Novel Compositions with Improved Characteristics
The present invention relates to novel compositions comprising cyanate ester resins and substituted bisimides (citracon-imides, bisitaconimide, citraconimido-itaconimide, bisnadicimide, bistetrahydroimide and mixtures thereof) as defined in claim 1 , and thermoset composite materials based on these compositions.
1 . A composition comprising components (a) and (b), wherein component (a) is one or more cyanate esters independently selected from
(i) a difunctional cyanate ester compound of formula (I)
wherein R 1 through R 8 are independently selected from the group consisting of hydrogen, linear C 1-10 alkyl, halogenated linear C 1-10 alkyl, branched C 4-10 alkyl, halogenated branched C 4-10 alkyl, C 3-8 cycloalkyl, halogenated C 3-8 cycloalkyl, linear C 2 -C 10 alkenyl, branched C 3 -C 10 alkenyl, C 1-10 alkoxy, halogen, phenyl and phenoxy,
wherein at least one of R 1 to R 8 is selected from the group consisting of linear C 2 -C 10 alkenyl and branched C 3 -C 10 alkenyl;
Z 1 indicates a direct bond or a divalent moiety selected from the group consisting of —O—, —S—, —S(═O)—, —S(═O) 2 —, —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) 2 —, —CH(CF 3 )—, —C(CF 3 ) 2 —, —C(═O)—, —C(═CH 2 )—, —C(═CCl 2 )—, —Si(CH 3 ) 2 —, linear C 1-10 alkanediyl, branched C 4-10 alkanediyl, C 3-8 cycloalkanediyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, —N(R 13 )— wherein R 13 is selected from the group consisting of hydrogen, linear C 1-10 alkyl, halogenated linear C 1-10 alkyl, branched C 4-10 alkyl, halogenated branched C 4-10 alkyl, C 3-8 cycloalkyl, phenyl and phenoxy, and moieties of formulas
wherein X is independently selected from hydrogen and halogen;
and oligomers, prepolymers, polymers or mixtures thereof; or
wherein (a) is a mixture of (i) and (ii), wherein
(ii) is a polyfunctional cyanate ester of formula (II)
wherein n is an integer from 1 to 20; and R 10 and R 11 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 4-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-1)
wherein n is an integer from 1 to 20; and R 30 , R 31 , R 32 and R 33 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-2)
wherein n is an integer from 1 to 20; and R 34 , R 35 and R 36 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-3)
wherein n is an integer from 1 to 20; and R 37 is selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-4)
wherein n is an integer from 1 to 20; and oligomers, prepolymers, polymers or mixtures thereof;
or any combination of polyfunctional cyanate esters of formulas (II), (IX-1), (IX-2), (IX-3), and (IX-4);
and
wherein component (b) is one or more substituted bisimide compound selected from the group consisting of biscitraconimide compound of formula (X1), bisitaconimide compound of formula (X2), and citraconimido-itaconimide compound of formula (X3)
wherein R is m-xylylene;
and oligomers, prepolymers, polymers or mixtures thereof;
wherein the ratio of component (a) to (b) is in the range of from 10-70 wt.-% component (a) to 90-30 wt.-% component (b) based on total amount of the resin composition.
2 . A composition according to claim 1 , wherein component (a) is one or more cyanate esters independently selected from
(i) a difunctional cyanate ester compound of formula (I)
wherein R 1 through R 8 are independently selected from the group consisting of hydrogen, linear C 1-10 alkyl, C 3-8 cycloalkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl,
wherein at least one of R 1 to R 8 is selected from the group consisting of linear C 2 -C 10 alkenyl and branched C 3 -C 10 alkenyl;
Z 1 indicates a direct bond or a divalent moiety selected from the group consisting of —O—, —S—, —S(═O)—, —S(═O) 2 —, —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) 2 —, —CH(CF 3 )—, —C(CF 3 ) 2 —, —C(═O)—, —C(═CH 2 )—, —C(═CCl 2 )—, —Si(CH 3 ) 2 —, linear C 1-10 alkanediyl, branched C 10 alkanediyl, C 3-8 cycloalkanediyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, —N(R 13 )— wherein R 13 is selected from the group consisting of hydrogen, linear C 1-10 alkyl, C 3-8 cycloalkyl, phenyl and phenoxy, and moieties of formulas
wherein X is independently selected from hydrogen and halogen; and oligomers, prepolymers, polymers or mixtures thereof; or
wherein (a) is a mixture of (i) and (ii), wherein
(ii) is a polyfunctional cyanate ester of formula (II)
wherein n is an integer from 1 to 20; and R 10 and R 11 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 4-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-1)
wherein n is an integer from 1 to 20; and R 30 , R 31 , R 32 and R 33 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-2)
wherein n is an integer from 1 to 20; and R 34 , R 35 and R 36 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-3)
wherein n is an integer from 1 to 20; and R 37 is selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-4)
wherein n is an integer from 1 to 20; and oligomers, prepolymers, polymers or mixtures thereof;
or any combination of polyfunctional cyanate esters of formulas (II), (IX-1), (IX-2), (IX-3), and (IX-4).
3 . A composition according to claim 1 , wherein component (a) is one or more cyanate esters independently selected from
(i) a difunctional cyanate ester compound of formula (I)
wherein R 1 through R 8 are independently selected from the group consisting of hydrogen, linear C 1-3 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl,
wherein at least one of R 1 to R 8 is selected from the group consisting of linear C 2 -C 10 alkenyl and branched C 3 -C 10 alkenyl;
Z 1 indicates a direct bond or a divalent moiety selected from the group consisting of —O—, —S—, —S(═O) 2 —, —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —C(═CCl 2 )—, branched C 4-6 alkanediyl, C 3-8 cycloalkanediyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene; and oligomers, prepolymers, polymers or mixtures thereof; or
wherein (a) is a mixture of (i) and (ii) wherein
(ii) is a polyfunctional cyanate ester of formula (II)
wherein n is an integer from 1 to 10; and R 10 and R 11 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-5 alkyl, branched C 4-6 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-1)
wherein n is an integer from 1 to 20; and R 30 , R 31 , R 32 and R 33 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-2)
wherein n is an integer from 1 to 20; and R 34 , R 35 and R 36 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-3)
wherein n is an integer from 1 to 20; and R 37 is selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-4)
wherein n is an integer from 1 to 20; and oligomers, prepolymers, polymers or mixtures thereof;
or any combination of polyfunctional cyanate esters of formulas (II), (IX-1), (IX-2), (IX-3), and (IX-4).
4 . A composition according to claim 1 , wherein component (a) is one or more cyanate esters independently selected from
(i) a difunctional cyanate ester compound of formula (I)
wherein the difunctional cyanate ester of formula I is independently selected from the group consisting of
i) R 1 and R 5 are allyl, R 2 and R 6 are methyl, R 3 , R 4 , R 7 and R 8 are hydrogen and wherein Z 1 is —CH 2 — (methylene);
ii) R 1 and R 5 are allyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen and wherein Z 1 is —CH 2 — (methylene);
iii) R 1 and R 5 are allyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen and wherein Z 1 is —C(CH 3 ) 2 —;
iv) R 1 and R 5 are allyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen and Z 1 is —C(═O)—;
v) R 1 and R 5 are allyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen and Z 1 is —S(═O)—;
vi) R 1 and R 5 are allyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen and Z 1 is —S—;
vii) R 1 and R 5 are allyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen and Z 1 is —C(CF 3 ) 2 —;
viii) R 1 and R 5 are allyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen and Z 1 is —C(═CCl 2 )—;
ix) R 1 and R 5 are allyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen and Z 1 is independently selected from the group consisting of
x) R 1 and R 5 are allyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen and Z 1 is
or
xi) R 1 and R 5 are allyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen and Z 1 is —CH(CH 3 )—;
and oligomers, prepolymers, polymers or mixtures thereof, or
wherein (a) is a mixture of (i) and (ii), wherein
(ii) is a polyfunctional cyanate ester of formula (II)
wherein the polyfunctional cyanate ester is independently selected from the group consisting of compound III, compound IV, compound V, compound VI, and oligomers, prepolymers, polymers or mixtures thereof
a polyfunctional cyanate ester of formula (IX-1)
wherein n is an integer from 1 to 20; and R 30 , R 31 , R 32 and R 33 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-2)
wherein n is an integer from 1 to 20; and R 34 , R 35 and R 36 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-3)
wherein n is an integer from 1 to 20; and R 37 is selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-4)
wherein n is an integer from 1 to 20; and oligomers, prepolymers, polymers or mixtures thereof;
or any combination of polyfunctional cyanate esters of formulas (II), (IX-1), (IX-2), (IX-3), and (IX-4).
5 . A composition according to claim 1 , wherein the ratio of component (a) to (b) is in the range of from 20-70 wt.-% component (a) to 80-30 wt.-% component (b) based on total amount of the resin composition.
6 . A composition according to claim 1 , wherein the composition further comprises a catalyst selected from the group consisting of aliphatic mono-, di- and polyamines, aromatic mono-, di- and polyamines, carbocyclic mono-, di and polyamines, heterocyclic mono-, di- and polyamines, compounds containing a five- or six-membered nitrogen-containing heterocyclic ring, hydroxyamines, phosphines, phenols, bisphenols, and mixtures thereof.
7 . A composition according to claim 6 , wherein the catalyst is a compound of formula (VII)
wherein R 1 through R 8 are independently selected from the group consisting of hydrogen, linear C 1-10 alkyl, linear C 2 -C 10 alkenyl, halogenated linear C 1-10 alkyl, branched C 4-10 alkyl, branched C 3 -C 10 alkenyl, halogenated branched C 4-10 alkyl, C 3-8 cycloalkyl, halogenated C 3-8 cycloalkyl, C 1-10 alkoxy, halogen, phenyl and phenoxy,
wherein at least one of R 1 to R 8 is selected from the group consisting of linear C 2 -C 10 alkenyl and branched C 3 -C 10 alkenyl;
Z indicates a direct bond or a divalent moiety selected from the group consisting of —O—, —S—, —S(═O)—, —S(═O) 2 —, —CH 2 —, —CH(CH 3 )—, —C(CH 3 ) 2 —, —CH(CF 3 )—, —C(CF 3 ) 2 —, —C(═O)—, —C(═CH 2 )—, —C(═CCl 2 )—, —Si(CH 3 ) 2 —, linear C 1-10 alkanediyl, branched C 4-10 alkanediyl, C 3-8 cycloalkanediyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, —N(R 13 )— wherein R 13 is selected from the group consisting of hydrogen, linear C 1-10 alkyl, halogenated linear C 1-10 alkyl, branched C 4-10 alkyl, halogenated branched C 4-10 alkyl, C 3-8 cycloalkyl, phenyl and phenoxy, and moieties of formulas
wherein X is independently selected from hydrogen and halogen;
and oligomers, prepolymers, polymers or mixtures thereof.
8 . A composition according to claim 6 , wherein the catalyst is present in an amount of about 0.01 to 20 wt.-% based on the total amount of the resin composition.
9 . A composition according to claim 1 , wherein the composition further comprises reinforcement fibres selected from the group consisting of carbon fibres, glass fibres (such as E glass fibres, S glass fibres), aramid fibres (including KEVLAR®), basalt fibres (geotextile fibers), natural fibres (such as flax, hemp, jute or sisal), fleeces and woven fabrics (multi-layered or single layered), and mixtures thereof.
10 . A composition according to claim 1 , wherein the composition further comprises a filler selected from the group consisting of organic fillers, such as thermoplastics and elastomers, inorganic fillers, wherein the inorganic filler is selected from glass microspheres, graphite, graphene/nano-graphen, carbon nanotubes (SWCNT and/or MWCNT) or silica, and mineral powder fillers, such as CaCO 3 , coated CaCO 3 , kaolin clay, SiO 2 , talc, graphite, corundum (α-Al 2 O 3 ), wollastonite, SiC, glass microspheres, mica, calcium silicate (Ca 2 O 4 Si), MgO, anhydrous calcium sulfate (CaSO 4 or anhydrite), ceramic hollow microspheres, fused mullite (Al 2 O 3 —SiO 2 ), boron nitride (BN), vermiculite, or basalt, and mixtures thereof.
11 . A composition according to claim 1 , wherein component (a) is one or more cyanate esters independently selected from
(i) a difunctional cyanate ester compound of formula (I)
wherein R 1 through R 8 are independently selected from the group consisting of hydrogen, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl,
wherein at least one of R 1 to R 8 is selected from the group of consisting of linear C 2 -C 10 alkenyl and branched C 3 -C 10 alkenyl,
preferably wherein R 1 and R 5 are each independently linear C 2 -C 10 alkenyl or branched C 3 -C 10 alkenyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen,
even more preferably wherein R 1 and R 5 are allyl and R 2 , R 3 , R 4 , R 6 , R 7 and R 8 are hydrogen; and
Z 1 is —C(CH 3 ) 2 —
and oligomers, prepolymers, polymers or mixtures thereof; or
wherein (a) is a mixture of (i) and (ii), wherein
(ii) is a polyfunctional cyanate ester of formula (II)
wherein the polyfunctional cyanate ester is independently selected from the group consisting of compound III, compound IV, compound V, and oligomers, prepolymers, polymers or mixtures thereof;
or
a polyfunctional cyanate ester of formula (IX-1)
wherein n is an integer from 1 to 20; and R 30 , R 31 , R 32 and R 33 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-2)
wherein n is an integer from 1 to 20; and R 34 , R 35 and R 36 are identical or different and independently from each other selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-3)
wherein n is an integer from 1 to 20; and R 37 is selected from the group consisting of hydrogen, linear C 1-10 alkyl, branched C 3-10 alkyl, linear C 2 -C 10 alkenyl, and branched C 3 -C 10 alkenyl; and oligomers, prepolymers, polymers or mixtures thereof; or
a polyfunctional cyanate ester of formula (IX-4)
wherein n is an integer from 1 to 20; and oligomers, prepolymers, polymers or mixtures thereof;
or any combination of polyfunctional cyanate esters of formulas (II), (IX-1), (IX-2), (IX-3), and (IX-4);
and wherein component (b) is a biscitraconimide compound of formula (X1)
wherein R is m-xylylene;
and oligomers, prepolymers, polymers or mixtures thereof.
12 . A method for the preparation of a composition according to claim 1 , comprising:
i) providing a mixture components according to any one of claims 1-11 ; and
ii) intimately mixing the components together.
13 . A method for the preparation of a thermoset composite material, comprising:
i) providing a mixture components according to claim 1 ;
ii) intimately mixing the components together;
iii) providing fibres, fillers, pigments and/or additives;
iv) contacting the mixture obtained in step ii) with the fibres, fillers, pigments and/or additives;
v) optionally casting the mixture into the desired form; and
vi) initiating polymerization of the mixture.
14 . Use of a composition as defined in claim 1 for producing a thermoset composite material.
15 . A thermoset composite material obtained by the method according to claim 13 , wherein the thermoset composite material exhibits a mass loss after 1000 h at 250° C. of less than about 2.5 wt.-%, preferably of less than about 2.0 wt.-%, more preferably of less than about 1.75 wt.-%.