RU2712547C1 - Reactive thinner of phthalonitrile resins and thermosetting composition based thereon - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to polymer chemistry and the technology of thermosetting polymers, specifically to a new class of active diluents for phthalonitrile resins and a thermosetting composition of a phthalonitrile binder containing said diluent. Reactive diluent for phthalonitrile resins includes a bis-benzonitrile monomer with general formula

, where X is a divalent substitute selected from the group:

, -SO₂-, bivalent alkyl, aryl or oxyaryl substituents, and the cyano group is in meta- or para-position with respect to fragment X. Disclosed is a polymer mixture for producing thermosetting compositions, which includes a reactive diluent, as well as a composition for producing polymer composite materials, including said polymer mixture.

EFFECT: obtaining a new diluent for phthalonitrile monomers, a polymerizable mixture containing a diluent, and a composition containing a polymerizable mixture.

8 cl, 1 tbl, 2 dwg

Description

Technical field

The invention relates to the field of polymer chemistry and technology of thermosetting polymers, and in particular to a new class of active diluents for phthalonitrile resins and a thermosetting phthalonitrile binder composition containing this diluent.

State of the art

In the prior art for the manufacture of polymer composite materials (PCM) using various matrices. Moreover, matrices for PCM based on phthalonitrile monomers are known as the most heat-resistant polymer matrices.

The first development of materials based on phthalonitrile resins dates back to the turn of the 1970s and 80s. For example, in the prior art document US 4056560 (US NAVY, 11/01/1977), a composition and method for producing bis-phthalonitrile monomers capable of polymerization to form a heat-resistant polymer (up to 350 ° C) are disclosed. The polymerization can take place thermally or in the presence of catalysts, which are salts of transition metals.

For a long time, phthalonitriles were not used as matrices for PCM, since such monomers had high melting points (> 170 ° C), as a result of which they were characterized by narrow processability intervals, since fast polymerization begins at a temperature of about 200 ° C: in US Pat. No. 4,587325 (US NAVY, 1986-05-06) indicates that the polymerization of phthalonitriles in the presence of amines begins at 200 ° C.

Previously, attempts were made to improve the properties of phthalonitrile matrices, creating on their basis more complex compositions from various phthalonitrile monomers.

One way to improve the monomers is to modify them by incorporating mobile organic fragments into the molecular structure of the phthalonitrile monomers, which can, for example, lead to a decrease in the glass transition temperature of the target products, or to improve the thermo-oxidative stability of polymers based on modified phthalonitriles, or to ensure the state of aggregation at room temperature as a viscous liquid or semi-solid.

Such approaches to improving properties are disclosed in patents RU 2638307, December 15, 2017, and RU 2580927, April 10, 2016 (INUMiT JSC), in which phthalonitriles modified with organophosphorus and organosilicon fragments were declared, and curable compositions based on these monomers were disclosed.

The disadvantages of these technical solutions can be attributed to the multi-stage production of these compounds, the high resource consumption of the process of their production, as well as a large amount of waste generated during production.

In addition, subsequent studies of phthalonitrile with organosilicon fragments according to patent RU 2580927, given in the source "Mechanical and physico-chemical properties of binders for polymer composite materials based on low-melting phthalononitrile monomers", Izvestiya Akademii Nauk, B.A. Bulgakov et al. Chemical Series, (1): 287-290, 2016 showed that this phthalonitrile has low elastic modulus values.

Another approach associated with improving the rheological properties of thermoset matrices based on phthalonitrile monomers with high melting points (above 150 ° C) is to create thermosetting compositions in the form of mixtures of monomers with functional additives, for example, plasticizers or diluents.

In the application US 2016168327, 2016-06-16, a thermoset composition based on phthalonitrile monomer consisting of diphthalonitrile monomer, reactive (mono-phthalonitrile) or non-reactive plasticizer and aromatic diamine is disclosed. As indicated in this application, the plasticizer allows to reduce the viscosity of the material to a suitable value for the required processing conditions.

In particular, it is said that a mixture of diphthalonitrile monomer precursors and a reactive monophthalonitrile resin may provide a low viscosity melt for processing this mixture into an article, fiber or film. Such mixtures can be used for the manufacture of composites by economical methods, such as, for example, RTM (Resin transfer molding - injection into a closed mold), infusion molding, or winding molding.

However, this known composition is cured at a temperature of 220-250 ° C, which complicates its use for the formation of polymer composite materials (PCM) by vacuum infusion, since this method is commonly used and debugged to produce polymer composite materials based on epoxy resins, auxiliary materials for infusions are designed for operation up to 200 ° C, not higher.

Also, the compositions described in this document have a high viscosity of 10-50 Pa · s, which also makes them unsuitable for use in the process of obtaining polymer composite materials by vacuum infusion or RTM - according to the prior art, the maximum allowable viscosity for RTM and vacuum infusion is 0.8 Pa⋅s (ASM Handbook Volume 21: Composites, Editor: DB Miracle and SL Donaldson, ASM International, 2001, chapter Resin Transfer Molding and Structural Reaction Injection Molding by CD Rudd, University of Nottingham), and the viscosity of the compositions is according to US 2016168327, as can be seen from this document, exceeds remembered value.

WO 2018175025 (M INNOVATIVE PROPERTIES CO, 2018-09-27) discloses a reactive diluent with the general formula:

where R ₁ , R ₂ , R ₃ , R ₄ are selected from hydrogen, an allyl group, a C ₁ -C ₂₀ alkyl group, an aryl group, an ether group, a thioether group, an aldehyde group, a ketone group, an ester group, an amide group, a nitro group , secondary and tertiary amino groups or combinations thereof.

Also disclosed is a thermoset composition in the form of a mixture containing diphthalonitrile monomer and said diluent.

As follows from the description of this application, the diluent, when added to multifunctional phthalonitrile resins, reduces the viscosity of the resin, reduces the curing time of the resin polymerization, its introduction avoids high-temperature post-cure at temperatures above 325 ° C.

However, known diluents are sewn into the polymer network from only one end of the molecule (phthalonitrile group), while the other end containing plasticizing substituents remains free. Such a topology of the polymer network leads to a decrease in the thermal and thermomechanical properties of the matrix due to the presence of movable unfixed fragments.

Thus, the known technical solutions create such technical problems as the increased viscosity of phthalonitrile compositions in the temperature range from 100 to 180 ° C or insufficient heat resistance.

Disclosure of Invention

The technical problem to be solved by the claimed invention is aimed at eliminating all the problems inherent in the known technical solution, as well as in providing new reactive diluents for phthalonitrile monomers which are bis-benzonitriles and thermosetting compositions having, after curing, increased heat resistance at temperatures not lower than 400 ° C, but in this case, prior to curing, the melt viscosity values in the range from 100 to 180 ° C are below 800 mPa⋅s, and in the range from 120 to 180 ° C below 300 mPa⋅s.

The technical result is to obtain polymerizable mixtures based on phthalonitrile resins with a melting temperature T _pl (T _article ) below 50 ° C, and in the curable compositions, the heat resistance after curing of these compositions remains above 400 ° C.

, где X представляет собой двухвалентный заместитель, выбранный из группы:The technical problem is solved by a reactive diluent for phthalonitrile resins, which includes a bis-benzonitrile diluent with the General formula

where X is a divalent substituent selected from the group:

, -SO₂-, двухвалентных алькильных, арильных или оксиарильных заместителей, а циано-группа находится в мета-или пара-положении по отношению к фрагменту X.

, -SO ₂ -, divalent alkyl, aryl or hydroxyaryl substituents, and the cyano group is in the meta or para position with respect to fragment X.

In particular embodiments of the invention, the technical problem is solved by selecting one or more bis-benzonitrile diluents from the group consisting of 4,4 '- [benzo-1,3-diylbis (hydroxy)] dibenzonitrile, 3.3' - [benzo-1,3- diylbis (oxy)] dibenzonitrile, 4,4 '- [benzo-1,4-diylbis (oxy)] dibenzonitrile, 3.3' - [benzo-1,4-diylbis (oxy)] dibenzonitrile, di (4-cyanophenyl ) phenyl phosphate, di (3-cyanophenyl) phenyl phosphate, tri (4-cyanophenyl) phosphate, tri (3-cyanophenyl) phosphate, 4,4 '- ((propane-2,2-diylbis (4,1-phenylene) ) bis (hydroxy)) dibenzonitrile, 4,4'-sulfonyl dibenzonitrile, 3,3'-sulfonyl dibenzonitrile.

The technical problem is also solved by the thermoset composition, which contains a polymerizable mixture and a polymerization initiator selected from the group comprising diamines and bisphenols in an amount of from 1 to 20 mass. % by weight of the polymerizable mixture with a boiling point in vacuum of at least 180 ° C, where the polymerized mixture includes at least one refractory bis-phthalonitrile monomer and the inventive diluent of the formula in the following ratio, wt. %:

Bis Phthalonitrile Monomer 20-80 Diluent 20-80.

In private embodiments of the invention, as the bis-phthalonitrile monomer, the polymerisable mixture may contain one or more compounds selected from the group consisting of 1,3-bis- (3,4-dicyanophenoxy) benzene, 1,4-bis- (3,4-dicyanophenoxy ) benzene, 4,4 '- {propan-2,2-diyl [(4,1-phenylene) oxy]} di (bezol-1,2-dicarbonitrile), 4,4' - [[1,1'- biphenyl] -4,4'-diyl (hydroxy)] di (benzene-1,2-dicarbonitrile).

In the best embodiments of the invention, the polymerizable mixture may contain from 30 to 70 mass. % bis-phthalonitrile monomer

In particular embodiments, the technical problem is solved by a composition which, as a polymerization initiator, contains a compound whose boiling point in vacuum is at least 180 ° C. At least one compound selected from 1,3-bis- (4-aminophenoxy) benzene, 1,3-bis- (3-aminophenoxy) benzene, 4,4'-diaminodiphenylsulfone, 3, 3-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, most preferably from 1,3-bis- (4-aminophenoxy) benzene, or 4,4'-diaminodiphenylsulfone.

A thermoset composition is a polymerizable mixture for producing polymer composite materials with a filler, which can be any carbon fiber, regardless of its origin, glass, basalt or aramizny fibers.

Brief Description of the Drawings

In FIG. 1 shows the viscosity profiles of polymerizable mixtures (binders) according to example 5 (dotted line, the most preferred option) and according to example 9.

In FIG. 2 shows the IR spectra of the polymerizable mixtures (binders) obtained in examples 5-7, cured according to the program of example 15: (1) example 7, (2) example 6, (3) example 5.

The implementation of the invention

Below is a more detailed description of the proposed method, which does not limit the scope of claims of the claimed invention, but demonstrates the possibility of carrying out the invention with the achievement of the claimed technical result. The invention consists in the following.

, где X представляет собой двухвалентный заместитель, выбранный из группы:The proposed reactive diluent is bis-benzonitrile with the stated General formula

where X is a divalent substituent selected from the group:

, -SO₂-, двухвалентных алкильных, арильных или оксиарильных заместителей, а циано-группа находится в мета- или пара-положении по отношению к фрагменту X эффективно уменьшает вязкость любых фталонитрильных смол в тех случаях, когда ее нужно эффективно снизить для каких-то целей.

, -SO ₂ -, divalent alkyl, aryl or hydroxyaryl substituents, and the cyano group is in the meta or para position with respect to fragment X, effectively reduces the viscosity of any phthalonitrile resins when it needs to be effectively reduced for some goals.

The claimed diluent is effective for thermosetting compositions based on refractory bis-phthalonitrile monomers.

By refractory bis-phthalonitrile monomer is meant a bis-phthalonitrile monomer with a melting point of more than 150 ° C, containing, as a rule, a hard binding fragment Y and between phthalonitrile rings in compounds of the general formula:

, где Y может представлять собой, но не ограничиваться следующими двухвалентными заместителями:

where Y may be, but not limited to, the following divalent substituents:

, где где X представляет собой двухвалентный заместитель, выбранный из группы:The curable composition, as follows from the claims, includes a polymerizable mixture consisting of a bis-phthalonitrile monomer and the inventive reaction diluent, which is used bis-benzonitrile with the General formula

where where X is a divalent substituent selected from the group:

, -SO₂-, двухвалентных алькильных, арильных или оксиарильных заместителей, а циано-группа находится в мета- или пара-положении по отношению к фрагменту X, а также содержит инициатор полимеризации.

, -SO ₂ -, divalent alkyl, aryl or hydroxyaryl substituents, and the cyano group is in the meta or para position with respect to fragment X, and also contains a polymerization initiator.

The claimed bis-nitrile was not previously used as a diluent for phthalonitrile resins. It turned out that when it is introduced into phthalonitrile resins, their melting temperature T _pl (T _st ) decreases below 50 ° C, and in cured compositions the heat resistance after curing of these compositions remains above 400 ° C.

It should be noted that bis-benzonitriles were also not previously considered as comonomers for phthalonitriles because of the low reactivity in polymerization, since their cyclotrimerization takes place under severe conditions: high pressures (up to 1000 bar) and temperatures (above 300 ° C) (AR Katritzky, C. A. Ramsden, EFV Scriven, RJK Taylor, Comprehensive heterocyclic chemistry III, Elsevier, 2008) or requires the use of catalysis by rare-earth metal compounds (D. Cui, M. Nishiura, Z. Hou, Lanthanide-Imido Complexes and Their Reactions with Benzonitrile, Angew. Chemie Int. Ed. 44 (2005) 959-962; JH Forsberg, VT Spaziano, SP Klump, KM Sanders, Lanthanide (III) ion c atalyzed reaction of ammonia and nitriles: Synthesis of 2,4,6-trisubstituted-s-triazines, J. Heterocycl. Chem. 25 (1988) 767-770; H. Tanaka, K. Shizu, H. Nakanotani, C. Adachi , Dual Intramolecular Charge-Transfer Fluorescence Derived from a Phenothiazine-Triphenyltriazine Derivative, J. Phys. Chem. C. 118 (2014) 15985-15994).

At the same time, it is known that inactive monomers can be involved in copolymerization by active monomers (MV Bermeshev, PP Chapala, Addition polymerization of functionalized norbornenes as a powerful tool for assembling molecular moieties of new polymers with versatile properties, Prog. Polym. Sci. 84 ( 2018) 1-46; ML Gringolts, MV Bermeshev, KL Makovetsky, ES Finkelshtein, Effect of substituents on addition polymerization of norbornene derivatives with two Me3 Si-groups using Ni (II) / MAO catalyst, Eur. Polym. J. 45 (2009 ) 2142-2149).

This mechanism is also valid for the claimed thermoset composition: active particles formed during the polymerization of phthalonitrile involve bis-benzonitriles in the copolymerization due to nucleophilic attack, and the copolymerization leads to cyclotrimerization of benzonitriles with the formation of triazine fragments.

ниже в спектре связующего из примера 5, что указывает на почти полное участие нитрильных групп в полимеризации (см. фиг. 2).Thus, bis-benzonitriles as reactive diluents are sewn into the three-dimensional phthalonitrile network at both ends through the cyclotrimerization reaction to form triazine network nodes. Such a mechanism is proved by IR spectroscopy data obtained for binders from Examples 5-7, cured according to the program from Example 15. Unreacted nitrile groups (absorption at 2223 cm ^-1 ) are present in all samples, which may be due to the fact that in cyclotrimerization phthalonitrile fragments involved only one vicinal nitrile group due to steric difficulties. The intensity of the resonant oscillations of residual

below in the spectrum of the binder from example 5, which indicates an almost complete participation of nitrile groups in the polymerization (see Fig. 2).

As a result, the reactive diluent is part of the polymer network and does not reduce the mechanical and thermal properties of the polymer, unlike, for example, plasticizers sewn to the network at one end or the known diluent according to WO 2018175025.

This reactive diluent is not a plasticizer for the polymer formed as a result of curing, but at the same time it is for uncured binders, improving their processability

The proposed curable composition also contains a polymerization initiator selected from aromatic diamines or bisphenols with a boiling point in vacuum of at least 180 ° C. This condition is necessary and sufficient to achieve the declared technical result and is due to the fact that in the manufacture of the binder, a degassing stage is meant, that is, mixing in vacuum, carried out at a maximum temperature of 180 ° C. The polymerization initiator should not boil under degassing conditions, because otherwise it will be removed from the binder, which will reduce the curing rate.

For private embodiments of the invention, some refinement of the parameters is possible, which will allow to obtain either additional technical results to the main one, or to improve this result.

могут быть использованы такие соединения, как 4,4'-[бензо-1,3-диилбис(окси)]дибензонитрил, 3,3'-[бензо-1,3-диилбис(окси)]дибензонитрил, 4,4'-[бензо-1,4-диилбис(окси)] дибензонитрил, 3,3'- [бензо-1,4-диилбис(окси)] дибензонитрил, ди(4-цианофенил) фенил фосфат, ди(3-цианофенил) фенил фосфат, три(4-цианофенил) фосфат, три(3-цианофенил) фосфат, 4,4'-((пропан-2,2-диилбис(4,1-фенилен))бис(окси))дибензонитрил, 4,4'-сульфонилдибензонитрил, 3,3'-сульфонилдибензонитрил. Специалистам должно быть понятно, что изобретение не ограничивается использованием только этих бис-бензонитрильных разбавителей и можно в составе композиции использовать и другие бис-бензонитрилы.So, as a bis-benzonitrile diluent, corresponding to the General formula

compounds such as 4,4 '- [benzo-1,3-diylbis (oxy)] dibenzonitrile, 3.3' - [benzo-1,3-diylbis (oxy)] dibenzonitrile, 4,4'- can be used [benzo-1,4-diylbis (oxy)] dibenzonitrile, 3,3'- [benzo-1,4-diylbis (oxy)] dibenzonitrile, di (4-cyanophenyl) phenyl phosphate, di (3-cyanophenyl) phenyl phosphate , tri (4-cyanophenyl) phosphate, tri (3-cyanophenyl) phosphate, 4.4 '- ((propane-2,2-diylbis (4,1-phenylene)) bis (hydroxy)) dibenzonitrile, 4.4' -sulfonyl dibenzonitrile; 3,3'-sulphonyl dibenzonitrile. It will be understood by those skilled in the art that the invention is not limited to the use of only these bis-benzonitrile diluents, and other bis-benzonitriles may be used in the composition.

These compounds are either commercially available or can be synthesized quite simply, for example, as described in GuipengYu, Cheng Liu, Jinyan Wang, Xiuping Li, Xigao Jian; Heat-resistant aromatic S-triazine-containing ring-chain polymers based on bis (ether nitrile) s: Synthesis and properties. Polymer Degradation and Stability (2010), 95 (12), 2445-2452.

As bis-phthalonitrile monomers, as indicated, any refractory bis-phthalonitrile monomers (having melting points above 150 ° C) can be used. In the dependent claims, monomers such as 1,3-bis- (3,4-dicyanophenoxy) benzene, 1,4-bis- (3,4-dicyanophenoxy) benzene, 4,4 '- {propane-2,2 -diylbis [(4,1-phenylene) oxy]} di (benzene-1,2-dicarbonitrile), 4,4 '- [[1,1'-biphenyl] -4,4'-diylbis (oxy)] di (benzene-1,2-dicarbonitrile). In this case, specialists should be clear that the invention is not limited to the use of only these bis-phthalonitrile compounds (http://www.chem.msu.ru/eng/theses/2016/2016-10-10-babkin/).

All these monomers have a melting point of at least 150 ° C, therefore, correspond to the composition of the claimed thermoset composition and can be easily synthesized in accordance with known technologies, for example, with the method described in Liu, Cheng; Wang, Jinyan; Lin, Encheng; Zong, Lishuai; Jian, Xigao. Synthesis and properties of phthalonitrile-terminated oligomeric poly (ether imide) s containing phthalazinone moiety. Polymer Degradation and Stability (2012), 97 (3), 460-468, using resorcinol, hydroquinone, bisphenol A, biphenyl alcohol and any diphenols as divalent aromatic alcohols.

As already indicated, it is important that the polymerization initiator selected from aromatic diamines or bisphenols in the thermoset composition is not volatile and its boiling point in vacuum, for example, 0.1 mm. Hg was at least 180 ° C.

There are a large number of such initiators that can be used to implement the claimed invention, for example, such as

Polymerization initiators suitable for carrying out the claimed inventions are commercially available, in particular from abcr GmbH, ACES Pharma, Merck KGaA, Ambinter Stock Screening Collection, Aurora Building Blocks, Aurora Screening Library, Sigma Aldrich.

However, the invention is not limited to these initiators used by us because of their availability, which a specialist should understand.

Changes in the content of components in the curable composition within the claimed intervals of the content of components are also possible for some cases of the invention, which allows you to vary the width of the technological interval and the parameters (temperature and time) of curing. With an increase in the content of bis-phthalonitrile monomer in the polymerisable mixture, the temperature range narrows, in which the binder can be processed, but the polymerisation rate increases, which is important in some cases, for example, when molding parts by injection into a mold at high pressure molding) or when pressing.

The viscosity was measured on a rheometer MCR 302 in accordance with GOST R 57950-2017.

The glass transition temperature of the binders was determined on a NETZSCH DSC 204 Phoenix differential scanning calorimeter in accordance with GOST R 55135-2012.

The heat resistance of polymers was determined by thermomechanical analysis in accordance with GOST 32618.2-2014. The glass transition temperature of the polymer was taken as heat resistance.

The present invention is illustrated by specific examples of execution, which are not the only possible, but clearly demonstrates the possibility of achieving the desired technical result.

Example 1

Di (4-cyanophenyl) phenyl phosphate was obtained. 1 g (0.008 mol) of anhydrous potassium bromide and 6.32 g (0.08 mol) of pyridine were added to a solution of 9.52 g (0.08 mol) of 4-cyanophenol in 50 ml of dry toluene and stirred at 70 ° C for 30 minutes in the atmosphere argon. Then, 8.44 g (0.04 mol) of phenyl dichlorophosphate was added dropwise. The mixture was stirred at 70 ° C. for 24 hours under argon. After that, the reaction mixture was cooled, filtered from pyridine hydrochloride and the filtrate was washed with water (3 × 30 ml). The aqueous layer was washed with toluene (3 × 10 ml) and the combined organic fraction was dried over sodium sulfate. After that, the solution was evaporated using a rotary evaporator and dried at 80 ° C for 2 hours at a pressure of 5 mm Hg. A yellowish solid was obtained in 95% yield (14.25 g).

Elemental analysis. Calculated for C ₂₀ H ₁₃ N ₂ O ₄ P: C 63.84, H 3.48, N 7.44. Found C 63.81, H 3.53, N 7.40.

Example 2

Di (3-cyanophenyl) phenyl phosphonate was obtained. 0.13 g (0.0008 mol) of anhydrous potassium iodide and 8.08 g (0.08 mol) of triethylamine were added to a solution of 9.52 g (0.08 mol) of 3-cyanophenol in 40 ml dry tetrahydrafuran and stirred at the boil for 30 minutes in an argon atmosphere. Then, 8.44 g (0.04 mol) of phenyl dichlorophosphate was added dropwise. The mixture was stirred at 60 ° C. for 12 hours under argon. After this, the reaction mixture was cooled, filtered from triethylamine hydrochloride and the filtrate was washed with water (3 × 30 ml). The aqueous layer was washed with toluene (3 × 10 ml) and the combined organic fraction was dried over sodium sulfate. After that, the solution was evaporated using a rotary evaporator and dried at 80 ° C for 2 hours at a pressure of 5 mm Hg. A yellowish solid was obtained in 97% yield (13.93 g)

Elemental analysis. Calculated for C ₂₀ H ₁₃ N ₂ O ₃ P: C 66.67, H 3.64, N 7.77. Found C 66.45, H 3.78, N 7.80

Example 3

Di (3-cyanophenyl) phenyl phosphate was obtained. 10.32 g (0.08 mol) of quinoline was added to a solution of 9.52 g (0.08 mol) of 3-cyanophenol in 50 ml of dry dimethylacetamide and stirred at 100 ° C for 10 minutes in an argon atmosphere. Then, 8.44 g (0.04 mol) of phenyl dichlorophosphate was added dropwise. The mixture was stirred at 100 ° C. for 6 hours under argon. After that, the reaction mixture was cooled and poured into 100 ml of water. The aqueous solution was extracted with methylene chloride (3 × 30 ml) and the combined organic fraction was dried over sodium sulfate. After that, the solution was evaporated using a rotary evaporator and dried at 80 ° C for 2 hours at a pressure of 5 mm Hg. A yellowish solid was obtained in 91% yield (13.65 g).

Elemental analysis. Calculated for C ₂₀ H ₁₃ N ₂ O ₄ P: C 63.84, H 3.48, N 7.44, Found C 63.77, H 3.49, N 7.42

Example 4

Di (4-cyanophenyl) butyl phosphate was obtained. 10.00 g (0.18 mol) of potassium hydroxide was added to a solution of 9.52 g (0.08 mol) of 4-cyanophenol in 60 ml of dry dimethyl sulfoxide and stirred at room temperature for 30 minutes in the atmosphere argon. Then, 8.44 g (0.04 mol) of butyl dichlorophosphate was added dropwise. The mixture was stirred at room temperature (22 ° C.) for 24 hours under argon. After this, the reaction mixture was cooled, filtered from the precipitate and poured into 150 ml of a 0.01% hydrochloric acid solution. The aqueous solution was extracted with toluene (3 × 30 ml) and the combined organic fraction was dried over sodium sulfate. After that, the solution was evaporated using a rotary evaporator and dried at 80 ° C for 2 hours at a pressure of 5 mm Hg. A yellowish solid was obtained with a yield of 94% (13.50 g).

Elemental analysis. Calculated for C ₁₈ H ₁₇ N ₂ O ₄ P: C 60.68, H 4.81, N 7.86. Found C 60.73, H 4.87, N 7.79

Example 5

150 g of 4.4 '- (1,3-phenylenebis (hydroxy)) diphthalonitrile and 350 g of bis (4-cyanophenyl) phenylphosphate were placed in a 3 L open aluminum container equipped with a mechanical stirrer. The tank was heated to 170 ° C to melt the components, after which stirring was turned on and heating was turned off. The mixture was allowed to cool to 100 ° C, 50 g of 1,3-bis- (4-aminophenoxy) benzene was added and stirred at 100 ° C for 10 minutes. After that, the mixture was poured onto a metal plate, allowed to cool and a green glassy mass with T _article = -2 ° C was obtained.

Example 6

250 g of 4.4 '- (1,3-phenylenebis (hydroxy)) diphthalonitrile and 250 g of bis (3-cyanophenyl) phenylphosphate were placed in a 2 L glass reactor equipped with a mechanical stirrer. The tank was heated to 170 ° C to melt the components, after which stirring was turned on and heating was turned off. The mixture was allowed to cool to 110 ° C, 50 g of 1,3-bis- (3-aminophenoxy) benzene was added and stirred at 110 ° C for 15 minutes. After this, the mixture was poured onto a metal plate, allowed to cool and a green glassy mass with T _article = 7 ° C was obtained.

Example 7

350 g of 4.4 '- (1,3-phenylenebis (hydroxy)) diphthalonitrile and 150 g of bis (4-cyanophenyl) phenylphosphate were placed in a 2 L glass reactor equipped with a mechanical stirrer. The tank was heated to 185 ° C to melt the components, after which stirring was turned on and heating was turned off. The mixture was allowed to cool to 120 ° C, 50 g of 1,4-bis- (4-aminophenoxy) benzene was added and stirred at 120 ° C for 15 minutes. After this, the mixture was poured onto a metal plate, allowed to cool and received a green glassy mass with T _article = 24 ° C

Example 8

150 g of 4.4 '- (1,4-phenylenebis (hydroxy)) diphthalonitrile and 350 g of 4.4' - (1,3-phenylenebis (hydroxy)) dibenzonitrile were placed in a 2 L glass reactor equipped with a mechanical stirrer. The container was heated to 120 ° C to melt the reactive diluent, after which stirring was turned on and the phthalonitrile monomer was dissolved, then the heating was turned off, the mixture was cooled to 100 ° C and 100 g of bis [4- (4-aminophenoxy) phenyl] sulfone was added and stirred at 100 ° C for 10 minutes. After that, the mixture was poured onto a metal plate, allowed to cool and received a green glassy mass with T _article = 8 ° C

Example 9

250 g of 4.4 '- (1,3-phenylenebis (hydroxy)) diphthalonitrile and 250 g of 4.4' - (1,4-phenylenebis (hydroxy)) dibenzonitrile were placed in an open 3 liter aluminum container equipped with a mechanical stirrer . The tank was heated to 160 ° C to melt the components, after which stirring was turned on and heating was turned off. The mixture was allowed to cool to 120 ° C., 100 g of bis [4- (4-aminophenoxy) phenyl] sulfone was added and stirred at 120 ° C. for 30 minutes. After that, the mixture was poured onto a metal plate, allowed to cool and a green glassy mass with T _article = 13 ° C was obtained.

Example 10

350 g of 4.4 '- (1,3-phenylenebis (hydroxy)) diphthalonitrile and 150 g of 4.4' - (1,3-phenylenebis (hydroxy)) dibenzonitrile were placed in an open 3 liter aluminum container equipped with a mechanical stirrer . The tank was heated to 170 ° C to melt the components, after which stirring was turned on and heating was turned off. The mixture was allowed to cool to 120 ° C., 100 g of bis [4- (4-aminophenoxy) phenyl] sulfone was added and stirred at 120 ° C. for 30 minutes. After that, the mixture was poured onto a metal plate, allowed to cool and a green glassy mass with T _article = 23 ° C was obtained.

Example 11

250 g of 4.4 '- [[1,1'-biphenyl] -4,4'-diylbis (hydroxy)] di (benzene-1,2-dicarbonitrile) was placed in an open 3 liter aluminum container equipped with a mechanical stirrer and 250 g of bis (4-cyanophenyl) butyl phosphate. The tank was heated to 150 ° C to melt the components, after which stirring was turned on and heating was turned off. The mixture was allowed to cool to 90 ° C, 10 g of 1,3-bis- (4-aminophenoxy) benzene was added and stirred at 90 ° C for 30 minutes. After that, the mixture was poured onto a metal plate, allowed to cool and a green glassy mass with T _article ⁼ 0 ° C was obtained.

Example 12

In a 2 L glass reactor equipped with a mechanical stirrer, 200 g of 4.4 '- {propane-2,2-diylbis [(4,1-phenylene) oxy]} di (benzene-1,2-dicarbonitrile) and 300 g 4,4'-sulfonyldibenzonitrile. The container was heated to 180 ° C to melt the components, after which stirring was turned on and heating was turned off, the mixture was cooled to 140 ° C and 20 g of bis [4- (4-aminophenoxy) phenyl] sulfone was added and stirred at 140 ° C for 30 minutes. After that, the mixture was poured onto a metal plate, allowed to cool and a green glassy mass with T _article = 17 ° C was obtained.

Example 13

150 g of 4.4 '- (1,3-phenylenebis (hydroxy)) diphthalonitrile and 250 g of 4.4' - ((propane-2,2-diylbis (4, 1-phenylene)) bis (hydroxy)) dibenzonitrile and 100 g of bis (4-cyanophenyl) phenylphosphate. The tank was heated to 170 ° C to melt the components, after which stirring was turned on and heating was turned off. The mixture was allowed to cool to 130 ° C, 50 g of 1,3-bis- (3-aminophenoxy) benzene was added and stirred at 130 ° C for 15 minutes. After that, the mixture was poured onto a metal plate, allowed to cool and a green glassy mass with T _article = 18 ° C was obtained.

Example 14

150 g of 4.4 '- (1,3-phenylenebis (oxy)) diphthalonitrile and 150 g of 4.4' - [biphenyl-4,4'-diylbis (oxy) were placed in a 2 L glass reactor equipped with a mechanical stirrer ] diphthalonitrile and 200 g of tri (4-cyanophenyl) phosphate. The container was heated to 190 ° C to melt the components, after which stirring was turned on and heating was turned off. The mixture was allowed to cool to 150 ° C., 25 g of 3,3′-diaminodiphenyl sulfone was added and stirred at 150 ° C. for 45 minutes in vacuo. After that, the mixture was poured onto a metal plate, allowed to cool and a green glassy mass with T _article = 24 ° C was obtained.

Example 15

The resulting binders were cured. To do this, 250 g of binder was placed in a 2 L glass reactor, the vacuum was turned on (0.1 mm Hg) and the binder was heated to a temperature of 110-180 ° C, then degassed for 15-30 minutes and poured into a metal mold . The mold was placed in an oven, after which it was held for 12 hours at 180 ° C. After that, the resin was removed from the mold, heated to 330 ° C (10 ° C / h) post-cured at 330 ° C for 8 hours.

Comparative example 1.

A 500 g 1,3-bis (3,4-dicyanophenoxy) benzene and 500 g bis (3- (3,4-dicyanophenoxy) phenyl) phenyl phosphate were placed in a 2 L glass reactor equipped with a mechanical stirrer. The reactor was evacuated (1 mmHg) and heated to 190 ° C until the binder components melted, after which stirring was switched on. After the mixture became homogeneous, 40 g of 1,3-bis- (4-aminophenoxy) benzene was added to the reactor and stirred at 160 ° C. for 30 minutes. After this, the mixture was poured onto a metal tray treated with a release agent and allowed to cool. Received an amorphous glassy mass of green T _article = 67 ° C. Melt viscosity at 180 ° C η ^{150 ° C} = 600 mPa⋅s. When measuring viscosity, a slow crystallization of the melt was observed.

Comparative Example 2

In a 2 L glass reactor equipped with a mechanical stirrer, 700 g of 1,3-bis (3,4-dicyanophenoxy) benzene, 300 g of bis (3- (3,4-dicyanophenoxy) phenyl) phenyl phosphate were placed. The reactor was evacuated (1 mmHg) and heated to 190 ° C until the binder components melted, after which stirring was switched on. After the mixture became homogeneous, 40 g of 1,3-bis- (4-aminophenoxy) benzene was added to the reactor and stirred at 160 ° C. for 30 minutes. After this, the mixture was poured onto a metal tray treated with a release agent and allowed to cool. Received an amorphous glassy mass of green with interspersed crystalline phase. _Mp = 165-185 ° C. The viscosity at 180 ° C η ^{150 ° C} was 1120 mPa⋅s.

Comparative example 3.

400 g of 4.4 '- (1,3-phenylenebis (hydroxy)) diphthalonitrile and 100 g of bis (4-cyanophenyl) phenylphosphate were placed in a 3 L open aluminum container equipped with a mechanical stirrer. The tank was heated to 180 ° C to melt the components, after which stirring was turned on and heating was turned off. The mixture was allowed to cool to 100 ° C, as a result of which the mixture crystallized. Reheating to 170 ° C led to the melting of the mixture, after which 50 g of 1,3-bis- (4-aminophenoxy) benzene was added to it and stirred at 170 ° C for 5 minutes. After this, the mixture was poured onto a metal plate, allowed to cool and a green amorphous mass was obtained with abundant inclusions of the crystalline phase, T _mp = 160-185 ° C.

Example 16. Cured binder obtained in examples 5-14 and comparative examples 1-3. For this, 50 g of the binder was placed in a 250 ml round-bottom flask equipped with a mechanical stirrer and outlet to a vacuum pump. The binders were melted at a temperature of 120-180 ° C, depending on the viscosity of the melt, after which they were stirred under vacuum (up to 0.1 mm Hg) for 15 minutes. After that, the mixture was poured into a prefabricated metal mold with a working chamber size of 10 mm × 10 mm × 2 mm, the mold was closed and heated to 180 ° C at a rate of 2 ° C / min, and then kept at 180 ° C / min for 12 hours . The mold was then assembled, the polymer plates removed and placed in a post-curing oven. Post-cure was carried out at a maximum temperature of 375 ° C for 8 hours.

Table 1 shows the properties of the compositions obtained in examples 5, 9, 11-13 and comparative examples 1-3, and in FIG. 1 shows the viscosity profile of the binder according to example 5 (dotted line, most preferred option) and according to example 9.

As follows from the data presented, the claimed diluent effectively performs its functions, the claimed composition using this diluent after curing has heat resistance above 400 ° C, and the values of the melt viscosities are below 800 mPa⋅s in the range from 100 to 180 ° C, which allows us to consider them as binders for molding polymer composite materials by efficient autoclave-free injection methods.

Claims (10)

1. A reactive diluent for phthalonitrile resins, characterized in that it includes a bis-benzonitrile monomer with the General formula

where X is a divalent substituent selected from the group:

-SO ₂ -, divalent alkyl, aryl or hydroxyaryl substituents, and the cyano group is in the meta or para position with respect to fragment X, Y is phenoxy, 4-cyanophenoxy, 3-cyanophenoxy, n-butoxy. 2. The diluent according to claim 1, characterized in that, as a bis-benzonitrile monomer, it contains one or more compounds selected from the group consisting of 4,4 '- [benzo-1,3-diylbis (hydroxy)] dibenzonitrile, 3 , 3 '- [benzo-1,3-diylbis (oxy)] dibenzonitrile, 4.4' - [benzo-1,4-diylbis (oxy)] dibenzonitrile, 3.3 '- [benzo-1,4-diylbis (hydroxy)] dibenzonitrile, di (4-cyanophenyl) phenyl phosphate, di (3-cyanophenyl) phenyl phosphate, tri (4-cyanophenyl) phosphate, three (3-cyanophenyl) phosphate, 4.4 '- ((propan-2 , 2-diylbis (4,1-phenylene)) bis (hydroxy)) dibenzonitrile, 4,4'-sulfonyldibenzonitrile, 3,3'-sulfonyldibenzonitri . 3. A polymerizable mixture to obtain thermoset compositions, characterized in that it includes at least one refractory bis-phthalonitrile monomer with a melting point above 150 ° C and a diluent in accordance with paragraph 1 in the following ratio of components, mass. %: Bis Phthalonitrile Monomer  20-80 Diluent                                      20-80 4. The mixture according to p. 3, characterized in that as a bis-phthalonitrile monomer it contains a compound selected from the group consisting of 1,3-bis- (3,4-dicyanophenoxy) benzene, 1,4-bis- (3 , 4-dicyanophenoxy) benzene, 4,4 '- {propan-2,2-diyl [(4,1-phenylene) oxy]} di (bezol-1,2-dicarbonitrile), 4,4' - [[1 , 1'-biphenyl] -4,4'-diyl (hydroxy)] di (benzene-1,2-dicarbonitrile). 5. The mixture according to p. 3, characterized in that the polymerized mixture contains from 30 to 70 mass. % bis-phthalonitrile monomer. 6. Thermoset composition for producing polymer composite materials, characterized in that it contains a polymerizable mixture according to claim 3 and a polymerization initiator selected from the group comprising diamines and bisphenols in an amount of from 1 to 20 mass. % by weight of the polymerizable mixture with a boiling point in vacuum of at least 180 ° C. 7. The composition according to p. 6, characterized in that as the polymerization initiator contains at least one compound selected from 1,3-bis- (4-aminophenoxy) benzene, 1,3-bis- (3-aminophenoxy ) benzene, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, most preferably from 1,3-bis- (4-aminophenoxy) benzene, or 4.4 '-diaminodiphenylsulfone. 8. The composition according to p. 6, characterized in that it is a binder composition for producing polymer composite materials.

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