Dynamic Covalent Chemistry of Spiropyrans for Synthesis of Photoswitchable Photoinitiators and Uses Thereof, and Process for Locally Polymerizing a Starting Material by Dual Color Photopolymerization

A spiropyran represented by the following formula 1:

• wherein X is selected from S, C, or N;
• if X is S, then R6, R7 may not be present accordingly;
• if X is N, then R7 may not be present accordingly,
• wherein Y is selected from O, S, or N;
• where Y is N, the substituent contains the atoms necessary to complete a cyclic structure with R13 selected from the group consisting of benzimidazole, indoline, indole, dihydroquinoline, and tetrahydroquinoline;
• wherein Z is selected from N or CR9;
• wherein R1 to R13 are independently selected from the group consisting of H;
• D;
• halogen;
• NO2;
• CN;
• OH;
• SH;
• substituted or unsubstituted C1-C20-alkyl;
• substituted or unsubstituted C3-C20-cycloalkyl;
• substituted or unsubstituted C6-C48-aryl;
• substituted or unsubstituted C2-C42-heteroaryl;
• substituted or unsubstituted C2-C49-alkyl acyl;
• substituted or unsubstituted C2-C49-aryl acyl;
• substituted or unsubstituted C1-C20-alkoxy;
• substituted or unsubstituted C6-C48-aryloxy;
• NH2;
• substituted or unsubstituted C1-C20-alkyl ester;
• substituted or unsubstituted C6-C48-aryl ester;
• substituted or unsubstituted C1-C20 alkyl amide;
• substituted or unsubstituted C6-C48-aryl amide;
• NR′2;
• SiR′3;
• —O—SiR′3, wherein R′ is independently selected from the group consisting of substituted or unsubstituted C1-C20-alkyl and substituted or unsubstituted C6-C48-aryl, two R′ may form a ring structure;
• substituted or unsubstituted carboxylic acids and salts thereof;
• substituted or unsubstituted sulfonic acids and salts thereof;
• substituted or unsubstituted sulfonic esters;
• substituted or unsubstituted sulfonic amides;
• formyl;
• ether;
• thioether;
• carbonate;
• carbonate ester;
• sulfates;
• boronic acids;
• boronic esters;
• phosphonic acids;
• phosphonic esters;
• phosphines;
• phosphates;
• peroxycarbonic acids;
• thiocarbonic acids;
• sulfinic acids;
• sulfinic esters;
• sulfonates;
• thiolesters, sulfoxides;
• sulfones;
• alkylsulfones;
• hydrazides;
• thioaldehydes;
• ketones;
• thioketones;
• oximes;
• hydrazines;
• nitroso;
• azo;
• diazo;
• diazonium;
• isocyanides;
• cyanate;
• isocyanate;
• thiocyanate;
• isothiocyanate;
• hydroperoxide;
• peroxide;
• acetals;
• ketal;
• orthoester;
• orthocarbonate esters;
• ammonium;
• imines;
• imides;
• sulfonium salts;
• iodonium salts;
• diazo;
• azide;
• nitrate;
• isonitrile;
• nitrosoxy;
• substituted or unsubstituted thiocarbamates;
• substituted or unsubstituted carbamates;
• substituted or unsubstituted ethers;
• substituted or unsubstituted polyether carbamates;
• substituted or unsubstituted arylazo;
• substituted or unsubstituted C2-C20-alkynyl and substituted or unsubstituted C2-C20-alkenyl;
• wherein two adjacent groups of may be linked to each other to form a fused ring structure;
• wherein the one or more substituents, if present in one or more of R1 to R13, are independently selected from the group consisting of D;
• halogen;
• NO2;
• CN, C2-C49-alkyl acyl;
• substituted or unsubstituted C1-C20-alkoxy;
• substituted or unsubstituted C6-C48-aryloxy;
• substituted or unsubstituted C2-C49-aryl acyl;
• (meth)acrylate;
• tosyl;
• sulfonic acid or salts thereof;
• carboxylic acid or salts thereof;
• boronic acid or salts thereof;
• phosphonic acid or salts thereof;
• NR′3, wherein R′ is independently selected from the group consisting of H, D, substituted or unsubstituted C1-C20-alkyl and substituted or unsubstituted C6-C48-aryl, two R′ may form a ring structure;
• NH2;
• and OH;
• wherein if present two adjacent groups of R10 to R13, and R2 to R5 may be independently linked to each other to form a fused ring structure;
• and
• wherein at least one substituent for R2 to R5 and R10 to R13 is selected from the group consisting of carbonyl;
• chlorine;
• bromine;
• iodine;
• formyl;
• carbonate;
• carbonate ester;
• ester;
• amide;
• CF3;
• substituted or unsubstituted C2-C49-alkyl acyl;
• substituted or unsubstituted C2-C49-aryl acyl;
• ketone;
• acyl;
• acetyl;
• benzoyl;
• oxime;
• aldehyde, NO2;
• CN;
• (meth)acrylate;
• sulfones;
• alkylsulfones;
• sulfonamides;
• SO2Me;
• SO2NH2;
• methoxy;
• and tosyl;
• or is selected from one of the following formulae:
• wherein R14 to R27 are independently selected from the group consisting of H;
• D;
• halogen;
• NO2;
• CN;
• OH;
• SH;
• CF3;
• benzoyl;
• substituted or unsubstituted C1-C20-alkyl;
• substituted or unsubstituted C3-C20-cycloalkyl;
• substituted or unsubstituted C6-C48-aryl;
• substituted or unsubstituted C2-C42-heteroaryl;
• substituted or unsubstituted C2-C49-alkyl acyl;
• substituted or unsubstituted C2-C49-aryl acyl;
• substituted or unsubstituted C1-C20-alkoxy;
• substituted or unsubstituted C6-C48-aryloxy, and NH2;
• substituted or unsubstituted C1-C20-alkyl ester;
• substituted or unsubstituted C6-C48-aryl ester;
• substituted or unsubstituted C1-C20 alkyl amide;
• substituted or unsubstituted C6-C48-aryl amide;
• NR′2, SiR′3, —O—SiR′3 wherein R′ is independently selected from the group consisting of substituted or unsubstituted C1-C20-alkyl and substituted or unsubstituted C6-C48-aryl, two R′ may form a ring structure;
• substituted or unsubstituted carboxylic acids and salts thereof;
• substituted or unsubstituted sulfonic acids and salts thereof;
• substituted or unsubstituted sulfonic esters;
• substituted or unsubstituted sulfonic amides;
• formyl;
• ether, thioether;
• carbonate;
• carbonate ester;
• sulfates;
• boronic acids;
• boronic esters;
• phosphonic acids;
• phosphonic esters;
• phosphines;
• phosphates;
• peroxycarbonic acids;
• thiocarbonic acids;
• sulfinic acids;
• sulfinic esters;
• sulfonates;
• thiolesters, sulfoxides;
• sulfones;
• alkylsulfones;
• hydrazides;
• thioaldehydes;
• ketones;
• thioketones;
• oximes;
• hydrazines;
• nitroso;
• azo;
• diazo;
• diazonium;
• isocyanides;
• cyanate;
• isocyanate;
• thiocyanate;
• isothiocyanate;
• hydroperoxide;
• peroxide;
• acetals;
• ketal;
• orthoester;
• orthocarbonate esters;
• ammonium;
• imines;
• imides;
• azide;
• nitrate;
• isonitrile;
• nitrosoxy;
• substituted or unsubstituted carbamates;
• substituted or unsubstituted ethers;
• substituted or unsubstituted polyether carbamates;
• substituted or unsubstituted arylazo;
• substituted or unsubstituted C2-C20-alkynyl and substituted or unsubstituted C2-C20-alkenyl;
• wherein the one or more substituents, if present in one or more of R14-R27, are independently selected from the group consisting of D;
• halogen;
• NO2;
• CN, C2-C49-alkyl acyl;
• substituted or unsubstituted C1-C20-alkoxy;
• substituted or unsubstituted C6-C48-aryloxy;
• substituted or unsubstituted C2-C49-aryl acyl;
• (meth)acrylate;
• tosyl;
• sulfonic acid or salts thereof, carboxylic acid or salts thereof, boronic acid or salts thereof, phosphonic acid or salts thereof, NR′3+, wherein R′ is independently selected from the group consisting of H, D, substituted or unsubstituted C1-C20-alkyl and substituted or unsubstituted C6-C48-aryl, two R′ may form a ring structure;
• NH2;
• and OH;
• and R15 and R16 may be linked to each other to form a unsubstituted or substituted ring structure,
• and
• wherein at least one other substituent for R2 to R5 and R10 to R13 is selected from the group consisting of chlorine;
• bromine;
• iodine;
• formyl;
• carbonate;
• carbonate ester;
• ester;
• amide;
• CF3;
• substituted or unsubstituted C2-C49-alkyl acyl;
• substituted or unsubstituted C2-C49-aryl acyl;
• ketone;
• acyl;
• oxime;
• aldehyde, NO2;
• CN;
• (meth)acrylate;
• sulfones;
• alkylsulfones;
• sulfonamides;
• SO2Me;
• SO2NH2;
• methoxy;
• and tosyl;
• and/or
• wherein at least one other substituent for R2 to R5 and R10 to R13 is selected from sulfonic acid or salts thereof;
• carboxylic acid or salts thereof;
• boronic acid or salts thereof;
• phosphonic acid or salts thereof;
• NR′3+, wherein R′ is independently selected from the group consisting of H, D, substituted or unsubstituted C1-C20-alkyl and substituted or unsubstituted C6-C48-aryl, two R′ may form a ring structure;
• substituted or unsubstituted sulfonic esters;
• substituted or unsubstituted sulfonic amides;
• phosphonic esters;
• phosphines;
• phosphates;
• sulfinic acids;
• sulfinic esters;
• sulfonates;
• sulfoxides;
• sulfones;
• alkylsulfones;
• oximes;
• isocyanides;
• cyanate;
• isocyanate;
• thiocyanate;
• isothiocyanate;
• ammonium;
• substituted or unsubstituted carbamates;
• (meth)acrylate;
• tosyl;
• NH2;
• and OH
• and/or
• the substituent on any of R14 to R27 may contain the atoms necessary to complete a cyclic structure with one of R5-R8 or R10-R13;
• and/or
• wherein
• R13 is
• and/or
• two or more of R2 to R5 and R10 to R13 are electron withdrawing groups,
• and/or
• R1 is selected from the group consisting of H, D, substituted or unsubstituted C1-C6-alkyl, —CH2—CH2—OH, —CH2—COOH, —CH2—CH2—COOH, —CH2—CH2—CH2—NMe3+, —CH2—CH2—CH2—SO3−, phenyl and benzyl.

A process for locally polymerizing a starting material by dual color photopolymerization and forming a shaped body, comprising:

• providing a container which is at least partially filled with a polymerizable starting material containing photoinitiator molecules, which can be converted by sequential optical excitation into a reactive state in which the photoinitiator molecules locally trigger polymerization of the starting material;
• and
• photopolymerizing the starting material in a container by irradiating light of a first wavelength and light of a second wavelength, different from the first wavelength, into the container, whereby in the local volume
• the photoinitiator molecules are converted, due to the absorption of the light of the first wavelength, from an initial state in which the photoinitiator molecules substantially do not absorb the light of the second wavelength, into an intermediate state with changed optical properties compared to the initial state, such that the photoinitiator molecules in the intermediate state absorb the light of the second wavelength;
• and
• the photoinitiator molecules are transferred from the intermediate state to the reactive state due to the absorption of the light of the second wavelength, which triggers the polymerization locally to form the shaped body;
• wherein
• the initial state of the photoinitiator in the photopolymerizable material has an extinction coefficient at the first wavelength in the range of 2500 to 10 L mol−1 cm−1.

A process for locally polymerizing a starting material by dual color photopolymerization, comprising:

• providing a polymerizable starting material containing photoinitiator molecules which can be converted by sequential optical excitation into a reactive state in which the photoinitiator molecules locally trigger polymerization of the starting material;
• and
• photopolymerizing the starting material in a local volume by irradiating light of a first wavelength and light of a second wavelength, different from the first wavelength, into the local volume, whereby in the local volume
• the photoinitiator molecules are converted, due to the absorption of the light of the first wavelength, from an initial state, into an intermediate state with changed optical properties compared to the initial state, such that the photoinitiator molecules in the intermediate state absorb the light of the second wavelength;
• and
• the photoinitiator molecules are transferred from the intermediate state to the reactive state due to the absorption of the light of the second wavelength, which triggers the polymerization locally;
• wherein the photoinitiator molecule comprises the following structural motif (BI)
• wherein
• X is selected from the group consisting of S, CRS2, and NRS;
• Y is selected from the group consisting of O, S, and NRS;
• Z is selected from the group consisting of N and CRS′;
• and
• RS are independently selected.

A process for locally polymerizing a starting material by dual color photopolymerization, comprising:

• providing a polymerizable starting material containing photoinitiator molecules which can be converted by sequential optical excitation into a reactive state in which the photoinitiator molecules locally trigger polymerization of the starting material;
• and
• photopolymerizing the starting material in a local volume by irradiating light of a first wavelength and light of a second wavelength, different from the first wavelength, into the local volume, whereby in the local volume
• the photoinitiator molecules are converted, due to the absorption of the light of the first wavelength, from an initial state, into an intermediate state with changed optical properties compared to the initial state, such that the photoinitiator molecules in the intermediate state absorb the light of the second wavelength;
• and
• the photoinitiator molecules are transferred from the intermediate state to the reactive state due to the absorption of the light of the second wavelength, which triggers the polymerization locally;
• wherein the polymerizable starting material has a Difference Ratio DR of 0.2 or less
• DR
• =
• Abs
• dif
• ,
• UV
• ,
• irr
• Abs
• dif
• ,
• vis
• ,
• irr
• wherein
• Absdif,vis,irr is the absorption of the polymerizable starting material at the absorption maximum of the difference spectrum at the second wavelength measured as set forth in the description;
• and
• Absdif,UV,irr is the absorption of the polymerizable starting material at the absorption maximum of the difference spectrum at the first wavelength measured as set forth in the description.