RU2744165C1 - Trifunctional phthalonitrile monomer, method for production thereof and binder-based composition thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention can be used in chemical industry and relates to monomer of formulas (I) or (II) for making polymer composite material (PCM) or prepregs for PCM;

a method for production thereof, compositions based thereon and a method for hardening said compositions. Method of producing monomer according to claim 1 is characterized by that in medium of aprotic polar solvent mixing corresponding hydroxyphenoxyphthalonitrile with organic amine in molar ratio from 1:1 to 1:1.2, followed by addition of 0.33 molar equivalents of phosphorus oxychloride, holding the reaction mixture and recovering the product. Binder compositions include a monomer according to 1, aromatic diamine or bisphenol, and can also contain monomers of general formula (III)

where X is selected from the group

where R is an unsubstituted benzene ring.

EFFECT: invention discloses novel monomers, an efficient method for production thereof, compositions based on said monomers and methods for their hardening, which enable to obtain polymer matrices with high modulus of elasticity.

10 cl, 23 ex, 1 tbl

Description

Technology area

The invention relates to the field of polymer chemistry and technology of polymer composite materials (PCM), namely to a trifunctional phthalonitrile monomer and a polymer based on it, which has an increased elastic modulus, and its mixtures with bis-phthalonitriles (binder), having increased elastic moduli in the cured form , a method for producing a monomer, a phthalonitrile binder composition for polymer composite materials with an increased modulus of elasticity, a method for producing it.

State of the art

In the prior art, various matrices are used to make polymer composites (PCMs). At the same time, binders for PCMs based on phthalonitrile monomers are known as the most heat-resistant polymer matrices.

The term phthalonitriles was first introduced in 1896. It referred to organic structures containing a benzene ring substituted with two nitrile groups in adjacent positions. The structure of phthalonitrile monomer suitable for use as a base for the polymer matrix of PCM is described in general form by formula (1).

When heated in the presence of metals or nucleophilic agents, such monomers form polyisoindoline, triazine, and phthalocyanine fragments that form a three-dimensional network. The first high temperature resin based on phthalonitrile was 4,4'-Bis (3,4-dicyanophenoxy) biphenyl (2) [T.M. Keller, Phthalonitrile-based high temperature resin, J. Polym. Sci. Part A Polym. Chem. 26 (1988) 3199-3212. doi: 10.1002 / pola.1988.080261207]. The polymerization of this monomer was carried out in the presence of metal salts. The obtained polymer compounds had a sufficiently high molecular weight and had a three-dimensionally cross-linked structure. However, polymerization of the monomer was sterically hindered, and the high processing temperature (above 250 ° C) made it difficult to obtain PCM.

Polyphthalocyanines prepared from N,N-bis(3,4-dicyanophenyl) alkanediamides, 1976]. Они быстро укрепили за собой репутацию одних из самых перспективных термостойких смол для использования в композиционных материалах за счет высокой температуры стеклования (350-450°С), выдающихся термической и термоокислительной стабильности (T_5% > 500°С), превосходной огнестойкости (КИ > 60%) [S.B. Sastri, Т.М. Keller, Phthalonitrile polymers: Cure behavior and properties, J. Polym. Sci. Part A Polym. Chem. 37 (1999) 2105-2111. doi:10.1002/(SICI)1099-0518(19990701)37:13<2105::AID-POLA25>3.0.CO; 2-A; M.L. Warzel, T.M. Keller, Tensile and fracture properties of a phthalonitrile polymer, Polymer (Guildf). 34 (1993) 663-666. doi:10.1016/0032-3861(93)90570-Z].Thermosetting polymers obtained from bis-phthalonitriles began to be actively developed in the 1980s in the laboratory of the US Navy in order to obtain heat-resistant incombustible materials for use in the construction of submarines [T.M. Keller, JR Griffith, The Synthesis of a New Class of Polyphthalocyanine Resins, Am. Chem. Soc. (1980) 25-34; TM Keller, JR Griffith, Polyphthalocyanine resins, Patent US 4234712 A, 1980; JR Griffith, JG

Polyphthalocyanines prepared from N, N-bis (3,4-dicyanophenyl) alkanediamides, 1976]. They quickly strengthened their reputation as one of the most promising heat-resistant resins for use in composite materials due to their high glass transition temperature (350-450 ° C), outstanding thermal and thermo-oxidative stability (T _5% > 500 ° C), excellent fire resistance (CI> 60%) [SB Sastri, T.M. Keller, Phthalonitrile polymers: Cure behavior and properties, J. Polym. Sci. Part A Polym. Chem. 37 (1999) 2105-2111. doi: 10.1002 / (SICI) 1099-0518 (19990701) 37:13 <2105 :: AID-POLA25>3.0.CO;2-A; ML Warzel, TM Keller, Tensile and fracture properties of a phthalonitrile polymer, Polymer (Guildf). 34 (1993) 663-666. doi: 10.1016 / 0032-3861 (93) 90570-Z].

The stiffness of the polymer matrix is one of the most important properties of polymer matrices, since matrices with a higher modulus of elasticity better redistribute the load on the reinforcing filler [ASM International. Handbook Committee., ASM Handbook Volume 21: Composites, ASM International, Novelty, OH, 2001. https://books.google.ru/books/about/ASM_Handbook.html?id=JG640u940cEC&redir_esc=y].

From the prior art, a mixture of phthalonitrile components (3) and (4) in a ratio of 1 to 1 by weight is known, showing the highest elastic modulus of 5.7 GPa among phthalonitrile binders [V.A. Bulgakov, A.V. Babkin, A.A. Bogolyubov, E.S. Afanas'eva, A.V. Kepman, Mechanical and physicochemical properties of matrices for fiber reinforced plastics based on low-melting phthalonitrile monomers, Russ. Chem. Bull. 65 (2016). doi: 10.1007 / sl 1172-016-1299-x.].

Examples of structures containing more than two phthalonitrile moieties in the structure are known from the prior art. The polymer obtained by curing trifunctional phthalonitrile based on resveratrol (5) in the presence of bis (3- (4-aminophenoxy) phenyl) sulfone is characterized by an elastic modulus of 1.6 GPa [V.A. Bulgakov, A.V. Sulimov, A.V. Babkin, A.V. Kepman, A.R. Malakho, V.V. Avdeev, Dual-curing thermosetting monomer containing both propargyl ether and phthalonitrile groups, J. Appl. Polym. Sci. (2017) 44786. doi: 10.1002 / app.44786.].

Another polymer prepared from the trifunctional phthalonitrile 1,1,1-tri- [4- (3,4-dicyanophenoxy) phenyl] ethane (6) showed a higher storage modulus of 3.7 GPa after curing at 400 ° C [B. Bulgakov, A. Sulimov, A. Babkin, I. Timoshkin, A. Solopchenko, A. Kepman, V. Avdeev, Phthalonitrile-carbon fiber composites produced by vacuum infusion process, J. Compos. Mater. 51 (2017) 4157-4164. doi: 10.1177 / 0021998317699452].

Closest to the claimed phthalonitrile monomer is a hexafunctional dendrimer based on phosphazene (7) [S.B. Sastri, J.P. Armistead, T.M. Keller, Phthalonitrile-carbon fiber composites, Polym. Compos. 17 (1996). doi: 10.1002 / pc.10674], because it contains more than two phthalonitrile fragments, which are also connected to the central fragment of the molecule through P-O bonds. For the synthesis of a monomer with the formula (7) and one of the claimed monomers, the same compound (8) is used. In this case, the preparation of monomer (7) is associated with a number of difficulties: the reaction yield is only 73% in 48 hours, and the product is purified by freeze drying, which is associated with the use of non-standard equipment and is not very suitable for scaling up the synthesis.

The polymer obtained by the interaction of the monomer (7) in the presence of the hardener (8) is characterized by a rather low modulus of elasticity of 2.7 GPa, and the value of the modulus of elasticity rapidly decreases with increasing temperature and turns out to be below 1 GPa at temperatures above 250 ° C.

Disclosure of invention

The technical problem of the present invention is to obtain new trifunctional phthalonitriles and binder compositions based on them for polymer composite materials (PCMs) having an elastic modulus of elasticity higher than 6 GPa after curing in comparison with the binders known from the prior art, while retaining an elastic modulus exceeding 1 GPa, at a temperature above the glass transition temperature (> 450 ° C), as well as the development of methods for obtaining the components of such compositions, providing a high yield of at least 81% and a simple way to isolate and purify products.

The technical result is achieved with tris-phthalonitrile of formula (I) or its structural isomer, intended for the manufacture of polymer composite material (PCM) or prepregs for PCM as a monomer for a binder composition.

The technical result is achieved by a method of synthesizing a new tris-phthalonitrile of formula (I) or its structural isomer, for example, formula (II), which consists in mixing in an organic aprotic solvent, for example, tetrahydrofuran (THF), toluene, chlorobenzene, chloroform or dioxane, 4- ( hydroxyphenoxy) phthalonitrile with an organic amine, which is triethylamine, pyridine, methylimidazole or diisopropylamine taken in a molar ratio of 1: 1 to 1: 1.2, followed by adding 0.33 molar equivalents of phosphorus oxychloride with stirring. After that, the resulting mixture is kept at room temperature for 3-24 hours. The reaction mixture is then separated from the triethylamine hydrochloride, for example by filtration on a porous glass filter, decantation or extraction with water, and the solvent is evaporated. The product is isolated by recrystallization from methanol.

or its structural isomer of the formula:

The technical result is also achieved by a binder composition intended for the manufacture of PCM or prepregs, containing:

1. Trifunctional monomer or its structural isomer and polymerization initiator (hardener), taken in an amount from 1 to 20 mass. % of the total mass of the monomer, selected from aromatic diamines or bisphenols having a boiling point under vacuum of 0.1 mm Hg. not less than 180 ° C. These include the following hardeners: 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone; or diphenols: bisphenol A, bisphenol C.

2. Or containing a polymerizable mixture, consisting of a trifunctional monomer or its structural isomer, taken in an amount from 20 to 80%, as well as a difunctional phthalonitrile monomer of the general formula:

where X is a bivalent substituent selected from the group:

,

,

where R is an unsubstituted benzene ring taken in an amount of 80 to 20 wt% of the total weight of phthalonitrile monomers, as well as a polymerization initiator (hardener), taken in an amount of 1 to 17 wt% of the total weight of the polymerized mixture, selected from aromatic diamines or bisphenols having a boiling point under vacuum of 0.1 mm Hg. not less than 180 ° C.

Also, the task is solved by the method of curing the binder composition according to the invention, including the stages at which the binder is degassed under vacuum conditions with stirring at a temperature of 150-180 ° C, the resulting degassed material in the form is heated to a temperature of 180-200 ° C and held until curing within 4-12 hours, after which the resulting product is separated from the mold and finally cured by heating to 375 ± 5 ° C at a rate of 5-10 ° C / hour and kept at this temperature for 6-12 hours, then cooled to room temperature with cooling rate no more than 5 ° С / min.

Implementation of the invention

All reagents used are commercially available, all procedures, unless otherwise stated, were carried out at room temperature or ambient temperature, that is, in the range from 18 to 25 ° C.

Example 1. Synthesis of tri (3- (3,4-dicyanophenoxy) phenyl) phosphate (TFN-1)

In a 250 ml three-necked round bottom flask equipped with a reflux condenser, 125 ml THF, 4- (3-hydroxyphenoxy) phthalonitrile (15 g, 0.064 mol) and triethylamine (6.43 g, 0.064 mol) were added. Thereafter, phosphorus oxychloride (3.25 g, 0.021 mol) was added dropwise through the septum with stirring. The mixture was then left under stirring for 3 hours at room temperature. The reaction mixture was filtered on a porous glass filter from triethylamine hydrochloride, the solvent was evaporated. The resulting product was washed with methanol. Yield 92% (14.5 g).

¹ H NMR (DMSO-d ₆ ) δ ppm 7.12 (d, 3 H, J = 8.07 Hz), 7.15 (s, 3 H), 7.26 (d, 3 H, J = 8.34 Hz), 7.42 (dd, 3 H, J = 8.71, 2.57 Hz), 7.55 (t, 3 H, J = 8.30 Hz), 7.83 (d, 3 H, J = 2.57 Hz), 8 , 10 (d, 3 H, J = 8.71 Hz)

¹³ C NMR (DMSO-d ₆₎ δ ppm 109.41, 112.88 (d, J = 5.53 Hz), 115.73, 116.23, 117.26, 117.56 (d, J = 4.42 Hz), 118.22, 123, 08, 123.63, 132.44, 136.79, 151.13 (d, J = 6.63 Hz), 155.42, 160.67

³¹ P NMR (CDCl ₃ ) δ ppm. -15.31

Example 2. Synthesis of tri (3- (3,4-dicyanophenoxy) phenyl) phosphate (TFN-1)

In a 250 ml three-necked round bottom flask equipped with a reflux condenser, 125 ml THF, 4- (3-hydroxyphenoxy) phthalonitrile (15 g, 0.064 mol) and 1-methylimidazole (5.25 g, 0.064 mol) were added. Thereafter, phosphorus oxychloride (3.25 g, 0.021 mol) was added dropwise through the septum with stirring. The mixture was then left under stirring for 5 hours at room temperature. The reaction mixture was filtered on a porous glass filter from 1-methylimidazole hydrochloride, the solvent was evaporated. The resulting product was washed with methanol. Yield 89% (14.0 g).

Example 3. Synthesis of tri (3- (3,4-dicyanophenoxy) phenyl) phosphate (TFN-1) In a round-bottom three-necked flask with a capacity of 250 ml, equipped with a reflux condenser, 125 ml of THF, 4- (3-hydroxyphenoxy) phthalonitrile (15 g, 0.064 mol) and diisopropylethylamine (8.27 g, 0.064 mol). Thereafter, phosphorus oxychloride (3.25 g, 0.021 mol) was added dropwise through the septum with stirring. The mixture was then left under stirring for 3 hours at room temperature. The reaction mixture was filtered on a porous glass filter from diisopropylethylamine hydrochloride, the solvent was evaporated. The resulting product was washed with methanol. Yield 91% (14.3 g).

Example 4. Synthesis of tri (4- (3,4-dicyanophenoxy) fensh) phosphate (TFN-2)

To a suspension of 9.44 grams of 4- (4-hydroxyphenoxy) phthalonitrile in 50 ml of toluene was added dropwise 2.05 grams of phosphorus oxychloride. Stirred for 24 hours until the evolution of hydrogen chloride ceases. Thereafter, the reaction mixture was washed with water (5 × 25 ml) until the weakly acidic reaction of the wash water. Thereafter, the organic layer was dried over anhydrous Na ₂ SO ₄ and the solvent was removed from the flask. Received the target substance in the form of a yellowish powder. Yield 87%.

¹ H NMR (DMSO-d ₆ ) δ ppm 6.72 (d, 3 H, J = 8.12 Hz), 7.07 (s, 3 H), 7.14 (d, 3 H, J = 8.25 Hz), 7.12 (d, 3 H, J = 8.07 Hz), 7.15 (s, 3 H), 7.26 (d, 3 H, J = 8.34 Hz), 7.32 (dd, 3 H, J = 8 , 62, 2.57 Hz), 7.50 (t, 3 H, J = 8.62 Hz), 7.62 (d, 3 H, J = 2.57 Hz), 7.89 (d, 3 H, J = 8.80 Hz)

¹³ C NMR (DMSO-d ₆ ) δ ppm 109.62, 115.28 (d, J = 5.09 Hz), 117.28, 118.92, 119.93, 120.24 (d, J = 4.24 Hz), 121.10, 121, 37, 123.25, 128.05, 135.18, 147.32 (d, J = 6.63 Hz), 151.26, 160.91

³¹ P NMR (CDCl ₃ ) δ ppm. -14.72

Example 5. Synthesis of tri (3- (3,4-dicyanophenoxy) phenyl) phosphate (TFN-1)

To a suspension of 9.44 grams of 4- (3-hydroxyphenoxy) phthalonitrile in 50 ml of chlorobenzene was added dropwise 2.05 grams of phosphorus oxychloride. Stirred for 12 hours in the presence of 5.3 g of dry triethylamine as base. After that, the reaction mixture was filtered on a glass filter from triethylammonium hydrochloride, washed with toluene (3 × 10 ml). The mixture was then washed with water (3 × 25 ml), dried over anhydrous Na ₂ SO ₄ and the solvent was removed from the flask. Received the target substance in the form of a yellowish powder. The yield is 88%.

Example 6. Synthesis of tri (4- (3,4-dicyanophenoxy) phenyl) phosphate (TFN-2)

To a suspension of 9.44 grams of 4- (4-hydroxyphenoxy) phthalonitrile in 50 ml of chloroform was added dropwise 2.05 grams of phosphorus oxychloride. Stirred for 6 hours in the presence of 10.6 g of strontium carbonate as base. Thereafter, the mixture was washed with water (3 × 25 ml), dried over anhydrous Na ₂ SO ₄ and the solvent was removed from the flask. Received the target substance in the form of a yellowish powder. Output 81%.

Example 7. Synthesis of tri (3- (3,4-dicyanophenoxy) phenyl) phosphate (TFN-1)

To a suspension of 9.44 grams of 4- (3-hydroxyphenoxy) phthalonitrile in 50 ml of dry dioxane was added dropwise 2.05 grams of phosphorus oxychloride. Stirred for 4 hours in the presence of 3.5 g of pyridine as base. After that, the reaction mixture was decanted from pyridine hydrochloride, 10 ml of dioxane was added to the residue and again decanted. The solutions were combined and the solvent was removed. The residue was washed with methanol and air dried. Received the target substance in the form of a yellowish powder. The yield is 90%.

Getting binder and prepregs

Example 7. Getting a binder

A 2 L reactor equipped with a mechanical stirrer was charged with 360 g of bis- (3- (3.4 dicyanophenoxy) phenyl) phenyl phosphate (FFN-1) and 240 g (40% by weight of monomers) trifunctional monomer tri (3- (3 , 4-dicyanophenoxy) phenyl) phosphate (TFN-1). The reactor was evacuated (0.1 mm Hg) and heated to 170 ° C until the binder components melted, after which stirring was turned on. After the mixture became homogeneous, 30 g (5% by weight of monomers) of the hardener 1,3-bis (4-aminophenoxy) benzene (APB) was added to the reactor and stirred at 150 ° C for 30 minutes. The mixture was then poured onto a metal tray treated with a release agent and allowed to cool. Got an amorphous glassy mass of green color. T _c = 29 ° C, η ^{150 ° C =} 27 mPa⋅s, t _g ^{180 ° C} = 130 min. In this and subsequent examples, the glass transition temperature was determined by differential scanning calorimetry (DSC), and the melt viscosity and gel time were determined in isothermal mode on a Brookfield viscometer of the cone-plate type.

Example 8. Getting a binder

Into a 2 L reactor equipped with a mechanical stirrer was placed 140 g of 1,3-bis- (3,4-dicyanophenoxy) benzene (FN-1) and 260 g of trifunctional monomer tri (4- (3,4-dicyanophenoxy) phenyl ) phosphate (TFN-2). The reactor was evacuated (0.1 mm Hg) and heated to 170 ° C to liquefy the binder components, after which stirring was turned on. To the resulting mixture was added 60 g of 1,3-bis (4-aminophenoxy) benzene and stirred at 160 ° C. for 15 minutes. After that, the mixture was unloaded from the reactor with a greenish plastic suspension.

Example 9. Getting a binder

In a 2 L reactor equipped with a mechanical stirrer, 480 g of 1,4-bis- (3,4-dicyanophenoxy) benzene (FN-2) and 120 g of trifunctional monomer tri (4- (3,4-dicyanophenoxy) phenyl) phosphate (TFN-2). The reactor was evacuated (0.1 mm Hg) and heated to 170 ° C to liquefy the binder components, after which stirring was turned on. To the resulting mixture was added 90 g (15% by weight of monomers) of the hardener 4,4'-diaminodiphenylsulfone (4-SDS) and stirred at 150 ° C for 15 minutes. After that, the mixture was unloaded from the reactor with a greenish plastic suspension.

Example 10. Getting a binder

In a reactor with a volume of 2 liters, equipped with a mechanical stirrer, 300 g of 4.4 '- (3,3' - (propane-2,2-diyl) bis (3,1-phenylene)) bis (oxy) diphthalonitrile (BAFN) and 300 g of tri (3- (3,4-dicyanophenoxy) phenyl) phosphate (TFN-1) trifunctional monomer. The reactor was evacuated (0.1 mm Hg) and heated to 150 ° C to liquefy the binder components, after which stirring was turned on. To the resulting mixture was added 120 g (20% by weight of monomers) of bisphenol-A hardener and stirred at 140 ° C for 10 minutes. After that, the mixture was unloaded from the reactor with a greenish plastic suspension.

Example 11. Getting a binder

In an open aluminum container with a volume of 3 liters, equipped with a mechanical stirrer, 160 g of 4,4 '- (3,3'-sulfonyl bis (3,1-phenylene) bis (oxy)) diphthalonitrile (BSFN) and 640 g of trifunctional monomer three (4- (3,4-dicyanophenoxy) phenyl) phosphate (TFN-2). The mixture was heated to 160 ° C to melt the binder components, after which stirring was turned on. To the resulting mixture was added 8 g (1% by weight of monomers) of bisphenol-C hardener and stirred at 150 ° C for 15 minutes. After that, the mixture was poured onto a metal plate, allowed to cool, and a green glassy mass was obtained. T _c = 74 ° C, η ^{150 ° C} = 31 mPa⋅s, t _g ^{180 ° C} = 100 min.

Example 12. Getting a binder

640 g of bis- (4- (3.4 dicyanophenoxy) phenyl) phenyl phosphate (FFN-2) and 160 g of trifunctional monomer tri (3- (3,4-dicyanophenoxy) phenyl) phosphate (TFN-1). The reactor was evacuated (0.1 mm Hg) and heated to 150 ° C until the binder components melted, after which stirring was turned on. After the mixture became homogeneous, 40 g (5% by weight of monomers) of bis-aminophenoxybenzene (diamine-P) hardener was added to the reactor and stirred at 140 ° C for 30 minutes. The mixture was then poured onto a metal tray treated with a release agent and allowed to cool. Got an amorphous glassy mass of green color. T _c = 23 ° C, η ^{140 ° C} = 27 mPa⋅s, t _g ^{180 ° C} = 130 min.

Comparative example 1. Obtaining a binder

In a 500 ml round bottom flask, 200 g of bis (3- (3.4 dicyanophenoxy) phenyl) phenyl) phosphate (FFN-1) was added without the addition of the trifunctional monomer. The reactor was evacuated (0.1 mm Hg) and heated to 180 ° C until the binder components melted, after which stirring was turned on. After the mixture became homogeneous, 10 g of 1,3-bis- (4-aminophenoxy) benzene was added to the reactor and stirred at 170 ° C for 30 minutes, then the mixture was poured onto a metal tray treated with a release agent and allowed to cool. ... Got an amorphous glassy mass of green color. T _c = 22 ° C, η ^{170 ° C} = 46 mPa⋅s, t _g ^{180 ° C} = 110 min.

Comparative example 2. Obtaining a binder

In a 500 ml round bottom flask, 200 g of 1,3-bis- (3,4-dicyanophenoxy) benzene (FFN-1) was added. The reactor was evacuated (0.1 mm Hg) and heated to 180 ° C until the binder components melted, after which stirring was turned on. After the mixture became homogeneous, 5 g of 4,4'-diaminodiphenylsulfone was added to the reactor and stirred at 180 ° C for 15 minutes. The mixture was then poured onto a metal tray treated with a release agent and allowed to cool. Received a crystalline mass of green. T _pl = 180 ° C, η ^{190 ° C} = 33 mPa⋅s, t _g ^{190 ° C} = 10 min.

Curing mixtures

Curing of binders was carried out in the presence of 1-20 wt. % of a hardener selected from the group of aromatic diamines or bisphenols having a boiling point under vacuum of 0.1 mm Hg. Art. not less than 180 ° С, in special metal forms 100 × 100 × 2. A mixture of monomers with a hardener was placed in a round-bottom flask, connected to a vacuum pump, melted and degassed at 150-180 ° C (depending on the composition of the mixture), after which the mixture was poured onto a metal plate bounded by a frame and covered with a second plate from above. The assembled structure was heated at 2 ° C / min. until reaching 180 ° C with a holding time of 8 hours, after which the primary hardened matrix was removed from the metal mold. Then it was subjected to heating 10 ° C / h to 375 ° C with a holding time of 8 hours.

Example 13. Curing of the binder

The binder obtained in Example 7 was poured onto a framed metal plate and covered with a second plate from the top. The assembled structure was heated at 2 ° C / min. until reaching 180 ° C with a holding time of 12 hours, after which the primary cured matrix was taken out of the metal mold. Then it was subjected to heating 10 ° C / h to 375 ° C with a holding time of 8 hours. Got a black solid polymer.

Example 14. Curing of the binder

The binder obtained in Example 8 was poured onto a framed metal plate and covered with a second plate from the top. The assembled structure was heated at 2 ° C / min. until reaching 180 ° C with a holding time of 4 hours, after which the primary cured matrix was taken out of the metal mold. Then it was subjected to heating 10 ° C / h to 375 ° C with a holding time of 8 hours. Got a black solid polymer.

Example 15. Curing of the binder

The binder obtained in Example 9 was poured onto a framed metal plate and covered with a second plate from the top. The assembled structure was heated at 2 ° C / min. until reaching 180 ° C with a holding time of 6 hours, after which the primary cured matrix was removed from the metal mold. Then it was subjected to heating 10 ° C / h to 375 ° C with a holding time of 8 hours. Got a black solid polymer.

Example 16. Curing of the binder

The binder obtained in Example 10 was poured onto a framed metal plate and covered with a second plate from the top. The assembled structure was heated at 2 ° C / min. until reaching 180 ° C with a holding time of 8 hours, after which the primary cured matrix was removed from the metal mold. Then it was subjected to heating 10 ° C / h to 375 ° C with a holding time of 8 hours. Got a black solid polymer.

Example 17 Binder Curing

The binder obtained in Example 11 was poured onto a framed metal plate and covered with a second plate from the top. The assembled structure was heated at 2 ° C / min. until reaching 180 ° C with a holding time of 8 hours, after which the primary cured matrix was removed from the metal mold. Then it was subjected to heating 10 ° C / h to 375 ° C with a holding time of 8 hours. Got a black solid polymer.

Example 18 Binder Curing

The binder obtained in Example 12 was poured onto a framed metal plate and covered with a second plate from the top. The assembled structure was heated at 2 ° C / min. until reaching 180 ° C with a holding time of 8 hours, after which the primary cured matrix was removed from the metal mold. Then it was subjected to heating 10 ° C / h to 375 ° C with a holding time of 8 hours. Got a black solid polymer.

Example 19. Curing of the binder

The binder obtained in Example 9 was poured onto a framed metal plate and covered with a second plate from the top. The assembled structure was heated at 2 ° C / min. until reaching 200 ° C with a holding time of 8 hours, after which the primary hardened matrix was taken out of the metal mold. Then it was subjected to heating 5 ° C / h to 375 ° C with a holding time of 12 hours. Got a black solid polymer.

Comparative example 3. Curing of the binder

The binder obtained in Comparative Example 1 was poured onto a framed metal plate; and covered with the second plate from the top. The assembled structure was heated at 2 ° C / min. until reaching 180 ° C with a holding time of 8 hours, after which the primary cured matrix was removed from the metal mold. Then it was subjected to heating 10 ° C / h to 375 ° C with a holding time of 8 hours. Got a black solid polymer.

Comparative example 4. Binder curing

The binder obtained in Comparative Example 2 was poured onto a framed metal plate and covered with the second plate from the top. The assembled structure was heated at 2 ° C / min. until reaching 180 ° C with an exposure of 2 hours, after which the primary cured matrix was taken out of the metal mold. Then it was subjected to heating 10 ° C / h to 375 ° C with a holding time of 8 hours. Got a black solid polymer.

Elastic modulus measurement

The elastic modulus of polymers of various compositions was measured by the dynamo-mechanical method. The results of measurements of the modulus of elasticity of the cured binders at room temperature (T = 25 ° C) from the previous section are given in table. It can be seen from the table that the use of 20 to 80% TPP in the mixture allows increasing the value of the modulus of elasticity of the thermosetting plastic.

Thus, the new trifunctional phthalonitrile for use as a monomer for binder-based composites for the preparation of polymer composite materials (PCMs) makes it possible to obtain polymers with an elastic modulus of more than 6 GPa at room temperature, and the value of the elastic modulus remains above 1 GPa at a temperature of 475 ° FROM.

Claims (14)

1. Trifunctional phthalonitrile monomer of formula (I) or its structural isomer of formula (II), intended for the manufacture of polymer composite material (PCM) or prepregs for PCM,

2. A method for producing tris-phthalonitrile according to claim 1, characterized in that the corresponding hydroxyphenoxyphthalonitrile is mixed with an organic amine in a medium of an aprotic polar solvent, taken in a molar ratio from 1: 1 to 1: 1.2, followed by adding with stirring 0, 33 molar equivalents of phosphorus oxychloride, after mixing the resulting mixture is kept at room temperature for 3-24 hours, then the reaction mixture is separated from the organic amine salts, the solvent is evaporated and the product is isolated by recrystallization from methanol. 3. The method according to claim 2, characterized in that tetrahydrofuran, toluene, chlorobenzene, chloroform or dioxane are used as the aprotic polar solvent. 4. The method according to claim 2, characterized in that triethylamine, diisopropylethylamine, methylimidazole or pyridine are used as the organic amine. 5. The method according to claim 2, characterized in that the separation is carried out by filtration on a porous glass filter, decantation or extraction with water. 6. Composition of a binder intended for the manufacture of a polymer composite material (PCM) or prepregs for PCM, including a trifunctional monomer according to claim 1 and a polymerization initiator (hardener) selected from aromatic diamines or bisphenols having a boiling point under vacuum of 0.1 mm Hg. not less than 180 ° C, taken in an amount from 1 to 20 mass. % of the total weight of the monomer. 7. A composition according to claim 6, characterized in that 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone or bisphenol A, bisphenol C are used as the polymerization initiator. 8. Composition of a binder intended for the manufacture of a polymer composite material (PCM) or prepregs for PCM, including the trifunctional monomer according to claim 1, taken in an amount from 20 to 80% of the mass. from the total mass of phthalonitrile monomers, as well as difunctional phthalonitrile monomer of general formula (III):

where X is a bivalent substituent selected from the group

where R represents an unsubstituted benzene ring, taken in an amount from 80 to 20% of the mass. from the total mass of phthalonitrile monomers, as well as a polymerization initiator (hardener), taken in an amount from 1 to 17 mass. % of the total mass of the polymerized mixture, selected from aromatic diamines or bisphenols having a boiling point under vacuum of 0.1 mm Hg. not less than 180 ° C. 9. A composition according to claim 8, characterized in that 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone or bisphenol A, bisphenol C are used as the polymerization initiator. 10. A method of curing a binder composition according to any one of claims. 6-8, characterized in that it includes the stages at which the binder is degassed under vacuum with stirring at a temperature of 150-180 ° C, the resulting degassed material is heated to a temperature of 180-200 ° C and held until curing for 4-12 hours , after which the resulting product is finally cured by heating to 375 ± 5 ° C at a rate of 5-10 ° C / h and kept at this temperature for 6-12 hours, then cooled to room temperature with a cooling rate of no more than 5 ° C / min.