WO2024115722A1

WO2024115722A1 - Asymmetrical phenylene bis imides and their preparation

Info

Publication number: WO2024115722A1
Application number: PCT/EP2023/083900
Authority: WO
Inventors: Jean Fournier; Magnus Abgottspon; Gaetano La Delfa; Flavio KIELIGER; Stefan Ellinger; Arne Jan STEPEN; Ulrich MAYERHOEFFER
Original assignee: Arxada AG
Current assignee: Arxada AG
Priority date: 2022-12-02
Filing date: 2023-12-01
Publication date: 2024-06-06
Anticipated expiration: 2025-06-02

Abstract

The invention discloses asymmetrical (phenylene-di- (2,2-propanol)-di-p/m-phenylene) bisimides, such as bis maleimides, bis nadic imides and methyl nadic imides and methylene bis phthalimides, their preparation and their use for the preparation of resins (m-I), (p-I).

Description

ASYMMETRICAL PHENYLENE BIS IMIDES AND THEIR PREPARATION

The invention discloses asymmetrical (phenylene-di-(2,2-propanol)-di-/?/m-phenylene) bisimides, such as bis maleimides, bis nadic imides and methyl nadic imides and methylene bis phthalimides, their preparation and their use for the preparation of resins.

BACKGROUND OF THE INVENTION

There is an increasing demand of resins with application properties meeting the demand of high-end applications.

JP2021116423 A discloses the use of bis maleimide derivatives, which are used for the preparation of resins.

W02018043380A1 teaches molded maleimide resins and methods for the production thereof.

W02020213640A1 discloses the use of symmetrically substituted phenylenebis(methylene)- bis malemides and uses thereof.

W02020054526A1 discloses a method for preparation of symmetrical (phenylene-di-(2,2- propanol) -di-p-phenylene) bismaleimide.

There was a need for resins which show good application properties, such as lower melting point and better solvent solubility combined with a higher glass transition temperature as compared to known bis maleimides resins.

Reduced melting point results in lower process temperatures and thus lower energy consumption, which is economically and environmentally advantageous. Improved solubility in common solvents and/or higher thermal stability enable easier processing and final performance.

Surprisingly, this need was met by the asymmetrical bis imides of the instant invention. ABBREVIATIONS alkyl linear or branched alkyl asym asymmetric eq equivalents; if not otherwise specified, the equivalents are molar equivalents Ex Example sym symmetric

SUMMARY OF THE INVENTION

Subject of the invention is a method for the preparation of a compound of formula (m-I) or (p-

I) or a mixture thereof

by a reaction (I) of a compound of formula (m-II ) or (p -II) or a mixture thereof, with maleic anhydride, citraconic anhydride, nadic anhydride, methyl-nadic-anhydride, 1, 2,3,6- tetrahydrophthalic anhydride or phthalic anhydride

wherein

* and ** each denote a covalent bond to the respective C atom denoted with * and ** of a residue (A); (A) is either a residue of formula (M), a residue of formula (P), a residue of formula (Q), a residue of formula (O), residue of formula (T) or residue of formula (S);

the residues R2L, R3L, R6L, R2R, R3R and R6R are identical or different and independently from each other selected from the group consisting of H, C_1-4 alkyl, Cl, Br, F and perfluoro alkyl (e.g., CF₃, CF₂-CF₃); with the proviso that at least one of the three pairs: 1. R2L and R2R

2. R3L and R3R 3. R6L and R6R are different residues.

DETAILED DESCRIPTION OF THE INVENTION

Preferably, R2, R3 and R6 are identical or different and independently from each other selected from the group consisting of H, methyl, ethyl, n-propyl, iso-propyl, and Cl, Br, F and perfluoro alkyl (e.g., CF₃, CF₂-CF₃); more preferably, R2, R3 and R6 are identical or different and independently from each other selected from the group consisting of H, methyl, ethyl, iso-propyl, and Cl, Br, F and perfluoro alkyl (e.g., CF₃, CF₂-CF₃); even more preferably, R2, R3 and R6 are identical or different and independently from each other selected from the group consisting of H, methyl, ethyl, n-propyl, iso-propyl, and Cl; most preferably, R2, R3 and R6 are identical or different and independently from each other selected from the group consisting of H, methyl, ethyl, iso-propyl, and Cl.

In a further preferred embodiment, R2, and R6 are identical or different and independently from each other selected from the group consisting of H, methyl, ethyl, n-propyl, isopropyl, and Cl, Br, F and perfluoro alkyl (e.g., CF₃, CF₂-CF₃), while R3 is independently selected from the group consisting of H, methyl, ethyl, n-propyl and isopropyl;

More preferably, R2 and R6 are identical or different and independently from each other selected from the group consisting of H, methyl, ethyl, iso-propyl, and Cl, Br, F and perfluoro alkyl (e.g., CF₃, CF₂-CF₃), while R3 is independently selected from the group consisting of H, methyl, ethyl and iso-propyl.

Preferably, the compound of formula (m - I I ) or (p - I I ) or a mixture thereof is reacted with maleic anhydride, citraconic anhydride, nadic anhydride, methyl-nadic-anhydride or phthalic anyhdride and (A) is a residue of formula (M), (Q), (O), (T) or (S).

Most preferably, the compound of formula (m - I I ) or (p - I I ) or a mixture thereof is reacted with maleic anhydride and (A) is a residue of formula (M). Preferred embodiments of the compound of formula (m-T) and (p-I) are selected from the group consisting of compound of formula (m-IIIa and p-IIIa; DIPDEAMEA-MI), compound of formula (m- 11 lb and p-IIIb; DIPDIP ADEA-MI), compound of formula (m- IIIc and p-I I I c ; DIPDIP AMEA-MI), compound of formula (m- 11 Id and p- II Id; DIPMIP ADEA-MI), compound of formula (m-IIIe and p-IIIe; DIPMIPADIP A-MI), compound of formula (m- 11 If and /’-Illf; DIPMEAMIPA-MI), compound of formula (m- Illg and p-Illg; DIPCDEAMEA-MI), compound of formula (m-I I Ih and p-IIIh; DIPCDEAMIPA-MI), compound of formula (m-IIIi and p -IIIi; DIPCDEADIPA-MI), compound of formula (m-I I Ij and p-IIIj ; DIPCDEADEA-MI), compound of formula (m- Illk and p-IIIk, DIP ANME A-MI), compound of formula (m-III1 and p-III1,

DIPANDEA-MI), compound of formula (m-IIIm and p-IIIm, DIP ANMIP A-MI), compound of formula (m-IIIn and p-I I I n , DIPANDIP A-MI), compound of formula (m- IIIo and p-IIIo, DIPANCDEA-MI), compound of formula (m- II Ip and p- II Ip, DIPANMA-MI), compound of formula (m- II Iq and p- II Iq, DIPMAMEA-MI), compound of formula (m-IIIr and p-IIIr, DIPMADEA-MI), compound of formula (m-

IIIs and p-Illg, DIPMAMIPA-MI), compound of formula (m-IIIt and p-lIlt, DIPMADIPA-MI) and compound of formula (m-IIIu and p-IIIu, DIPMACDEA-MI).

More preferred embodiments of the compound of formula (m-T) or (p-I ) are selected from the group consisting of compound of formula (m-IIIa and p-IIIa; DIPDEAMEA-MI), compound of formula (m- 11 lb and p-IIIb; DIPDIP ADEA-MI), compound of formula (m- IIIc and p -IIIc; DIPDIP AMEA-MI), compound of formula (m- 11 Id and p- II Id;

DIPMIP ADEA-MI), compound of formula (m-IIIe and p-IIIe; DIPMIPADIPA-MI), compound of formula (m- 11 If and p -IIIf; DIPMEAMIPA-MI), compound of formula (m- Illk and p-IIIk, DIPANMEA-MI), compound of formula (m-III1 and p-III1,

DIPANDEA-MI), compound of formula (m-IIIm and p-IIIm , DIPANMIPA-MI), compound of formula (m-IIIn and p-I I In, DIPANDIPA-MI), compound of formula (m- IIIp and p-I I Ip, DIPANMA-MI), compound of formula (m-I I Iq and p-I I Iq, DIPMAMEA-MI), compound of formula (m- 11 Ir and p-IIIr, DIPMADEA-MI), compound of formula (m- 111 s and p-IIIs, DIPMAMIPA-MI) and compound of formula (m-IIIt and p-IIIt, DIPMADIPA-MI).

Preferably, the molar amount of maleic anhydride, citraconic anhydride, nadic anhydride, methyl-nadic-anhydride, 1,2,3,6-tetrahydrophthalic anhydride or phthalic anhydride is from 2 to 4 fold, more preferably from 2 to 3 fold, even more preferably from 2 to 2.5 fold, of the molar amount of compound of formula (m-II) or (p-II), or the total amount of the compounds of formula (m-II) and (p-II), in the case of a mixture.

Reaction (I) can be done in the presence of a catalyst (I); preferably, catalyst (I) is p-toluene sulfuric acid or p-toluene sulfuric acid monohydrate.

Preferably, the molar amount of catalyst (I) is from 0.1 to 1 fold, more preferably from 0.2 to 0.9 fold, even more preferably from 0.3 to 0.75 fold, of the molar amount of compound of formula (m-II) or (p-II), or the total amount of the compounds of formula (m-II) and (p-II), in the case of a mixture.

Reaction (I) can be done in a solvent (I). Preferably, solvent (I) is a non-polar solvent that is capable of forming an azeotrope with water, preferably a positive azeotrope. Solvents are generally considered to be non-polar, if they have a dielectric constant of 15 or less. A positive azeotrope is a mixture of solvents which exhibits a boiling point that is lower than the boiling point of any of its constituents. More preferably, solvent (I) is toluene, a xylene isomer or a mixture of any of the aforementioned.

Preferably, the molar amount of solvent (I) is from 5 to 50 fold, more preferably from 10 to 30 fold, of the molar amount of compound of formula (m-II or p-II), or the total amount of the compounds of formula (m-II and p-II), in the case of a mixture.

Preferably, reaction (I) is done at a reaction temperature of from 50 to 200 °C, more preferably of from 75 to 175 °C, even more preferably of from 100 to 175 °C, especially of from 110 to 160 °C. Preferably, the reaction time of reaction (I) is from 1 to 12 h, more preferably of from 2.5 to 10 h, even more preferably of from 3 to 8 h.

Reaction (I) can be done under ambient pressure or under elevated pressure. Elevated pressure is for example applied when reaction (I) is done in a solvent (I) and the chosen temperature is above the boiling point of solvent (I).

After reaction (I), compound of formula (m-V) or (p-I ) or a mixture thereof can be isolated according to standard methods which are known to the skilled person, such as removal of any solvent (I) that was used, preferably by distillation; adjusting the pH to an alkaline pH by addition of a base, preferably the base is sodium bicarbonate, more preferably an aqueous solution of sodium bicarbonate; separation of any aqueous phase from an organic phase; washing of an organic phase with water; removal of any solvent from an organic phase, preferably by distillation.

Preferably, a compound of formula (m-II ) or (p- II ) or a mixture thereof is prepared by a reaction (II) of compound of formula (IVa; AML) and compound of formula (IVb; AMR) with 1,3 -diisopropenylbenzene or 1,4-diisopropenylbenzene, respectively, or a mixture thereof;

(IVa; AML) (IVb; AMR) wherein

R2L, R3L, R6L, R2R, R3R and R6R are as defined herein, also with all their embodiments.

In a preferred embodiment, a compound of formula (m-II) or (p- II ) or a mixture thereof, which is prepared by reaction (II), is obtained as a mixture (I). Mixture (I) is a mixture of compound of formula (m-II) or (p-II) or a mixture thereof with compound of formula (m-Va and/or m-Va; DIPL) and compound of formula (m-Vb and/or p -Vb; DIPR);

wherein R2L, R3L, R6L, R2R, R3R and R6R are as defined herein, also with all their embodiments. Preferred embodiments of compound of formula (m-Va and p -Va; DIPL) and compound of formula (m-Vb or p -Vb; DIPR) are selected from the group consisting of compound of formula (m-VIa and p-VIa; DIPDEA), compound of formula (m-VIb and p-VIb;

DIPDIP A), compound of formula (m-VIc and p -VIc; DIPMIPA), compound of formula (m-VId and p-VId; DIPMEA), compound of formula (m-VIe and p-VIe; DIPCDEA), compound of formula (m-VIf and p-VIf; DIPAN), compound of formula (m-VIg and p- Vlg; DIPMA).

More preferred embodiments of compound of formula (m-Va and p-Va; DIPL) and compound of formula (m-Vb or p -Vb; DIPR) are selected from the group consisting of compound of formula (m-VIa and p-VIa; DIPDEA), compound of formula (m-VIb and p-VIb;

BISDIP A), compound of formula (m-VIc and p -VIc ; DIPMIPA), compound of formula (m -VId and p-VId; DIPMEA), compound of formula (m-VIf and p-VIf; DIPAN), compound of formula (m-VIg and p-VIg; DIPMA). Compound of formula (m-Va or p-Va; DIPL) is symmetrically substituted and is obtained by reaction (III) of about 1 eq 1,3-diisopropenylbenzene or 1,4-diisopropenylbenzene with about 2 eq of compound of formula (m-IVa or p-IVa), reaction (III) occurs as a side reaction in reaction (II). Compound of formula (m-Vb or p -Vb; DIPR) is symmetrically substituted and is obtained by reaction (IV) of about 1 eq 1,3 -diisopropenylbenzene or 1,4-diisopropenylbenzene with about 2 eq of compound of formula (m-I Vb or p-IVb), reaction (IV) occurs as a side reaction in reaction (II).

In one embodiment, compound of formula (m - I I ) or (p-II) or a mixture thereof is used for and in reaction (I) in form of mixture (I).

Preferably, mixture (I) comprises compound of formula (m - 11 ) or (p-II) or a mixture thereof in an amount of at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt%, at least 70 wt% or at least 80 wt%, more preferably in an amount of at least at least 40 wt% or at least 50 wt%, most preferably in an amount of at least at least 40 wt%.

In a further preferred embodiment, mixture (I) comprises compound of formula (m -! I ) or (p- II) or a mixture thereof in an amount that is larger than the amount of compound of formula (m-Va and/or m-Va; DIPL) and compound of formula (m-Vb and/or p -Vb; DIPR) in the mixture.

When compound of formula (m-II) or (p-I I ) or a mixture thereof is used for reaction (I) in form of mixture (I), then compound of formula (m-I) or (p-I ) or a mixture thereof is obtained from reaction (I) in form of a mixture (II). Mixture (II) is a mixture of compound of formula (m-I) or (p-I) with compound of formula (m- Vila or p-VIIa;

DIPL-MI) and compound of formula (m-VIIb or p- VI lb ; DIPR-MI);

with *, **, R2L, R3L, R6L, R2R, R3R and R6R are as defined herein, also with all their embodiments.

Preferred embodiments of compound of formula (m- Vila or p-VIIa; DIPL-MI) and compound of formula (m-VIIb or p-VIIb; DIPR-MI) are selected from the group consisting of compound of formula (m-VIIIa or p- Villa; DIPDEA-MI), compound of formula (m- Vlllb or p-VIIIb; DIPDIP A-MI), compound of formula (m-VIIIc or p-VIIIc; DIPMIPA- MI), compound of formula (m-VIIId or p-VIIId; DIPMEA-MI), compound of formula (m-VIIIe or p-VIIIe; DIPCDEA-MI), compound of formula (m-VIIIf or p-VIIIf; DIPAN-MI) and compound of formula (m-VIIIg or p-VIIIg; DIPMA-MI).

More preferred embodiments of compound of formula (m- Vila or p-VIIa; DIPL-MI) and compound of formula (m-VIIb or p-VIIb; DIPR-MI) are selected from the group consisting of compound of formula (m-VIIIa or p- Villa; DIPDEA-MI), compound of formula (m-VIIIb or p-VIIIb; DIPDIP A-MI), compound of formula (m-VIIIc or p-VIIIc; DIPMIPA-MI), compound of formula (m- Vllld or p- VII Id; DIPMEA-MI), compound of formula (m-VIIIf or p- VI I If; DIPAN-MI) and compound of formula (m-VIIIg or p- Vlllg; DIPMA-MI).

Preferably, mixture (II) comprises compound of formula (m-T) or (p-I) or a mixture thereof in an amount of at least 20 wt%, at least 30 wt%, at least 40 wt%, at least 50 wt%, at least 60 wt% or at least 70 wt%, more preferably in an amount of at least at least 30 wt% or at least 40 wt%, most preferably in an amount of at least 30 wt%. In a particularly preferred embodiment, mixture (II) comprises compound of formula (m-V) or (p-I) or a mixture thereof in an amount of at least 40 wt%.

In a further preferred embodiment, mixture (II) comprises compound of formula (m-V) or (p-I) or a mixture thereof in an amount that is larger than the amount of compound of formula (m-VIIa or -VIIa; DIPL-MI) and compound of formula (m-VIIb or p- VI lb; DIPR-MI) in the mixture.

Absolute or relative amounts of compounds of formula (m-V) or (p-I) and further compounds disclosed herein may be determined by various analytical methods known to the skilled artisan, for example by reversed phase high performance liquid chromatography (rpHPLC), followed by quantification by determination of UV absorbance at a suitable wave length (e.g., 269 nm).

If desired, compound of formula (m-V) or (p-I) or a mixture thereof or compound of formula (m - 11 ) or ( -II) or a mixture thereof may be purified from a reaction mixture by established purification methods, such as crystallization or distillation, preferably distillation, more preferably short column distillation.

Compound of formula (m-II) or (p- 11 ) or a mixture thereof, which is prepared by reaction (II), is preferably prepared and obtained as a mixture (I), in which case compound of formula (m-V) or (p-I) or a mixture thereof is obtained from reaction (I) in form of a mixture (II), as described herein, including all embodiments of compound of formula (m -II) or ( -II), reaction (II), mixture (I), compound of formula (m-V) or ( -I), reaction (I) and/or mixture (II).

In a further embodiment, compound of formula (m - 11 ) or (p-II) or a mixture thereof is used for and in reaction (I) in essentially pure form, i.e., it comprises compound of formula (m- Va and/or p-Va; DIPL) and compound of formula (m -Vb and/or p -Vb; DIPR) in a collective amount of less than 30 wt%, less than 20 wt%, less than 10 wt% or less than 5 wt%. The molar ratio of compound of formula (IVa) to compound of formula (IVb) may vary in a wide range; preferably, the molar amounts of compound of formula (IVa) and compound of formula (IVb) are comparable. Thus, preferably the molar ratio of compound of formula (IVa) to compound of formula (IVb) is from 4:1 to 1:4, more preferably from 2:1 to 1:2, even more preferably from 1.5:1 to 1:1.5, especially from

1.3:1 to 1: 1.3.

The choice of compound of formula (IVa) and compound of formula (IVb) in reaction (II) determines what specific mixture (I) is obtained from reaction (II); and the choice of mixture (I) in reaction (I) determines, what specific mixture (II) is obtained from reaction (I).

Table 1 shows preferred combinations of compound of formula (IVa; AML) and compound of formula (IVb; AMR) and the resulting compounds in mixture (I) obtained from reaction (II) and mixture (II) obtained from reaction (I).

More preferred combinations of compound of formula (IVa; AML) and compound of formula (IVb; AMR) according to Table 1 do not include CDEA (Xe). Preferably, the reaction time of reaction (II) is from 1 to 12 h, more preferably of from 2.5 to

10 h, even more preferably of from 4 to 8 h.

Reaction (II) can be done under ambient pressure or under elevated pressure. Elevated pressure is for example applied when reaction (II) is done in a solvent (II) and the chosen temperature is above the boiling point of solvent (II).

Preferred embodiments of compound of formula (m - 11 ) or (p-II) are selected from the group consisting of compound of formula (m-IXa and p-IXa; DIPDEAMEA), compound of formula (m-IXb and p-IXb; DIPDIP ADEA), compound of formula (m-IXc and p-IXc; DIPDIP AMEA), compound of formula (m-IXd and p-IXd; DIPMIPADEA), compound of formula (m-IXe and p-IXe; DIPMIPADIPA), compound of formula (m-IXf and p- IXf; DIPMIPAMEA), compound of formula (m-IXg and p-IXg; DIPCDEAMEA), compound of formula (m-IXh and p-IXh; DIPCDEAMIPA), compound of formula (m- IXi and p-IXi; DIPCDEADIPA), compound of formula (m -IXj and p- IXj ; DIPCDEADEA), compound of formula (m-IXk and p-IXk; DIPANMEA), compound of formula (m-IXl and p-IXl; DIPANMIPA), compound of formula (m-IXm and p-IXm; DIPANDIP A), compound of formula (m-IXn and p-IXn; DIPANDEA), compound of formula (m-IXo and p-IXo; DIPANCDEA), compound of formula (m-IXp and p-IXp; DIPANMA), compound of formula (m-IXq and p-IXq; DIPMAMEA), compound of formula (m-IXr and p-IXr; DIPMAMIPA), compound of formula (m-IXs and p-IXs; DIPMADIPA), compound of formula (m-IXt and p-IXt; DIPMADEA) and compound of formula (m-IXu and »-IXu; DIPMACDEA).

More preferred embodiments of compound of formula (m-II) or (p-II) are selected from the group consisting of compound of formula (m-IXa and p-IXa; DIPDEAMEA), compound of formula (m-IXb and p-IXb; DIPDIP ADEA), compound of formula (m- IXc and p-IXc; DIPDIP AMEA), compound of formula (m-IXd and p-IXd;

DIPMIPADEA), compound of formula (m-IXe and p-IXe, DIPMIPADIPA), compound of formula (m-IXf and p-IXf; DIPMIPAMEA), compound of formula (m-IXk and p- IXk; DIPANMEA), compound of formula (m-IXl and p-IXl; DIPANMIPA), compound of formula (m-IXm and p-IXm; DIPANDIP A), compound of formula (m-IXn and p- IXn; DIPANDEA), compound of formula (m-IXp and p-IXp; DIPANMA), compound of formula (m-IXq and p-IXq; DIPMAMEA), compound of formula (m-IXr and p-IXr; DIPMAMIPA), compound of formula (m-IXs and p-IXs; DIPMADIPA) and compound of formula (m-IXt and p-IXt; DIPMADEA). Preferred embodiments of compound of formula (IVa) and compound of formula (IVb) are selected from the group consisting of compound of formula (Xa; MEA), compound of formula (Xb; DEA), compound of formula (Xc; DIP A), compound of formula (Xd; MIPA), compound of formula (Xe; CDEA), compound of formula (Xf; aniline, AN) and compound of formula (Xg; 2-methylaniline, MA).

(Xf; aniline) (Xg; 2-methylaniline)

More preferred embodiments of compound of formula (IVa) and compound of formula (IVb) are selected from the group consisting of compound of formula (Xa; ME A), compound of formula (Xb; DEA), compound of formula (Xc; DIP A), compound of formula (Xd; MIPA), compound of formula (Xf; AN) and compound of formula (Xg; MA).

In reaction (II), further anilines can be present, preferably 1, 2 or 3 further anilines, such as compound of formula (XI; AM), which are different from compound of formula (IVa) and from compound of formula (IVb);

(XI; AM) wherein R2, R3 and R6 are identical or different and independently from each other selected from the group consisting of H, C_1-4 alkyl, Cl, Br, F and CF₃, preferably wherein R2 and

R6 are identical or different and independently from each other selected from the group consisting of H, C_1-4 alky and Cl and R3 is selected from the group consisting of H or C_1-4 alkyl, Cl, Br, F and CF₃. The presence of such further aniline in reaction (II) results in the respective mixtures of asymmetrical methylene-bis-anilines with respective symmetrical methylene-bis- anilines, which are possible to be obtained from any of the combinations of two anilines out of all anilines which are present in reaction (II); the use of such mixtures in reaction (I) results in the respective mixtures of asymmetrical methylene-bis-maleimides with symmetrical methylene-bis-maleimides.

Table 2 shows an embodiment, wherein three anilines have been used in reaction (II) and the mixtures which are thereby obtained from reaction (II) and thereafter from reaction (I).

Further subject of the invention is a compound of formula (m-Y) or (p-I ) and mixtures thereof; with the compound of formula m-Y) or (p-I ) as defined herein, also with all its embodiments.

Further subject of the invention is a compound of formula (m-II) or (p-II) and mixtures thereof; with the compound of formula (m-I I) or ( -II) as defined herein, also with all its embodiments.

Further subject of the invention is a mixture of compound of formula m-Y) or (p-I ) or a mixture thereof with compound of formula (m-VIIa or p -VIIa; DIPL-MI) and compound of formula (m-VIIb or p -VIIb; DIPR-MI); with the compound of formula (m- I) or (p-I ), the compound of formula (m- Vila or p -VIIa; DIPL-MI) and the compound of formula (m-VIIb or p -VIIb; DIPR-MI) as defined herein, also with all their embodiments.

Further subject of the invention is the use of compound of formula (m-Y) or (p -I) or a mixture for the preparation of resins; with the compound of formula (m-Y) or (p -I) or a mixture as defined herein, also with all its embodiments.

Further subject of the invention is a resin comprising

(i) a reactant of a cyanate compound (A) and a polybutadiene (B) and/or

(ii) a reactant of a polymerized product of the cyanate compound (A) and the polybutadiene (B); and a maleimide compound of formula (m-Y) or (p -I) or a mixture thereof, wherein the polybutadiene (B) comprises a 1,2-adduct and a 1,4-adduct at a mass ratio of 1:3 to 3:1, and the maleimide compound of formula (m-I) or (p-I ) is as defined herein, also with all its embodiments.

Another subject of the invention is a prepreg comprising a base material and a resin composition with which the base material is impregnated or coated, wherein the resin composition comprises

(i) a reactant of a cyanate compound (A) and a polybutadiene (B) and/or

(ii) a reactant of a polymerized product of the cyanate compound (A) and the polybutadiene (B); and a maleimide compound of formula (m-I) or (p-I ) or a mixture thereof, wherein the polybutadiene (B) comprises a 1,2-adduct and a 1,4-adduct at a mass ratio of 1 :3 to 3: 1, and the maleimide compound of formula (m-I) or (p-I ) or a mixture thereof is as defined herein, also with all its embodiments.

Yet another object of the invention is a metal foil-clad laminate comprising at least one or more of the prepregs disclosed herein laminated, and a metal foil disposed on one surface or both surfaces of the prepreg.

A further object of the invention is a printed wiring board comprising an insulating layer and a conductor layer formed on a surface of the insulating layer, wherein the insulating layer comprises a resin composition disclosed herein.

In one embodiment, the cyanate compound (A) comprises at least one cyanate compound (Al) selected from a group consisting of a bisphenol A-based cyanate compound, a bisphenol E-based cyanate compound, a bisphenol F-based cyanate compound, and a novolac-based cyanate compound. In one embodiment, the cyanate compound (A) further comprises a cyanate compound (A2) other than the cyanate compound (Al). In a further embodiment, the resin further comprises any one or more of a group selected from an epoxy resin, a phenolic resin, an oxetane resin, a benzoxazine compound, and a compound having a polymerizable unsaturated group.

Another subject of the invention is a resin comprising

(i) an isocyanate resin; or (ii) an epoxy resin; and a compound of formula (m-II) or (p-II) or a mixture thereof as defined herein, also with all its embodiments.

A further aspect of the invention is a process for the preparation of a polyamine epoxy resin, comprising (i) mixing an epoxy resin and a compound of formula (m-II) or (p- 11 ) or a mixture thereof, and (ii) curing the mixture to obtain the polyamine epoxy resin, wherein the compound of formula (m-II) or (p-II) is as defined herein, also with all its embodiments.

A further aspect of the invention is a process for the preparation of a polyurea resin, comprising (i) mixing an isocyanate resin and a compound of formula (m-II) or (p-II) or a mixture thereof, and (ii) curing the mixture to obtain the polyurea resin, wherein the compound of formula (m-II) or (p-II) is as defined herein, also with all its embodiments.

Another aspect of the invention is a use of a compound of formula (m-II) or (p-II) or a mixture thereof for the preparation of a resin, wherein the resin preferably is a polyamine epoxy resin, a polyurea resin or a polyurethane resin.

A further aspect of the invention is a use of a compound of formula (m-II) or (p-II) or a mixture thereof as hardener for an epoxy resin.

A further aspect of the invention is a use of a compound of formula (m-II) or (p-II) or a mixture thereof as hardener and/or chain extender for a polyurethane or a polyurea resin.

As the isocyanate compound, those generally known can be used, as long as they are compounds having two or more isocyanate groups in one molecule. Specific examples thereof include Suprasec® 2008 (a prepolymerised diphenyl methane diisocyanate), methylene diphenyl diisocyanate (MDI), aromatic diisocyanates such as p-phenylene diisocyanate, m- phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; diisocyanates having an aliphatic or alicyclic structure such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'- dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbomene diisocyanate, and lysine diisocyanate; polyisocyanates such as biurets of one or more types of isocyanate monomers or isocyanates obtained by 3 amounts of the diisocyanate compound; and polyisocyanates obtained by urethane-forming reaction of the isocyanate compound and a polyol compound. In a preferred embodiment, the isocyanate is MDI, 2,4-TDI, 2,6-TDI or Suprasec® 2008.

As the epoxy resin, those generally known can be used as long as they are compounds having two or more epoxy groups in one molecule. The type of the epoxy resin is not particularly limited. Specific examples thereof include bisphenol A-based epoxy resins (e.g., Epikote Resin 828 LVEL, a liquid epoxy resin produced from bisphenol A resin and epichlorohydrin), bisphenol E-based epoxy resins, bisphenol F-based epoxy resins, bisphenol S-based epoxy resins, bisphenol A novolac-based epoxy resins, biphenyl-based epoxy resins, phenol novolac-based epoxy resins, cresol novolac-based epoxy resins, xylene novolac-based epoxy resins, polyfunctional phenol-based epoxy resins, naphthalene-based epoxy resins, naphthalene skeleton-modified novolac-based epoxy resins, naphthylene ether-based epoxy resins, phenol aralkyl-based epoxy resins, anthracene-based epoxy resins, trifunctional phenol-based epoxy resins, tetrafunctional phenol-based epoxy resins, triglycidyl isocyanurate, glycidyl ester-based epoxy resins, alicyclic epoxy resins, dicyclopentadiene novolac-based epoxy resins, biphenyl novolac-based epoxy resins, phenol aralkyl novolac- based epoxy resins, naphthol aralkyl novolac-based epoxy resins, aralkyl novolac-based epoxy resins, biphenyl aralkyl-based epoxy resins, naphthol aralkyl-based epoxy resins, dicyclopentadiene-based epoxy resins, polyol-based epoxy resins, phosphorus-containing epoxy resins, glycidyl amines, compounds obtained by epoxidizing double bonds of butadiene, compounds obtained by reaction of hydroxyl group-containing silicone resins and epichlorohydrin, or halides thereof. One of these epoxy resins can be used alone, or two or more of these epoxy resins can be used in combination. In a preferred embodiment, the epoxy resin is a bisphenol A-based epoxy resins (e.g., Epikote Resin 828 LVEL). EXAMPLES

Abbreviations: wt% weight percent MEK methyl ethyl ketone ppm parts per million eq. equivalents

T_g glass transition temperature

TMA thermal mechanical analysis GT gel time

DIDP diisodecyl phthalate

PU polyurea

RT room temperature mp melting point

Materials

Maleic anhydride CAS 108-31-6, >=99.0%, Sigma- Aldrich p-toluenesulfonic acid monohydrate CAS 6192-52-5, >=98%, Sigma- Aldrich Epikote Resin 828 LVEL CAS 1675-54-3, medium viscosity liquid epoxy resin produced from bisphenol A resin and epichlorohydrin; Westlake Epoxy

Suprasec 2008 prepolymerised diphenyl methane diisocyanate, Huntsman

Methods

Preparation of compound of formula (m-II )

Example 1: Preparation of compound of formula ( -VIc)

AlCl₃ (11.63 g, 0.06 eq.) and 2-isopropyl-6-methylanilin (230 g, 1.00 eq.) were mixed in a reactor and heated up to 120 °C. After the temperature was reached, 1,3- diisopropenylbenzene (162.42 g, 0.67 eq.) was slowly dosed within 7 h to the reaction mixture. After the dosing was finished, the reaction was stirred for another 20 h at 120 °C. The reaction mixture was cooled to 90 °C and toluene (266.96 g, 0.47 eq.) and NaOH (aq., 25%, 327.93 g, 1.33 eq.) were added to quench the reaction. The reaction mixture was stirred vigorously at 70 °C. After 60 minutes two separated clear phases could be observed. The organic phase was slowly cooled down to 0 °C. The precipitate was filtered off to obtain the crude product 4,4'-(l,3-phenylenebis(propane-2,2-diyl))bis(2-isopropyl-6-methylaniline) as a beige solid (230.85 g, 0.50 mmol, 64.4 %). The product was used without any further purification for the next step. The product can be further purified by washing with hexane to obtain a white solid.

¹HNMR (400 MHz, CDCl₃) δ ppm 1.22 (d, 12H), 1.65 (s, 12H), 2.22 (s, 6H), 2.99 (sep, 2H), 4.25 (s, br, 4H), 6.82 (m, 2H), 6.92 (m, 2H), 7.05 (m, 2H), 7.20 (m, 2H).

Example 2: Preparation of compound of formula ( -VId)

AlCh (18.42 g, 0.06 eq.) and 2-methyl-6-ethylanilin (330 g, 1.00 eq.) were mixed in a reactor and heated up to 120 °C. After the temperature was reached, 1,3 -diisopropenylbenzene (257.21 g, 0.67 eq.) was slowly dosed within 7 h to the reaction mixture. After the dosing was finished, the reaction was stirred for another 20 h at 120 °C. The reaction mixture was cooled to 90 °C and toluene (422.78 g, 0.47 eq.) and NaOH (aq., 25%, 519.33 g, 1.33 eq.) were added to quench the reaction. The reaction mixture was stirred vigorously at 70 °C. After 60 minutes two separated clear phases could be observed. The organic phase was slowly cooled down to 0 °C. The precipitate was filtered off to obtain the crude product 4,4'-(l ,3 - phenylenebis(propane-2,2-diyl))bis(2-ethyl-6-methylaniline) as a beige solid (306.5 g, 0.72 mmol, 58.6 %). The product was used without any further purification for the next step. The product can be further purified by washing with hexane to obtain a white solid.

¹HNMR (400 MHz, CDCl₃) δ ppm 1.20 (t, 6H), 1.63 (s, 12H), 2.23 (s, 6H), 2.59 (q, 4H), 6.79 (m, 4H), 7.07 (m, 2H), 7.19 (m, 2H).

Example 3: Preparation of compound of formula (m-IXf)

AlCl₃ (16.81g, 0.09 eq.), 2-methyl-6-ethylanilin (181.20 g, 1.00 eq.) and 2-isopropyl-6- methylanilin (200 g, 1.00 eq.) were mixed in a reactor and heated up to 120 °C. After the temperature was reached, 1,3 -diisopropenylbenzene (233.27 g, 1.10 eq.) was slowly dosed within 7 h to the reaction mixture. After the dosing was finished, the reaction was stirred for another 20 h at 120 °C. The reaction mixture was cooled to 90 °C and toluene (464.28 g, 0.94 eq.) and NaOH (aq., 25%, 570.31 g, 2.66 eq.) were added to quench the reaction. The reaction mixture was stirred vigorously at 70 °C. After 60 minutes two separated clear phases could be observed. The organic phase was slowly cooled down to 0 °C. The precipitate was filtered off to obtain the crude product mixture of 4-(2-(3-(2-(4-amino-3-ethyl-5- methylphenyl)propan-2-yl)phenyl)propan-2-yl)-2-isopropyl-6-methylaniline, 4,4'-(l,3- phenylenebis(propane-2,2-diyl))bis(2-ethyl-6-methylaniline) and 4,4'-(l,3-phenylene- bis(propane-2,2-diyl))bis(2-isopropyl-6-methylaniline) as a beige solid (234.7 g, 0.53 mmol, 39.6 %). The product was used without any further purification for the next step. The product can be further purified by washing with hexane to obtain a white solid. ¹H NMR (400 MHz, CDCI₃) 6 ppm 1.21 (m, 9H), 1.63 (m, 12H), 2.23 (m, 6H), 2.39 (m, 2H), 2.58 (q, 2H), 3.03 (m, 1H), 6.85 (m, 4H), 7.06 (m, 2H), 7.19 (m, 4H).

Preparation of compound of formula m-I

Example 4: Preparation of compound of formula ( -VIIIc), DIPMIPA-MI

p-Toluenesulfonic acid monohydrate (36.8 g, 0.46 eq.) and maleic anhydride (104.8 g, 2.3 eq.) were mixed in toluene (838.9 g, 17 eq.) and heated under reflux in a Dean-Stark apparatus. Within 1 h a mixture of 4,4'-(l,3-phenylenebis(propane-2,2-diyl))bis(2-isopropyl- 6-methylaniline) (Example 1, 212.3 g, 1 eq.) and toluene (838.9 g, 17 eq.) were added. The reaction was heated for 7.5 h until no more water was separated. 20 vol% toluene were distilled off to obtain a clear brownish solution. NaHCO₃ (8% in water, 1953 g) was added slowly at 40 °C under gas evolution and stirred for 5 min at 70 °C. The organic phase was separated and washed with water (3x, 100 g). The solvent was removed under reduced pressure to obtain l, l'-((l,3-phenylenebis(propane-2,2-diyl))bis(2-isopropyl-6-methyl-4,l- phenylene))bis(lH-pyrrole-2, 5-dione) as a yellow-orange solid (180.04 g, 0.25 mol, 63.5 %).

¹HNMR (400 MHz, CDCI₃) δ ppm 1.09 (d, 12H), 1.68 (s, 12H), 2.05 (s, 6H), 2.63 (sep, 2H), 2.58 (q, 2H), 6.89 (s, 4H), 7.00 (m, 2H), 7.08 (m, 3H), 7.20 (m, 2H), 7.27 (m, 2H), 7.28 (m, 2H).

Example 5: Preparation of compound of formula (m -VII Id). DIPMEA-MI

p-Toluenesulfonic acid monohydrate (44.4 g, 0.46 eq.) and maleic anhydride (126.5 g, 2.3 eq.) were mixed in toluene (878.5 g, 17 eq.) and heated under reflux in a Dean-Stark apparatus. Within 1 h a mixture of 4,4'-(l,3-phenylenebis(propane-2,2-diyl))bis(2-ethyl-6- methylaniline) (Example 2, 240.4 g, 1 eq.) and toluene (878.5 g, 17 eq.) were added. The reaction was heated for 7.5 h until no more water was separated. 20 vol% toluene were distilled off to obtain a clear brownish solution. NaHCO₃ (8% in water, 2356.0 g) was added slowly at 40 °C under gas evolution and stirred for 5 min at 70 °C. The organic phase was separated and washed with water (3x, 100 g). The solvent was removed under reduced pressure to obtain 1, 1'-((l,3-phenylenebis(propane-2,2-diyl))bis(2-ethyl-6-methyl-4, 1- phenylene))bis(lH-pyrrole-2, 5-dione) as a yellow solid (171.34 g, 0.28 mol, 50.8 %).

¹HNMR (400 MHz, CDCI₃) δ ppm 1.07 (t, 6H), 1.68 (s, 12H), 2.05 (s, 6H), 2.37 (m, 4H), 6.89 (s, 4H), 7.01 (m, 4H), 7.06 (d, 1H), 7.08 (d, 2H), 7.21 (m, 1H), 7.28 (m, 1H), 7.30 (t, 1H).

Example 6: Preparation of compound of formula (m-II If). DIPMEAMIPA-MI

p-Toluenesulfonic acid monohydrate (26.8 g, 0.46 eq.) and maleic anhydride (76.4 g, 2.3 eq.) were mixed in toluene (530.8 g, 17 eq.) and heated under reflux in a Dean-Stark apparatus. Within 1 h a mixture of 4-(2-(3-(2-(4-amino-3-ethyl-5-methylphenyl)propan-2- yl)phenyl)propan-2-yl)-2-isopropyl-6-methylaniline, 4,4'-(l,3-phenylenebis(propane-2,2- diyl))bis(2-ethyl-6-methylaniline) and 4,4'-(l,3-phenylene-bis(propane-2,2-diyl))bis(2- isopropyl-6-methylaniline) (Example 3, 150.0 g, 1 eq.) and toluene (530.8 g, 17 eq.) were added. The reaction was heated under reflux for 7.5 h until no more water was separated. 20 vol% toluene were distilled off to obtain a clear brownish solution. NaHCO₃ (8% in water, 1423.2 g) was added slowly at 40 °C under gas evolution and stirred for 5 min at 70 °C. The organic phase was separated and washed with water (3x, 100 g). The solvent was removed under reduced pressure to obtain l-(4-(2-(3-(2-(4-(2,5-dioxo-2,5-dihydro-lH-pyrrol-l-yl)-3- ethyl-5-methylphenyl)propan-2-yl)phenyl)propan-2-yl)-2-isopropyl-6-methylphenyl)-lH- pyrrole-2, 5-dione, l,l'-((l,3-phenylenebis(propane-2,2-diyl))bis(2-ethyl-6-methyl-4,l- phenylene))bis(lH-pyrrole-2, 5-dione) and l,l'-((l,3-phenylenebis(propane-2,2-diyl))bis(2- isopropyl-6-methyl-4,l-phenylene))bis(lH-pyrrole-2, 5-dione) as an orange solid (201.2 g, 0.33 mol, 98.2 %).

'H NMR (400 MHz, CDCI₃) δ ppm 1.08 (m, 9H), 1.68 (s, 12H), 2.05 (s, 6H), 2.37 (m, 3H), 2.63 (m, 1H), 6.89 (s, 4H), 7.01 (m, 3H), 7.07 (m, 3H), 7.21 (m, 2H), 7.28 (m, 2H). (4) Solubility analysis:

Solubility was determined using a Mettler Toledo halogen dryer (Mettler-Toledo GmbH; GieBen, Germany). A saturated solution of each compound was prepared in the respective solvent and the dissolved amount (wt%) in the liquid phase determined after filtration using a syringe filter (1pm pore size) on the halogen dryer. The results of the solubility analysis are summarized in Table 6 (BMPI-300 is a 1 :1 mixture ofDIPDEA-MI (formula Villa) and DIPMIPA-MI (formula VIIIc); BMI-5100 is DIPMEA-MI (formula Vllld)).

(5) Gel time analysis:

Gel times were determined using a GELNORM® Gel Timer (Gel Instrumente

AG, Thalwil, Switzerland), according to manufacturer’s instructions. The results of the solubility analysis are summarized in Table 7.

(6) Glass transition temperature analysis:

The temperature resistance as expressed glass transition temperature T_g by onset was measured by TMA (thermal mechanical analysis).

Glass transition temperature is the temperature, at which the physical properties of a polymeric materials change from amorphous rigid, glassy or crystalline state to a flexible rubbery state. The glass transition temperature T_g is measured by thermal mechanical thermal analysis (TMA) and given as the Onset.

(7) Melting point analysis

Melting points were determined with a standard melting point apparatus.

(8) Epoxy Amine characterization:

(A)DIPMIPA in Epoxy:

20.51 g Epikote Resin 828 LVEL and 12.55 g DIPMIPA were combined in a 250 mL flask and stirred at 80 °C for several minutes. 12 g of the mixture were used for gel time (GT) measurements. 12 g of the mixture were used to cast a disc.

Disc Cure Cycle: Mixture was heated from 90-130 °C, temperature was kept at 130 °C for

4 h, mixture was heated from 130-160 °C, temperature was kept at 160 °C for 4h, mixture was heated from 160-190 °C, temperature was kept at 190 °C for 4 h.

(B)DIPMEA in Epoxy:

20.48 g Epikote Resin 828 LVEL and 11.85 g DIPMEA were combined in a 250 mL flask and stirred at 80 °C for several minutes. 12 g of the mixture were used for gel time (GT) measurements. 12 g of the mixture were used to cast a disc. Disc Cure Cycle: Mixture was heated from 90-130 °C, temperature was kept at 130 °C for

(C) DIPMIPA-MEA in Epoxy:

20.58 g Epikote Resin 828 LVEL and 12.2 g DIPMIPAMEA were combined in a 250 mL flask and stirred at 80 °C for several minutes. 12 g of the mixture were used for GT measurements. 12 g of the mixture were used to cast a disc.

Glass transition temperature (T_g), CTE 40-T_g (coefficient of thermal expansion, measured from 40 °C to T_g) and gel time (GT) of the cured epoxy resins (A) to (C) were determined as described hereinabove, with the following results (Table 10).

(9) Polyurea (PU) Amine characterization:

(A) DIPMIPA in PU:

5.52 g DIPMIPA and 11.18 g DIDP were combined in a vial and put in the oven at 90 °C for

10 to 15 min.. The mixture was regularly shaken to dissolve and homogenize everything.

After obtaining a homogenous liquid, 14.07 g of it were transferred into a cup and left to cool to RT. Then 10.23 g Suprasec 2008 were added and the mixture was stirred by hand. The reaction was immediate.

(B)DIPMEA in PU:

5.2 g DIPMEA and 10.41 g DIDP were combined in a vial and put in the oven at 100 °C for 10 to 15 min.. The mixture was regularly shaken to dissolve and homogenise everything.

After obtaining a homogenous liquid, 15.4 g of it were transferred into a cup and left to cool to RT. Then, 10.04 g Suprasec 2008 were added and the mixture was stirred by hand. The reaction was immediate.

(C) DIPMIPA-MEA in PU:

5.38 g DIPMIPA-MEA and 10.78 g DIDP were combined in a vial and put in the oven at 100 °C for 10 to 15 min.. The mixture was regularly shaken to dissolve and homogenise everything. After obtaining a homogenous liquid, 15.21 g of it were transferred into a cup and left to cool to RT. Then 10.36 g Suprasec 2008 were added and the mixture was stirred by hand. The reaction was immediate.

Gel time (GT) of the polyurea resins (A) to (C) was determined as described hereinabove, with the following results (Table 11).

Example 7: HPLC analysis of synthetically obtained phenylene-di-(2,2-propanol)-di- p/m-phenylene bisimides

Products obtained in Examples 4 (compound of formula (m-VIIIc), DIPMIPA-MI), 5 (compound of formula (m-VIIId), DIPMEA-MI) and 6 (compound of formula (m-IIIf), DIPMEAM1PA-MI) were analyzed by reversed phase HPLC, using a Waters XBridge BEH Shield RP18 (150mm x 3.0mm x 3.5pm) column on an Agilent Technologies 1100 device, under the following conditions (Table 12):

Detection (UV-Vis) was performed at 269 nm using a Diode Array Detector (DAD) or a Variable Wavelength Detector (VWD) (peakwidth > 0.05 min (1 s)).

The results are summarized below in Table 13 (relative amounts indicated in % area of UV- Vis chromatogram).

(Tol = toluene; Ex. 4, Ex. 5, Ex. 6 = products obtained according to Examples 4, 5 or 6, respectively; OT-DIP = 1,3 -diisopropenylbenzene)

Claims

Claims A method for the preparation of a compound of formula (m-T) or (p-I ) or a mixture thereof

by a reaction (I) of a compound of formula (m-II) or (p- I I) or a mixture thereof, with maleic anhydride, citraconic anhydride, nadic anhydride, methyl-nadic-anhydride 1,2,3,6-tetrahydrophthalic anhydride or phthalic anhydride;

wherein

* and ** each denote a covalent bond to the respective C atom denoted with * and ** of a residue (A);

(A) is either a residue of formula (M), a residue of formula (P), a residue of formula (Q), a residue of formula (O), residue of formula (T) or residue of formula (S);

the residues R2L, R3L, R6L, R2R, R3R and R6R are identical or different and independently from each other selected from the group consisting of H, C_1-4 alkyl and Cl, Br, F and perfluoro alkyl (e.g., CF₃, CF₂-CF₃); with the proviso that at least one of the three pairs:

1. R2L and R2R

2. R3L and R3R

3. R6L and R6R are different residues.

2. The method according to claim 1, wherein

(i) R2, R3 and R6 are identical or different and independently from each other selected from the group consisting of a) H, methyl, ethyl, n-propyl, iso-propyl, Cl, Br, F and perfluoro alkyl (e.g., CF₃, CF₂-CF₃) b) H, methyl, ethyl, n-propyl, iso-propyl, and Cl; or c) H, methyl, ethyl, iso-propyl, and Cl; and/or

(ii) the compound of formula (II) is reacted with maleic anhydride, citraconic anhydride, nadic anhydride, methyl-nadic-anhydride or phthalic anyhdride and (A) is a residue of formula (M), (Q), (O) (T) or (S). The method according to any one of the preceding claims, wherein the compound of formula (m-V) and (p-I) are selected from the group consisting of compound of formula (m -IIIa and p-I I la; DIPDEAMEA-MI), compound of formula (m-IIIb and p-IIIb; DIPDIP ADEA-MI), compound of formula (m-IIIc and p-IIIc; DIPDIP AMEA-MI), compound of formula (m- II Id and p- 11 Id; DIPMIP ADEA-MI), compound of formula (m- Ille and p- 11 le; DIPMIP ADIPA-MI), compound of formula (m- 11 If and p-IIIf; DIPMEAMIPA-MI), compound of formula (m- II Ig and p- II Ig; DIPCDEAMEA-MI), compound of formula (m- 11 Ih and p-IIIh; DIPCDEAMIPA-MI), compound of formula (m- Illi and -I IIi; DIPCDEADIPA-MI) compound of formula (m-IIIj and p-IIIj ; DIPCDEADEA-MI), compound of formula (m-IIIk and p-IIIk, DIPANMEA-MI), compound of formula (m- 11 II and p-IIIl, DIPANDEA-MI), compound of formula (m-I I I m and p-IIIm, DIPANMIPA-MI), compound of formula (m-IIIn and p-IIIn, DIPANDIPA- MI), compound of formula (m-IIIo and -I I Io, DIPANCDEA-MI), compound of formula (m- II Ip and p-IIIp, DIPANMA-MI), compound of formula (m- 11 Iq and p-IIIq, DIPMAMEA-MI), compound of formula (m- 11 Ir and p-IIIr, DIPMADEA-MI), compound of formula (m- 111 s and p-IIIs, DIPMAMIPA-MI), compound of formula (m- II It and p-IIIt, DIPMADIPA-MI) and compound of formula (m-IIIu and p-IIIu, DIPMACDEA-MI).

The method according to any one of the preceding claims, wherein the compound of formula (m-II) or (p-II) are selected from the group consisting of compound of formula (m -IXa and p-IXa; DIPDEAMEA), compound of formula (IXb; DIPDIP ADEA), compound of formula (IXc; DIPDIP AMEA), compound of formula (IXd; DIPMIPADEA), compound of formula (IXe; DIPMIPADIPA), compound of formula (IXf; DIPMIPAMEA), compound of formula (IXg; DIPCDEAMEA), compound of formula (IXh; DIPCDEAMIPA), compound of formula (IXi; DIPCDEADIPA) and compound of formula (IXj; DIPCDEADEA), compound of formula (m-IXk and p-IXk; DIPANMEA), compound of formula (m-IXl and p-IXl; DIPANMIPA), compound of formula (m-IXm and p-IXm; DIPANDIP A), compound of formula (m-IXn and p-IXn; DIPANDEA), compound of formula (m-IXo and p-IXo; DIPANCDEA), compound of formula (m-IXp and p-IXp; DIPANMA), compound of formula (m-IXq and p-IXq; DIPMAMEA), compound of formula (m-IXr and p-IXr; DIPMAMIP A), compound of formula (m-IXs and p-IXs; DIPMADIPA), compound of formula (m-IXt and p-IXt; DIPMADEA) and compound of formula (m-IXu and p-IXu; DIPMACDEA).

method according to any one of the preceding claims, wherein a) the molar amount of maleic anhydride, citraconic anhydride, nadic anhydride, methyl-nadic-anhydride, 1,2,3,6-tetrahydrophthalic anhydride or phthalic anhydride is from 2 to 4 fold of the molar amount of compound of formula (m-II) or (p-II), or the total amount of the compounds of formula (m-II) and (p- 11 ), in the case of a mixture; b) wherein reaction (I) is done in the presence of a catalyst (I); optionally wherein

(i) catalyst (I) is p-toluene sulfuric acid or p-toluene sulfuric acid monohydrate; and/or

(ii) the molar amount of catalyst (I) is from 0.1 to 1 fold of the molar amount of compound of formula (m-II) or (p- 11 ), or the total amount of the compounds of formula (m-II) and (p- 11 ), in the case of a mixture; c) reaction (I) is done in a solvent (I); optionally wherein

(i) solvent (I) is a non-polar solvent that is capable of forming an azeotrope with water; and/or

(ii) the molar amount of solvent (I) is from 5 to 50 fold of the molar amount of compound of formula (m-II or p-II), or the total amount of the compounds of formula (m-II and p-II), in the case of a mixture; d) reaction (I) is done at a reaction temperature of from 50 to 200 °C; and/or e) the reaction time of reaction (I) is from 1 to 12 h. The method according to any one of the preceding claims, wherein a compound of formula (m-II) or (p-II) or a mixture thereof is prepared by a reaction (II) of compound of formula (IVa) and compound of formula (IVb) with 1,3-diisopropenylbenzene or 1,4- diisopropenylbenzene, respectively, or a mixture thereof;

(IVa) (IVb) wherein R2L, R3L, R6L, R2R, R3R and R6R are as defined in any one of claims 1 or 2(i); optionally wherein the compound of formula (IVa) and compound of formula (IVb) are selected from the group consisting of compound of formula (Xa; MEA), compound of formula (Xb; DEA), compound of formula (Xc; DIP A), compound of formula (Xd; MIPA), compound of formula (Xe; CDEA), compound of formula (Xf; AN, aniline) and compound of formula (Xg; MA, 2-methylaniline).

(Xb; DEA) (Xa; MEA) (Xd; MIPA)

(Xf; aniline) (Xg; 2-methylaniline) The method according to claim 6, wherein the compound of formula (m-II) or (p-II) or a mixture thereof is obtained as a mixture (I), wherein mixture (I) is a mixture of compound of formula (m-II) or (p-II) or a mixture thereof with compound of formula (m-Va and/or m-Va; DIPL) and compound of formula (m-Vb and/or p -Vb; DIPR);

wherein R2L, R3L, R6L, R2R, R3R and R6R are as defined in any one of claims 1 or 2(i); optionally wherein compound of formula (Va) and compound of formula (Vb) are selected from the group consisting of compound of formula (m-VIa and p-VIa; DIPDEA), compound of formula

(m-VIb and p-VIb; DIPDIP A), compound of formula (m-VIc and p-VIc; DIPMIPA), compound of formula (m-VId and p-VId; DIPMEA), compound of formula (m-VIe and p- Vle; DIPCDEA), compound of formula (m-VIf and p-VIf; DIPAN), compound of formula (m-VIg and p-VIg; DIPMA).

The method according to any one of the preceding claims, wherein the compound of formula (m-II) or (p-II) or a mixture thereof is used for and in reaction (I) in form of mixture (I), wherein compound of formula (m-V) or (p-I) or a mixture thereof is obtained in form of a mixture (II), wherein mixture (II) is a mixture of compound of formula (m-I) or (p-I) or a mixture thereof with compound of formula (m-VIIa or p-VIIa; DIPL-MI) and compound of formula (m-VIIb or p-VIIb; DIPR-MI);

with *, **, R2L, R3L, R6L, R2R, R3R and R6R are as defined in any one of claims 1 or 2(i); optionally wherein compound of formula (m- Vila or p-VIIa; DIPL-MI) and compound of formula (m-VIIb or p-VIIb; DIPR-MI) are selected from the group consisting of compound of formula (m-VIIIa or p- Villa; DIPDEA-MI), compound of formula (m-VIIIb or p-Vnib; DIPDIP A-MI), compound of formula (m-VIIIc or p-VIIIc; DIPMIPA-MI), compound of formula (m-VIIId or p-VIIId; DIPMEA-MI), compound of formula (m-VIIIe or p-VIIIe; DIPCDEA-MI), compound of formula (m-VIIIf or p-VIIIf; DIPAN-MI) and compound of formula (m-VIIIg or p- VI I Ig; DIPMA-MI)

9. The method according to claim 8, wherein mixture (II) comprises compound of formula (m-I) or (p-I) or a mixture thereof in an amount of at least 20 wt%, at least 30 wt% or at least 40 wt%, preferably at least 40 wt%.

10. The method according to any one of claims 6 to 9, wherein the molar ratio of compound of formula (IVa) to compound of formula (IVb) is from 4: 1 to 1 :4. 11. The method according to any one of claims 8 to 10, wherein the compound of formula

(IVb) and the compound of formula (IVa) are as defined in Table A, resulting in a mixture (II) comprising the compounds as defined in Table A.

12. The method according to any one of the preceding claims, wherein in reaction (II) further anilines are present, optionally wherein 1, 2 or 3 further anilines are present, further optionally wherein the further anilines are compounds of formula (XI), which are different

5 from compound of formula (IVa) and from compound of formula (IVb);

wherein R2, R3 and R6 are identical or different and independently from each other selected from the group consisting of H, C_1-4 alkyl, Cl, Br, F and CF₃.

13. A compound of a) formula (m-V) or (p-I ) or a mixture thereof; wherein said compound of formula (m- I) or (p-I ) is as defined in any one of claims 1 to 3; or b) formula (m-II) or (p-II) or a mixture thereof; wherein said compound of formula (m -II) or (p-II) is as defined in any one of claims 1, 2(i) or 4.

14. A mixture of compound of formula (m-V) or (p-I ) or a mixture thereof with compound of formula (m-VIIa or p-VIIa) and compound of formula (m-VIIb or p-VIIb); wherein the compound of formula (m-1) or (p-I ) is defined in any one of claims 1 to 3 and the compound of formula (m- Vila or p-VIIa) and compound of formula (m- Vllb or p-VIIb) are as defined in claim 8.

15. Mixture according to claim 14, wherein the mixture comprises compound of formula (m- I) or (p-I) or a mixture thereof in an amount of at least 20 wt%, at least 30 wt% or at least 40 wt%, preferably at least 40 wt%.

16. Use of compound of formula (m-V) or (p-I) or a mixture thereof for the preparation of resins.

17. Resin comprising

(i) a reactant of a cyanate compound (A) and a polybutadiene (B) and/or

(ii) a reactant of a polymerized product of the cyanate compound (A) and the polybutadiene (B); and a maleimide compound of formula m-V) or (p-I) or a mixture thereof, as defined in any one of claims 1, 2(i) or 3, wherein the polybutadiene (B) comprises a 1,2-adduct and a 1,4-adduct at a mass ratio of 1 :3 to 3 : 1.

18. Use of a compound of formula (m-II) or (p-II) or a mixture thereof for the preparation of a resin, wherein the resin preferably is a polyamine epoxy resin, a polyurea resin or a polyurethane resin.

19. Use of a compound of formula (m-II) or ( -II) or a mixture thereof as hardener for an epoxy resin. 0. Use of a compound of formula (m-II) or (p-II) or a mixture thereof as hardener and/or chain extender for a polyurethane or a polyurea resin.