Composition of Phthalonitrile Resin Matrix for Polymer Composite Materials, Method for Fabrication Thereof, Method for Manufacturing of Polymer Composite Material, and Material Obtained by this Method

Abstract

This invention is related to a resin matrix composition intended for production of a polymer composite material (PCM) or prepregs for PCM, to variants of methods for producing resin matrix compositions, to a method for curing the resin matrix composition, to a polymer composite material and method for its fabrication. The resin matrix composition includes: (1) polymerizable mixture containing one or more bis-phthalonitrile monomers with the general formula:

##STR00001## where X, Y, Z are each independently selected from the group consisting of H, F, Cl, Br and CH.sub.3, taken in the amount of 20-94 wt % of the polymerizable mixture weight; one or more reactive plasticizers-antipyrenes with the general formula:

##STR00002## where

##STR00003##

group can be in the meta- or para-position relative the oxygen atom bonded to the benzene ring, and R is selected from an aryl, oxyaryl, alkyl, or oxyalkyl group, or plasticizers-antipyrenes with the general formula:

##STR00004## where R is selected from an aryl, oxyaryl, alkyl, or oxyalkyl group, taken in the amount of 5-80 wt % of the total polymerizable mixture weight; one or more active diluents with the general formula:

##STR00005## where R can be in meta- or para-position relative to the oxygen bonded to the benzene ring, and stands for H, CN, NH.sub.2 or N(C.sub.3H.sub.3).sub.2, in the amount from 1 to 50% of the total polymerizable mixture weight. The resin matrix composition also includes (2) curing agent in the amount from 1 to 20% of the total polymerizable mixture weight selected from aromatic diamines or bisphenols that have boiling points of at least 180° C. under vacuum of 0.1 mm Hg. The total content of the polymerizable mixture and the curing agent is from 60 to 100 wt % of the total resin matrix weight. The invention allows to increase the thermal stability of the resin matrix and obtain composite material which after curing possesses increased thermal stability at temperatures up to 450° C., have melting points or glass transition temperatures of no more than 50° C., provide melt viscosities below 800 mPa.Math.s at temperatures from 100 to 180° C. and below 300 mPa.Math.s at temperatures from 120 to 180° C.

Claims

1. A resin matrix composition intended for producing a polymer composite material (PCM) or prepregs for PCM, comprising: (1) a polymerizable mixture comprising: one or more bis-phthalonitrile monomers selected from monomers of the following general formula: ##STR00061## where X, Y, Z are independently selected from the group consisting of H, F, Cl, Br, and CH.sub.3, in an amount of 20 to 94 wt % of the polymerizable mixture; one or more reactive plasticizers-antipyrenes selected from compounds of the following general formula ##STR00062## where group ##STR00063## can be in either meta- or para-position relative to the oxygen atom bonded to the benzene ring, and R is selected from an aryl, oxyaryl, alkyl, or oxyalkyl group, or compounds of the following general formula ##STR00064## where R is selected from an aryl, oxyaryl, alkyl, or oxyalkyl group, the reactive plasticizers-antipyrenes comprising 5 to 80 wt % of the polymerizable mixture; and one or more reactive diluents selected from compounds of the following general formula ##STR00065## where R can be in meta- or para-position relative to the oxygen atom bonded to the benzene ring and is either H, CN, NH.sub.2, or N(C.sub.3H.sub.4).sub.2, the reactive diluents comprising 1 to 50% of a total weight of the polymerizable mixture; and (2) a polymerization initiator (curing agent) comprising 1 to 20 wt % of the total weight of the polymerization mixture, the polymerization initiator selected from aromatic diamines or bisphenols with a boiling point of at least 180° C. at 0.1 mm Hg vacuum; wherein a total content of the polymerizable mixture and the polymerization initiator is 60-100 wt % of a total resin matrix weight of the resin matrix composition.

2. The composition of claim 1, wherein the reactive diluent is selected from one or more compounds from the group consisting of 4-[3-(dipropargylamino)phenoxy]phthalonitrile, 4-[4-(dipropargylamino)phenoxy]phthalonitrile, 4-(4-cyanophenoxy)-benzene-1,2-dicarbonitrile, 4-(4-cyanophenoxy)-phthalonitrile, 4-(3-cyanophenoxy)-phthalonitrile and 4-(4-aminophenoxy)-phthalonitrile, the most preferably from one or more following compounds 4-(4-cyanophenoxy)-benzene-1,2-dicarbonitrile, 4-[3-(dipropargylamino)phenoxy]phthalonitrile, 4-[4-(dipropargylamino)phenoxy]phthalonitrile.

3. The composition of claim 1, wherein the active diluent is present in an amount from 1 to 40 wt % of the total weight of the mixture or from 10 to 50 wt % of the total weight of the mixture, or from 10 to 40 wt % of the total weight of the mixture, or from 20 to 40 wt % of the total weight of the mixture, or from 20 to 35 wt % of the total weight of the mixture, or from 20 to 30 wt % of the total weight of the mixture, preferably from 10 to 40% of the total weight of the mixture, or in the amount of 10 to 30% of the total weight of the mixture.

4. The composition of claim 1, wherein said aryl is an optionally substituted aryl C.sub.6-C.sub.20, preferably an aryl C.sub.6-C.sub.18, more preferably an unsubstituted aryl C.sub.6-C.sub.10 or a substituted aryl C.sub.6, wherein the substituent may be methyl, fluoro, chloro, bromo, or trifluoromethyl group, preferably the aryl is a phenyl; said oxyaryl is a —O(C.sub.6-C.sub.20) oxyaryl, preferably a —O(C.sub.6-C.sub.18) oxyaryl, more preferably an unsubstituted —O(C.sub.6-10) oxyaryl or a substituted —O(C.sub.6) oxyaryl, wherein the substituent may be methyl, fluoro, chloro, bromo, or trifluoromethyl group, preferably the oxyaryl is an oxyphenyl; said alkyl is a straight-chain or branched-chain C.sub.1-C.sub.8 alkyl, preferably C.sub.2-C.sub.6 alkyl, most preferably C.sub.3-C.sub.4 alkyl; said oxyalkyl is a straight-chain or branched-chain —O(C.sub.1-C.sub.8) oxyalkyl, preferably —O(C.sub.2-C.sub.6) oxyalkyl, most preferably —O(C.sub.3-C.sub.4) oxyalkyl.

5. The composition of claim 1, wherein the monomer is selected from one or more compounds from the group consisting of 1,3-bis-(3,4-dicyanophenoxy) benzene, 1,3-bis-(3,4-dicyanophenoxy)-2-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-chlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-chlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-bromobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-bromobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2,4-difluorobenzene, 1,5-bis-(3,4-dicyanophenoxy)-2,4-dichlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-methylbenzene, more preferably from 1,3-bis-(3,4-dicyanophenoxy) benzene, 1,3-bis-(3,4-dicyanophenoxy)-2-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2,4-difluorobenzene, the most preferably 1,3-bis-(3,4-dicyanophenoxy) benzene.

6. The composition of claim 1, wherein the reactive plasticizer-antipyrene is selected from one or more compounds from the group consisting of bis-(4-cyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)-1-naphthylphosphate, bis-(4-cyanophenoxy)-phenylphosphonate, bis-(3-(3,4-dicyanophenoxy)phenyl)-phenylphosphonate, bis-(3-(3,4-dicyanophenoxy)phenyl)-isopropylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-butylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-propargylphosphate, bis-(4-cyanophenyl)phenylphosphate, bis-(3-cyanophenoxy)phenylphosphate and bis-4-(3,4-dicyanophenoxy)phenyl)phenylphosphate, more preferably from bis-(4-cyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-isopropylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-butylphosphate.

7. The composition of claim 1, wherein the curing agent is selected from the following compounds: ##STR00066## or from compounds of the following general formula ##STR00067## where Z stands for H or F, or from compounds of the following general formula ##STR00068## where Z is H or F, or bisphenols, or more preferably from 1,3-bis-(4-aminophenoxy)benzene, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,3′-[(2,3,5,6-tetrafluorobenz-1,4-diyl)bis(oxy)]dianiline, 4,4′-[(2,3,5,6-tetrafluorobenz-1,4-diyl)bis(oxy)]dianiline, bis[4-(4-aminophenoxy)phenyl]sulfone or bisphenol A, the most preferably from 1,3-bis-(4-aminophenoxy)benzene or bis[4-(4-aminophenoxy)phenyl]sulfone.

8. The composition of claim 1, wherein the monomer is present in an amount of 20-80 wt % of weight of the polymerizable mixture or 30-80 wt % of weight of the polymerizable mixture, or 20-70 wt % of weight of the polymerizable mixture, more preferebly 30-70 wt % of weight of the polymerizable mixture, or 40-70 wt % of weight of the polymerizable mixture, or 40-55 wt % of weight of the polymerizable mixture, more preferably in an amount of 30-70 wt % of weight of the polymerizable mixture.

9. The composition of claim 1, distinguished by the fact that the plasticizer is present in the amount of 5-70 wt % of the total weight of the polymerizable mixture, or in the amount of 5-60 wt % of the total weight of the polymerizable mixture, or in the amount of 20-70 wt % of the total weight of the polymerizable mixture, or in the amount of 20-60 wt % of the total weight of the polymerizable mixture, or in the amount of 25-60 wt % of the total weight of the polymerizable mixture, or in the amount of 25-50 wt % of the total weight of the polymerizable mixture, or in the amount of 30-60 wt % of the total weight of the polymerizable mixture, or in the amount of 30-50% of the total weight of the polymerizable mixture.

10. The composition of claim 1, wherein the curing agent is present in the amount from 2 to 20 wt % of the total weight of the polymerizable mixture, or from 5 to 20 wt % of the total weight of the polymerizable mixture, or from 5 to 15 wt % of the total weight of the polymerizable mixture, or more preferably from 5 to 10% of the total weight of the polymerizable mixture.

11. The composition of claim 1, wherein the composition is intended for preparation of a prepreg for PCM producing and further contains an inert filler selected from a quartz powder, carbon black, barium sulfate, metal phthalocyanides, pyrogenic silica, titanium oxide, and any mixture of at least two of said materials in the amount up to 40 wt % of the total resin matrix weight or in the amount of 9-30 wt % of the total resin matrix weight, or in the amount of 9-28 wt % of the total resin matrix weight.

12. A method for producing a resin matrix composition of claim 1, the method comprising a preparation of a polymerizable mixture in a reactor, the polymerizable mixture comprising one or more bis-phthalonitrile monomers selected from monomers of the following general formula: ##STR00069## where X, Y, Z are independently selected from the group consisting of H, F, Cl, Br, and CH.sub.3, in an amount of 20 to 94 wt % of the polymerizable mixture, one or more reactive plasticizers-antipyrenes selected from compounds of the following general formula ##STR00070## where group ##STR00071## can be in either meta- or para-position relative to the oxygen atom bonded to the benzene ring, and R is an aryl, oxyaryl, alkyl, or oxyalkyl group, or compounds of the following general formula ##STR00072## where R is selected from aryl, oxyaryl, alkyl, or oxyalkyl group, the reactive plasticizers-antipyrenes comprising 5 to 80 wt % of a total weight of the polymerizable mixture, and one or more reactive diluents selected from compounds of the following general formula ##STR00073## where R can be in meta- or para-position relative to the oxygen atom bonded to the benzene ring and is either H, CN, NH.sub.2, or N(C.sub.3H.sub.4).sub.2, to the reactive diluents comprising 1 to 50% of the total weight of the polymerizable mixture; and putting the reactor under vacuum and heating to a temperature in the range of 100 to 180° C. until complete homogenization of the mixture, adding a polymerization initiator to the obtained homogeneous mixture in an amount from 1 to 20 wt % of the total weight of the polymerizable mixture, wherein the polymerization initiator is selected from aromatic diamines and bisphenols having a boiling point of at least 180° C. under vacuum of 0.1 mm Hg; stirring of thus obtained mixture at a temperature in the range of 100 to 160° C. for 5-180 minutes and discharging of the obtained composition without cooling followed by allowing the composition to cool.

13. The method of claim 12, wherein said one or more reactive diluents are added in an amount from 1 to 40 wt % of the total weight of the mixture or from 10 to 50 wt % of the total weight of the mixture, or from 10 to 40 wt % of the total weight of the mixture, from 20 to 40 wt % of the total weight of the mixture, or from 20 to 35 wt % of the total weight of the mixture, or from 20 to 30 wt % of the total weight of the mixture, preferably from 10 to 40% of the total weight of the mixture, or in an amount from 10 to 30% of the total weight of the mixture.

14. The method of claim 13, wherein the reactive diluent is selected from one or more compounds from the group consisting of 4-[3-(dipropargylamino)phenoxy]phthalonitrile, 4-[4-(dipropargylamino)phenoxy]phthalonitrile, 4-(4-cyanophenoxy)-phthalonitrile, 4-(3-cyanophenoxy)-phthalonitrile and 4-(4-aminophenoxy)-phthalonitrile, 4-(3-aminophenoxy)-phthalonitrile, the most preferably from 4-(4-cyanophenoxy)-phthalonitrile, 4-[3-(dipropargylamino)phenoxy]phthalonitrile.

15. The method of claim 12, wherein said aryl is an optionally substituted C.sub.6-C.sub.20 aryl, preferably C.sub.6-C.sub.18 aryl, more preferably an unsubstituted C.sub.6-C.sub.10 aryl or substituted C.sub.6 aryl, where the substituent may be methyl, fluoro, chloro, bromo, or trifluoromethyl group, preferably the aryl is a phenyl; said oxyaryl is a —O(C.sub.6-C.sub.20) oxyaryl, preferably a —O(C.sub.6-C.sub.18) oxyaryl, more preferably an unsubstituted —O(C.sub.6-10) oxyaryl or a substituted —O(C.sub.6) oxyaryl, where the substituent may be methyl, fluoro, chloro, bromo, or trifluoromethyl group, preferably the oxyaryl is an oxyphenyl; said alkyl is a straight-chain or branched-chain C.sub.1-C.sub.8 alkyl, preferably C.sub.2-C.sub.6 alkyl, the most preferably C.sub.3-C.sub.4 alkyl; said oxyalkyl is a straight-chain or branched-chain —O(C.sub.1-C.sub.8) oxyalkyl, preferably —O(C.sub.2-C.sub.6) oxyalkyl, the most preferably —O(C.sub.3-C.sub.4) oxyalkyl.

16. The method of claim 12, wherein the monomer is selected from one or more compounds from the group consisting of 1,3-bis-(3,4-dicyanophenoxy) benzene, 1,3-bis-(3,4-dicyanophenoxy)-2-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-chlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-chlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-bromobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-bromobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2,4-difluorobenzene, 1,5-bis-(3,4-dicyanophenoxy)-2,4-dichlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-methylbenzene, more preferably from 1,3-bis-(3,4-dicyanophenoxy) benzene, 1,3-bis-(3,4-dicyanophenoxy)-2-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2,4-difluorobenzene, the most preferably 1,3-bis-(3,4-dicyanophenoxy) benzene.

17. The method of claim 12, wherein the reactive plasticizer-antipyrene is selected from one or more compounds from the group consisting of bis-(4-cyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)-1-naphthylphosphate, bis-(4-cyanophenoxy)-phenylphosphonate, bis-(3-(3,4-dicyanophenoxy)phenyl)-phenylphosphonate, bis-(3-(3,4-dicyanophenoxy)phenyl)-isopropylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-butylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-propargylphosphate, bis-(4-cyaonphenyl)phenylphosphate, bis-(3-cyanophenoxy)phenylphosphate and bis-4-(3,4-dicyanophenoxy)phenyl)phenylphosphate, more preferably from bis-(4-cyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-isopropylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-butylphosphate.

18. The method of claim 12, wherein the curing agent is selected from the following compounds: ##STR00074## or from compounds of the following general formula ##STR00075## where Z is H or F, or from compounds of the following general formula ##STR00076## where Z is H or F, or bisphenols, or more preferably from 1,3-bis-(4-aminophenoxy)benzene, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,3′-[(2,3,5,6-tetrafluorobenz-1,4-diyl)bis(oxy)]dianiline, 4,4′-[(2,3,5,6-tetrafluorobenz-1,4-diyl)bis(oxy)]dianiline, bis[4-(4-aminophenoxy)phenyl]sulfone or bisphenol A, most preferably from 1,3-bis-(4-aminophenoxy)benzene or bis[4-(4-aminophenoxy)phenyl]sulfone.

19. The method of claim 12, wherein the monomer is used in the amount of 20-80 wt % of weight of the polymerizable mixture or 30-80 wt % of weight of the polymerizable mixture, or 20-70 wt % of weight of the polymerizable mixture, more preferably 30-70 wt % of weight of the polymerizable mixture, or 40-70 wt % of weight of the polymerizable mixture, or 40-60 wt % of weight of the polymerizable mixture, or 40-55 wt % of weight of the polymerizable mixture, more preferably in the amount of 30-70 wt % of weight the polymerizable mixture.

20. The method of claim 12, wherein the plasticizer is used in the amount of 5-70 wt % of the total weight of the polymerizable mixture, or in the amount of 5-60 wt % of the total weight of the polymerizable mixture, or in the amount of 20-70 wt % of the total weight of the polymerizable mixture, or in the amount of 20-60 wt % of the total weight of the polymerizable mixture, or in the amount of 25-60 wt % of the total weight of the polymerizable mixture, or in the amount of 25-50 wt % of the total weight of the polymerizable mixture, or in the amount of 30-60 wt % of the total weight of the polymerizable mixture, or in the amount of 30-50% of the total weight of the polymerizable mixture.

21. The method of claim 12, wherein the polymerization initiator is used in the amount from 2 to 20 wt % of the total weight of the polymerizable mixture, or from 5 to 20 wt % of the total weight of the polymerizable mixture, or from 5 to 15 wt % of the total weight of the polymerizable mixture, or more preferably from 5 to 10% of the total weight of the polymerizable mixture.

22. The method of claim 12, wherein the polymerizable mixture is heated to the temperature of 100-180° C. for homogenization, more preferably in the range of 100-140° C.

23. The method of claim 12, wherein the mixture obtained after adding the initiator to the polymerizable mixture is stirred at a temperature in the range of 100 to 160° C., more preferably at a temperature in the range of 100 to 140° C., more preferably at a temperature in the range of 100 to 120° C., for 10-180 minutes, more preferably for 10-120 minutes, more preferably for 60-120 minutes.

24. A method for producing the resin matrix composition intended for producing prepegs for a polymer composite materials (PCM) of claim 1, the method comprising mixing a polymerizable mixture in a reactor, the polymerizable mixture comprising one or more bis-phthalonitrile monomers selected from monomers of the following general formula: ##STR00077## where X, Y, Z are independently selected from the group consisting of H, F, Cl, Br, and CH.sub.3, in an amount of 20 to 94 wt % of weight of the polymerizable mixture, one or more reactive plasticizers-antipyrenes selected from compounds of the following general formula ##STR00078## where group ##STR00079## can be in either meta- or para-position relative to the oxygen atom bonded to the benzene ring, and R is selected from an aryl, oxyaryl, alkyl, or oxyalkyl group, or compounds of the following general formula ##STR00080## where R is selected from aryl, oxyaryl, alkyl, or oxyalkyl group, the reactive plasticizers-antipyrenes comprising 5 to 80 wt % of the polymerizable mixture, and one or more reactive diluents selected from compounds of the following general formula ##STR00081## where R can be in meta- or para-position relative to the oxygen atom bonded to the benzene ring and is either H, CN, NH.sub.2, or N(C.sub.3H.sub.4).sub.2, the reactive diluents comprising 1 to 50% of total weight of the polymerizable mixture; wherein the plasticizer and the diluent are added to the reactor first, then heating is conducted to a temperature in the range 100-140° C. until the components are liquified, followed by stirring is initiated and the monomer powder is added, which is not allowed to dissolve, adding a polymerization initiator to the obtained suspension in an amount from 1 to 20 wt % of the total weight of the polymerizable mixture, wherein the polymerization initiator is selected from aromatic diamines or bisphenols having a boiling point of at least 180° C. under vacuum of 0.1 mm Hg, stirring of thus obtained mixture at a temperature in the range of 100 to 160° C. for 5-180 minutes and discharging the resulting composition without cooling followed by allowing it to cool.

25. The method of claim 24, wherein said one or more reactive diluents are added in an amount from 1 to 40 wt % of the total weight of the mixture or from 10 to 50 wt % of the total weight of the mixture, or from 10 to 40 wt % of the total weight of the mixture, from 20 to 40 wt % of the total weight of the mixture, or from 20 to 35 wt % of the total weight of the mixture, or from 20 to 30 wt % of the total weight of the mixture, preferably from 10 to 40% of the total weight of the mixture, or in the amount from 10 to 30% of the total weight of the mixture.

26. The method of claim 24, wherein the reactive diluent is selected from one or more compounds from the group consisting of 4-[3-(dipropargylamino)phenoxy]phthalonitrile, 4-[4-(dipropargylamino)phenoxy]phthalonitrile, 4-(4-cyanophenoxy)-phthalonitrile, 4-(3-cyanophenoxy)-phthalonitrile and 4-(4-aminophenoxy)-phthalonitrile, 4-(3-aminophenoxy)-phthalonitrile, the most preferably from 4-(4-cyanophenoxy)-phthalonitrile, 4-[3-(dipropargylamino)phenoxy]phthalonitrile, and 4-(4-aminophenoxy)-phthalonitrile.

27. The method of claim 24, wherein said aryl is an optionally substituted C.sub.6-C.sub.20 aryl, preferably a C.sub.6-C.sub.18 aryl, more preferably an unsubstituted C.sub.6-C.sub.10 aryl or a substituted C.sub.6 aryl, where the substituent may be methyl, fluoro, chloro, bromo, or trifluoromethyl group, preferably the aryl is a phenyl; said oxyaryl is a —O(C.sub.6-C.sub.20) oxyaryl, preferably a —O(C.sub.6-C.sub.18) oxyaryl, more preferably an unsubstituted —O(C.sub.6-10) oxyaryl or a substituted —O(C.sub.6) oxyaryl, where the substituent may be methyl, fluoro, chloro, bromo, or trifluoromethyl group, preferably the oxyaryl is an oxyphenyl; said alkyl is a straight-chain or branched-chain C.sub.1-C.sub.8 alkyl, preferably C.sub.2-C.sub.6 alkyl, the most preferably C.sub.3-C.sub.4 alkyl; said oxyalkyl is a straight-chain or branched-chain —O(C.sub.1-C.sub.8) oxyalkyl, preferably —O(C.sub.2-C.sub.6) oxyalkyl, most preferably —O(C.sub.3-C.sub.4) oxyalkyl.

28. The method of claim 24, wherein the monomer is selected from one or more compounds from the group consisting of 1,3-bis-(3,4-dicyanophenoxy) benzene, 1,3-bis-(3,4-dicyanophenoxy)-2-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-chlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-chlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-bromobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-bromobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2,4-difluorobenzene, 1,5-bis-(3,4-dicyanophenoxy)-2,4-dichlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-methylbenzene, more preferably from 1,3-bis-(3,4-dicyanophenoxy) benzene, 1,3-bis-(3,4-dicyanophenoxy)-2-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2,4-difluorobenzene, the most preferably 1,3-bis-(3,4-dicyanophenoxy) benzene.

29. The method of claim 24, wherein the reactive plasticizer-antipyrene is selected from one or more compounds from the group consisting of bis-(4-cyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)-1-naphthylphosphate, bis-(4-cyanophenoxy)-phenylphosphonate, bis-(3-(3,4-dicyanophenoxy)phenyl)-phenylphosphonate, bis-(3-(3,4-dicyanophenoxy)phenyl)-isopropylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-butylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-propargylphosphate, bis-(4-cyanophenyl)phenylphosphate, bis-(3-cyanophenoxy)phenylphosphate and bis-4-(3,4-dicyanophenoxy)phenyl)phenylphosphate, more preferably from bis-(4-cyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)-phenylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-isopropylphosphate, bis-(3-(3,4-dicyanophenoxy)phenyl)-butylphosphate.

30. The method of claim 24, wherein the polymerization initiator is selected from the following compounds: ##STR00082## or from compounds with the general formula ##STR00083## where Z is H or F, or from compounds of the following general formula ##STR00084## where Z is H or F, or bisphenols, or more preferably from 1,3-bis-(4-aminophenoxy)benzene, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 3,3′-[(2,3,5,6-tetrafluorobenz-1,4-diyl)bis(oxy)]dianiline, 4,4′-[(2,3,5,6-tetrafluorobenz-1,4-diyl)bis(oxy)]dianiline, bis[4-(4-aminophenoxy)phenyl]sulfone or bisphenol A, the most preferably from 1,3-bis-(4-aminophenoxy)benzene or bis[4-(4-aminophenoxy)phenyl]sulfone.

31. The method of claim 24, wherein the monomer is used in an amount of 20-80 wt % of weight of the polymerizable mixture or 30-80 wt % of weight of the polymerizable mixture, or 20-70 wt % of weight of the polymerizable mixture, in more preferable case 30-70 wt % of weight of the polymerizable mixture, or 40-70 wt % of weight of the polymerizable mixture, or 40-60 wt % of weight of the polymerizable mixture, or 40-55 wt % of weight of the polymerizable mixture, more preferably in an amount of 30-70 wt % of weight of the polymerizable mixture.

32. The method of claim 24, wherein the plasticizer is used in the amount of 5-70 wt % of the total weight of the polymerizable mixture, or in the amount of 5-60 wt % of the total weight of the polymerizable mixture, or in the amount of 20-70 wt % of the total weight of the polymerizable mixture, or in the amount of 20-60 wt % of the total weight of the polymerizable mixture, or in the amount of 25-60 wt % of the total weight of the polymerizable mixture, or in the amount of 25-50 wt % of the total weight of the polymerizable mixture, or in the amount of 30-60 wt % of the total weight of the polymerizable mixture, or in the amount of 30-50% of the total weight of the polymerizable mixture.

33. The method of claim 24, wherein the polymerization initiator is used in the amount from 2 to 20 wt % of the total weight of the polymerizable mixture, or from 5 to 20 wt % of the total weight of the polymerizable mixture, or from 5 to 15 wt % of the total weight of the polymerizable mixture, or more preferably from 5 to 10% of the total weight of the polymerizable mixture.

34. The method of claim 24, wherein the polymerizable mixture is heated to a temperature in the range of 100 to 180° C. for homogenization, more preferably in the range of 100 to 160° C., most preferably in the range of 100 to 140° C.

35. The method of claim 24, wherein the mixture obtained after adding the initiator to the polymerizable mixture is stirred at a temperature in the range of 100 to 160° C., more preferably at a temperature in the range of 100 to 140° C., more preferably at a temperature in the range of 100 to 120° C., for 10-180 minutes, more preferably for 10-120 minutes, even more preferably for 10-30 minutes.

36. The method of claim 24 further comprising a step during which an inert filler selected from a quartz powder, a carbon black, barium sulfate, metal phthalocyanides, pyrogenic silica, titanium oxide, and any mixture of at least two of said materials is added to the component mixture in an amount up to 40 wt % of the total weight of the resin matrix or in an amount of 9-30 wt % of the total weight of the resin matrix, or in an amount of 9-28 wt % of the total weight of the resin matrix, wherein the filler is added either prior to adding the polymerization initiator or to the final mixture before it cools.

37. A method for curing of a resin matrix composition of claim 1, the method comprising steps during which the resin matrix is degassed under vacuum while stirring at a pressure of no more than 1333 Pa and temperature in the range of 100 to 180° C., the obtained degassed material is heated to a temperature in the range of 180 to 190° C. and held to cure for 1-12 hours, after which the obtained product is post-cured by heating in such a way that the transition of the resin matrix from a glass to a rubbery state of devitrification is avoided by maintaining the heating temperature at a level below a glass transition temperature of the matrix at every moment.

38. The method of claim 37 wherein the material is heated at a rate of 10° C./min-10° C./h to the temperature in the range of 250 to 375° C. and held for 2-12 hours, while the post-curing can be carried out in the mold or without it.

39. A method for producing a polymer composite material containing a reinforcing material selected from carbon, aramid, or glass materials, and a resin matrix, wherein a resin matrix composition of claim 1 is used to impregnate the reinforcing material, the impregnating is conducted at a temperature in the range of 100 to 160° C. and the resin matrix composition is cured by degassing the resin matrix under vacuum while stirring at a pressure of no more than 1333 Pa and temperature in the range of 100 to 180° C., heating the obtained degassed material to a temperature in the range of 180 to 190° C. and held to cure for 1-12 hours, after which the obtained product is post-cured by heating in such a way that the transition of the resin matrix from a glass to a rubbery state of devitrification is avoided by maintaining the heating temperature at a level below a glass transition temperature of the matrix at every moment.

40. The method of claim 39, wherein the impregnation of the reinforcing material with the resin matrix composition is carried out by vacuum infusion.

41. The method of claim 39, wherein the impregnation of the reinforcing material with the resin matrix composition is carried out by resin transfer molding (RTM) or winding.

42. The method of claim 39, wherein the carbon material is used as the reinforcing filler.

43. The method of claim 39 further comprising steps, during which at least 2 layers of carbon fabric are laid out, packed into a vacuum bag, and the carbon material is impregnated with the resin matrix composition at the temperature of 100-140° C.

44. The method of claim 39, wherein the carbon material used is a chopped (discrete) carbon fiber, an unidirectional carbon tape, a carbon fabric with two-dimensional or three-dimensional weaving.

45. A polymer composite material obtained using from the resin matrix composition of claim 1.

46. The polymer composite material of claim 45, wherein the fraction of a resin matrix in it makes up from 30 to 40 wt %.

Description

EMBODIMENTS OF THE INVENTION

[0170] The monomers suitable for embodiment of the proposed inventions can be obtained via methods described in, for instance, Liu, Cheng; Wang, Jinyan; Lin, Encheng; Zong, Lishuai; Jian, Xigao. Synthesis and properties of phthalonitrile-terminated oligomeric poly(ether imide)s containing a phthalazinone moiety. Polymer Degradation and Stability (2012), 97(3), 460-468.

[0171] Monomers 1,3-bis-(3,4-dicyanophenoxy)-2-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-fluorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-chlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-chlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-bromobenzene, 1,3-bis-(3,4-dicyanophenoxy)-4-bromobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2,4-difluorobenzene, 1,5-bis-(3,4-dicyanophenoxy)-2,4-dichlorobenzene, 1,3-bis-(3,4-dicyanophenoxy)-2-methylbenzene were obtained via methods analogous to the one used to obtain 1,3-bis-(3,4-dicyanophenoxy) benzene as described in literature (Alexander V. Babkin, Elvek B. Zodbinov, Boris A. Bulgakov, Alexey V. Kepman, and Viktor V. Avdeev. Low-melting siloxane-bridged phthalonitriles for heat-resistant matrices. European Polymer Journal, 66:452-457, 2015.), where instead of resorcin, respective substituted derivatives of resorcin are used: 2-fluororesorcin, 4-fluororesorcin, 2-chlororesorcin, 4-chlororesorcin, 2-bromoresorcin, 4-bromoresorcin, 2,4-difluororesorcin, 2,4-dibromoresorcin, 2-methylresorcin.

[0172] The plasticizers-antipyrenes suitable for embodiment of the proposed inventions can be obtained via methods described, for instance, in the document RU 2638307 or in B. A. Bulgakov, A. V. Babkin, P. B. Dzhevakov, A. A. Bogolyubov, A. V. Sulimov, A. V. Kepman, Yu G. Kolyagin, D. V. Guseva, V. Yu Rudyak, and A. V. Chertovich. Low-melting phthalonitrile thermosetting monomers with siloxane- and phosphate bridges. European Polymer Journal, (84):205-217, 2016, using 4-(3-hydroxyphenoxy)benzene-1,2-dicarbonitrile, 4-(4-hydroxyphenoxy)benzene-1,2-dicarbonitrile, 4-cyanophenol, 3-cyanophenol as the aromatic alcohols.

[0173] The curing agents suitable for embodiment of the proposed inventions are commercially available, for instance, from abcr GmbH, ACES Pharma, Merck KGaA, Ambinter Stock Screening Collection, Aurora Building Blocks, Aurora Screening Library, Sigma Aldrich.

[0174] The reactive diluents suitable for embodiment of the proposed inventions can be obtained via methods analogous to those described in Sheng, Haitong; Peng, Xuegang; Guo, Hui; Yu, Xiaoyan; Naito, Kimiyoshi; Qu, Xiongwei; Zhang, Qingxin. Synthesis of high performance bisphthalonitrile resins cured with self-catalyzed 4-aminophenoxyphthalonitrile. Thermochimica Acta (2014) 577, 17-24 (amino-phthalonitriles), and in https://patents.google.com/patent/WO2010024203A1/en?oq=WO+2010024203 (cyanophenoxy phthalonitriles).

[0175] Mixing of components in accordance with the invention, their heating and stirring can be carried out in any reactor of open or closed type fabricated, for instance, from aluminium, glass, stainless steel, hastelloy (a nickel alloy), titanium, high-carbon porcelain coated steel, etc.

[0176] Viscosity measurements were carried out using a rheometer MCR 302 according to GOST (Russian National Standard) 57950-2017.

[0177] Glass transition temperatures of resins were determined using differential scanning calorimeter NETZSCH DSC 204 Phoenix according to GOST (Russian National Standard) 55135-2012.

[0178] Thermogravimetric analysis studies were carried out using NETZSCH TG 209 F3 Tarsus. To conduct measurements in argon atmosphere a sample weight (4-10 mg) was placed in the instrument in a gold crucible. Weighing precision −10.sup.−5 g. Measurements were conducted relative to baseline for empty crucible in argon atmosphere, volume flow rate of 150 mL/min. Measurements were conducted in the temperature range from 40 to 900° C. Heating rate was 10° C./min.

[0179] Interlaminar shear strength was determined using Tinius Olsen 50ST setup according to GOST (Russian National Standard) 32659-2014.

[0180] .sup.1H and .sup.13C NMR spectra were recorded using spectrometer Bruker Avance III with operational frequencies of 600 and 150 MHz respectively. Deuterated dimethyl sulfoxide was used as the solvent.

[0181] Further are provided non-limiting examples for this application the goal of which is to illustrate the possibility of implementing the proposed inventions to reach the declared technical results.

Preparation of Resin Matrices

Example 1

[0182] 4-(4-(dipropargylamino)phenoxy)phthalonitrile was prepared. In a triple-neck flask (1000 mL) equipped with a reflux condenser and a dropping funnel, 50 g (0.2 mol) of 4-(4-aminophenoxy)phthalonitrile were dissolved in 450 mL of anhydrous DMAc. Potassium carbonate (55 g, 0.4 mol) and potassium bromide (4.75 g, 0.04 mol) were added to the system after complete dissolution of the added compound. The reaction mixture was stirred for 30 minutes, after which small portions of propargylchloride (37.5 g, 0.5 mol) were added over 20 minutes. The reaction mixture was heated to 60° C. and left to stir for 12 hours. Then a large excess of water (about 2500 mL) was added to the mixture, mixed, and left undisturbed for more hours. In the course of 2-3 hours the target product precipitate formed. The precipitate was filtered off and washed with more portions of hot water, after which the product was placed in an oven. The resulting product—orange-brown powder. Yield—59.5 g (96%).

[0183] .sup.1H NMR (DMSO-d.sub.6) δ ppm 8.06 (d, J=8.80 Hz, 1H), 7.70 (d, J=2.57 Hz, 1H), 7.29 (dd, J=8.80, 2.57 Hz, 1H), 7.11 (d, J=4.7 Hz, 2H), 7.03 (d, J=4.77 Hz, 2H), 4.18 (d, J=2.20 Hz, 4H), 3.19 (s, 2H)

[0184] .sup.13C NMR (DMSO-d.sub.6) δ ppm 75.66 (s) 80.21 (s) 83.31 (s) 107.86 (s) 115.92 (s) 116.45 (s) 116.91 (s) 117.01 (s) 121.51 (s) 121.64 (s) 122.41 (s) 136.72 (s) 145.71 (s) 145.96 (s) 162.50 (s).

[0185] Elemental analysis for C.sub.20H.sub.13N.sub.3O: Calculated values: C (77.17), H (4.18), N (13.50). Experimental values: C (77.11), H (4.22), N (13.48).

Example 2

[0186] 4-(3-(dipropargylamino)phenoxy)phthalonitrile was obtained according to the method repeating the method for producing 4-(4-(dipropargylamino)phenoxy)phthalonitrile (Example 1), except 4-(3-aminophenoxy)phthalonitrile was used instead of 4-(4-aminophenoxy)phthalonitrile. Yield—94%.

[0187] .sup.1H NMR (600 MHz, DMSO-d.sub.6) δ ppm 8.09 (d, J=8.80 Hz, 1H) 7.76 (d, J=2.38 Hz, 1H) 7.29-7.42 (m, 2H) 6.86 (dd, J=8.25, 2.02 Hz, 1H) 6.71 (broad s, 1H) 6.58 (dd, J=7.79, 1.65 Hz, 1H) 4.18 (d, J=1.83 Hz, 4H) 3.16 (m, 2H).

[0188] Elemental analysis for C.sub.20H.sub.13N.sub.3O: Calculated values: C (77.17), H (4.18), N (13.50). Experimental values: C (77.19), H (4.20), N (13.63).

Example 3

[0189] 500 g of 1,3-bis(3,4-dicyanophenoxy)benzene, 200 g of 4-[4-(dipropargylamino)phenoxy]phthalonitrile, and 300 g of bis(4-(3,4-dicyanophenoxy)phenyl) phenylphosphate were added to a 2-L reactor equipped with a mechanical stirrer. The reactor was put under vacuum (5 mm Hg) and heated to 180° C. until the resin components melted, after which stirring was initiated. Once the mixture was homogenized, 50 g of 1,3-bis-(4-aminophenoxy)benzene were added and stirred at 140° C. for 30 minutes. Then the mixture was poured onto a metal tray treated with an antiadhesive and left to cool. A green amorphous glassy substance was obtained. T.sub.g=36° C., η.sup.150° C.=25 mPa.Math.s, t.sub.gel.sup.180° C.=190 min. In this and the following exampled glass transition temperature was determined via differential scanning calorimetry (DSC), and melt viscosity and gelation time were determined in the isothermal mode using Brookfield cone and plate viscometer.

Example 4

[0190] 500 g of 1,3-bis(3,4-dicyanophenoxy)benzene and 500 g of bis(3-(3,4-dicyanophenoxy)phenyl) phenylphosphate were added to a 2-L reactor equipped with a mechanical stirrer. The reactor was put under vacuum (5 mm Hg) and heated to 160° C. until the resin components melted, after which stirring was initiated. Once the mixture was homogeneous, 40 g of 1,3-bis-(4-aminophenoxy)benzene and 10 g of 4-(4-aminophenoxy)phthalonitrile were added to the reactor and stirred at 130° C. for 30 minutes. Then the mixture was poured onto a metal tray treated with an antiadhesive and left to cool. A green amorphous glassy substance was obtained. T.sub.g=19° C. η.sup.150° C.=33 mPa.Math.s, t.sub.gel.sup.180° C.=175 min.

Example 5

[0191] 100 g of bis(3-(3,4-dicyanophenoxy)phenyl) phenylphosphate H 300 r bis-(4-cyanophenoxy)phenylphosphate and 100 g of 4-(4-cyanophenoxy)phthalonitrile were added to a 2-L reactor equipped with a mechanical stirrer. The reactor was put under vacuum (0.1 mm Hg) and heated to 120° C. to liquify the resin components, after which stirring was initiated. Powdered 1,3-bis-(3,4-dicyanophenoxy)benzene (500 g) was slowly added and not allowed to dissolve. 50 g of 1,3-bis-(4-aminophenoxy)benzene were added to the obtained suspension and stirred at 130° C. for 15 minutes. Then the mixture was unloaded from the reactor and a green moldable suspension was obtained and used for prepreg preparation.

Example 6

[0192] 500 g of bis(4-(3,4-dicyanophenoxy)phenyl)phenylphosphate, 200 g of bis-(3-(3,4-dicyanophenoxy)phenyl)phenylphosphate, and 50 g of 4-(3-aminophenoxy)benzene-1,2-dicarbonitrile were added to a 2-L reactor equipped with a mechanical stirrer. The reactor was put under vacuum (0.1 mm Hg) and heated to 100° C. to liquify the resin components, after which stirring was initiated. Powdered 1,3-bis-(3,4-dicyanophenoxy)-2-fluorobenzene (300 g) was slowly added and not allowed to dissolve. 50 g of 1,3-bis-(4-aminophenoxy)benzene were added to the obtained suspension and stirred at 130° C. for 15 minutes. Then the mixture was unloaded from the reactor and a green moldable suspension was obtained and used for prepreg preparation.

Example 7

[0193] 300 g of bis-(3-(3,4-dicyanophenoxy)phenyl)-propargylphosphate and 100 g of 4-(4-cyanophenoxy)-phthalonitrile were added to a 2-L reactor equipped with a mechanical stirrer. The reactor was put under vacuum (1 mm Hg) and heated to 140° C. to liquify the resin components, after which stirring was initiated. Powdered 1,3-bis-(3,4-dicyanophenoxy)-2-fluorobenzene (300 g) was slowly added and not allowed to dissolve. 150 g of bisphenol A were added to the obtained suspension and stirred at 140° C. for 10 minutes. Then the mixture was unloaded from the reactor and a green moldable suspension was obtained and used for prepreg preparation.

Example 8

[0194] 200 g of bis(3-(3,4-dicyanophenoxy)phenyl) isopropylphosphate and 300 g of 4-(4-cyanophenoxy)phthalonitrile were added to an open aluminium 3-L vessel equipped with a mechanical stirrer. The mixture was heated to 140° C. to melt the resin components, after which stirring was initiated. Powdered 1,5-bis-(3,4-dicyanophenoxy)-2,4-difluorobenzene (600 g) was added in small portions making sure each portion dissolved before the next one was added. 150 g of 1,3-bis-(4-aminophenoxy)benzene were added to the obtained melt and stirred at 140° C. for 15 minutes. Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=21° C. η.sup.150° C.=27 mPa.Math.s, t.sub.gel.sup.180° C.=90 min.

Example 9

[0195] 50 g of bis(3-(3,4-dicyanophenoxy)phenyl) butylphosphate and 350 g of 4-(4-cyanophenoxy)benzene-1,2-dicarbonitrile were added to an open aluminium 3-L vessel equipped with a mechanical stirrer. The mixture was heated to 140° C. to melt the resin components, after which stirring was initiated. Powdered 1,3-bis-(3,4-dicyanophenoxy)benzene (600 g) was added in small portions making sure each portion dissolved before the next one was added. 100 g of 4,4′-diaminodiphenylsulfone were added to the obtained melt and stirred at 140° C. for 15 minutes. Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=27° C., η.sup.150° C.=45 mPa.Math.s, t.sub.gel.sup.180° C.=146 min.

Example 10

[0196] 475 g of 1,3-bis-(3,4-dicyanophenoxy)benzene were added to a 2-L glass reactor equipped with a mechanical stirrer. The vessel was heated to 190° C. to melt the monomer, after which stirring was initiated. Powdered 4-(4-aminophenoxy)phthalonitrile (25 g) was added, followed by heated to 170° C. melt of 100 g of bis(3-(3,4-dicyanophenoxy)phenyl) propargylphosphate. The mixture was cooled to 160° C., and 30 g of 1,3-bis-(4-aminophenoxy)benzene were added and then stirred at 160° C. for 15 minutes. Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=42° C., η.sup.150° C.=123 mPa.Math.s, t.sub.gel.sup.180° C.=230 min.

Example 11

[0197] 225 g of 1,3-bis-(3,4-dicyanophenoxy)benzene and 225 g of 4-(3-cyanophenoxy)phthalonitrile were added to a 2-L glass reactor equipped with a mechanical stirrer. The mixture was heated to 160° C. to melt, the resin components, after which stirring was initiated. Bis(3-(3,4-dicyanophenoxy)phenyl)phenylphosphate (50 g) was slowly added in small portions making sure each portion dissolved before the next one was added. The vessel was cooled to 120° C. 50 g of 1,3-bis-(4-aminophenoxy)benzene and 11 g of 3,3′-diaminodiphenylsulfone were added to the obtained melt, then stirred at 120° C. for 15 minutes under vacuum 0.1 mm Hg). Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=18° C., η.sup.150° C.=17 mPa.Math.s, t.sub.gel.sup.180° C.=160 min.

Example 12

[0198] 375 g of 1,3-bis-(3,4-dicyanophenoxy)benzene and 375 g of 4-(4-cyanophenoxy)phthalonitrile were added to an open aluminium 3-L vessel equipped with a mechanical stirrer. The vessel was heated to 160° C. to melt the resin components, after which stirring was initiated. Melted at 130° C. bis(3-(3,4-dicyanophenoxy)phenyl)phenylphosphonate (250 g) was slowly added in small portions. The vessel was cooled to 120° C. 50 g of bis[4-(4-aminophenoxy)phenyl]sulfone were added to the obtained melt and stirred at 110° C. for 15 minutes. Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=19° C., η.sup.150° C.=21 mPa.Math.s, t.sub.gel.sup.180° C.=165 min.

Example 13

[0199] 200 g of 1,3-bis-(3,4-dicyanophenoxy)benzene and 200 f of 4-(3-cyanophenoxy)phthalonitrile were added to an open aluminium 3-L vessel equipped with a mechanical stirrer. The vessel was heated to 170° C. to melt the resin components, after which stirring was initiated. Melt of bis(3-(3,4-dicyanophenoxy)phenyl)phenylphosphate (100 g) was slowly added in small portions making sure each portion dissolved before the next one was added. The vessel was cooled to 120° C. 75 g of 4,4′-[(2,3,5,6-tetrafluorobenz-1,4-diyl)bis(oxy)]dianiline were added to the obtained melt and stirred at 120° C. for 15 minutes. Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=19° C. η.sup.150° C.=16 mPa.Math.s, t.sub.gel.sup.180° C.=120 min.

Example 14

[0200] 150 g of 1,3-bis-(3,4-dicyanophenoxy)benzene and 200 g of 4-(3-cyanophenoxy)phthalonitrile were added to an open aluminium 3-L vessel equipped with a mechanical stirrer. The vessel was heated to 150° C. to melt the resin components, after which stirring was initiated. Bis(3-(3,4-dicyanophenoxy)phenyl)isopropylphosphate (150 g) was slowly added in small portions making sure each portion dissolved before the next one was added. The vessel was cooled to 120° C. 100 g of bisphenol A were added to the obtained melt and stirred at 100° C. for 15 minutes. Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=13° C., η.sup.150° C.=15 mPa.Math.s, t.sub.gel.sup.180° C.=130 min.

Example 15

[0201] 250 g of 1,3-bis-(3,4-dicyanophenoxy)benzene were added to a 2-L glass reactor equipped with a mechanical stirrer. The reactor was heated to 170° C. to melt the resin, after which stirring was initiated and the reactor was put under vacuum (1 mm Hg). A melt of bis-(3-cyanophenoxy)phenylphosphate (150 g) was slowly added in small portions making sure each portion dissolved before the next one was added. The vessel was cooled to 140° C. 100 g of 4-(4-aminophenoxy)phthalonitrile and 25 g of 1,3-bis-(3-aminophenoxy)benzene were added to the obtained melt and stirred at 100° C. for 15 minutes. Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=20° C., η.sup.150° C.=33 mPa.Math.s, t.sub.gel.sup.180° C.=43 min.

Example 16

[0202] 300 g of 1,3-bis-(3,4-dicyanophenoxy)benzene were added to an open aluminium 3-L vessel equipped with a mechanical stirrer. The vessel was heated to 170° C. to melt the resin, after which stirring was initiated. A melt of bis(4-(3,4-dicyanophenoxy)phenyl)phenylphosphate (150 g) was slowly added in small portions making sure each portion dissolved before the next one was added. The vessel was cooled to 120° C. 50 g of 4-(4-(dipropargylamino)phenoxy)phthalonitrile and 5 g of 1,3-bis-(3-aminophenoxy)benzene were added to the obtained melt and stirred at 120° C. for 15 minutes. Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=33° C., η.sup.150° C.=36 mPa.Math.s, t.sub.gel.sup.180° C.=110 min.

Example 17

[0203] 300 g of 1,3-bis-(3,4-dicyanophenoxy)benzene were added to an open aluminium 3-L vessel equipped with a mechanical stirrer. The vessel was heated to 170° C. to melt the resin, after which stirring was initiated. A melt of bis(4-(3,4-dicyanophenoxy)phenyl)phenylphosphate (150 g) was slowly added in small portions making sure each portion dissolved before the next one was added. The vessel was cooled to 120° C. 50 g of 4-(3-(dipropargylamino)phenoxy)phthalonitrile and 50 g of 1,3-bis-(3-aminophenoxy)benzene were added to the obtained melt and stirred at 120° C. for 15 minutes. Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=26° C., η.sup.150° C.=22 mPa.Math.s, t.sub.gel.sup.180° C.=30 min.

Example 18

[0204] 200 g of 1,3-bis-(3,4-dicyanophenoxy)-2-methylbenzene were added to a 2-L glass reactor equipped with a mechanical stirrer. The reactor was heated to 180° C. to melt the resin, after which stirring was initiated and the reactor was put under vacuum (1 mm Hg). Melts of bis-(3-(3,4-dicyanophenoxy)-1-naphthylphosphate (300 g), bis-(4-cyanophenyl)phenylphosphate (300 g), and (4-cyanophenoxy)phthalonitrile (200 g) were slowly added in small portions making sure each portion dissolved before the next one was added. The vessel was cooled to 100° C. 100 g of 3,3′-diaminodiphenylsulfone were added to the resulting melt and then stirred at 100° C. for 15 minutes. Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=16° C., η.sup.150° C.=14 mPa.Math.s, t.sub.gel.sup.180° C.=165 min.

Example 19

[0205] 300 g of 1,3-bis-(3,4-dicyanophenoxy)-2-bromobenzene were added to an open aluminium 3-L vessel equipped with a mechanical stirrer. The vessel was heated to 180° C. to melt the resin, after which stirring was initiated. A melt of bis(4-(3,4-dicyanophenoxy)phenyl)propargylphosphate (200 g) was slowly added in small portions making sure each portion dissolved before the next one was added. The vessel was cooled to 140° C. 50 g of 1,3-bis-(3-aminophenoxy)benzene, 50 g of bisphenol A were added to the resulting melt and stirred at 140° C. for 15 minutes. Then the mixture was poured onto a metal plate, left to cool, and a green glassy substance was obtained. T.sub.g=29° C., η.sup.150° C.=28 mPa.Math.s, t.sub.gel.sup.180° C.=80 min.

Example 20

[0206] 100 g of bis(3-(3,4-dicyanophenoxy)phenyl) phenylphosphate and 300 g bis-(4-cyanophenoxy)phenylphosphate and 100 g of 4-(4-cyanophenoxy)phthalonitrile were added to a 2-L glass reactor equipped with a mechanical stirrer. The reactor was put under vacuum (0.1 mm Hg) and heated to 120° C. to liquify the resin components, after which stirring was initiated. Powdered 1,3-bis-(3,4-dicyanophenoxy)benzene (500 g) was slowly added and not allowed to dissolve. Then 400 g of quartz powder (GOST 9077-82) were added to the reactor in portions (5 times 80 g) while making sure it was evenly distributed in the entire volume. 50 g of 1,3-bis-(4-aminophenoxy)benzene were added to the mixture and stirred at 130° C. for 15 minutes. Then the mixture was unloaded from the reactor, and a green-yellow moldable suspension was obtained and used to prepare a prepreg.

Example 21

[0207] 100 g of bis(3-(3,4-dicyanophenoxy)phenyl) phenylphosphate and 300 g of bis-(4-cyanophenoxy)phenylphosphate and 100 g of 4-(4-cyanophenoxy)phthalonitrile were added to a 2-L reactor equipped with a mechanical stirrer. The reactor was put under vacuum (0.1 mm Hg) and heated to 120° C. to liquify the resin components, after which stirring was initiated. Powdered 1,3-bis-(3,4-dicyanophenoxy)benzene (500 g) was slowly and not allowed to dissolve. Then 100 g of copper phthalocyanide (dye phthalocyanine blue) were added to the reactor in portions (2 times 50 g) while making sure it was evenly distributed in the entire volume. 50 g of 1,3-bis-(4-aminophenoxy)benzene and 12 g of pyrogenic silica (https://products-re.evonik.com/www2/uploads/productfinder/AEROSIL-R-202-EN.pdf) were added to the mixture, put under vacuum (1 mm Hg), and stirred at 130° C. for 15 minutes at maximum stirrer rotation speed (300 rpm). Then the mixture was unloaded from the reactor, and a dark green suspension was obtained and used to prepare a prepreg.

Example 22

[0208] 500 g of resin obtained in example 5 were melted in a 2-L reactor at 120° C. 200 g of carbon black (http://www.vulcascot.co.at/media/content/downloads/noritsa4pah.pdf) were added to the reactor and stirred under vacuum (1 mm Hg) at 120° C. Then the mixture was unloaded from the reactor, and a black suspension was obtained and used to prepare a prepreg.

Example 23

[0209] The prepreg was produced on an automated line designed by ZAO “INUMIT” (disclosed in RU106897 U1, 27 Jul. 2011). The resin matrix composition obtained as described in example 5, 6, 20, 21, or 22 was used. The prepared resin was placed in a dispensing container, then the resin was dispensed on siliconized paper using heated rolls by forming a 100-110 micrometer thin film in the antiadhesive surface of the paper at paper movement rate of 0.2 m/min. The paper with resin was put together with carbon tape (carbon tape IMS65 on 24K fibers laid out in 0 direction) on a rolling press, then covered by a second layer of siliconized paper, and impregnated the fabric with resin matrix by putting through the heated rolling press under pressure. The even distribution of prepreg density was ensured by the even pressing of the rolls in the press. After impregnation the top layer of siliconized paper was automatically removed and winded onto a roll. The prepreg is smoothed, cooled, and wound on a spool.

[0210] It was preferred for the temperature of the dispensing container and on the impregnation rolls to be between 90° C. and 130° C. in order for optimal results to be obtained. At lower temperatures the viscosity of the resin is not always sufficient for effective application of film on the siliconized paper and impregnation of carbon tape, and at higher temperatures the value remains the same as that at 90-130° C. Therefore, heating to higher temperatures leads to additional energy costs that do not result in increased process efficiency.

[0211] The effect of the rate of the material passage through the setup was investigated. Samples were obtained at belt movement rates of 1, 2, 5 m/min. On one hand, high material movement rate ensures higher throughput, but also leads to the loss of sample quality. It was determined that for material feed rates above 1 m/min in some cases zones with insufficient impregnation of prepreg with resin matrix were observed, which resulted in delamination of the composite material.

[0212] Curing of Resin Matrices

Example 24

[0213] The resin obtained in example 9 was cured in a metal mold. The melt of resin was degassed under vacuum (1 mm Hg (133.32 Pa)) at 160° C. and stirring, then poured into a metal mold treated with an antiadhesive and placed in a programmable convection oven. The sample was cured at 180° C. for 6 hours, after which the mold was disassembled, and the material was heated to 375° C. at the rate of 10° C./h and held at 375° C. for 8 hours.

Example 25

[0214] The resin obtained in example 3 was cured in a metal mold. The melt of resin was degassed under vacuum (1 mm Hg) at 160° C. and stirring, then poured into a metal mold treated with an antiadhesive and placed in a programmable convection oven. The sample was heated to 180° C. at the rate of 2° C./min and cured for 8 hours, then taken out of the metal mold and heated at the rate of 10° C./h to 250° C. and held for 6 hours, then to 300° C. at the rate of 2° C./min and cured for 4 hours, then heated to 375° C. at the rate of 2° C./min and held at 375° C. for 8 hours.

Example 26

[0215] The resin obtained in example 4 was cured in a metal mold. The melt of resin was degassed under vacuum (1 mm Hg) at 160° C. and stirring, then poured into a metal mold treated with an antiadhesive and placed in a programmable convection oven and heated to 190° C. for 2 acoB. The mold was disassembled, the free sample was heated to 250° C. at the rate of 2° C./min and cured for 4 hours, then to 300° C. at the rate of 2° C./min and cured for 4 hours, then the material was heated to 375° C. at the rate of 2° C./min and held at 375° C. for 8 hours.

Example 27

[0216] The resin obtained in example 12 was cured in a metal mold. The melt of resin was degassed under vacuum (1 mm Hg) at 140° C. and stirring, then poured into a metal mold treated with an antiadhesive and placed in a programmable convection oven. The sample was heated to 180° C. at the rate of 5° C./min and cured for 6 hours, then to 300° C. at the rate of 2° C./min and cured for 4 hours, then the material was heated to 375° C. at the rate of 2° C./min and held at 375° C. for 8 hours.

Example 28

[0217] The resin obtained in example 13 was cured in a metal mold. The melt of resin was degassed under vacuum (1 mm Hg) at 120° C. and stirring, then poured into a metal mold treated with an antiadhesive and placed in a programmable convection oven. The sample was heated to 180° C. at the rate of 5° C./min and cured for 6 hours, after which it was taken out of the mold and heated to 330° C. at the rate of 10° C./h and held at that temperature for 4 hours.

Example 29

[0218] The resin obtained in example 14 was cured in a metal mold. The melt of resin heated to 120° C. under stirring was poured into a metal mold treated with an antiadhesive and placed in a programmable convection oven. The sample was heated to 180° C. at the rate of 2° C./min and cured for 8 hours, after which it was taken out of the metal mold and heated to 350° C. at the rate of 5° C./h and held at that temperature for 6 hours.

Example 30

[0219] The resin obtained in example 15 was cured in a metal mold. The melt of resin heated to 120° C. under stirring was poured into a metal mold treated with an antiadhesive and placed in a programmable convection oven. The sample was heated to 180° C. at the rate of 2° C./min and cured for 3 hours, after which it was taken out of the metal mold and heated to 300° C. at the rate of 5° C./h and held at that temperature for 12 hours.

Example 31

[0220] The resin obtained in example 10 was cured in a metal mold. The melt of resin heated to 140° C. under stirring was poured into a metal mold treated with an antiadhesive and placed in a programmable convection oven. The sample was heated to 190° C. at the rate of 2° C./min and cured for 4 hours, after which it was taken out of the metal mold and heated to 375° C. at the rate of 10° C./h and held at that temperature for 8 hours.

TABLE-US-00004 TABLE 2 Properties of cured matrices. Resin matrix T.sub.g, ° C. T.sup.Ar.sub.5%, ° C. Y.sup.Ar.sub.c, % T.sup.B.sub.5%, ° C. Y.sup.B.sub.c, % Example 24 412 515 77 490 14 Example 25 460 489 75 490 23 Example 26 428 490 76 490 18 Example 27 423 503 78 495 19 Example 28 361 485 74 480 13 Example 29 401 520 81 522 21 Example 30 323 488 72 476 9

[0221] Preparation of PCM Samples by Vacuum Infusion.

[0222] Sample of carbon reinforced plastics were obtained by vacuum infusion. The bag was assembled on a stainless-steel mount coated with a silicon antiadhesive. Carbon fabric with 2×2 twill weaving and density of 200 g/m.sup.2 (HTA-40 fiber, 3 k https://www.teijincarbon.com/ru/produkci%D1%8F/uglerodn%D1%8Be-volokna-tenax%C2%AE/zzgut%D1%8B-tenax%C2%AE/) was cut into 30×30 cm pieces and laid out according to [0].sub.12 formula. Then the vacuum bag was assembled, placed in an oven and heated to 100-140° C. The resin (600 g) was degassed in a glass reactor at the temperature of 100-140° C. and lowered pressure, then poured into a metal cup, moved to the oven, a tube connected to the bag was placed into the cup, and impregnation was started. After 10-15 minutes the resin matrix was coming out of the bag indicating the completion of the impregnation process. The bag was sealed, the temperature increased to 180° C.-250° C. at the rate of no more than 2° C./min and held at that temperature for 3-12 hours. Then the bag was disassembled, the precured sample was taken out and postcured as a free part according to the following program: heating to 180° C.-250° C. at the rate of no more than 2° C./min, holding for 15-60 min, heating to the post-curing temperature (300-375° C.) at the rate of 2° C./min-10° C./h, holding for 4-12 hours. The lower the heating rate, the better the mechanical properties of the material, the optimal rate is in the range of 10-30° C./h. The resulting carbon reinforced plastics contained 30-40 wt % of resin matrix.

[0223] The interlaminar shear strength (τ.sub.13) was determined according to the ASTM D2344 standard.

[0224] The in-plane shear strength (τ.sub.12) was determined according to the ASTM D3579 standard.

[0225] τ.sub.13—Interlaminar shear strength

[0226] τ.sub.12—In-plane shear strength

Example 32

[0227] A sample of carbon reinforced plastic was obtained according to the method shown above. A resin obtained according to example 12 was heated to 130° C., degassed. Impregnation was carried out in an ovenat 130° C. Upon impregnation completion temperature in the heating cabined was raised to 180° C. and curing was carried out according to the program described in example 30. PCM containing 32 wt % of resin matrix was obtained.

Example 33

[0228] A sample of carbon reinforced plastic was obtained according to the method described in example 32, but using unsized carbon fabric. The resin matrix content was 31 wt %.

Example 34

[0229] A sample of carbon reinforced plastic was obtained according to the method described above in example 32. A resin obtained according to example 3 was heated to 140° C., degassed. Impregnation was carried out in an oven at 140° C. Upon impregnation completion temperature in the heating cabined was raised to 180° C. and curing was carried out according to the program described in example 29. PCM containing 34 wt % of resin matrix was obtained.

Example 35

[0230] A sample of carbon reinforced plastic was obtained according to the method described above. A resin obtained according to example 12 was heated to 120° C., degassed. Impregnation was carried out in an oven at 120° C. Upon impregnation completion temperature in the heating cabined was raised to 180° C. and curing was carried out according to the program described in example 29. PCM containing 35 wt % of resin matrix was obtained.

Example 36

[0231] A sample of carbon reinforced plastic was obtained according to the method described above. A resin obtained according to example 4 was heated to 140° C., degassed. Impregnation was carried out in an ovenat 140° C. Upon impregnation completion temperature in the heating cabined was raised to 180° C. and curing was carried out according to the program described in example 28. PCM containing 33 wt % of resin matrix was obtained.

Example 37

[0232] A sample of carbon reinforced plastic was obtained according to the method described above. A resin obtained according to example 15 was heated to 140° C., degassed. Impregnation was carried out in an ovenat 140° C. Upon impregnation completion temperature in the heating cabined was raised to 180° C. and curing was carried out according to the program described in example 24. PCM containing 34 wt % of resin matrix was obtained.

Example 38

[0233] A sample of carbon reinforced plastic was obtained according to the method described above. A resin obtained according to example 13 was heated to 120° C., degassed. Impregnation was carried out in an oven at 120° C. Upon impregnation completion temperature in the heating cabined was raised to 180° C. and curing was carried out according to the program described in example 28. PCM containing 38 wt % of resin matrix was obtained.

Example 39

[0234] A sample of carbon reinforced plastic was obtained according to the method described above. A resin obtained according to example 14 was heated to 120° C., degassed. Impregnation was carried out in an oven at 100° C. Upon impregnation completion temperature in the heating cabined was raised to 180° C. and curing was carried out according to the program described in example 30. PCM containing 37 wt % of resin matrix was obtained.

Example 40

[0235] A sample of carbon reinforced plastic was obtained according to the method described above. A resin obtained according to example 18 was heated to 120° C., degassed. Impregnation was carried out in an oven at 110° C. Upon impregnation completion temperature in the heating cabined was raised to 180° C. and curing was carried out according to the program described in example 29. PCM containing 40 wt % of resin matrix was obtained.

TABLE-US-00005 Interlaminar shear strength, τ.sub.13, MPa Material 25° C. 300° C. 350° C. 400° C. 450° C. Example 32 39 37 36 30 28 Example 33 36 43 41 48 33 Example 34 35 32 31 29 — Example 35 32 30 30 — — Example 36 44 40 35 31 30 Example 37 28 27 24 20 — Example 38 45 47 37 — — Example 39 51 43 29 — —

[0236] Raising the post-curing temperature leads to the decreased composite strength but also increases its operational temperature (the temperature at which the material strength is maintained at a sufficient level, at least 50% of the original value).

Comparative Example 1

[0237] 700 g of 1,3-bis-(3,4-dicyanophenoxy)benzene, 300 g of bis(3-(3,4-dicyanophenoxy)phenyl)phenylphosphate were placed in a 2-L glass reactor equipped with a mechanical stirrer. The reactor was put under vacuum (1 mm Hg) and heated to 190° C. until the resin matrix components melted, after which stirring was initiated. Once the mixture was homogenized, 40 g of 1,3-bis-(4-aminophenoxy)benzene were added to the reactor and stirred at 160° C. for 30 minutes. Then the mixture was poured onto a metal tray treated with an antiadhesive and left to cool. A green amorphous glassy substance with crystalline phase inclusions was obtained. Determination of viscosity at 150° C. was not possible due to resin matrix components crystallization between the cone and the rheometer plate.

Comparative Example 2

[0238] 500 g of 1,3-bis-(3,4-dicyanophenoxy)benzene, 500 g of bis(3-(3,4-dicyanophenoxy)phenyl)phenylphosphate were placed in a 2-L glass reactor equipped with a mechanical stirrer. The reactor was put under vacuum (1 mm Hg) and heated to 190° C. until the resin matrix components melted, after which stirring was initiated. Once the mixture was homogenized, 40 g of 1,3-bis-(4-aminophenoxy)benzene were added to the reactor and stirred at 160° C. for 30 minutes. Then the mixture was poured onto a metal tray treated with an antiadhesive and left to cool. A green amorphous glassy substance was obtained. The viscosity at 150° C. was determined to η.sup.150° C.=600 mPa.Math.s. Slow crystallization of the melt was observed in the process of viscosity determination.

Comparative Example 3

[0239] A sample of carbon reinforced plastic was obtained from a resin obtained according to Comparative Example 3. Carbon fabric with 2×2 twill weaving and density of 200 g/m.sup.2 (HTA-40 fiber, 3 k) was cut into 30×30 cm pieces and laid out according to [0].sub.12 formula. Then a vacuum bag was assembled, placed in an oven, heated to 150° C. The resin (600 g) was degassed in a glass reactor at 160° C. and lowered pressure and then poured into a metal cup, transferred to the heating cabinet, the inlet tube of the bag was placed into it, and the impregnation process was started. After 10-15 minutes the resin came out of the bag indicating the completion of impregnation. The bag was hermetically sealed, the temperature in the heating cabinet was raised to 200° C. at the rate of 1° C./min and kept at that temperature for 24 hours. Then the bag was disassembled, the precured sample was taken out and then post-cured free-standing according to the following program: heating to 200° C.-250° C. at the rate of 2° C./min, holding for 15-60 minutes and heating to the post-curing temperature of 375° C. at the rate of 2° C./h, holding for 8 hours. A sample containing 37 wt % of resin matrix was obtained.

Comparative Example 4

[0240] 500 g of 4,4′-bis-(3,4-dicyanophenoxy)biphenyl were placed in a 2-L glass reactor equipped with a mechanical stirrer and melted at 250° C.; 8 g of 1,3-bis-(4-aminophenoxy)benzene were added. The mixture was vigorously stirred at 250° C. for 15 minutes. A prepolymer was obtained with glass transition temperature of 80-90° C. and melting point of 220° C. The viscosity was 400-600 mPa.Math.s at 260° C.

Comparative Example 5

[0241] A sample of fiberglass reinforced plastic was obtained by vacuum infusion, to which end 12 layers of glass fabric were laid out and impregnation was carried out at 260° C., then the sample was held in the mold for 1 hour, then heated at the rate of 4° C./min to 325° C., held for 8 hours, after which it was held at 375° C. for 8 hours. A composite containing 54 vol. % of fiber was obtained.