RU2575339C2 - Randomised phosphonate/carbonate copolymers based on bisphenols having high molecular weight - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: randomised phosphonate/carbonate copolymer comprises randomly distributed ionomer links produced from carboxylic and phosphonic monomers. The copolymer has a weight-average molecular weight from approximately 10000 g/mol to approximately 100000 g/mol and a polydispersity from approximately 2 to approximately 7.

EFFECT: producing the randomised phosphonate/carbonate copolymers having a high molecular weight and a narrow molecular-weight distribution, and related products.

25 cl, 4 tbl, 23 ex

Description

Cross reference to related applications

This application claims the benefit of provisional application US No. 61/383697 entitled "Synthesis And Composition Of Linear, High Molecular Weight, Random, Bisphenol A-Based Copoly (Phosphonate Carbonate) s That Have A Specific Phosphonate Content And A Narrow Molecular Weight Distribution" , filed September 16, 2010, and provisional application US No. 61/383686, entitled "High Molecular Weight, Random, Bisphenol Based Copoly (Phosphonate Carbonate) s", filed September 16, 2010, which are incorporated herein by reference in their full volume.

Government investment: Not foreseen

Parties to the joint research agreement: Not foreseen

Inclusion of material provided on the CD-ROM by reference: Not provided

Prerequisites: Not foreseen.

Summary of the invention

Various embodiments of the invention are directed to flame retardant / flame retardant statistical copolymers of phosphonate and carbonate obtained using at least 20 mol%. diphenylmethylphosphonate (DPP), based on the total number of DPP transesterification components, and diphenyl carbonate (DPC), and bisphenol A (BPA), and a specific volatile transesterification catalyst with both high molecular weight and narrow molecular weight distribution. Various other embodiments are directed to a process and method for their manufacture using high purity DPP and at least one specific volatile metal-free catalyst, for example tetraphenylphosphonium phenolate (TPPP).

Other embodiments provide flame retardant / refractory properties of the structural statistical phosphonate and carbonate copolymers and polymer compositions comprising these statistical phosphonate and carbonate copolymers and another oligomer or polymer. These phosphonate-carbonate copolymers and polymer compositions, as a rule, can exhibit an excellent combination of properties, including good melt processability, good mechanical properties, good hydrolytic stability and good thermal stability (resistance to thermal aging), which is measured using the temperature of deformation when heated ( HDT).

Additional other embodiments are directed to industrial products made from random copolymers of the phosphonate and carbonate of the invention, as well as from polymer compositions including random copolymers of the phosphonate and carbonate of the invention and another oligomer or polymer. Flame retardant / flame retardant structural statistical copolymers of phosphonate and carbonate and polymer compositions of the invention can be used as coatings, or they can be used for the manufacture of adhesive compositions reinforced with fiber prepregs, individual films, fibers, foams, molded products and fiber-reinforced composite materials . They can be used as such or in any combination with other monomers, polymers, copolymers, oligomers, catalysts and fillers. Flame retardant / flame retardant structural statistical phosphonate and carbonate copolymers and polymer compositions can in turn be used as components, subcomponents or parts of more complex devices, such as household electronic equipment (such as televisions, computers, printers, photocopiers, fax machines , video players, electronic gaming systems, modems, cell phones and a number of other electronic devices and components).

I. Detailed Description

The above summary of the present invention is not intended to describe each illustrated embodiment or each possible implementation of the present invention. The detailed description that follows specifically illustrates these embodiments.

Before considering the described compositions and methods of the present invention, it should be noted that they are not limited to the specific compositions, methodologies or protocols described, as they may vary. It should also be noted that the terminology used in the description serves only the purpose of describing specific versions or embodiments and is not intended to limit their scope, which will be limited only by the attached paragraphs of the Formula.

It should also be noted that, as used in this document and in the attached paragraphs, the singular forms “a”, “an”, and “the” include the plural, unless the context clearly dictates otherwise. Unless otherwise specified, all technical and scientific terms used in this document have meanings identical to those commonly understood by one of ordinary skill in the art. Although any methods and substances similar or equivalent to the methods and substances described herein can be used in the practice or testing of the disclosed embodiments, preferred methods, devices and materials will be described below.

“Optional” or “optionally” means that a sequentially described phenomenon or circumstance may or may not occur, and that the description includes examples where this phenomenon occurs and examples where it does not occur.

“Significantly not” means that a sequentially described phenomenon can occur at least about 10% of the time, or a sequentially described component can comprise at least about 10% of the total composition, in some embodiments, and in others at least about less than 5%, and in additional others, at least about less than 1%.

The term "carbonate", as used herein, is given in its generally accepted meaning, for example, in the meaning of a carbonic acid salt containing a divalent, negatively charged CO radical group or an uncharged ester of this acid. "Diaryl carbonate" is a carbonate with at least two aryl groups linked to a radical group CO, where the predominant example of diaryl carbonate is diphenyl carbonate; however, the definition of diaryl carbonate is not limited to this specific example.

The term "aromatic dihydroxide" is believed to encompass any aromatic compounds with at least two substitutions via attached hydroxyl groups. Examples of “aromatic hydroxides” include, but are not limited to, benzene diols such as hydroquinone and any bisphenol or bisphenol-containing compounds.

The term “alkyl” or “alkyl group” refers to a branched or unbranched hydrocarbon or a group of 1-20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, octyl, decyl, but is not limited to tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. "Cycloalkyl" or "cycloalkyl groups" are branched or unbranched hydrocarbons in which all or some of the carbons are located in the ring, such as, but not limited to, cyclopentyl, cyclohexyl, methylcyclohexyl and the like. The term "lower alkyl" includes an alkyl group with 1-10 carbon atoms.

The term “aryl” or “aryl group” refers to monovalent aromatic hydrocarbon radical groups or to groups consisting of one or more fused rings in which at least one ring is aromatic in nature. Aryls may include, but are not limited to phenyl, naphthyl, biphenyl ring systems and the like. An aryl group may be unsubstituted or substituted by a variety of substituents, including, but not limited to, alkyl, alkenyl, halide, benzyl, alkyl or aromatic ether, nitro group, cyano group and the like.

"Substituent" refers to a molecular group that replaces hydrogen in a compound and may include trifluoromethyl, nitro, cyano, C ₁ -C ₂₀ alkyl, aromatic group or aryl, halide (F, Cl, Br, I), C ₁ -C ₂₀ alkyl ether, benzyl halide, benzyl ether, aromatic or aryl ether, hydroxy group, alkoxy group, amino group, alkylamino group (-NHR '), dialkylamino group (-NR'R'') or other groups that do not affect the formation of diaryl- alkylphosphonate, but not limited to this.

As defined herein, an “arylol” or “arylol group” is an aryl group with hydroxyl, OH, a substituent group on the aryl ring. Non-limiting examples of aryol are phenol, naphthalene and the like. A wide variety of aryols can be used in embodiments of the invention and are commercially available.

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

The term "alkenol" or "alkenol group" refers to a compound comprising an alkene with 2-20 carbon atoms or more, having at least one substituent hydroxyl group. Hydroxyl can be located in any isomeric configuration (cis or trans). Alkenols may be further substituted with one or more substituents as described above, and may be used instead of alkanols in some embodiments of the invention. Alkenols are known to those skilled in the art, and many are commercially readily available.

The terms “flame retardant”, “flame retardant”, “fire resistant” or “fire resistance”, as used herein, mean that the composition exhibits a limiting oxygen index (LOI) of at least 27. In addition to these terms may relate to criteria V0, V1 or V2 of the reference combustibility standard for UL-94 electronic product material compositions.

The term "hydrolytic stability", which is used in this document, is defined as the ability of a polymer to be resistant to hydrolysis in a test by boiling a sample in water. The ability to be resistant to hydrolysis can be measured by changing the relative viscosity after exposure, which indicates a change in molecular weight. For example, a sample of pure resin can be placed in clean water (three times distilled) for up to 168 hours under reflux conditions at normal pressure. At certain intervals, the samples can be taken and the relative viscosity (ŋ _rel ) can be determined by dissolving the sample in dichloromethane at 25 ° C at a concentration of 0.5 g of polymer / liter and by measuring the viscosity of the solution on a Ubbelode viscometer. A significant change in ŋ _rel after boiling in water is an indicator of a change in the molecular weight of the polymer due to hydrolysis. As a result of this test, a polymer with good hydrolytic stability will not show a significant change in ŋ _rel .

"Molecular mass", as used herein, can be determined using relative viscosity (ŋ _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 this solution and for a pure solvent to pass through a specially designed capillary (viscometer) at a constant temperature. Relative viscosity is a measure that serves as an indicator of the molecular weight of a polymer. It is also well known that a decrease in relative viscosity indicates a decrease in molecular weight, and a decrease in molecular weight causes a 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 the polymer is important with respect to properties such as thermal oxidative stability (due to the different number of end groups), toughness, melt flow and fire resistance, for example, low molecular weight polymers when burned are more likely to drip.

The term "toughness", as used in this document, is defined qualitatively on a film or on a molded sample.

Polycarbonates (PCs) are well-known structural thermoplastic materials that have an excellent combination of properties, such as high heat deformation temperature (HDT), low coloring ability, transparency, melt processability and exceptional impact strength. These materials are used in a wide variety of applications and are produced in large quantities in industry. However, polycarbonates do not have the necessary fire resistance, and there is still a need and need for fire resistant PCs, which at the same time retain their other advantageous properties. A variety of approaches have been used to impart fire resistance to these materials, but these approaches have been very unsuccessful since they have impaired the important internal properties possessed by PCs.

In all prior art materials regarding random copolymers of phosphonate and carbonate obtained by melt polycondensation of DPC, DPP and BPA, the formation of a high molecular weight random copolymer based on BPA with only a narrow molecular weight distribution has not been achieved. Another regular problem arising from the use of DPP in combination with polycarbonates is the reduced hydrolytic stability of the synthesized product. Thus, there is a need for a new process and a new method for producing phosphonate-carbonate copolymers containing significant amounts of DPP and exhibiting improved hydrolytic stability compared to materials known in the art.

Embodiments of the invention typically relate to a statistical phosphonate-carbonate copolymer and to processes and methods for their manufacture using melt polycondensation. In some embodiments, the implementation of these statistical copolymers of phosphonate and carbonate may include at least 20 mol%. high purity diaryl alkylphosphonate or optionally substituted diaryl alkylphosphonate, one or more diaryl carbonates and one or more aromatic dihydroxides, where the molar percentage of high purity diaryl alkylphosphonate is based on the total number of transesterification components, i.e. the total amount of diaryl- alkyl phosphonates and total diaryl carbonates. The term “statistical” means that the monomers of the copolymers of phosphonate and carbonate in various embodiments are incorporated into the polymer chain randomly. Therefore, the polymer chain may include alternating phosphonate and carbonate monomers linked by aromatic dihydroxide and / or various segments in which several phosphonate or several carbonate monomers form oligophosphonate or polyphosphonate or oligocarbonate or polycarbonate segments. In addition, the length of various oligo- or polyphosphonate, oligo- or polycarbonate segments may vary in individual copolymers of phosphonate and carbonate.

The phosphonate and carbonate content of the phosphonate and carbonate copolymers may vary between embodiments, and the embodiments are not limited to the phosphonate and / or carbonate content or the range of phosphonate and / or carbonate content. For example, in some embodiments, the phosphonate-carbonate copolymers may have a phosphorus content that is indicative of a phosphonate content of about 1% to about 20% by weight relative to the total phosphonate-carbonate copolymer, and in other embodiments, the phosphorus content of the phosphonate copolymers and the carbonate of the invention may be from about 2% to about 10% by weight relative to the total polymer.

The phosphonate and carbonate copolymers of various embodiments show both a high molecular weight and a narrow molecular weight distribution (i.e., low polydispersity). For example, in some embodiments, the phosphonate and carbonate copolymers may have a weight average molecular weight (Mw) of from about 10,000 g / mol to about 100,000 g / mol, as determined by ŋ _rel or the GPC method, and in other embodiments, the phosphonate and carbonate copolymers can have an Mw of from about 12,000 to about 80,000 g / mol, which is determined using ŋ _rel or the GPC method. The number average molecular weight (Mn) in such embodiments may be from about 5000 g / mol to about 50,000 g / mol or from about 8000 g / mol to about 15000 g / mol, and in some embodiments, the Mn may be more than about 9000 g / mol. The narrow molecular weight distribution (i.e., Mw / Mn) for such phosphonate-carbonate copolymers may be from about 2 to about 7 in some embodiments, and from about 2 to about 5 in other embodiments. In additional other embodiments, the implementation of the statistical copolymers of phosphonate and carbonate may have a relative viscosity of from about 1.10 to about 1.40.

Not wishing to be bound by any theory, it is believed that the use of diaryl alkylphosphonate or optionally substituted diaryl alkylphosphonate of high purity and in particular embodiments of high purity DPP in the preparation of the phosphonate and carbonate copolymers of the invention can provide improved properties compared to statistical copolymers of the prior art. Diaryl alkylphosphonate or optionally substituted “high purity” diaryl alkylphosphonate and DPP in various embodiments may include total acidic components in an amount of less than about 0.15% by weight, less than about 0.10% by weight, and in some embodiments exercise less than about 0.05% by weight. Such acidic components are known in the art and may include, but are not limited to, phosphoric acid, phosphonic acid, methylphosphonic acid and monophenyl methylphosphonic acid ester. Since the amounts of diaryl alkylphosphonate or optionally substituted diaryl alkylphosphonate or DPP used in the preparation of the statistical copolymers of the invention include low levels of such acidic components, the statistical phosphonate and carbonate copolymers obtained using these high-purity phosphonate monomers may include significantly reduced levels of contaminants based on acidic components. In some embodiments, the implementation of the statistical copolymers of phosphonate and carbonate may not substantially include contaminants based on acidic components, and in other embodiments, the implementation of the statistical copolymers of phosphonate and carbonate may include, for example, a total amount of acidic components of less than about 0.15% a mass of less than about 0.10% by mass, and in some embodiments, less than about 0.05% by mass.

Statistical copolymers of phosphonate and carbonate according to the invention, as a rule, exhibit a high molecular weight and a narrow molecular weight distribution, which, in turn, can give these materials an excellent combination of properties. For example, random copolymers of phosphonate and carbonate according to embodiments are typically tough (hard), extremely fire resistant, and exhibit excellent hydrolytic stability. In addition, the copolymers of phosphonate and carbonate according to the options for implementation, as a rule, exhibit an excellent combination of technological characteristics, including, for example, good thermal and mechanical properties.

In some embodiments, the statistical phosphonate and carbonate copolymers according to the invention can be used as such as a structural polymer, and in other embodiments, the statistical phosphonate and carbonate copolymers can be used as additives that are combined with other polymers to provide fire resistance without compromising other important properties. Some embodiments include industrial products and coatings derived from random copolymers of phosphonate and carbonate according to the invention per se or in combination with another polymer. In further other embodiments, structural polymers from the random copolymers of phosphonate and carbonate according to the invention and polymer compositions comprising the random copolymers of phosphonate and carbonate according to the invention can be combined with a reinforcing substance, such as, for example, glass, carbon black, silicon carbide, organic fibers and the like and combinations thereof, to obtain composite materials having an advantageous combination of fire resistance and dimensionally stable while maintaining a high temperature of deformation upon heating (HDT) close to the HDT of an unmodified structural polymer.

Other embodiments are directed to methods and processes for producing random copolymers of phosphonate and carbonate. For example, in some embodiments, such methods may include the steps of coupling one or more diaryl alkylphosphonates or optionally substituted diaryl alkylphosphonates, one or more diaryl carbonates, one or more aromatic dihydroxides and a transesterification catalyst and reacting one or more diaryl alkylphosphonates or optionally substituted diaryl alkylphosphonates, one or more diaryl carbonates, one or more aromatic dihydroxides, and a per esterification in the melt. In such embodiments, the diaryl alkylphosphonate may be a high purity diaryl alkylphosphonate and may be provided in an amount of at least 20 mol%. based on the total number of transesterification components of diaryl-alkylphosphonate and diaryl-carbonate in combination with BPA biphenol. In some embodiments, the diaryl alkylphosphonate may be DPP. As discussed above, high purity diaryl alkylphosphonate or optionally substituted diaryl alkylphosphonate in various embodiments may include all acidic components in an amount of less than about 0.15% by weight, less than about 0.10% by weight, and in some embodiments exercise less than about 0.05% by weight.

The polycondensation of various embodiments is carried out using a melt transesterification process, which is carried out under vacuum. Not wishing to be bound by any theory, it is believed that the transesterification under vacuum may involve the removal of volatile by-products. The transesterification in the melt can be carried out in a continuous or multi-stage (discontinuous) method, and in some embodiments, the transesterification in the melt can be carried out using a continuous process. The preparation of the diaryl carbonate used in the melt transesterification process for aromatic polycarbonates and copolymers of phosphonate and carbonate, for example, using a process at the phase boundary, is described generally in the literature, see, for example, publication in Chemistry and Physics of Polycarbonates , Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964), pages 50/51, which is hereby incorporated by reference in its entirety into this document.

Transesterification in the melt can be carried out in one stage or in several stages. For example, in some embodiments, the method may include a pre-condensation step in which the dihydroxyaryl compound (bisphenol) is reacted with a diaryl carbonate and diaryl-alkylphosphonate using at least one volatile catalyst to separate the phenol formed during the condensation, and in some embodiments, the method may include a post-reaction processing step in which the molecular weight of the condensate is increased after pre-condensation using one or more stages of evaporation of the reaction mass in the evaporator. The number of reaction steps 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.

In some embodiments, the reaction temperature for each step of the method may be from about 150 ° C. to about 400 ° C., and in other embodiments, the reaction temperature for each step of the method can be from about 180 ° C. to about 330 ° C. In such embodiments, the residence time at each stage can be from about 15 minutes to about 6 hours, and the pressure at each stage can be from about 250 mbar to about 0.01 mbar. In some embodiments, the reaction temperature may increase from one stage to another, and the pressure may decrease from one stage to the next. In embodiments comprising a two-step process, the transesterification reaction of aromatic dihydroxide, diaryl carbonate, diaryl alkyl phosphonate and at least one catalyst in the melt is preferably carried out in two stages. In a first step, the melting of aromatic dihydroxide, diaryl carbonate and diaryl alkylphosphonate 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 some embodiments, from about 120 ° C up to approximately 190 ° C. The first stage can be carried out at atmospheric pressure and can be carried out over a period of time from about 0 hours to about 5 hours, and in some embodiments, from about 0.25 hours to about 3 hours. After melting, a catalyst can be added to the melt, and phosphonate and carbonate co-oligomers of aromatic dihydroxide, diaryl carbonate and diaryl-alkyl phosphonate can be obtained by vacuum (up to about 2 mmHg), temperature increase (up to about 260 ° C), and the distillation of monophenol obtained as a by-product of polycondensation. The phosphonate and carbonate co-oligomer thus obtained may have an average molecular weight Mw (determined by measuring the relative viscosity of the solution in dichloromethane or in mixtures with equal amounts by weight of phenol / ortho-dichlorophenol with light scattering calibration) in the range of from about 2000 to about 18000 and in some embodiments, from about 4,000 to about 15,000. In such embodiments, up to about 80% monophenol can be recovered from the process.

In a second step, a phosphonate-carbonate copolymer can be obtained from phosphonate-carbonate co-oligomers obtained in a first step by increasing the reaction temperature from about 250 ° C. to 320 ° C. or from about 270 ° C. to about 295 ° C. and reducing the pressure to less than than approximately 2 mmHg By-products, monophenols, can be recovered in a second step. The amount of monophenol obtained in the second stage may be less than the amount of monophenol obtained in the first stage, since monophenol is the result of loss of end groups in the phosphonate and carbonate co-oligomers and in the phosphonate and carbonate copolymers in this reaction. For example, the amount of monophenol produced may be less than about 5%, less than about 2%, or less than about 1%, relative to the amount of monophenol that is obtained in the first step.

The methods of various embodiments can be carried out using a batch mode or a continuous mode, for example, in stirred reactors, thin-film evaporators, falling film evaporators, cascaded reactors, in extruders, in mixers, simple disk reactors, in disk reactors for high viscosity substances and their combinations. Devices, apparatuses and reactors suitable for individual stages of evaporation of the reaction mixture may depend on the process and may include heat exchangers, flash units, separators, columns, evaporators, mixing containers, reactors and any other industrially produced apparatuses that provide the necessary residence time at selected temperatures and pressures, but not limited to this. The selected devices should provide the necessary heat input to the reactor and should be designed so that they are suitable for the ever-increasing viscosity in the melt. Various devices can be connected to each other through pumps, pipelines, valves and the like, and combinations thereof. The pipelines between all components of the equipment are preferably as short as possible, and the number of bends in the pipes is kept as small as possible in order to avoid an unnecessary increase in residence times.

Embodiments of the invention are not limited to a specific transesterification catalyst, and any transesterification catalyst known in the art can be used in the methods described above. However, in some embodiments, the catalyst may be a volatile catalyst, and in other embodiments, the metal-free volatile catalyst. In specific embodiments, the implementation of the catalysts may be volatile compounds of General formula I:

Where

R ₁ , R ₂ , R ₃ and R ₄ are each independently C ₁ -C ₁₈ alkylene, C ₆ -C ₁₀ aryl or C ₅ -C ₆ cycloalkyl; and

X ^- is an anion, where the corresponding acid-base pair H ⁺ + X ^- → HX has pKb <11. Non-limiting examples of catalysts falling within the group of compounds encompassed by Formula I include, but are not limited to, tetraphenylphosphonium tetraphenylborate and tetraphenylphosphonium phenolate. In some embodiments, the catalyst may be tetraphenylphosphonium phenolate. The amount of catalyst of formula I provided for the reaction can vary from one embodiment to another and can be, for example, 10 ^-2 -10 ^-8 mol per mole of aromatic dihydroxide or 10 ^-3 -10 ^-6 mole per mole of aromatic dihydroxide.

In some embodiments, the reaction may further include one or more cocatalysts, which can be provided in addition to one or more catalysts to increase the rate of polymerization. Such cocatalysts can be, for example, salts including alkali metal salts and alkaline earth metal salts, such as, for example, hydroxides, alkoxides and aryloxides of lithium, sodium and potassium. In some embodiments, the alkali metal salt may be sodium hydroxide, alkoxide, or aryl oxide, and in some embodiments, the cocatalyst may be sodium hydroxide and sodium phenolate. The amount of cocatalyst provided may vary, for example, from about 1 μg / kg to about 200 μg / kg, from 5 μg / kg to 150 μg / kg, and in some embodiments, from about 10 μg / kg to about 125 μg / kg, calculated in each case for the mass of aromatic dihydroxide used, calculated in each case for sodium. In some embodiments, the phosphonate and carbonate copolymers of the invention can be prepared without cocatalysts.

Not wishing to be bound by any theory, it is believed that the use of high-purity diaryl-alkylphosphonate in the preparation of phosphonate-carbonate copolymers can provide particularly advantageous properties, including improved melt processability, improved mechanical properties, improved hydrolytic stability and improved thermal stability ( resistance to thermal aging), which is evaluated by measuring the temperature of deformation during heating (HDT), in comparison with copolymers of phosphonate and carbon the one obtained using diaryl alkylphosphonates lesser purity which have been previously described, and these improved properties are better than would be expected based on the previous descriptions of phosphonate and carbonate copolymers. High purity diaryl alkylphosphonates used in the embodiments described above may have a total acid content of less than about 0.15% by weight, less than about 0.10% by weight, and in some embodiments, less than about 0.05% by weight, while the diaryl alkylphosphonates used before had a total acid content of more than about 0.20% by weight or about 0.19% by weight. In specific embodiments, the implementation of the copolymers of phosphonate and carbonate can be obtained with at least 20 mol%. high purity diaryl alkylphosphonates based on the total number of transesterification components (diaryl alkylphosphonate and diaryl carbonate). In some embodiments, such phosphonate-carbonate copolymers can be prepared using a volatile transesterification catalyst, and the properties of the phosphonate-carbonate copolymers according to the invention can be further improved when bisphenol is only BPA.

In some embodiments, monophenols that are removed during the transesterification of aromatic dihydroxide, diaryl carbonate, diaryl-alkylphosphonate in the preparation of a phosphonate-carbonate copolymer can be purified and isolated prior to use in the synthesis of diaryl carbonate. The crude monophenols released during the transesterification may be contaminated, including diaryl carbonates, diaryl-alkylphosphonates, aromatic dihydroxide, salicylic acid, isopropenylphenol, phenyl-phenoxybenzoate, xanton, hydroxymonoaryl-carbonate and the like, depending on the condition, depending on transesterification, etc. distillation conditions. The purification can be carried out using conventional purification processes, for example by distillation or recrystallization. The purity of monophenols after purification can be more than 99%, more than 99.8%, or more than 99.95%.

Statistical copolymers of phosphonate and carbonate according to the invention can be used as such or in combination with other polymeric materials, including oligomers, copolymers and polymers of the same or other substances. For example, in some embodiments, the phosphonate and carbonate copolymers of the invention may be combined with one or more structural plastics for consumer goods to provide fire resistance without significantly compromising process performance or hydrolytic or thermal stability. The engineering plastics that are used in this application include both thermoplastics and thermosetting resins and may include polycarbonates, epoxides, polymer derivatives, polyepoxides (for example, polymers resulting from the reaction of one or more epoxy monomers or oligomers with one or more chain extenders or curing agents such as mono- or multifunctional phenol, amine, benzoxazine, anhydride or a combination thereof), benzoxazines, polyacrylates, polyacrylonitriles, are complex polyesters such as poly (ethylene terephthalate), poly (trimethylene terephthalate) and poly (butylene terephthalate), unsaturated polyesters, polyamides, polystyrenes, including high impact polystyrene, polyureas, polyurethanes, polyphosphonates, polyphosphates, ( acrylonitrile butadiene styrene, polyimides, polyarylates, poly (arylene ether) s, polyethylene, polypropylene, polyphenylene sulfide, vinyl ester polymers, bis-maleimide polymers, polyanhydrides, liquid crystalline polymers, cellulose polymers or any of their com bination (commercially available, for example, from Sabic Plastics, Pittsfield, MA; Rohm & Haas Co., Philadelphia, PA; Bayer corp. - Polymers, Akron, OH; Reichold DuPont; Huntsman LLC, West Deptford, NJ; BASF Corp., Mount Olive, NJ; Dow Chemical Co., Midland, MI; GE Plastics; DuPont; Bayer; Dupont; ExxonMobil Chemical Corp., Houston, TX; ExxonMobil; Mobay Chemical Corp., Kansas City, KS; Goodyear Chemical, Akron, OH; BASF Corp .; 3M Corp., St. Paul, MN; Solutia, Inc., St. Louis, MO; DuPont; and Eastman Chemical Co., Kingsport, TN, respectively), but are not limited to this. In specific embodiments, the phosphonate and carbonate copolymers of the invention can be used in combination with polyepoxides.

In other embodiments, the structural polymer compositions of the invention, which include the phosphonate and carbonate copolymers of the invention as such or the phosphonate and carbonate copolymers of the invention in combination with another structural polymer, such as the structural polymers described above, may include one or more additional components or additives commonly used with these materials, such as, for example, fillers, fibers, surfactants, organic binders, polymer binders, crosslinkers, coupling reaction agents, anti-drip agents during polymer burning, such as fluorinated polyolefins, organosilicon compounds, and aramid fibers, lubricants, release agents to facilitate the removal of molds, such as pentaerythritol tetrastearate, nucleating additives, antistatic additives such as conductive soot, carbon fibers, carbon nanotubes, and organic antiseptics such as polyalkylene simple ethers, alkylsulfonates and poliamidsoderzhaschie polymers, catalysts, colorants, inks, dyes, antioxidants, stabilizers and the like and any combination thereof. In such embodiments, one or more additional components or additives may comprise from about 0.001% of the mass. to about 1% of the mass., from about 0.005% of the mass. to about 0.9% of the mass., from about 0.005% of the mass. to about 0.8% of the mass., from about 0.004% of the mass. up to about 0.8% of the mass. and in specific embodiments, implementation of from about 0.04% of the mass. up to about 0.6% of the mass. based on the weight of the entire composition. In other embodiments, additional components, such as fiberglass or other fibers, may be provided in high concentrations. For example, in some embodiments, the implementation of the copolymers of phosphonate and carbonate may include up to about 30% of the mass. fiberglass, and in other embodiments, the implementation of the copolymers of phosphonate and carbonate according to the invention may include from about 5% of the mass. to about 30% of the mass., from about 10% of the mass. to about 25% of the mass., or from about 15% of the mass. up to about 20% of the mass. fiberglass.

Compositions including copolymers of phosphonate and carbonate and other structural polymers and / or additional components or additives can be obtained using commonly used means. For example, in some embodiments, the respective constituents may be mixed in a known manner and subjected to melt kneading and / or melt extrusion at temperatures such as from about 200 ° C. to about 400 ° C., in conventional plants such as closed mixers, extruders or twin screw units. The mixing of individual components can be carried out either sequentially, or simultaneously and either at approximately room temperature (approximately 20 ° C), or at a higher temperature. For example, in some embodiments, structural plastic and / or all additional components or additives may be introduced into the copolymer of phosphonate and carbonate by kneading. In other embodiments, individual components may be separately introduced into the melt of the phosphonate-carbonate copolymer at various stages of the manufacturing process. For example, additives can be introduced during or at the end of transesterification of aromatic dihydroxides with organic carbonates and diphenylmethylphosphonate, before or during the formation of phosphonate and carbonate co-oligomers, or before or after polycondensation of phosphonate and carbonate co-oligomers, into the melt of the phosphonate and carbonate copolymer. The administration form of the compounds of the invention is not limited. For example, structural plastics and / or additional components or additives may be added in the form of solids, for example in the form of a powder, in the form of a concentrate in a polycarbonate powder in solution. In industrial embodiments, a transverse head extruder can be operated with a capacity of, for example, 200-1000 kg of a phosphonate-carbonate copolymer per hour.

The polymer compositions of the invention can be used as coatings or adhesives, or they can be used in the manufacture of products such as single films, prepregs, fibers, foams, molded products and fiber-reinforced composite materials. In the case of fiber-reinforced composite materials, the reinforcing material may be in the form of continuous, woven or cut fibers, including but not limited to fiberglass, carbon fiber, silicon carbide fiber and organic fibers. These products may be well suited for a number of applications as substrate elements, electrical parts, electrical connectors, laminated plates for printed wiring, housings, simple elements and parts in consumer goods that must comply with the safety standard (UL) or other typical fire resistance standards.

Statistical copolymers of phosphonate and carbonate obtained as described above, or compositions of structural polymers, including the statistical copolymers of phosphonate and carbonate according to the invention and the structural polymer, are usually self-extinguishing, that is, they stop burning when removed from the flame, and any drops resulting from melting in a flame, stop burning and quench almost instantly and do not easily spread the flame to any surrounding materials. In addition, these polymer compositions do not form noticeable smoke when exposed to flame.

EXAMPLES

Although the present invention has been described in great detail with reference to some preferred embodiments thereof, other versions are possible. Thus, the nature and scope of the attached paragraphs should not be limited to the description and preferred versions that are within the scope of this description of the invention. Various aspects of the present invention will be illustrated with reference to the following non-limiting examples. The following examples are given for illustrative purposes only and should not be construed as limiting the invention in any way.

Analytical characterization

The amount of acid components in diphenyl methylphosphonate (DPP) is determined by gas chromatography (GC) on a non-polar column (Optima 5) by analyzing the sample after derivatization with MSTFA (N-Methyl-N- (trimethylsilyl) trifluoroacetamide), taking into account the area under corresponding peaks obtained by the GC method.

Molecular weight distributions are determined by measuring 0.2% solutions of the polymer in dichloromethane using gel permeation chromatography (GPC) with detection in the UV region (at a wavelength of 254 nm). Calibration of the device is carried out using linear polycarbonate standards with known molecular weights. The weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity (Mw / Mn), called PD, are estimated based on chromatograms using WinGPC software.

Determination of hydrolytic stability is carried out using a test by boiling a sample in water. Samples of statistical copolymers of phosphonate and carbonate, representing granules weighing 10 g, are placed in 100 ml of pure water (three times distilled) for a period of time up to 168 hours under reflux conditions at atmospheric pressure. Samples are periodically taken out and relative viscosity (ŋ _rel ) is measured on a Ubbelode viscometer at a concentration of 0.5 g of polymer / liter in dichloromethane at 25 ° C. The change in ŋ _rel in a boiling water test is measured and this change is used to evaluate hydrolytic stability.

EXAMPLE 1

Phosphonate-Carbonate Block Copolymer

Comparative example according to US patent No. 7645850

The block copolymer of phosphonate and carbonate is synthesized by the reaction of oligo-phosphonates and oligo-carbonates obtained in two separate reactors. In a 6-liter stainless steel reactor equipped with a mechanical stirrer and reflux condenser, 2.2-bis (4-hydroxyphenyl) propane (BPA) (1140 g, 5,000 mol), diphenyl carbonate (DPC) (1110 g, 5.187 mol) are added under nitrogen. and a catalyst, tetraphenylphosphonium phenolate (TPPP, 0.3 g, 70% phenol solution, 0.49 mmol). The monomer / catalyst mixture is heated to 250 ° C. under a slightly reduced pressure (933 mbar). After 15 minutes at 250 ° C, the pressure is reduced to 667 mbar and then gradually to 13 mbar over a total period of 2 hours 45 minutes. The phenol by-product is removed by distillation and collected in a graduated receiving flask. A total of 860 ml of phenol is collected.

In a second 12-liter stainless steel reactor equipped with a mechanical stirrer and two reflux condensers connected in series, 2.2-bis (4-hydroxyphenyl) propane (BPA, 554 g, 2.430 mol), diphenyl methylphosphonate (DPP) are added under nitrogen ( 603.0 g, 2.431 mol) and a catalyst, tetraphenylphosphonium phenolate (TPPP, 0.192 g, 70% phenol solution, 0.310 mmol). Analysis of DPP before carrying out this reaction showed that this batch contains 0.02% acidic components. The monomer / catalyst mixture is heated to 265 ° C. under a slightly reduced pressure (933 mbar). After 15 minutes at 250 ° C, the pressure is reduced to 280 mbar and then gradually to 5.3 mbar over a total period of 5 hours. The phenol by-product is removed by distillation and collected in a graduated receiving flask. Only 390 ml of phenol is collected. The phosphonate oligomer-based product is transferred using a stainless steel adapter to a 6-liter stainless steel reactor containing a carbonate oligomer-based product maintained at 265 ° C. An additional catalyst, tetraphenylphosphonium phenolate (TPPP, 0.450 g, 70% phenol solution, 0.80 mmol) was added. After 30 minutes, the reaction temperature was increased to 305 ° C. and the pressure was reduced to <0.4 mbar. The oligomers are allowed to react until a torque of 11.30 Newton meters (6 hours 15 minutes) is reached. The final product is extruded through an extrusion die at the bottom of the reactor into a water bath and granulated using a granulator.

EXAMPLES 2 AND 3

Statistical copolymers of phosphonate and carbonate

Comparative Example

Statistical copolymers of phosphonate and carbonate are synthesized in a multi-stage process. First, the monomers 2,2-bis (4-hydroxyphenyl) propane (BPA) (79.67 g = 0.349 mol), diphenyl carbonate (DPC) (55.033 g, 0.257 mol), diphenyl methylphosphonate (DPP) (27.329 g, 0.110 mol ) and the catalyst, tetraphenylphosphonium phenolate (TPPP, 0.0943 g, 68% solution in phenol, 0.148 mmol) are placed in a three-necked flask equipped with a distillation nozzle and a mechanical stirrer. Analysis of DPP before carrying out this reaction shows that this portion contains 0.19% acidic components. The monomer / catalyst mixture is heated to a temperature of 190 ° C. in order to melt the solids at atmospheric pressure and under nitrogen. After melting, the mixture is stirred for 45 minutes at a stirrer speed of 400 revolutions per minute (rpm). After stirring for 45 minutes at 190 ° C, the temperature was raised to 200 ° C. After reaching 200 ° C, the pressure is reduced to 200 mbar. The reaction is initiated and the phenol by-product is removed by distillation and collected in a receiving flask, which is kept cold with ice water. After a reaction time of 20 minutes, the pressure is reduced to 100 mbar, and the temperature is increased to 215 ° C. After an additional period of reaction time of 20 minutes, the pressure is reduced to 50 mbar, and the temperature is increased to 250 ° C. After an additional reaction period of 20 minutes, the pressure is reduced to 25 mbar, and the temperature is increased to 260 ° C. After a period of 20 minutes, the pressure is reduced to 4 mbar, and the temperature is increased to 290 ° C. After a reaction period of 5 minutes, the rotation speed of the mixer is reduced to 250 rpm. After an additional reaction time of 20 minutes, the speed of the stirrer is reduced to 100 rpm. After an additional reaction time of 20 minutes, the pressure is reduced to 1 mbar, and the temperature is increased to 310 ° C. After an additional reaction period of 45 minutes, the speed of the mixer is reduced to 50 rpm. After an additional period of reaction time of 15 minutes, the first samples are removed for analysis behavior (1-hour sample means 1 hour at a high vacuum stage of 1 mbar). After an additional hour at 310 ° C, 1 millibar and a stirrer speed of 50 rpm, a second sample was taken out for analysis (2-hour sample means 2 hours at a high vacuum stage of 1 millibar).

EXAMPLE 4

Statistical copolymer of phosphonate and carbonate

Comparative Example

Example 4 includes a repeat of Example 2 except that the DPP used contains 0.337% acidic components.

Examples 2-3 are given for comparison, and samples of these Examples are prepared using the synthesis conditions of the present invention, except that DPP with a lower degree of purity (approximately 0.19% acidic components) is used.

EXAMPLES 5-11

Statistical copolymers of phosphonate and carbonate according to the invention

For samples of Examples 5-11, a high purity DPP series with an acid content of ≤0.12% is used. In addition, the amount of catalyst used varies. The reaction conditions for Examples 5-11 are identical and are described below.

Statistical copolymers of phosphonate and carbonate are synthesized in a multi-stage process. First, the monomers 2,2-bis (4-hydroxyphenyl) propane (BPA) (79.67 g = 0.349 mol), diphenyl carbonate (DPC) (55.033 g, 0.257 mol), diphenyl methylphosphonate (DPP) (27.329 g, 0.110 mol ) and the catalyst, tetraphenylphosphonium phenolate (TPPP, 0.0943 g, 68% solution in phenol, 0.148 mmol) are placed in a three-necked flask equipped with a distillation nozzle and a mechanical stirrer. Analysis of DPP before carrying out this reaction shows that this series contains 0.12% acidic components. The monomer / catalyst mixture is heated to a temperature of 190 ° C. in order to melt the solids at atmospheric pressure and under nitrogen. After melting, the mixture is stirred for 45 minutes at a stirrer speed of 400 revolutions per minute (rpm). After stirring for 45 minutes at 190 ° C, the temperature was raised to 200 ° C. After reaching 200 ° C, the pressure is reduced to 200 mbar. The reaction is initiated and the phenol by-product is removed by distillation and collected in a receiving flask, which is kept cold with ice water. After a reaction time of 20 minutes, the pressure is reduced to 100 mbar, and the temperature is increased to 215 ° C. After an additional period of reaction time of 20 minutes, the pressure is reduced to 50 mbar, and the temperature is increased to 250 ° C. After an additional reaction period of 20 minutes, the pressure is reduced to 25 mbar, and the temperature is increased to 260 ° C. After a period of 20 minutes, the pressure is reduced to 4 mbar, and the temperature is increased to 290 ° C. After a reaction period of 5 minutes, the rotation speed of the mixer is reduced to 250 rpm. After an additional reaction time of 20 minutes, the speed of the stirrer is reduced to 100 rpm. After an additional reaction time of 20 minutes, the pressure is reduced to 1 mbar, and the temperature is increased to 310 ° C. After an additional reaction period of 45 minutes, the speed of the mixer is reduced to 50 rpm. After an additional period of reaction time of 15 minutes, the first samples are removed for analysis behavior (1-hour sample means 1 hour at a high vacuum stage of 1 mbar). After an additional hour at 310 ° C, 1 millibar and a stirrer speed of 50 rpm, a second sample was taken out for analysis (2-hour sample means 2 hours at a high vacuum stage of 1 millibar).

An accurate description of the starting weights of all reagents and the amount of acidic by-products in DPP are given in Table 1.

EXAMPLES 12-17

Statistical copolymers of phosphonate and carbonate: according to the invention

DPP used in examples 12-17 has a total acid content of at most 0.034%.

Statistical copolymers of phosphonate and carbonate are synthesized using a multi-stage process. First, BPA monomers (9000 ± 200 g), DPC (6500 ± 200 g), DPP (2900 ± 100 g) and TPPP catalyst (10.8 ± 0.2 g, 68% phenol solution) are placed in a mixing vessel and heated to 190 ° C. at atmospheric pressure and under nitrogen. The solids are melted and the reaction mixture is stirred for 45 minutes at 400 rpm. The molar ratio (DPP + DPC) / BPA is 1.06 and 1.07, respectively, relative to a BPA concentration of 1.0 at the start of the reaction. The amount of DPP is set in such a way that the ratio of DPP to the sum of DPP + DPC based on the mass is 31%. An exact description of each composition with all the initial weights is shown in Table 2.

After a reaction time of 45 minutes at 190 ° C. at atmospheric pressure, the reaction mixture was transferred to the lower part of the falling film evaporator. The falling film evaporator has a temperature of 190 ° C. and is under atmospheric pressure under nitrogen. After the transfer is complete, the pressure in the falling film evaporator is reduced to 200 mbar. The reaction mixture is pumped into the production cycle through a transfer pipe, which is heated from the outside. The amount injected into the technological cycle is kept constant throughout the experiment, and it amounts to a total of four times the amount of liquid initially transferred to the evaporator with a falling film per hour at the beginning. The phenol that is produced during the reaction is removed by distillation and collected in a separate container, whereby it is removed from the reaction mixture. After a period of 20 minutes, the pressure is reduced to 100 mbar, and the temperature is increased to 220 ° C. In the meantime, the reaction mixture is pumped into the production cycle through a transfer pipe. After a period of reaction time of 20 minutes, the pressure is reduced to 50 mbar, and the temperature is increased to 250 ° C, while the reaction mixture is continuously pumped into the production cycle through a transfer pipe. After a period of reaction time of 20 minutes, the pressure is reduced to 35 mbar, and the temperature is increased to 265 ° C, while the reaction mixture is continuously pumped into the production cycle through a transfer pipe. After a period of 20 minutes, the reaction mixture is pumped into a disk reactor. In a disk reactor, polymerization is carried out further at 270 ° C. under a pressure of 4 mbar at a disk rotation speed of 2.5 rpm. All this time, phenol, which is produced during the reaction, is removed by distillation. After a reaction period of 45 minutes, the pressure is reduced to 1 millibar, and the temperature is increased to 305 ° C, and the speed of rotation of the disks is reduced to 1 rpm. The reaction is continued until the final viscosity is reached (see Table 2 for details). After reaching the final viscosity, the polymer is pumped out of the reactor through the mouthpiece and into the water bath. The solid polymer is then granulated using a granulator.

EXAMPLES 18-20

Statistical copolymers of phosphonate and carbonate: according to the invention

The reaction conditions regarding temperatures, pressures, stirrer speeds and residence time periods exactly match the reaction conditions for Examples 5-11, with the exception of various DPP / (DPP + DPC) ratios, see Table 3.

The starting weights of all monomers used in these examples and the amount of acidic by-products in DPP are described in Table 3.

EXAMPLES 21-23

Samples of Examples 21-23 are prepared using DPP, which is either manufactured in the laboratory or obtained from Rhodia. DPP, which is manufactured in the laboratory, contains 0.03% acidic components. DPP, which is obtained in Rhodia, contains 0.92% acidic components.

Example 21. In a 6-liter reactor equipped with a distillation column and a mechanical stirrer, 2.2-bis- (4-hydroxyphenyl) propane (bisphenol A, 1.411 kg, 6.19 mol), high purity diphenyl ester, are placed (DPP) (0.50 kg, 2.013 mol), diphenyl carbonate (0.929 kg, 4.34 mol) and 1.67 g of catalyst, tetraphenylphosphonium phenolate (TPPP) (70% phenol solution). Analysis of DPP before carrying out this reaction shows that this series contains 0.03% acidic components. The mixture is heated to 250 ° C with a decrease in pressure from 700 to 4 mm Hg. over a period of time of approximately 5 hours. The distillate collected was 1101 g. The product of this mixture was an oligomer of carbonate and phosphonate.

Then the mixture is heated from 250 to 300 ° C with a decrease in pressure from 10 to 1.5 mm Hg over a period of time of approximately 5 hours. Approximately 138 g of distillate is collected during this reaction. The carbonate / phosphonate copolymer product is extruded from the reactor into a water bath to obtain strands (strands) and subsequently granulated. The yield of the copolymer product from the reactor is 1586 g. The copolymer is transparent, has a toughness (is hard) and has a yellowish tint.

Example 22 was carried out in accordance with the same procedure as described for Example 21. Instead of TPPP, sodium phenolate was used as a catalyst.

Example 23. In a 6-liter reactor equipped with a distillation column and a mechanical stirrer, 2.2-bis- (4-hydroxyphenyl) propane (bisphenol A, 1.411 kg, 6.19 mol), high purity diphenyl ester, are placed (DPP) (0.50 kg, 2.013 mol), diphenyl carbonate (0.929 kg, 4.34 mol) and 1.67 g of catalyst, tetraphenylphosphonium phenolate (TPPP) (70% phenol solution). DPP is obtained from Rhodia, and a DPP analysis prior to this reaction indicates that this series contains 0.92% acidic components. The mixture is heated to 250 ° C with a decrease in pressure from 700 to 4 mm Hg. over a period of time of approximately 5 hours. The distillate collected is 1130 g. The product of this mixture is an oligomer of carbonate and phosphonate.

Then the mixture is heated from 250 to 300 ° C with a decrease in pressure from 10 to 1.5 mm Hg over a period of time of approximately 1 hour. A sharp increase in viscosity is observed in the last half hour. About 133 g of distillate is collected during this reaction. The product based on a carbonate / phosphonate copolymer could not be extruded from the reactor in the form of strands (strands) due to the high viscosity and rubber-like nature of the change in properties. The yield of the copolymer product from the reactor is 1492 g.

The composition of the samples of Examples and the results of analytical characterization are presented in Tables 1-4.

Table 1
The composition and characterization of the samples of Examples 1-11 Example one 2 3 four 5 6 7 8 9 10 eleven Monomers Bisphenol A (BPA) [g] 1694 79.67 79.67 79.67 79.67 79.67 79.67 79.67 79.67 79.67 79.67 Diphenyl Carbonate (DPC) [g] 1110 55,033 55,033 55,033 55,033 55,033 55,033 55,033 55,033 55,033 55,033 Diphenylmethylphosphonate (DPP) [g] 603 27.33 27.33 27.33 27.33 27.33 27.33 27.33 27.33 27.33 27.33 Tetraphenylphosphonium phenolate (TPPP) [g] 0.942 ** 0.0943 0.0943 0.0943 0.0943 0,1509 0.0943 0.0472 0.0472 0,0283 0,066 The content of Acid components in DPP [%] 0.02 0.19 0.19 0.337 0.12 0.12 0,033 0,033 0,033 0,033 0,033 The ratio of DPP / (DPP + DPC) [% wt.] 35,2 33,2 33,2 33,2 33,2 33,2 33,2 33,2 33,2 33,2 33,2 The ratio of DPP / (DPP + DPC) [% mol] 31.9 30,0 30,0 30,0 30,0 30,0 30,0 30,0 30,0 30,0 30,0 Ratio (DPP + DPC) / BPA [mol / mol] 1,026 1,052 1,052 1,052 1,052 1,052 1,052 1,052 1,052 1,052 1,052 The period of stay at the stage of high vacuum 1 mbar at 310 ° C [hour] one 2 one 2 2 2 one 2 2 2 Relative viscosity (ŋ _rel ) 1,268 1,075 1,087 1,086 1,283 1,263 1,261 1,218 1.24 1,233 1,252 Weight average molecular weight (Mw) [g / mol] 29800 5451 6886 6395 29207 33919 28413 22359 28169 26270 29532 Polydispersity (PD) (Mw / Mn) 2.23 2,586 2,543 2,423 2.67 2.93 2.45 2.42 2,56 2,55 2.67 Hydrolytic stability Change in relative viscosity (Δŋ _rel ) After 24 hours -0.009 n.d. n.d. n.d. -0.008 -0.008 -0.007 n.d. -0.004 -0.005 -0.006 After 48 hours -0.046 n.d. n.d. n.d. -0.016 -0.017 -0.016 n.d. -0.013 -0.015 -0.023 After 72 hours -0.106 n.d. n.d. n.d. -0.033 -0.033 -0.029 n.d. -0.023 -0.026 -0.051 After 168 hours -0.196 n.d. n.d. n.d. -0.085 -0.085 -0.08 n.d. -0.061 -0.065 -0.104 nd: not defined
* The content of acid components in DPP: The total content of phosphoric acid, phosphonic acid, methylphosphonic acid and monophenyl ester of methylphosphonic acid.
** Initially, the amount of TPPP is 0.492 g, 0.450 g is added during the post-condensation step.

table 2
The composition and characterization of the samples of Examples 12-17 Example 12 13 fourteen fifteen 16 17 Monomers Bisphenol A (BPA) [g] 8872 9192 8869 8869 8973 9142 Diphenyl Carbonate (DPC) [g] 6419 6650 6417 6417 6492 6553 Diphenylmethylphosphonate (DPP) [g] 2284 2987.8 2882.8 2882.8 2916.6 2944 Tetraphenylphosphonium phenolate (TPPP) [g] 10.6 11.0 10.6 10.6 10.7 10.9 The content of Acid components in DPP [%] 0,031 0,03 0,034 0,029 0,022 0.013 The ratio of DPP / (DPP + DPC) [% wt.] 31,0 31,0 31,0 31,0 31,0 31,0 The ratio of DPP / (DPP + DPC) [mol%] 27.9 27.9 27.9 27.9 27.9 27.9 Ratio (DPP + DPC) / BPA [mol / mol] 1,070 1,070 1,070 1,070 1,070 1,060 The period of stay at the high vacuum stage of 1 mbar at 305 ° C [hour] 2.5 2,8 2.25 2.18 3.45 4.28 Relative viscosity (ŋ _rel ) 1.28 1,282 1,287 1,280 1,276 1,312 Weight average molecular weight (Mw) [g / mol] 32564 33973 34401 33693 32405 37643 Polydispersity (PD) (Mw / Mn) 2.63 2.74 2.80 2.90 2,56 2.80 Hydrolytic stability Change in relative viscosity (Δŋ _rel ) After 24 hours -0.010 -0.010 -0.011 n.d. -0.010 -0.012 After 48 hours -0.017 -0.014 -0.019 n.d. -0.019 -0.025 After 72 hours -0.028 -0.024 -0.035 n.d. -0.029 -0.044 After 168 hours -0.070 -0.058 -0.079 n.d. -0.073 -0.109 nd: not defined
* The content of acid components in DPP: The total content of phosphoric acid, phosphonic acid, methylphosphonic acid and monophenyl ester methylphosphonic acid

Table 3
The composition and characterization of samples of Examples 18-20 Example eighteen 19 twenty Monomers Bisphenol A (BPA) [g] 79.67 79.67 79.67 Diphenyl Carbonate (DPC) [g] 74.69 62,895 43.24 Diphenylmethylphosphonate (DPP) [g] 4,55 18.23 40,99 Tetraphenylphosphonium phenolate (TPPP) [g] 0,04715 0.0943 0.1886 The content of Acid components in DPP [%] 0.007 0.007 0.007 The ratio of DPP / (DPP + DPC) [% wt.] 5.7 22.5 48.7 The ratio of DPP / (DPP + DPC) [mol%] 5,0 20,0 45.0 Ratio (DPP + DPC) / BPA [mol / mol] 1,052 1,052 1,051 The period of stay at the high vacuum stage of 1 mbar at 305 ° C [hour] 2 2 2 Relative viscosity (ŋ _rel ) 1.23 1,246 1,231 Weight average molecular weight (Mw) [g / mol] 21674 26403 42820 Polydispersity (PD) (Mw / Mn) 2.21 2.43 3.89 Hydrolytic stability Change in relative viscosity relative to the initial value (ΔEta _rel ) After 24 hours -0.001 -0.004 -0.015 After 48 hours -0.003 -0.009 -0.043 After 72 hours -0.004 -0.013 -0.077 After 168 hours -0.007 -0.030 -0.154 * The content of acidic components in DPP: The total content of phosphoric acid, phosphonic acid, methylphosphonic acid and monophenyl ester methylphosphonic acid

Table 4
The composition and characterization of the samples of Examples 21-23 Example 21 22 23 Monomers Bisphenol A (BPA) [g] 1411 1411 1411 Diphenyl Carbonate (DPC) [g] 929 929 929 Diphenylmethylphosphonate (DPP) [g] 500 500 500 Tetraphenylphosphonium phenolate (TPPP) [g] 1,67 1,67 Sodium Phenolate [g] 0.05 The content of Acid components in DPP [%] 0,03 0,03 0.92 The ratio of DPP / (DPP + DPC) [% wt.] 35 35 35 The ratio of DPP / (DPP + DPC) [mol%] 31.7 31.7 31.7 Ratio (DPP + DPC) / BPA [mol / mol] 1,027 1,027 1,027 The total reaction time [minutes] 615 615 355 Torque at the end of the reaction [Newton meters] 8.4 10.7 8.9 Relative viscosity (ŋ _rel ) 1,237 1.25 1,247 Weight average molecular weight (Mw) [g / mol] 26715 28900 31900 The number average molecular weight (Mn) [g / mol] 11400 12600 7600 Polydispersity (PD) (Mw / Mn) 2,34 2.29 4.18 Hydrolytic stability Change in relative viscosity relative to the initial value (ΔEta _rel ) After 24 hours -0.009 0 -0.032 After 48 hours -0.015 -0.007 -0.051 After 72 hours -0.015 -0.022 -0.044 * The content of acidic components in DPP: The total content of phosphoric acid, phosphonic acid, methylphosphonic acid and monophenyl ester methylphosphonic acid

The analysis involved samples of various examples, the sample of comparative example 1 is a block copolymer using DPP of high purity (acid content of 0.02%). The phosphonate-carbonate block copolymer exhibits a high weight average molecular weight Mw and a polydispersity (PD) value of 2.23. The sample of Example 1 shows a relatively low hydrolytic stability after 168 hours of testing by boiling the sample in water with a decrease in relative viscosity by 0.196 (Table 1).

Samples of Examples 2-4 are statistical phosphonate and carbonate copolymers obtained from at least 20% DPP, DPC, BPA and TPPP, but the DPP purity is lower, 0.19% acidic components for samples 2 and 3, and 0.337 acidic components for sample 4 (Table 1). As shown in Table 1, these three comparative samples do not achieve high molecular weight, which is determined both using the viscosity of the solutions and using measurements by GPC (gel permeation chromatography). Therefore, the process cannot be carried out properly under these conditions on an industrial scale.

For the samples of Examples 5-11, which are representative of the present invention, high purity DPP (≤0.15% acidic components) is used in the synthesis of random copolymers of phosphonate and carbonate. In all seven examples, a high weight average molecular weight Mw was obtained, ranging from about 22,000 to 34,000 g / mol. The polydispersity values, PD, are in the range of 2.42 to 2.93. Hydrolytic stability is excellent with reductions in relative viscosities ranging from about 0.06 to 0.10 after 168 hours of testing by boiling the samples in water (Table 1).

For the samples of Examples 12-17 that are representative of the present invention, high purity DPPs (≤0.034% acidic components) are used in the synthesis of random copolymers of phosphonate and carbonate in a multi-stage process. The reagents and catalyst are first melted together in a mixing vessel and then transferred to a falling film evaporator, which facilitates the removal of phenol. Upon completion of this step, the reaction mixture is transferred to a disk reactor to complete the polymerization. In all six examples, a high weight average molecular weight Mw was obtained, ranging from about 32,400 to 37,600 g / mol. Polydispersity values, PD, range from 2.56 to 2.90. Hydrolytic stability is excellent with reductions in relative viscosities ranging from about 0.06 to 0.10 after 168 hours of testing by boiling the samples in water (Table 2).

For the samples of Examples 18-20 that are representative of the present invention, high purity DPPs (≤0.15% acidic components) are used in the synthesis of random copolymers of phosphonate and carbonate, following the same process used for the samples of Examples 5-11. In these three samples, however, different monomer ratios are used (Table 3). In all of these three examples, a high weight average molecular weight Mw was obtained, ranging from about 21,000 to 42,000 g / mol. The polydispersity values, PD, are in the range of 2.21 to 3.89. Hydrolytic stability is excellent with reductions in relative viscosities ranging from about 0.007 to 0.15 after 168 hours of testing by boiling the samples in water (Table 3).

Comparison of the samples of Examples 21 and 22 with the samples of Example 23 shows that using DPP with a significantly low level of acidic components, it is possible to obtain a polymer with a sufficiently high number average molecular weight Mn (> 10000 g / mol) and with a narrow polydispersity, which has a value of less than 3. When using DPP with a relatively high level of acidic components (almost 1%), the torque on the mixer, which is used to mix the reaction mixture (which is a measure of the viscosity of the mixture and, accordingly, Mw of the reaction cm Yes), is increasing rapidly. As a result, it is necessary to stop the reaction after only ~ 6 hours in order to be able to remove material from the reactor. However, although Mw is obtained which is comparable to reactions using high purity DPP, Mn is not high enough (e.g., higher than 9000 g / mol). The resulting high polydispersity of approximately 4 indicates branched or crosslinked material. A relatively high level of acidic components can give rise to adverse reactions that result in such a high PD value.

In addition, the hydrolytic stability of a material made using DPP with a lower degree of purity (sample of Example 23) has poorer hydrolytic stability than materials that are made using DPP with a high degree of purity (samples of Examples 21 and 22).

Claims (25)

1. A statistical phosphonate-carbonate copolymer containing randomly distributed monomer units derived from carbonate and phosphonate monomers and having a weight average molecular weight of from about 10,000 g / mol to about 100,000 g / mol, as determined by gel permeation chromatography, and a polydispersity value of from about 2 to about 7. 2. The statistical phosphonate-carbonate copolymer according to claim 1, wherein the statistical phosphonate-carbonate copolymer has a number average molecular weight of from about 5000 g / mol to about 50,000 g / mol, as determined by gel permeation chromatography. 3. The statistical copolymer of phosphonate and carbonate according to claim 1, where the statistical copolymer of phosphonate and carbonate has a polydispersity value of from about 2 to about 4. 4. The statistical copolymer of phosphonate and carbonate according to claim 1, where the statistical copolymer of phosphonate and carbonate contains phosphorus from about 2% to about 10% by weight relative to the total amount of the statistical copolymer of phosphonate and carbonate 5. The statistical copolymer of phosphonate and carbonate according to claim 1, where the statistical copolymer of phosphonate and carbonate has a total acid content obtained from phosphonate monomers of less than about 0.15% by weight. 6. The statistical copolymer of phosphonate and carbonate according to claim 1, containing monomer units derived from diphenylmethyl phosphonate, diphenyl carbonate and 2,2-bis (4-hydroxyphenyl) propane. 7. The statistical phosphonate-carbonate copolymer according to claim 1, wherein the statistical phosphonate copolymer does not contain monomer units derived from a branching reagent. 8. The statistical copolymer of phosphonate and carbonate according to claim 1, additionally containing fillers, fibers, surfactants, organic binders, polymeric binders, crosslinking additives, coupling reaction agents, additives that prevent dripping during burning of polymers, lubricants, release agents additives to facilitate the removal of molds, nucleating additives, antistatic additives, catalysts, coloring agents, inks, dyes, antioxidants, stabilizers, or combinations thereof ui. 9. The polymer mixture used to obtain the product of industrial production, including a random copolymer of phosphonate and carbonate, containing randomly distributed monomer units derived from carbonate and phosphonate monomers, and having a phosphorus content of from about 2% to about 10% by weight relative to the total the amount of a statistical phosphonate-carbonate copolymer and the total acid component content obtained from phosphonate monomers is less than about 0.15% by weight; and at least one other polymer, oligomer or combination thereof to prepare a mixture / combination or mixture. 10. The polymer mixture of claim 9, wherein the other polymer, oligomer or combination thereof comprises carbonates, epoxides, benzoxazine, acrylates, acrylonitriles, esters, terephthalates, or combinations thereof. 11. The polymer mixture of claim 9, wherein the other polymer, oligomer, or combination thereof includes an unsaturated polyester, polyamide, polystyrene (including high impact polystyrene), polyurea, polyurethane, polyphosphonate, poly (acrylonitrile butadiene styrene), polyimide , polyarylate, poly (arylene ether), poly (ethylene terephthalate), poly (trimethylene terephthalate), poly (butylene terephthalate), polyethylene, polypropylene, polyphenylene sulfide, vinyl ester polymer, polyvinyl chloride, bis-maleimide polymer , polyanhydride, liquid crystalline Emer, cellulosic polymer or combinations thereof. 12. The polymer mixture according to claim 9, additionally containing fillers, fibers, surfactants, organic binders, polymer binders, crosslinking agents, coupling reaction agents, additives that prevent dripping during burning of polymers, lubricants, release agents to facilitate dredging products from molds, nucleating additives, antistatic additives, catalysts, coloring agents, inks, dyes, antioxidants, stabilizers, or combinations thereof. 13. The polymer mixture used to obtain the product of industrial production, including: a statistical copolymer of phosphonate and carbonate containing randomly distributed monomer units obtained from carbonate and phosphonate monomers, and having a weight average molecular weight of from about 10,000 g / mol to about 100,000 g / mol, as determined by gel permeation chromatography, and a polydispersity value of from about 2 to about 7; and at least one other polymer, oligomer or combination thereof to prepare a mixture / combination or mixture. 14. The polymer mixture of claim 13, wherein the other polymer, oligomer or combination thereof comprises carbonates, epoxides, benzoxazine, acrylates, acrylonitriles, esters, terephthalates, or combinations thereof. 15. The polymer mixture of claim 13, wherein the other polymer, oligomer, or combination thereof includes an unsaturated polyester, polyamide, polystyrene (including high impact polystyrene), polyurea, polyurethane, polyphosphonate, poly (acrylonitrile butadiene styrene), polyimide , polyarylate, poly (arylene ether), poly (ethylene terephthalate), poly (trimethylene terephthalate), poly (butylene terephthalate), polyethylene, polypropylene, polyphenylene sulfide, vinyl ester polymer, polyvinyl chloride, bis-maleimide polymer , polyanhydride, liquid crystalline a size, cellulosic polymer, or combinations thereof. 16. The polymer mixture of claim 13, further comprising fillers, fibers, surfactants, organic binders, polymeric binders, crosslinking agents, coupling reaction agents, anti-drip agents during polymer burning, lubricants, release agents to facilitate dredging products from molds, nucleating additives, antistatic additives, catalysts, coloring agents, inks, dyes, antioxidants, stabilizers, or combinations thereof. 17. Industrial product, including a random copolymer of phosphonate and carbonate, containing randomly distributed monomer units derived from carbonate and phosphonate monomers, and having a weight average molecular weight of from about 10,000 g / mol to about 100,000 g / mol, as determined by gel permeation chromatography; and a polydispersity value of from about 2 to about 7. 18. The industrial product according to claim 17, in which the statistical copolymer of phosphonate and carbonate contains phosphorus from about 2% to about 10% by weight relative to the total amount of the statistical copolymer of phosphonate and carbonate. 19. The industrial product according to claim 17, in which the statistical copolymer of phosphonate and carbonate has a total acid content obtained from phosphonate monomers of less than about 0.15% by weight. 20. The industrial product according to claim 17, in which the statistical copolymer of phosphonate and carbonate is presented in a mixture with at least one other polymer, oligomer, or a combination thereof. 21. The industrial product according to claim 20, where the other polymer, oligomer, or a combination thereof contains carbonates, epoxides, benzoxazine, acrylates, acrylonitriles, esters, terephthalates, or combinations thereof. 22. The industrial product according to claim 20, where the other polymer, oligomer or a combination thereof includes an unsaturated polyester, polyamide, polystyrene (including high impact strength polystyrene), polyurea, polyurethane, polyphosphonate, poly (acrylonitrile butadiene styrene), polyimide, polyarylate, poly (arylene ether), poly (ethylene terephthalate), poly (trimethylene terephthalate), poly (butylene terephthalate), polyethylene, polypropylene, polyphenylene sulfide, vinyl ester polymer, polyvinyl chloride, bis-maleimide polymer, polyanhydride, liquid crystalline polymer, cellulosic polymer, or combinations thereof. 23. The industrial product according to claim 17, further comprising fillers, fibers, surfactants, organic binders, polymer binders, crosslinking agents, coupling reaction agents, additives that prevent dripping during burning of polymers, lubricants, release agents for facilitate the removal of molds, nucleating additives, antistatic additives, catalysts, coloring agents, inks, dyes, antioxidants, stabilizers, or combinations thereof. 24. The industrial product according to claim 17, where the industrial product includes a coating, adhesive, prepreg, foam, film, fiber, molded product, fiber reinforced layered material, or a combination thereof. 25. An industrial product according to claim 17, wherein the industrial product includes consumer goods or a part or part thereof.