or more, 4% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, 9 mol% or more, or 10 mol% or more. In certain embodiments, more than the total phosphonate monomer and the branching agent can be included in the monomer mixture (and in specific examples, including carbonate components, phosphonate monomers, branching agents, and carbonates) The molar excess of the monomer) provides a co-monomer (such as an aromatic dihydroxy compound, a dihydric phenol, a bisphenol, or a combination thereof). Without wishing to be bound by theory, the molar excess of the dihydroxy compound can increase the number of terminal hydroxyl groups in the reactive highly branched oligomers of the present invention, allowing for the manufacture of oligomers having a majority of terminal hydroxyl groups.

The methods of the specific examples may generally require a catalyst, and any catalyst known in the art to facilitate transesterification or condensation may be used and described herein. Method connection. For example, in some embodiments, the oligomerization catalyst can include a catalyst mixture, and in some cases, a common catalyst. In some embodiments, the catalyst can be an alkali gold, alkaline earth or other metal catalyst such as, but not limited to, sodium phenoxide.

In other embodiments, the catalyst useful in the methods of the present invention may not include alkali gold, alkaline earth or other metal cations. This catalyst can be removed by evaporation, sublimation or thermal decomposition with other volatile components by heating during the condensation reaction. Because the materials produced do not include metals, an additional advantage of the reactive highly branched oligomers can be improved hydrolytic stability. In a particular embodiment, the oligomerization catalyst can be XV: Wherein Y may be nitrogen, phosphorus or arsenic; +c represents a charge associated with Y; and R _a , R _b , R _c and R _d may each independently be phenyl, tert-butyl, methyl, ethyl, or propyl. a butyl or butyl group, provided that the catalyst acts as an oligomerization catalyst; and a system A counter anion such as, but not limited to, a phenate, acetate, borohydride, halogen, hydroxide , propionate, formate, butyrate, and the like; and -c are the charge associated with A. In certain embodiments, Y is phosphorus; R _a , R _b , R _c and R _d are phenyl; and anionic phenate or acetate. In some embodiments, the catalyst can be a catalyst such as, for example, a tetraphenylphosphonium catalyst or a derivative thereof and related anions such as tetraaryl borohydrides, halides, and substituted or Unsubstituted phenate group). In a particular embodiment, the catalyst can be phenyltetraphenylphosphonium.

The oligomerization catalyst can be added in any form. For example, the catalyst can be added to the reaction mixture or monomer mixture, such as a solid (such as a powder) dissolved in a solvent, or as a melt. This catalyst can be provided in any amount required to promote oligomerization, and the amount of the catalyst can be used to control the reaction rate and control the molecular weight. A skilled person can determine the appropriate amount of catalyst to be used in the methods embodied herein. In some embodiments, the molar amount of catalyst used (relative to the molar amount of comonomer or bisphenol) can range from about 0.00004 moles to about 0.0012 moles per mole of comonomer. If it is desired to increase the molecular weight of the oligomeric phosphonate, the amount of catalyst (catalyst having a lower vapor pressure) or the lower pressure of the vessel can be used to increase the molecular weight.

In certain embodiments, in addition to the one or more catalysts, the reaction can further comprise one or more co-catalysts (which can be provided to increase the oligomerization rate). The cocatalyst may, for example, be a salt of an alkali metal salt or an alkaline earth metal salt such as, for example, a hydroxide, an alkoxide or an aryloxide of lithium, sodium and potassium. In certain embodiments, the alkali metal salt can be a sodium hydroxide, alkoxide or aryloxide salt, and in certain embodiments, the cocatalyst can be sodium hydroxide and sodium phenoxide. The amount of co-catalyst provided can vary and can be, for example, from about 1 microgram/kg to about 200 micrograms/kg, from 5 micrograms/kg to 150 micrograms/kg, and in some embodiments, from about 10 micrograms/kg to about 125 μg/kg, in each case based on the mass of the aromatic dihydroxide used, in each case in terms of sodium. In certain embodiments, the oligomeric phosphonates of the invention can be prepared without a cocatalyst.

Generally, the methods described herein include a heating step in which a reaction mixture comprising a phosphonate monomer, a comonomer, and a catalyst is added. Heat to a suitable reaction temperature. In this embodiment, the reaction mixture can be heated to a temperature at which the components of the reaction mixture are melted and oligomerized (when the molten component of the reaction mixture is stirred). Therefore, the reaction proceeds "in the melt". In certain embodiments, the reaction temperature can range from about 100 °C to about 350 °C, and in other embodiments, the reaction temperature can range from about 200 °C to about 310 °C. In a further embodiment, the temperature can be varied within the range provided above during the reaction without limitation.

In various embodiments, the oligomerization process of the invention can be carried out under reduced pressure, and in certain embodiments, the reaction mixture can be rinsed. The pressure of the reaction vessel is typically selected to assist in the removal of volatile reaction products, excess reagents, and volatile oligomerization catalysts (such as the above-described catalysts) from the reaction vessel during oligomerization. In some embodiments, the pressure can be selected to allow removal of volatile compounds, such as phenols produced by the reaction and heating. Without limitation, the pressure may range from greater than atmospheric to subatmospheric, and one of ordinary skill in the art may determine the appropriate pressure to achieve this effect based on the composition of the reaction mixture. In a more specific exemplary embodiment, during any reaction, at any point in time, the pressure in the reaction vessel is from about 760 mm Hg to about 0.05 mm Hg, from about 500 mm Hg to about 0.1 mm Hg, Or about 400 mm Hg to about 0.3 mm Hg.

Generally, when a certain amount of excess reagent and volatile reaction product is removed from the vessel, the reaction is completed to provide a desired transparency, _Tg , _Mw , relative viscosity, and polydispersity for consideration. An oligomeric phosphonate for the intended use. The reaction time may depend on a number of factors including, but not limited to, reaction temperature, component concentration, total volume of the reaction mixture, rate of removal of reactants from the vessel, addition of catalyst, including multiple heating steps, and Similar factors and combinations thereof. During the oligomerization, volatile compounds such as phenol are released and can be evaporated at elevated temperatures, under reduced pressure and/or flushed with an inert gas. The reaction can continue until the desired degree of condensation is reached, and in some embodiments, the degree of condensation can be determined based on the reduction or termination of the evolution of the volatile compound. In some embodiments, the reaction time can be less than about 10 hours. For example, in various embodiments, the reaction time can range from about 3 hours to about 8 hours, from about 4 hours to about 6 hours, or any time in between.

A number of specific examples are directed to methods of oligomerization in "melts" under the conditions required for "melt oligomerization." The reaction conditions for the melt oligomerization are not particularly limited, and melt oligomerization can be carried out under a wide range of operating conditions. In a particular embodiment, melt oligomerization can be referred to as achieving a combination of a diaryl alkylphosphonate or a diaryl alkylphosphonate (with a diaryl carbonate (a diaryl ester or oligomer thereof) And the conditions required for the reaction between one or more dihydroxy aromatic comonomers and a volatile transesterification catalyst. Generally, this reaction can be carried out in a moisture-free and oxygen-free environment under reduced pressure and/or an inert gas such as, for example, nitrogen or argon. The temperature of the reaction vessel of this melt oligomerization process can range from about 100 °C to 350 °C, or in some embodiments, from 200 °C to 310 °C.

In certain embodiments, the melt oligomerization can be carried out in one or more stages, such as those described above, and in particular embodiments, the oligomerization stage can include the addition of an additional oligomerization catalyst. For example, in some embodiments, the oligomerization catalyst and/or co-catalyst may be added to the reaction mixture melt together in one stage, and in other embodiments, in one stage The oligomerization catalyst is added to the reaction mixture and the co-catalyst can be added to the reaction mixture in different stages. In still other embodiments, an oligomerization catalyst can be added to the reaction mixture in a continuous or semi-continuous manner, wherein one or more stages of the process are combined to form a continuous process. Thus, specific examples include the preparation of oligomeric phosphonates, random or block co-oligomers (phosphonates) and co-oligomeric (phosphonate carbonates) and highly branched oligomeric phosphines in batch or continuous flow processes. Acid esters, random or block co-oligomers (phosphonates) and co-oligomers (phosphonate carbonates).

In still other embodiments, a reaction mixture can be produced by combining a diaryl phosphonate, a diaryl or diaryl carbonate monomer, and an aromatic dihydroxy co-monomer with a catalyst, and heating the reaction mixture. The mixture is used to prepare a co-oligo (phosphonate) and a co-oligo (phosphonate carbonate). When the monomers are oligomerized, the branching agent can be added during the heating step or additional branching agents can be added. In a further embodiment, the method can be carried out in the absence of a branching agent to provide substantially unbranched oligomeric phosphonates, random co-oligomers (phosphonates), and co-oligomeric (phosphonate carbonates) Ester), and block co-oligomers (phosphonates) and co-oligomers (phosphonate carbonates).

In general, heating can be stopped when volatile by-products (such as phenols) of the reaction are no longer released from the reaction; however, in some embodiments, it can be used after the volatile by-products have ceased to be evolved. A second heating step. This second heating step provides a devolatization step whereby the remaining monomers are removed, and in some embodiments, the remaining comonomer and remaining volatile byproducts are not added to the oligomeric phosphonate. The molecular weight of the co-oligomer (phosphonate) or co-oligomer (phosphonate carbonate).

Some specific examples include a method in which the terminal hydroxyl group accounts for the majority of the terminal groups of the oligomeric phosphonate to change the composition of the terminal group. For example, in certain embodiments, the highly branched terminal hydroxyl group is the majority of the oligomeric phosphonates by combining the highly branched terminal hydroxyl groups with the majority of the oligomeric phosphonates and the effective amount of epichlorohydrin. It is converted to a highly branched terminal epoxy oligophosphonate. The mixture can be reacted for a period of time sufficient to allow epichlorohydrin to react with the terminal hydroxyl group to produce an epoxy group at one end, as set forth below: Wherein B represents the highly branched oligomer, which may be an oligomeric phosphonate having a terminal hydroxyl group, a random or block co-oligomer (phosphonate) or a co-oligo (phosphonate carbonate). Although four terminal hydroxyl groups are illustrated for simplicity, the highly branched oligomers of various embodiments may include any number of branches. The terminal epoxy-based highly branched oligomers produced by this method can be reacted with various chemical functional groups present on monomers, oligomers or polymers, such as alcohols, organic carboxylic acids and salts, anhydrides, sulfhydryl groups. Chlorine, aldehyde, ketone, amine, mercaptan, Glina reagent, water, sodium hydroxide inorganic acid and salt.

In certain embodiments, the pressure and temperature during the oligomerization reaction can be adjusted to produce two or more stages during the reaction sequence, and in some embodiments, one or more of the stages can be The reactant or oligomerization catalyst was added to the reaction mixture during the course of the reaction. For example, in some embodiments, the reaction can have at least two stages: the first stage is performed until The production of volatile compounds has ceased or decreased significantly, and the second post-reaction phase has minimal production of volatile compounds. In this embodiment, the first stage may be from about 1 hour to about 6 hours, and the second stage may be from about 1 hour to about 6 hours, and the reaction temperatures of the first and second stages may each independently be From about 100 ° C to about 350 ° C, and both the first and second stages can be carried out under reduced pressure. It is not intended to be limited by theory, and the method comprising the second stage produces an oligomeric phosphonate having a hydrolytic stability better than a method having only one stage.

In other embodiments, the method may consist of one or more than two stages. For example, in certain embodiments, when the volatile compound is produced, the reaction temperature can be incrementally increased to control the rate of reaction, the rate of evolution of volatile compounds, and/or the pressure in the reaction vessel. In each individual step, pressure, temperature, or both temperature and pressure can be increased or decreased. For example, in some embodiments, the temperature can be increased in the first step while maintaining the pressure fixed, and the pressure can be increased in the second step while the temperature is still fixed. In the third step, the temperature can be increased and the pressure can be decreased simultaneously, and in the fourth step, the temperature can be lowered and the pressure can be increased simultaneously. Specific examples may further include the step of maintaining the temperature and pressure within the container. These steps can be combined in any order, and in other exemplary embodiments, additional similar steps can be incorporated into the method of the specific example. The number of such reaction steps or stages is not limited, and in various embodiments, the number of reaction steps may be from 2 to 10, from 3 to 8, and in some embodiments, from 5 to 7 and between these ranges Any number.

In certain exemplary embodiments, the reaction temperature for each step of the process can range from about 150 ° C to about 400 ° C, and in other embodiments, the party The reaction temperature for each step of the process can range from about 180 °C to about 330 °C. In this particular example, the residence time for each step can range from about 15 minutes to about 6 hours, and the pressure for each step can range from about 250 mbar to about 0.01 mbar. In some embodiments, the reaction temperature can be increased from one step to another, and the pressure can be reduced from one step to the next.

For example, in some embodiments, the aromatic dihydroxide, the diaryl carbonate, the diaryl alkylphosphonate, and the transesterification of at least one catalyst in the melt are carried out in a two-step process. Preferably. In the first stage, the melting of the aromatic dihydroxide, the diaryl carbonate and the alkylphosphonic acid diaryl ester can be carried out at a temperature of from about 80 ° C to about 250 ° C, from about 100 ° C to about 230 ° C, and In certain embodiments, from about 120 °C to about 190 °C. This first stage can be carried out at atmospheric pressure and can be carried out for from about 0 hours to about 5 hours, and in certain embodiments, from about 0.25 hours to about 3 hours. After melting, a catalyst may be added to the melt, and the co-oligomer (phosphonate carbonate) may be applied from an aromatic dihydric acid, a diaryl carbonate, and an alkyl aryl diaryl ester by application. Vacuum (up to about 2 mm Hg), increased temperature (up to about 260 ° C), and evaporation of monophenols produced as by-products of the condensation. The co-oligomer (phosphonate carbonate) thus prepared may have an average molecular weight Mw (by measuring a relative solution in a mixture of phenol/o-dichlorophenol in methylene chloride or in an equal amount (by weight)) Viscosity, as determined by light scattering correction, ranges from about 1000 to about 18,000, and in some embodiments, from about 1,000 to about 11,000. In this particular example, up to about 80% monophenol can be recovered from the process.

In the second stage, the reaction temperature can be increased to between about 250 ° C and 320 ° C or from about 270 ° C to about 295 ° C, and the pressure can be reduced to less than about 2 mm Hg. Additional by-product monophenols can be recovered in the second step. The amount of monophenol produced in the second step may be less than the amount of monophenol produced in the first step because the monophenol is the end group in the co-oligomer (phosphonate carbonate) in the reaction. Lost results. For example, the amount of monophenol produced can be less than about 5%, less than about 2%, or less than about 1% of the amount of monophenol produced in the first step.

In the manufacture of the oligomeric phosphonate of the present invention, the monophenol which is eliminated during the transesterification of the aromatic dihydroxide, the diaryl carbonate, the diaryl aryl phosphonate can be used in the diaryl carbonate. The ester is purified and isolated before synthesis. The crude monophenol separated during the transesterification may be contaminated, in particular, containing a diaryl carbonate, a dialkyl aryl phosphonate, an aromatic dihydroxide, water, depending on the transesterification conditions and evaporation conditions. Salicylic acid, isopropenylphenol, phenyl phenoxybenzoate, Ketones, hydroxycarbonic acid monoaryl esters and the like. This purification can be achieved by conventional purification methods such as evaporation or recrystallization. The purity of the monophenol after purification may be greater than 99%, greater than 99.8%, or greater than 99.95%.

The process for making the oligomeric phosphonates of the present invention can be carried out in batch, semi-batch or continuous processes. The reactor structure used in this method is not particularly limited as long as the reactor has ordinary stirring, heating, decompression capabilities, and includes reagents for adding and removing reagents, solvents, removable catalysts, and/or Or the reaction of by-products. The reactor may be equipped with, for example, a temperature controlled condenser or a finger condenser for selectively removing by-product hydroxyaromatic compounds or phenol derived compounds produced during oligomerization.

A plurality of specific examples of methods can be used, for example, in a stirred tank, a membrane evaporator, a falling film evaporator, a stirred tank cascade, an extruder, a kneader, a simple tray reactor, and a disk reaction for a high viscosity substance. And its combination Row. Apparatus, equipment, and reactors suitable for the respective reaction evaporator stages may be in accordance with the procedures of the method, and may include, but are not limited to, heat exchangers, flashers, separators, columns, evaporators, stirred vessels , reactor and any other commercially available equipment (which provides the residence time required at the selected temperature and pressure). The device selected must permit the necessary heat input and must be designed to be suitable for continuously increasing melt viscosity. A variety of devices can be connected to each other via pumps, lines, valves, and the like, and combinations thereof. The line between all facilities is as short as possible and the number of bends in the conduit is kept as small as possible to avoid unnecessary extended residence time.

Other specific examples of the invention are directed to at least one oligomeric phosphonate, random or block co-oligo (phosphonate) and co-oligo (phosphonate carbonate) and highly branched oligomeric phosphonates. , random or block co-oligomer (phosphonate) and co-oligomer (phosphonate carbonate) and oligomer composition of at least one polymer or second oligomer or monomer. This includes oligomeric phosphonates and polymers or compositions of second oligomers or monomers referred to herein as "polymeric compositions." The at least one polymer or second oligomer or monomer can be any commercial or engineering plastic, and the polymer composition can be made by blending, mixing or combining the constituent polymers and oligomers. As used herein, "engineering plastic" includes both thermoplastic plastics and thermosetting resins, and may include, but is not limited to, polycarbonates, epoxide-derived polymers, polyepoxides (eg, from One or more epoxy-based monomers or oligomers with one or more chain extenders or hardeners (such as mono- or polyfunctional phenols, amines, benzoates) , anhydride or a combination thereof), benzo Classes, polyacrylates, polyacrylonitriles, polyesters [such as poly(ethylene terephthalate), poly(p-propyl phthalate) and poly(butylene phthalate)], unsaturated polyesters Polyamides, polystyrenes (including high impact polystyrene), polyureas, polyurethanes, polyphosphonates, polyphosphates, poly(acrylonitrile butadiene styrene), Polyimine, polyarylate, poly(aryl ether), polyethylene, polypropylene, polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride, double mala An imine polymer, a polyanhydride, a liquid crystal polymer, a cellulose polymer, or any combination thereof. Thus, the polymer or second oligomer may comprise or partially comprise one or more of polycarbonate, polyacrylate, polyacrylonitrile, polyester, polyamine, polystyrene, polyurethane, poly Epoxy resin, poly(acrylonitrile butadiene styrene), polyimide, polyarylate, poly(aryl ether), polyethylene, polypropylene, polyphenylene sulfide, poly(vinyl Ester), polyvinyl chloride, bismaleimide polymer, polyanhydride, liquid crystal polymer, polyether, polyphenylene ether, cellulose polymer, benzo Hydrolyzed, stable polyphosphonates, and analogs thereof, and combinations of these. In certain embodiments, the polymer or second oligomer or monomer can include a functional group capable of chemically reacting with a terminal group of an oligomeric phosphonate of a specific example, and comprising an oligophosphonate in the oligomeric phosphonate In some specific examples of the majority of terminal hydroxyl groups or epoxy groups or vinyl groups, the polymer or second oligomer may include a functional group capable of reacting with a hydroxyl group or an epoxy group or a vinyl terminal group.

Due to the structure and nature of the oligomeric phosphonates of this specific example, the polymer compositions described herein can have unusual flame resistance and good melt processing characteristics. For example, in general, the polymer composition of the present invention can have a limiting oxygen index (LOI) of at least about 27. The oligomeric phosphonates of the present invention further provide flame resistance and dimensional stability while maintaining a high heat distortion temperature (HDT) close to the unmodified engineered polymer.

In certain embodiments, the oligomeric phosphonates of the present invention can be combined with a prepolymer mixture of selected components to produce polymers such as those described above under conditions suitable for polymerization. For example, in various embodiments, oligomeric phosphonates such as those described above can be used with to produce polycarbonates, polyacrylates, polyacrylonitriles, polyesters, polyamines, polystyrenes, polyamines. Formate, polyurea, polyepoxy, poly(acrylonitrile butadiene styrene), polyimide, polyarylate, poly(aryl ether), polyethylene, polypropylene, polyphenylene Thioether, poly(vinyl ester), polyvinyl chloride, bismaleimide polymer, polyanhydride, liquid crystal polymer, polyether, polyphenylene ether, cellulose polymer, benzo a prepolymer mixture of hydrolyzed stabilized polyphosphonates and monomers thereof, and which can be heated and mixed until a viscous polymer is formed, or in other embodiments, the mixture can be hardened The agent and the mixture can continue to be mixed until a hardened polymer is formed.

In a particular embodiment, the polymer associated with the oligomeric phosphonate of the present invention can be an epoxy resin. For example, in certain embodiments, the oligomeric phosphonate (and, in particular, the highly branched oligomeric phosphonate) can be combined with an epoxy resin or a prepolymer or mixture of suitable monomers to produce an epoxy. Resin. In this particular example, any epoxy resin can be used, and in certain embodiments, the resin can comprise a glycidyl group, an alicyclic epoxy group, oxygen A group, an ethoxyline group, or a similar epoxy group, or a combination thereof, can be reacted with a hydroxyl group or an epoxy resin bound to the oligomeric phosphonate. Such epoxy resins are well known in the art and include, but are not limited to, novolak type epoxy resins, cresol novolac epoxy resins, trisphenol type epoxy resins, aralkyl type epoxy resins, having a biphenyl skeleton Aralkyl type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, heterocyclic type epoxy resin, epoxy resin containing naphthalene ring, bisphenol-A type epoxy compound, a bisphenol-F type epoxy compound, a quinone type epoxy resin, a trimethylol-propane type epoxy resin, a terpene-modified epoxy resin, obtained by oxidizing an olefin bond with peracetic acid or a similar peracid Linear aliphatic epoxy resin, cycloaliphatic epoxy resin or sulfur-containing epoxy resin. In some embodiments, the epoxy resin can be composed of two or more epoxy resins of any of the foregoing types. In a particular embodiment, the epoxy resin can be an aralkyl type epoxy resin, such as an epoxy resin derived from bisphenol A or methylene diphenylamine. The epoxy resin may also include one or more additional components such as, for example, benzo a compound or a resin, and in some embodiments, the oligomeric phosphonate can be used as an epoxy modifier, a crosslinking agent for an epoxy resin, or in an epoxy resin polymer composition. Epoxy resin hardener.

In certain embodiments, the polymer compositions described herein may further comprise additional components, fillers, fibers (such as, but not limited to, shredded or continuous glass fibers, metal fibers, linalyl fibers, Carbon fiber or ceramic fiber), surfactant, organic adhesive, polymer adhesive, crosslinker, diluent, coupling agent, flame retardant, anti-dripping agent (such as fluorinated polyolefin, polyfluorene) And lubricants, mold release agents (such as neopentyl glycol tetrastearate), nucleating agents, antistatic agents (such as conductive carbon black, carbon nanotubes), and organic antistatic agents (such as polyalkylene oxide) Carboxyl ether, alkyl sulfonate, perfluorosulfonic acid, perfluorobutane sulfinate potassium salt and polyamine-containing polymer), catalyst, colorant, ink, dye, antioxidant, stabilizer, and Its analogs and any combination thereof. In this specific example, the one or more additional components or additives may constitute From 0.001% by weight to about 1% by weight, from about 0.005% by weight to about 0.9% by weight, from about 0.005% by weight to about 0.8% by weight, from about 0.04% by weight to about 0.8% by weight, and in a particular embodiment, about 0.04% by weight % to about 0.6% by weight based on the total composition. In other embodiments, additional components (such as glass fibers or other fillers) may be provided at higher concentrations (up to 70 vol. %). For example, in some embodiments, the oligomeric phosphonate polymer composition can include up to about 70% by volume of glass fibers, and in other embodiments, the oligomeric polymer composition can include about 5 volumes. % to about 70% by volume, from about 10% by volume to about 60% by volume, or from about 20% by volume to about 50% by volume of glass fibers.

Polymer compositions comprising oligomeric phosphonates and other engineering polymers and/or additional components or additives can be prepared by conventional methods. For example, in some embodiments, the individual constituents can be mixed in a known manner and in a conventional concentrator (such as a closed kneader, extruder or twin propeller apparatus) at a temperature of about 200 ° C to about It is subjected to melt compounding and/or melt extrusion at 400 °C. The individual constituents can be taken sequentially or simultaneously and at about room temperature (about 20 ° C) or at a higher temperature. For example, in some embodiments, engineering plastics and/or all additional components or additives can be introduced into the oligomeric phosphonate by compounding. In other embodiments, the individual constituents can be separately introduced into the melt comprising the oligomeric phosphonate in different stages of the preparation process. Thus, for example, during or at the end of the transesterification of the aromatic dihydroxide with the organic carbonate and diphenylmethyl phosphonate, before or during the formation of the oligomeric phosphonate, or in the oligomeric phosphine The additive is introduced into the melt before or after the polycondensation of the acid ester.

The form in which the compound according to the invention is added is not limited. For example, engineering plastics and/or additional components or additives may be added as a solid (such as a powder) as a concentrate of the polycarbonate powder in solution. In an industrial embodiment, the side extruder can be operated, for example, at a throughput of from 200 to 1000 kilograms of oligomeric phosphonate per hour.

The polymer composition of a plurality of specific examples can be used in any application useful for the flame retardant polymer system. For example, in certain embodiments, the polymer composition of the present invention can be used as a coating on plastic, metal, glass, carbon, ceramic or wood products, wherein the product can be in a variety of forms, such as fibers, Models, laminates, foams, extruded shapes or the like, and in other embodiments, the polymer compositions of the present invention can be used to make free standing films, fibers, foams, molded articles and fibers Reinforced complex. This item is well suited for applications that require flame resistance. The oligomeric phosphonate of the present invention and the polymer composition comprising the same can have significant flame resistance and good melt process capability, so that these materials are used in applications requiring significant flame retardancy and high temperature performance. Useful in the automotive and electronics sectors with melting process capabilities. In addition, these items are well suited for a variety of applications, such as support parts, electrical components, electrical connectors, printed circuit laminates, electrical or electromagnetic enclosures that meet UL or other standardized fire resistance standards, electricity in consumable products, or Electromagnetic secondary components and components.

In certain embodiments, the polymeric composition comprising the oligomeric phosphonate of the present invention can be combined with other components or reinforcing materials. For example, in various embodiments, continuous or shredded glass fibers, carbon black or carbon fibers, ceramic particles or fibers, or other may be included in the polymer composition of the present invention. Machine material. In a particular embodiment, continuous or shredded glass fibers, carbon fibers, ceramic fibers, or other organic materials can be combined with a polymer blend including an epoxy resin to produce a prepreg to prepare a laminate. The laminate can be used to fabricate components (such as laminated circuit boards) that can be incorporated into articles of manufacture, such as electronic products, such as, for example, televisions, computers, laptops, printers, cellular phones. Video game consoles, DVD players, stereos and other consumable electronics.

The oligomeric phosphonates prepared as described above and the polymer compositions comprising these oligomeric phosphonates typically self-extinguish, i.e., they stop burning and remove any droplets produced by melting in the flame when the flame is removed. Stop burning and extinguish it almost immediately and it is not easy to spread the fire to any surrounding material. Moreover, these polymer compositions do not release significant smoke when a flame is applied.

Example

Although the invention has been described in great detail with reference to certain preferred embodiments thereof, other versions are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description and preferred versions included in the specification. The various aspects of the invention are set forth with reference to the following non-limiting embodiments. The following examples are for illustrative purposes only and are not to be construed as limiting the invention in any way.

Analysis feature

The amount of acidic component in diphenyl methylphosphonate (DPP) was measured by gas chromatography (GC) using a non-polar column (Optima 5). The sample after derivatization with N-methyl-N-(trimethyldecyl)trifluoroacetamide MSTFA was analyzed based on the area under the respective GC peaks.

The molecular weight distribution was determined by gel permeation chromatography (GPC) with UV detection (at 254 nm) by measuring 0.2% polymer solution in tetrahydrofuran. Instrumental calibration was performed with linear polystyrene (PS) standards of known molecular weight. Weight average (Mw), number average (Mn), and polydispersity (Mw/Mn) (referred to as PD) were evaluated from the chromatogram using WinGPC software.

End group analysis was performed using a Bruker Daltonics Reflex III matrix assisted laser desorption/ionization time-of-flight (MALDI-TOF) instrument. A sample was prepared using dihydroxynonanol as a matrix material, tetrahydrofuran (THF) as a solvent and no exogenous metal cation. The end group is determined by analysis of the peak mass (m/z) distribution obtained from the spectrum of each sample. The number of hydroxyl groups (mg KOH/g) was obtained by titration using an acetonitrile method. The oligomer sample was dissolved in an acetamidine solution (acetic anhydride in dry pyridine). Then, a catalyst (5% N-dimethylaminopyridine in dry pyridine) was added and stirring was allowed for 1 hour. Deionized water was added and stirred for half an hour before titration with alcohol to potassium hydroxide to the end point (from yellow to blue). Thymol blue was used as an indicator.

Example 1 Synthesis of hydroxyl terminated oligomers

A phosphonate oligomer having a hydroxyl end group is synthesized via a two-stage melt condensation method. The first stage was carried out in a 12 liter stainless steel reactor equipped with a mechanical stirrer and two serially connected reflux columns. 2,2-bis-(4-hydroxyphenyl)propane (BPA, 1800 g, 7.895 mol), diphenyl methylphosphonate (DPP) (1305 g, 5.262 Mo) was added to the reactor under nitrogen. Ear), and catalyst phenol tetraphenylphosphonium (TPPP (30% phenol), 0.51 g, 0.83 mmol). in The monomer/catalyst mixture was heated at 265 ° C for 5 hours with a gradual reduction in vacuum to 4 mm Hg. Both the top and bottom reflux column were heated to 135 °C. After 105 minutes, the bottom column temperature was increased to 150 ° C and the top column was lowered to 120 ° C. The phenol by-product was distilled off and collected in a graduated flask designated to be graduated. After 5 hours, the product was transferred via a stainless steel bridge to a 6 liter stainless steel reactor at 250 ° C under nitrogen. The reaction temperature was maintained at 250 ° C, maximum vacuum (< 0.5 mm Hg) for 3 hours and the distillation column was maintained at 200 °C. The product is extruded through a die at the bottom of the reactor into a liquid nitrogen bath and separated, such as a coarse white powder. See Table 1 for the characteristics.

Example 2 Synthesis of hydroxyl terminated oligomers

Phosphonate oligomers having a high degree of bishydroxy end group termination (>90%) were synthesized via a two-stage melt condensation process. This first stage was carried out in a 12 liter stainless steel reactor equipped with a mechanical stirrer and two serially connected reflux columns. 2,2-bis-(4-hydroxyphenyl)propane (BPA, 1800 g, 7.895 mol), diphenyl methylphosphonate (DPP) (1305 g, 5.262 Mo) was added to the reactor under nitrogen. Ear), and catalyst phenol tetraphenylphosphonium (TPPP (30% phenol), 0.51 g, 0.83 mmol). The monomer/catalyst mixture was heated at 265 ° C for 5 hours with a gradual reduction in the degree of vacuum to 10 mm Hg. Both the top and bottom reflux column were heated to 135 °C. After 105 minutes, the temperature of the bottom column was increased to 150 °C and the top column was lowered to 120 °C. The phenol by-product was distilled off and collected in a graduated flask designated to be graduated. After 5 hours, the product was transferred via a stainless steel bridge to a 6 liter stainless steel reactor maintained at 265 °C under nitrogen. At the beginning of the second phase, additional catalyst will be added (2.55 g) added to the reactor. The reaction was maintained at 265 ° C / 10 mm Hg for 2 hours while the distillation column was at 150 ° C. The distillation column temperature was then increased to 200 ° C and a maximum vacuum (< 0.5 mm Hg) was applied for 1 hour. The product is extruded through a die at the bottom of the reactor into a liquid nitrogen bath and separated, such as a coarse white powder. Table 1 provides a comparison of the characteristic data of the products obtained by the reactions described in Example 1 and Example 2 with respect to the processing conditions. Mw data was obtained by calibration of polystyrene standards using GPC (in THF). The end group composition was determined using MALDI-TOF analysis. The amount of the chain having a reactive hydroxyl group at both ends of the chain is represented by bis-OH.

The melt condensation is thermodynamically controlled as described above. Without any special precautions, this reaction will typically have an oligomer chain with a reactive hydroxyl group at the two ends, a chain having a hydroxyl group at one end and a non-reactive phenyl group at the other end, or two at the two ends. A chain of non-reactive phenyl groups produced a statistical distribution. Typically, the amount of any of these three types of chains is less than 80% when no special conditions are used. Example 1 shows that the amount of bis-OH chain is only 72%, which is relatively low for effective use in, for example, epoxy resin applications. When the specific reaction conditions as described in Example 2 were used, the amount of the bis-OH chain was surprisingly high.

Example 3 Synthesis of terminal hydroxyl co-oligomers (phosphonate carbonates)

Linear terminal hydroxyl co-oligomers (phosphonate carbonates) are synthesized using a two-stage melt condensation process. 2,2-bis-(4-hydroxyphenyl)propane (BPA, 1800 g, 7.895) was added to a 12 liter stainless steel reactor equipped with a mechanical stirrer and two serially connected reflux columns under nitrogen. Mohr), diphenyl methylphosphonate (DPP) (457 g, 1.843 mol), diphenyl carbonate (DPC, 732 g, 3.421 mol) and catalyst phenol tetraphenyl hydrazine (TPPP (30%) Phenol), 0.51 g, 0.83 mmol. The monomer/catalyst mixture was heated at 250 ° C for 5 hours with a gradual reduction in the degree of vacuum to 10 mm Hg. Both the top and bottom reflux column were heated to 135 °C. After 105 minutes, the temperature of the bottom column was increased to 150 ° C and the top column was lowered to 120 ° C. The phenol by-product was distilled off and collected in a graduated flask designated to be graduated. After 5 hours, the product was transferred via a stainless steel bridge to a 6 liter stainless steel reactor maintained at 250 ° C under nitrogen. At the beginning of the second stage, additional catalyst (0.51 grams) was added to the reactor. The reaction was maintained at 250 ° C / 10 mm Hg for 2 hours and the distillation column was at 150 ° C. The temperature of the distillation column was increased to 200 ° C and a maximum vacuum (< 0.5 mm Hg) was applied for 1 hour. The product is extruded through a die at the bottom of the reactor into a liquid nitrogen bath and separated, such as a coarse white powder. Characteristics: GPC (THF): Mw 2600, Mn 1300; Tg 85 ° C, 98% bis-OH (MALDI-TOF analysis). Surprisingly, the addition of DPC to the reaction mixture produces a composition of oligomeric phosphonates having an extremely high degree of at least two reactive hydroxyl groups.

Example 4 Synthesis of highly branched hydroxyphosphonate oligomers

Highly branched hydroxyl oligophosphonates via two-stage melt condensation Method synthesis. The first stage was carried out in a 12 liter stainless steel reactor equipped with a mechanical stirrer and two tandem connected reflux columns. 2,2-bis-(4-hydroxyphenyl)propane (BPA, 1764 g, 7.737 mol), diphenyl methylphosphonate (DPP) (1305 g, 5.262 Mo) was added to the reactor under nitrogen. Ear), 1,1,1-tris(4-hydroxyphenyl)ethane (THPE) (48.1 g, 0.157 mol) and catalyst phenol tetraphenylphosphonium (TPPP (30% phenol), 0.51 g, 0.83) Millions of ears). The monomer/catalyst mixture was heated at 265 ° C for 5 hours and the degree of vacuum was gradually reduced to 10 mm Hg. Both the top and bottom reflux column were heated to 135 °C. After 105 minutes, the temperature of the bottom column was increased to 150 ° C and the top column was lowered to 120 ° C. The phenol by-product was distilled off and collected in a graduated flask designated to be graduated. After 5 hours, the product was transferred via a stainless steel bridge to a 6 liter stainless steel reactor maintained at 265 ° C under nitrogen. At the beginning of the second stage, additional catalyst (2.55 grams) was added to the reactor. The reaction was maintained at 265 ° C / 10 mm Hg for 2 hours and the distillation column was at 150 ° C. The temperature of the distillation column was increased to 200 ° C and a maximum vacuum (< 0.5 mm Hg) was applied for 1 hour. The product is extruded through a die at the bottom of the reactor into a liquid nitrogen bath and separated, such as a coarse white powder. Characteristics: GPC (THF): Mw 2700, Mn 1400; Tg 82 ° C; hydroxyl number 76, 84% bis-OH, composed of 4% branched OH oligomer (MALDI analysis).

Example 5 Synthesis of highly branched hydroxyphosphonate oligomers

The highly branched hydroxyl oligophosphonates are synthesized via a two-stage melt condensation process. The first stage was carried out in a 0.5 liter glass reactor equipped with a mechanical stirrer and a reflux column. Add 2,2-bis-(4- to this reactor under nitrogen Hydroxyphenyl)propane (BPA, 95.4970 g, 0.4188 mol), diphenyl methylphosphonate (DPP) (84.6861 g, 0.3415 mol), 1,1,1-tris(4-hydroxyphenyl)B Alkane (THPE) (19.2780 g, 0.0630 mol) and catalyst phenol tetraphenylphosphonium (TPPP (30% phenol), 0.4019 g, 0.63 mmol). The monomer/catalyst mixture was heated at 265 ° C for 5 hours and the degree of vacuum was gradually reduced to 10 mm Hg. The reflux column was heated to 135 ° C and then lowered to 120 ° C after 105 minutes. Phenol by-products were collected in a graduated graduated flask. After 5 hours, the reflux column was closed and the reaction flask was attached to a glass bridge column that had been heated to 150 °C. At the beginning of this second stage, additional catalyst (2.0096 grams) was added to the reactor. The reaction was maintained at 265 ° C / 10 mm Hg for 1 hour, increased to 290 ° C for 0.5 hours, and then at maximum vacuum to 300 ° C for 10 minutes. The product was cooled to room temperature and isolated as a light brown solid. Characteristics: GPC (THF): Mw 14, 600, Mn 3700, PD 3.95, Tg 101 °C.

Example 6 Synthesis of terminal hydroxyl oligomers with higher Mw

Phosphonate oligomers having a hydroxyl end group and a higher molecular weight (as compared to in Example 2) are synthesized by varying the stoichiometry of the monomers and the reaction conditions. In a 12 liter stainless steel reactor equipped with a mechanical stirrer and two tandem reflux columns, 2,2-bis-(4-hydroxyphenyl)propane (BPA, 1870 g, 8.22) was added under nitrogen. Mohr), diphenyl methylphosphonate (DPP) (1695 g, 6.835 mol) and catalyst phenol tetraphenylphosphonium (TPPP (30% phenol), 0.585 g, 0.95 mmol). The monomer/catalyst mixture was heated at 265 ° C for 5 hours with a gradual reduction in vacuum to 4 mm Hg. Both the top and bottom reflux column were heated to 135 °C. After 105 minutes, the bottom column The temperature was increased to 150 ° C and the top column was lowered to 120 ° C. The phenol by-product was distilled off and collected in a graduated flask designated to be graduated. After 5 hours, the product was transferred via a stainless steel bridge to a 6 liter stainless steel reactor at 265 °C under nitrogen. The reaction temperature was increased to 300 ° C and allowed to react for 1 hour at maximum vacuum (< 0.5 mm Hg). The distillation column was set to 200 °C. The product is extruded through a die at the bottom of the reactor into a liquid nitrogen bath and separated, such as a coarse white powder. Features: GPC (THF): Mw 4400, Mn 3000; Tg 78 ° C; hydroxyl number 37 mg KOH / gram.

Example 7 Synthesis of terminal epoxy phosphonate oligomers:

Reaction of a terminal hydroxyphosphonate oligomer (Example 5) with an epoxy resin (diepoxypropyl ether of bisphenol A) at a ratio of 1:2 (based on reactive OH: epoxy equivalent) Touch (EPON) 828)). First, the oligomer was melted at 140 ° C before the epoxy resin was added. After 30 minutes, the catalyst 2-ethyl-4-methylimidazole (0.1 phr) was added and the reaction allowed for an additional 1.5 hours. The product was solid at room temperature and was soluble in MEK and THF. GPC results for the product in THF: Mw 4900; Mn 3200.

Example 8 Preparation of prepolymers based on phosphonates:

A 50 wt% terminal hydroxyphosphonate oligomer solution (Example 5) was prepared in DPP by stirring at 100 ° C for 6 hours. The solution was cooled to room temperature to produce a slightly yellow, clear, viscous liquid. The phosphonate oligomer solution in DPP was reacted with methylene diisocyanate in a 60:40 ratio (oligomer: MDI) to produce a phosphonate-based prepolymer.

Example 9 Hydroxyl oligomers in polyurethane-urea coatings:

A polyurethane-urea film was prepared by spraying a combination of A-side (diisocyanate) and B-side (diamine) onto a 6 inch x 18 inch poured concrete slab for combustion. Test (Scheme 1). The prepolymer 60/40 (oligomer/MDI) prepared in Example 8 was added to the A-side at 50% load. Each coating was 90 mils (0.09 inch) thick.

plan 1. Preparation of polyurethane-urea coating Example 10 Flame Retardant (FR) Behavior Testing of Polyurethane-Urea Coatings

The FR test is carried out in accordance with ASTM E-162, "Standard Method of Surface Burning Degree of Test Materials Using Radiant Thermal Energy Sources." The spray coated panels were mounted in the frame facing the radiant panel, but were angled down 30 degrees from the top. The pilot burner is adjusted to provide a 6" to 7" flame to provide ignition of the sample at the tip. Under the test, the material was burned down and the results were recorded by the Flame Diffusion Index (FSI), which measured the flame at the 3, 6, 9, 12 and 15 inch intervals from the top of the sample. Development time to determine. The maximum temperature increase resulting from the combustion sample was measured by eight thermometers connected in parallel and fixed in a stack of foils on the test sample. The FSI is derived from the following formula: Is=Fs×Q Among them, Is is the flame diffusion index, Fs is the flame diffusion factor and Q is the heat evolution factor. The flame spread classification system used by most of the model building codes and the National Fire Protection Association Life Safety Code, NFPA No. 101, includes the following:

Grade A (I)-0 to 25 flame diffusion index

Grade B (II) -26 to 75 flame diffusion index

Grade C (III) - 76 to 100 Flame Diffusion Index The results of the FSI test of the polyphosphate-urea coating containing the phosphonate-polyol prepared in Example 9 are provided in Table 2.

Example 11 Synthesis of terminal vinyl-hydroxy oligo

A phosphonate oligomer containing a vinyl ester, an isopropenyl end group, and a hydroxyl end group is synthesized via a two-stage melt condensation method. The first stage was carried out in a 12 liter stainless steel reactor equipped with a mechanical stirrer and two tandem connected reflux columns. 2,2-bis-(4-hydroxyphenyl)propane (BPA, 1800 g, 7.895 mol), diphenyl methylphosphonate (DPP) (1305 g, 1.843 Mo) was added to the reactor under nitrogen. Ear) and catalyst phenol tetraphenyl hydrazine (TPPP (30% phenol), 5.1 g, 8.3 mmol). The monomer/catalyst mixture was heated at 265 ° C for 5 hours with a gradual reduction in the degree of vacuum to 10 mm Hg. Will top Both the bottom reflux column and the column were heated to 135 °C. After 105 minutes, the temperature of the bottom column was increased to 150 ° C and the top column was lowered to 120 ° C. The phenol by-product was distilled off and collected in a graduated flask designated to be graduated. After 5 hours, the product was transferred via a stainless steel bridge to a 6 liter stainless steel reactor maintained at 265 °C under nitrogen. The reaction was carried out at 265 ° C / 10 mm Hg for 2 hours and the distillation column was at 150 ° C. The temperature of the distillation column was then increased to 200 ° C and a maximum vacuum (< 0.5 mm Hg) was applied for 1 hour. The product is extruded through a die at the bottom of the reactor into a liquid nitrogen bath and separated, such as a coarse white powder. Characteristics: GPC (THF): Mw 3100, Mn 1600; Tg 85 ° C; P% 9.1, hydroxyl number 77 mg KOH/g, MALDI-6% vinyl ester end group.

Claims (21)

A composition comprising an oligomeric phosphonate, wherein from about 60% to about 100% of the total oligomeric phosphonate has two or more reactive end groups, wherein the reactive end group is selected from the group consisting of A group of oxy, vinyl, vinyl ester, isopropenyl, isocyanate, and combinations thereof. The composition of claim 1, wherein the oligomeric phosphonate comprises an oligomeric phosphonate, a random co-oligomer (phosphonate), a block co-oligomer (phosphonate), and a random Oligomer (phosphonate carbonate) or block co-oligomer (phosphonate carbonate). The composition of claim 1, wherein the oligomeric phosphonate comprises a linear oligomeric phosphonate, a branched oligomeric phosphonate, or a combination thereof. The composition of claim 1, wherein the oligomeric phosphonate comprises a number average molecular weight of from about 500 g/m to about 5000 g/mole. The composition of claim 1, wherein the oligomeric phosphonate comprises a unit derived from bisphenol. The composition of claim 1, wherein the oligomeric phosphonate comprises a unit of formula I: Wherein: the Ar-based aromatic group and the -O-Ar-O- system are derived from a dihydroxy compound having one or more aryl rings; R-based C _1-20 alkyl, C _2-20 olefin, C _2-20 An alkyne, a C _5-20 cycloalkyl group or a C _6-20 aryl group; and n is an integer from 1 to about 10. The composition of claim 6 wherein the -O-Ar-O- is derived from resorcinol, hydroquinone, bisphenol A, bisphenol F, and 4,4'-bisphenol, phenolphthalein, 4 4'-thiodiphenol, 4,4'-nonyldiphenol, 3,3,5-trimethylcyclohexyldiol or a combination thereof. A polymer composition comprising: an oligomeric phosphonate, wherein from about 60% to 100% of the total oligomeric phosphonate has two or more reactive end groups, the reactive end groups being selected from a group consisting of an epoxy group, a vinyl group, a vinyl ester, an isopropenyl group, an isocyanate, and combinations thereof; and at least one polymer. The polymer composition of claim 8 wherein the oligomeric phosphonate comprises an oligomeric phosphonate, a random co-oligo (phosphonate), a block co-oligomer (phosphonate), A total oligo (phosphonate carbonate), block co-oligomer (phosphonate carbonate) or a combination thereof. The polymer composition of claim 8 wherein the oligomeric phosphonate comprises a linear oligomeric phosphonate, a branched oligomeric phosphonate or a combination thereof. The polymer composition of claim 8 wherein the oligomeric phosphonate comprises a number average molecular weight of from about 500 g/m to about 5000 g/mole. The polymer composition of claim 8 wherein the oligomeric phosphonate comprises units derived from bisphenol. The polymer composition of claim 8 wherein the oligomeric phosphonate comprises a unit of formula I: Wherein: the Ar-based aromatic group and the -O-Ar-O- system are derived from a dihydroxy compound having one or more aryl rings; R-based C _1-20 alkyl, C _2-20 olefin, C _2-20 An alkyne, a C _5-20 cycloalkyl group or a C _6-20 aryl group; and n is an integer from 1 to about 10. The polymer composition of claim 13 wherein the -O-Ar-O- is derived from resorcinol, hydroquinone, bisphenol A, bisphenol F, and 4,4'-bisphenol, phenolphthalein. 4,4'-thiodiphenol, 4,4'-nonyldiphenol, 3,3,5-trimethylcyclohexyl diphenol, or a combination thereof. The polymer composition of claim 8, wherein the polymer is an epoxy group or a polyurea. A polymer composition comprising: an oligomeric phosphonate, wherein from about 60% to about 100% of the total oligomeric phosphonate has two or more reactive end groups selected from the group consisting of And a combination of an epoxy group, a vinyl group, a vinyl ester, an isopropenyl group, an isocyanate, and combinations thereof; and an engineering polymer. The polymer composition of claim 16, wherein the engineering polymer is selected from the group consisting of polycarbonate, epoxide, epoxy-derived polymer, polyepoxide Benzo Classes, polyacrylates, polyacrylonitriles, polyesters, poly(ethylene terephthalate), poly(propylene terephthalate), poly(butylene phthalate), unsaturated polyester, poly Indoleamine, polystyrene, high impact polystyrene, polyurea, polyurethanes, polyphosphonates, polyphosphonates, poly(acrylonitrile butadiene styrene), polyphthalamide Amine, polyarylate, poly(aryl ether), polyethylene, polypropylene, polyphenylene sulfide, poly(vinyl ester), polyvinyl chloride, bismaleimide polymerization , polyanhydrides, liquid crystal polymers, cellulosic polymers, and combinations thereof. The polymer composition of claim 16 of the patent application, further comprising a filler, a cut or continuous glass fiber, a metal fiber, an organic fiber, an arylamine fiber, a carbon fiber, a carbon nanofiber, or a ceramic fiber, and an interfacial activity Agents, organic adhesives, polymer adhesives, crosslinkers, diluents, coupling agents, anti-pigmentation agents, fluorinated polyolefins, polyfluorenes, lubricants, mold release agents, tetrastearate Tetraol ester, nucleating agent, antistatic agent, conductive carbon black, carbon nanotube, organic antistatic agent, polyalkylene ether, alkyl sulfonate, perfluorosulfonic acid, perfluorobutane sulfinic acid Potassium salt, polyamine-containing polymer, catalyst, colorant, ink, dye, antioxidant, stabilizer, metal phosphinate, melamine cyanurate, melamine derivative, flame retardant, and combination. A manufactured article comprising an oligomeric phosphonate, wherein from about 60% to about 100% of the total oligomeric phosphonate has two or more reactive end groups selected from the group consisting of epoxy A group consisting of a vinyl group, a vinyl group, a vinyl ester, an isopropenyl group, an isocyanate, and combinations thereof. The article of manufacture of claim 19, wherein the article of manufacture is a coating selected from the group consisting of plastic, metal, ceramic or wood products, free-standing films, fibers, foams, molded articles, fiber-reinforced composites Supporting parts, electrical components, electrical connectors, printed circuit laminates, covers, secondary components and components, televisions, computers, laptops, printers, cellular phones, video game consoles, DVD players, Stereo, digital music player, portable VCR and touch screen. The article of manufacture of claim 19, wherein the article of manufacture is a laminate or fiber reinforced composite used in the following: electrical components, electrical connectors, printed wiring boards, printed circuit boards, televisions, computers, knees Upscale portable computers, printers, photocopiers, scanners, cellular mobile phones, video game consoles, DVD players, stereos, digital music players, portable video recorders or touch screens.