PHOTOPOLYMERIZATION METHOD

PRIORITY

This patent application claims priority to European Patent Application n° EP 14158217.1 filed on 6 March 2014, the entire contents of which are hereby incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to a new method of light induced photopolymerization under mild irradiation conditions, copper initiator complexes to be used in such method and a polymers obtained by such method.

In the present document, the numbers between brackets ([ ]) refer to the List of References provided at the end of the document. BACKGROUND OF THE INVENTION

In recent years, photopolymerization, including cationic photopolymerization, has been the object of intense research because of the continued growth of academic and industrial applications for new monomers and / or photoinitiator systems. The use of photoinitiators increases steadily not only for traditional applications such as coatings, inks and adhesives but also more recently in high-tech applications such as optoelectronics, stereolithography and nanotechnology.

Photopolymerization offers many advantages compared to conventional thermal polymerization, such as the spatial control of the initiation, and the fact that polymerization can be carried out without solvent and therefore to reduced cost. Another important advantage is that it can be performed at room temperature, unlike thermal polymerization which often requires a high temperature, thereby allowing gains in terms of economic and energy cost savings. Finally, cationic polymerization is generally not oxygen-sensitive, which is a major advantage because it does not require the use of an inert atmosphere. Thus, cationic photopolymerization combines ail the aforementioned advantages.

Thus far, most of the formulations used in photopolymerization have been usable only with high intensity UV lamps. This results in safety problems for the operator due to the wavelength used, in addition to a non-optimal energetic efficiency, thereby reducing the scope of this approach. To overcome these problems, the use of mild irradiation conditions is therefore a major challenge and the development of new highly absorbent in the visible and allowing the use of light emitting in the visible and low consumption initiators are actively sought both at industrial level and academic.

Therefore, there remains a need for the development of new initiator systems that trigger photopolymerization under mild conditions, for example using visible light.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1. (a) UV-vis absorption spectra of El, Gl and G2 in dichloromethane and (b) UV-vis absorption spectra of Gl in dichloromethane (DCM) and acetonitrile (ACN). Figure 2. UV-vis spectra of Gl in (a) DCM and (b) ACN after different irradiation (laser diode at 405 nm) time.

Figure 3. Cyclic voltammogram of El in acetonitrile.

Figure 4. ESR spectra of the radical generated in Gl/Iodl upon the halogen lamp exposure and trapped by PBN in toluene: (a) experimental and (b) simulated spectra. Figure 5. Steady state photolysis of (a) El/Iod2, (b) Gl/Iod2, and (c) G2/Iod2 ([Iod2] = 2.2 mM) in DCM upon the laser diode at 405 nm exposure; UV-vis spectra recorded at different irradiation time.

Figure 6. Decay trace of El monitored at 480 nm immediately after the laser excitation at 355 nm.

Figure 7. Decay curves of Gl with the addition of different amount of lodl monitored at 600 nm immediately after the laser excitation at 355 nm in nitrogen-saturated dichloromethane.

Figure 8. Photopolymerization profiles of TMPTA in the presence of (a) El/Iod2 (0.2%/2%, w/w) upon the laser diode at 405 nm or 457 nm exposure in laminate; (b) Gl/Iod2 (0.2%/2% w/w) upon the laser diode at 405 nm (curve 1) or 457 nm (curve 2), or halogen lamp (curve 3) exposure in laminate; Gl/Iod2/NVK (0.2%/2%/3%, w/w/w) upon the halogen lamp exposure in laminate (curve 4) or under air (curve 5); (c) G2/Iod2 (0.2%/2% w/w) upon the laser diode at 405 nm (curve 1) or 457 nm (curve 2), or halogen lamp (curve 3) exposure in laminate.

Figure 9. (a) Photopolymerization profile and (b) IR spectra recorded before and after the photopolymerization of EPOX in the presence of Gl/Iodl/NVK (0.2%/2%/3%, w/w/w) upon the halogen lamp exposure under air. Figure 10. Photopolymerization profiles of EPOX/TMPTA blend (50%/50%, w/w) in the presence of Gl/Iod2/NVK (0.1 %/3 %/5 %, w/w/w) (a) under air or (b) in laminate upon the halogen lamp exposure.

Figure 11. The emission spectrum of the halogen lamp.

Figure 12. UV-vis spectra of (a) El and (b) G2 in DCM after different irradiation (laser diode at 405 nm) time.

Figure 13. UV-vis spectra of Gl/Iodl in DCM before and after LFP experiments.

Figure 14. Interpenetrated polymer network obtained from the photopolymerization of TMPTA/EPOX blend (50%/50%) using the initiating system described in Example 11. No phase separation is observed by optical analysis.

DEFINITIONS

To facilitate an understanding of the present invention, a number of terms and phrases are defined below:

In general, the term "substituted" whether preceded by the term "optionally" or not, and substituents contained in formulae of this invention, refer to the replacement of hydrogen radicals in a given structure with the radical of a specified substituent. When more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. As used herein, the term "substituted" is contemplated to include all permissible substituents of organic compounds.

As used herein, the term "aliphatic", refers to alkyl, alkenyl and alkynyl moieties, as defined below.

As used herein, the term "alkyl", refers to straight and branched alkyl groups. An analogous convention applies to other generic terms such as "alkenyl", "alkynyl" and the like. In certain embodiments, as used herein, "lower alkyl" is used to indicate those alkyl groups (substituted, unsubstituted, branched or unbranched) having about 1-6 carbon atoms. Illustrative alkyl groups include, but are not limited to, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, tert-pentyl, n-hexyl, sec-hexyl, moieties and the like, which again, may bear one or more substituents. Alkenyl groups include, but are not limited to, for example, ethenyl, propenyl, butenyl, l-methyl-2-buten-l-yl, and the like. Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl and the like. In general, the term "aromatic moiety" or "aryl", as used herein, refers to stable substituted or unsubstituted unsaturated mono- or polycyclic hydrocarbon moieties having preferably 3-14 carbon atoms, comprising at least one ring satisfying the Hiickel rule for aromaticity. Examples of aromatic moieties include, but are not limited to, phenyl, indanyl, indenyl, naphthyl, phenanthryl and anthracyl.

As used herein, the term "alkylaryl" refers to an aryl moiety bearing at least one alkyl substituent, the alkylaryl moiety being bound to the rest of the molecule via any of the aryl ring atoms not already bearing a substituent. As an example, the term "C6-C14 alkylaryl" refers to an alkyl aryl moiety, as defined above, which contains a total of 6 to 14 carbon atoms between the alkyl and aryl groups. For example, a methylphenyl moiety is a C7alkylaryl. For example, "C6-C14 alkylaryl" encompasses C0-C4alkylC6-C10aryl moieties.

Similarly, the term "aralkyl" refers to an alkyl moiety bearing at least one aryl substituent, the aralkyl moiety being bound to the rest of the molecule via any of the alkyl chain atoms not already bearing a substituent. As an example, the term "C6-C14 aralkyl" refers to an aralkyl moiety, as defined above, which contains a total of 6 to 14 carbon atoms between the alkyl and aryl groups. For example, a phenylethyl moiety, which contains a total of 8 carbon atoms, is a C8aralkyl. For example, "C6-C14 aralkyl" encompasses C6- C10arylC0-C4alkyl moieties.

In general, the term "heteroaromatic moiety", "heteroaryl" or "heteroaryl", as used herein, refers to stable substituted or unsubstituted aromatic moieties, as defined above, having from about five to about ten ring atoms of which one ring atom is selected from S, O and N; zero, one or two ring atoms are additional heteroatoms independently selected from S, O and N; and the remaining ring atoms are carbon, the radical being joined to the rest of the molecule via any of the ring atoms, such as, for example, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl , quinolinyl, isoquinolinyl, and the like.

As used herein, the term "silyl" refers to a -Si(R)3 or -Si(R ₂ )- moiety wherein each occurrence of R is independently a Cl -C6alkyl or C6-C10aryl moiety.

As used herein, the expression "C _x -C _y , preferably C _x i-C _y i, alkylaryl, aralkyl or aryl", where x, y, xl and yl represent integers denoting the number of carbon atoms in the chemical moiety to which it refers (e.g., "alkylaryl", "aralkyl", "aryl")), means "C _x - C _y alkylaryl, C _x -C _y aralkyl or C _x -C _y aryl, preferably C _x i-C _y ialkylaryl, C _x i-C _y i aralkyl or C _x r C _y iaryl". Likewise, the expression "C _x -C _y alkylaryl, aralkyl or aryl", means "C _x - C _y alkylaryl, C _x -C _y aralkyl or C _x -C _y aryl".

DETAILED DESCRIPTION OF CERTAIN PREFERRED EMBODIMENTS OF THE INVENTION

As noted above, there has been increasing interest in recent years in the development of complex initiators that catalyze polymerization reactions under mild irradiation conditions, for example under visible light irradiation. Iridium and ruthenium complexes have been reported, that achieve this. However, these structures are expensive and difficult to synthesize and are therefore have a very limited scope of application; specifically, they are not suitable for industrial applications. Other attempts have been made with Ni, Zn, Fe, Cr, and Co complexes. But these attempts have failed. The inventors found that the field is completely unpredictable, because it is difficult to determine the correct combination of metal atom and ligands that will yield a photoinitiator complex with suitable properties for inducing photopolymerization under mild light irradiation, for example under visible light. Specifically, to be useful for such purpose, the resulting complex should have a balance of suitable properties, including:

Capacity to absorb light, preferably under mild irradiation conditions Life-time of the excited state that is compatible with initiating free radical polymerization

- Suitable redox properties

Reversibility of redox reaction

Advantageously, the resulting complex may exhibit the following properties:

A capacity to absorb light in mild irradiation conditions such as in the 200- 900 nm range; for example in the visible range 390-700 nm;

- A life-time > 10 ps;

Redox properties in the -2 to 2 V range;

Reversibility of redox reaction better than 50%.

The inventors have discovered that copper with a proper selection of ligands, can form complexes that have the required aforementioned properties suitable to serve as photoinitiator of free radical photopolymerization; in addition to free radical promoted cationic photopolymerization when used in conjunction with a proper vinyl cation initiator. In this context, there is provided herein a novel photopolymerization method for free radical and/or cationic polymerization under mild light irradiation, for example under visible light irradiation, further employing a novel catalyst species. According to the present invention, in one aspect, there is provided a method for effecting free radical and/or cationic photopolymerisation under mild light irradiation conditions, for example under visible light irradiation, comprising the step of polymerizing at least one polymerisable component selected from the group consisting of:

(i) an ethylenically unsaturated monomer, the polymerization of which may be effected by free radical polymerization; and/or

(ii) an ethylenically unsaturated monomer or an epoxy-containing monomer; the polymerization of which may be effected by cationic polymerization; in the presence of:

A) mild light irradiation; preferably in the λ=200-900 nm range, for example in the visible range λ=390-700 nm;

B) an initiator complex of formula I or II

wherein

Qi represents a conjugated polyaromatic system containing two nitrogen atoms whose lone pair of electrons forms a bond with the copper atom;

(¾ and Q3 independently represent a conjugated polyaromatic system containing one nitrogen atom whose lone pair of electrons forms a bond with the copper atom;

W represents a phosphorus or nitrogen atom;

Ri, R ₂ , R ₃ , R4, R5 and R6 each independently represents an aliphatic or aromatic moiety, preferably C .20 alkyl or Ce-io aryl moiety; wherein the alkyl and/or the aryl moieties may be, individually, further substituted with one or more linear or branched Ci_ ₆ alkyl or Ce-io aryl moieties; and wherein R ₃ and R4, together with the P, Cu and W atoms, may form a 6- to 8-membered ring; X represents a suitable counterion; preferably BF ₄ ^~ , PF _6, SbF ₆ ^" or CI ^" ;

C) an iodonium salt of formula (R ^A ) ₂ I ⁺ ; wherein each occurrence of R ^A independently represents a Ce-io aryl moiety; wherein the aryl moiety may be, individually, further substituted with one or more aliphatic or aromatic moiety, preferably one or more linear or branched or Ce-io aryl moieties; and provided that, when at least one polymerisable component is an ethylenically unsaturated monomer or an epoxy-containing monomer; whose polymerization is effected by cationic polymerization, the photopolymerisation method is additionally carried out in presence of :

D) a vinyl cation initiator having the structure III or IV:

(Ill) (IV) wherein R ₇ represents a linear or branched or Ci.ioheteroalkenyl moiety or a C6_ioaryl moiety; and

Rg and R ₉ independently represent a linear or branched moiety or a C _& . _l oaryl moiety; where Rg and R ₉ together may form a cyclic heteroaryl moiety.

As the reader will understand, depending on the type of monomer(s) used (i.e., whether the monomer polymerizes according to a free radical mechanism, or a cationic mechanism), and depending on the use or not of a vinyl cation initiator D) in combination with the copper photoinitiator B) and iodonium salt C), the photopolymerization method according to the invention may achieve :

free radical photopolymerization

cationic photopolymerization; or

both free radical and cationic polymerization.

In other words, the vinyl cation initiator D) is optional, and may be used if cationic photopolymerization is desired. As such, the photopolymerization method according to the invention may comprise A), B) and C), as defined above, and in variants below. In addition, the photopolymerization method according to the invention may comprise A), B), C) and D), as defined above, and in variants below. Advantageously, when D) is used, the photopolymerization method further comprises, in combination with the vinyl cation initiator having the structure III or IV, a silane moiety of formula (R ^B ) ₃ SiH; wherein each occurrence of R ^B independently represents -S1R ₃ wherein each occurrence of R independently represents a linear or branched moiety.

a) Polymerizable component

Advantageously, the polymerizable component may be an ethylemcally unsaturated monomer, the polymerization of which may be effected by free radical polymerization. As used herein, the term "ethylemcally unsaturated monomer" refers to a monomer that contains at least one carbon-carbon double bond. Preferably, ethylemcally unsaturated monomers whose polymerization may be effected by free radical polymerization, contains at least one carbon-carbon double bond that is conjugated with an aryl moiety (e.g., phenyl), a carboxyl (C=0) group, or another double bond. Such monomers in this category include for example acrylates -[(ROCO)CHCH ₂ ]- (acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, etc .), methacrylates -[(ROCO)C(Me)CH ₂ ]- (methacrylic acid, methyl methacrylic acid, etc .), styrene, ethylene, propylene, N-vinyl acrylamide, N-vinylpyrolidone. For example, the polymerizable component may be trimethylolpropane tri

Advantageously, the polymerizable component may be an ethylemcally unsaturated monomer or an epoxy-containing monomer whose polymerization may be effected by cationic polymerization. Examples of these monomers include vinyl ethers -[ROCHCH ₂ ]- such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; and epoxy monomers. As used herein, the term "epoxy monomer" refers to a moiety comprising an oxirane

moiety having the structure: point of attachment of the oxirane moiety to the rest of the monomer. For example, the polymerizable component may be the epoxide monomer (EPOX) having the following structure:

Advantageously, the polymerizable component may be a mixture of two or more components which are polymerizable via different polymerization mechanisms: free radical polymerization or cationic polymerization, respectively. For example, the polymerizable component may be a mixture of TMPTA and EPOX. Other examples include mixtures vinylether/acrylate and vinylether/epoxy.

One important advantage of the copper photoinitiator complexes described herein is twofold: (i) they generate free radicals under very mild irradiation conditions (e.g., λ=200- 900nm, for example under the visible light range λ=390-700 nm), and (ii) they undergo a photoredox catalytic cycle that initiates free radical promoted cationic photopolymerization, when combined with a suitable cationic vinyl initiator. Accordingly, the use of the copper photoinitiator complexes of the invention under mild light irradiation conditions allow concomitant free radical and cationic polymerizations when a mixture of monomers with these distinct polymerization mechanisms is used. This allows the preparation of interpenetrated networks of polymers that have different polymerization mechanisms (free radical and cationic), with a single photoinitiator. This is a striking advantage, as compared to existing methods, which require the use of two different polymerization initiators: a photoinitiator for the free radical polymerization, and a cationic initiator for the cationic polymerization. Necessarily, the use of two different initiators, means different initiating times, and thus polymerizations that may go at different speed and/or with different efficiencies, thereby leading to interpenetrated polymer networks far less homogeneous than those obtainable by the photopolymerization method of the invention. b) Mild light irradiation

As used herein, the term "mild light irradiation" refers to the visible and middle-to-near UV spectrum, ranging from 200-900 nm in wavelengths.

Advantageously, the mild light irradiation may be provided by a source of visible light. Advantageously, any source of visible light may be used to carry out the photopolymerization method according to the invention. By visible light is meant the visible spectrum in the wavelengths from about 390 to 700 nm. For example, light emitted from LED bulbs, laser diode, green fluorescence bulbs, halogen lamps, household lamps including energy-saving lamps, or natural light may be used.

Advantageously, the mild light irradiation may be provided by a source of middle-to-near UV light. Advantageously, any source of middle-to-near UV light may be used to carry out the photopolymerization method according to the invention. By middle-to-near UV light is meant the light spectrum in the wavelengths from about 200 to 390 nm. For example, light emitted from BLB type lamps, Mercury- vapor lamps, Sodium vapor lamps or Xenon arc lamps may be used.

An important advantage of the invention is that photopolymerization can be effected under very mild irradiation conditions. For example, a simple household halogen lamp may be used. c) Initiator complex

Advantageously, in the initiator complex of formula I :

Qi may have the formula:

wherein

R ^Q1 and R ^Q2 independently represent H or a linear or branched moiety; R ^Q3 and R^ ⁴ independently represent H or -NR ^C R ^D wherein R ^c and R ^D independently represent a linear or branched moiety or a C6_ioaryl moiety; where R ^c and R ^D together may form a 5- or 6- membered heterocyclic moiety wherein the heterocyclic moiety may be further substituted with -CN, a linear or branched moiety, a C _& . _l oaryl or Ce-nheteroaryl moiety;

R ^Q5 and R ^Q6 independently represent H or a linear or branched Ci_ioalkyl moiety; wherein the alkyl moieties may be independently further substituted with -NR ^E R ^F wherein R ^E and R ^F independently represent a linear or branched moiety or a C6-ioaryl moiety, or wherein R ^E and R ^F together with the nitrogen atom to which they are attached form a mono- or polycyclic C _& . ^heterocyclic moiety;

R ^Q7 and R ^QB independently represent H, a linear or branched moiety or a C _& . i ₀ aryl moiety.

Advantageously, in the initiator complex of formula I, Ql is a fused polycyclic heteroaryl moiety having the formula:

wherein

R ^Q1 and R ^Q2 independently represent H or a linear or branched moiety; and

R ^Q3 and R^ ⁴ independently represent H or -NR ^C R ^D wherein R ^c and R ^D independently represent a linear or branched moiety or a C6-ioaryl moiety; where R ^c and R ^D together may form a 5- or 6- membered heterocyclic moiety wherein the heterocyclic moiety may be further substituted with -CN, a linear or branched moiety, a . _l oaryl or Ce-nheteroaryl moiety.

Advantageously, in the initiator complex of formula II :

(¾ and Q3 independently may have the formula:

wherein R ^Q9 represents H or -Ν¾¾ ^Η wherein R ^G and R ^H independently represent a linear or branched moiety or a C6_ioaryl moiety.

(I ^A ) (II ^A ) wherein Qi, Q ₂ and Q3 are as defined above; and R ¹ and R ¹¹ independently represent H or a linear or branched moiety.

Advantageously, the initiator complex may have formula I or II :

(I ^B ) (II ^B ) wherein Qi, Q ₂ and Q3 are as defined above; and R ¹ and R ¹¹ independently represent H or a linear or branched moiety.

Advantageously, the initiator complex may have formula I ^c :

(I ^c )

wherein

R ^Q1 and R ^Q2 independently represent H or a linear or branched moiety;

R ^Q3 and R ^Q4 independently represent H or -NR ^C R ^D wherein R ^c and R ^D independently represent a linear or branched moiety or a C6-ioaryl moiety; where R ^c and R ^D together may form a 5- or 6- membered heterocyclic moiety wherein the heterocyclic moiety may be further substituted with linear or branc moiety or a C6_ioaryl or C6-i ₂ heteroaryl moiety; and

R ¹ and R ¹¹ independently represent H or a linear or branched iety. Advantage

(i ^D )

wherein

R ^Q1 and R ^Q2 independently represent H or a linear or branched moiety;

R ^Q3 and R ^Q4 independently represent H or -NR ^C R ^D wherein R ^c and R ^D independently represent a linear or branched moiety or a C6-ioaryl moiety; where R ^c and R ^D together may form a 5- or 6- membered heterocyclic moiety wherein the heterocyclic moiety may be further substituted with linear or branc moiety or a C6_ioaryl or C6-i ₂ heteroaryl moiety; and

R ¹ and R ¹¹ independently represent H or a linear or branched iety.

Advantageously, the initiator complex may have one of the following structures:





In complexes lb and 2b above, « X=H,H » means that the corresponding positions quinolinyl groups are unsubstituted.

Preferably, the initiator complex may have one of the following structures:

Advantageously, in the initiator complex of formula I or II, the counterion X ^" may represent BF ₄ ^" , PF _6, SbF ₆ ^" or CI ^" . d) iodonium salt Advantageously, in the iodonium salt of formula (R ^A ) ₂ I ⁺ , each occurrence of R ^A independently represents a phenyl moiety; wherein the phenyl moiety may be, individually, further substituted with one or more linear or branched moieties. For example, the phenyl moiety may bear methyl, ethyl, n-propyl, i-propyl, t-butyl groups, preferably in ortho position relative to the iodine atom.

Advantageously, the counterion of the iodonium salt of formula (R ^A ) ₂ I ⁺ may be any suitable negatively charged counterion. For example, it may be B(PhF ₆ ) f, PF ₆ ^" _; SbF ₆ ^" or cr.

Advantageously, the iodonium salt may have one of the following structures:

e) vinyl cation initiator Advantageously, the vinyl cation initiator may have formula III O _s wherein

R ₇ may represent -(CH ₂ -CH ₂ )-0-(CH ₂ -CH ₂ )-0-(CH ₂ -CH ₂ )-0-CH=CH ₂ (i.e., the vinyl cation initiator may be triethyleneglycol divinyl ether).

Advantageously, the vinyl cation initiator may have formula IV , wherein R ₈ and R9 together may form a cyclic heteroaryl moiety. For example, the vinyl cation initiator has the following structure:

Advantageously, the vinyl cation initiator of formula III or IV may be used in combination with a silane moiety of formula (R ^B ) ₃ SiH; wherein each occurrence of R ^B independently represents -S1R ₃ wherein each occurrence of R independently represents a linear or branched moiety. For example, the silane moiety may have the following structure:

f) Polymer

In another aspect, there is provided a polymer material obtainable by the photopolymerization method according to the present invention. The variants described above for the various components for the photopolymerization method are applicable mutadis mutandis to this section, and will be understood to apply to the definition of the polymer material(s) obtained by the method of the invention.

Advantageously, the polymer material may be obtained by photopolymerizing at least in part an ethylenically unsaturated monomer whose polymerization is effected by free radical polymerization, and an ethylenically unsaturated monomer or an epoxy- containing monomer whose polymerization is effected by cationic polymerization, according to the mild-light induced photopolymerization according to the invention; to form an interpenetrated network of polymers generated by concomitant free radical and cationic polymerizations.

g) Liquid compositions

In another aspect, there is provided liquid composition, curable by exposure to mild light irradiation; preferably in the λ=200-900 nm range, for example in the visible range λ=390-700 nm; containing:

(a) at least one polymerisable component selected from the group consisting of:

(b) an ethylenically unsaturated monomer, the polymerization of which may be effected by free radical polymerization; and/or

(ii) an ethylenically unsaturated monomer or an epoxy-containing monomer; the polymerization of which may be effected by cationic polymerization; (b) a photoinitiator complex of formula I

(I) (II) wherein

Qi represents a conjugated polyaromatic system containing two nitrogen atoms whose lone pair of electrons forms a bond with the copper atom;

Q2 and Q3 independently represent a conjugated polyaromatic system containing one nitrogen atom whose lone pair of electrons forms a bond with the copper atom;

W represents a phosphorus or nitrogen atom;

Ri, R2, R3, R4, R5 and R6 each independently represents a Ce-2o alkyl or Ce-io aryl moiety; wherein the alkyl and/or the aryl moieties may be, individually, further substituted with one or more linear or branched moieties; and wherein R ₃ and R4, together with the P, Cu and W atoms, may form a 6- to 8-membered ring;

X represents a suitable counterion; preferably BF ₄ ^" , PF ₆ , SbF ₆ ^" or CI ^" ;

(c) an iodonium salt of formula (R ^A ) ₂ I ⁺ ; wherein each occurrence of R ^A independently represents a C6_io aryl moiety; wherein the aryl moiety may be, individually, further substituted with one or more linear or branched moieties; and provided that,

(d) when at least one polymerisable component (a) is an ethylenically unsaturated monomer or an epoxy-containing monomer; the polymerization of which may be effected by cationic polymerization, the liquid composition further comprises a vinyl cation initiator having the structure III or IV:

(Ill) (IV) wherein R ₇ , R ₈ and R9 independently represent a linear or branched moiety or a C6_ioaryl moiety; where Rg and R9 together may form a cyclic heteroaryl moiety. The variants described above for the various components for the photopolymerization method are applicable mutadis mutandis to this section, and will be understood to apply to the definition of the liquid composition defined above.

Advantageously, the liquid composition may further comprise, in combination with the vinyl cation initiator having the structure III or IV, a silane moiety of formula (R ^B ) ₃ SiH; wherein each occurrence of R ^B independently represents -S1R ₃ wherein each occurrence of R independently represents a linear or branched moiety. h) Uses

In another aspect, there is provided the use of a copper complex of formula I or II as initiator for free radical photopolymerisation or cationic photopolymerisation under mild light irradiation conditions (preferably in the 200-900 nm range), for example under visible light irradiation (preferably in the 390-700 nm range). In another aspect, there is provided the use of a copper complex of formula I or II for the preparation of an interpenetrated network of at least two polymers whose polymerization is effected by free radical photopolymerization and cationic photopolymerization, respectively, under mild light irradiation conditions (preferably in the λ=200-900 nm range), for example under visible light irradiation (preferably in the λ=390-700 nm range).

Likewise, the variants described above for the various components for the photopolymerization method are applicable mutadis mutandis to this section, and will be understood to apply to the definition of the uses defined above. i) Synthetic methods

The practitioner has a well-established literature of ligand and heterocyclic chemistry to draw upon, in combination with the information contained herein, for guidance on synthetic strategies, protecting groups, and other materials and methods useful for the synthesis of the copper complexes of this invention. For example, the reader may refer to the Exemplification section below, and references cited therein for synthetic approaches suitable for the preparation of some of the ligands described herein. In addition, the reader may refer to ref 41-45 for synthetic approaches to specific copper complexes suitable for carrying out the present invention. The synthesis of the copper complexes according to the invention is straightforward : it involves reacting a suitable copper starting material, with the proper ligands in equimolar ratios.

For examples, copper initiator complexes of formula I may be prepared according to the general scheme below:

Similarly, copper initiator complexes of formula II may be prepared according to the general scheme below:

[Cu(CH ₃ CN) ₄ ]X

EQUIVALENTS

The representative examples that follow are intended to help illustrate the invention, and are not intended to, nor should they be construed to, limit the scope of the invention. Indeed, various modifications of the invention and many further embodiments thereof, in addition to those shown and described herein, will become apparent to those skilled in the art from the full contents of this document, including the examples which follow and the references to the scientific and patent literature cited herein. It should further be appreciated that the contents of those cited references are incorporated herein by reference to help illustrate the state of the art.

The following examples contain important additional information, exemplification and guidance that can be adapted to the practice of this invention in its various embodiments and the equivalents thereof. EXEMPLIFICATION

The complexes of this invention, their preparation and uses in mild-light induced photopolymerization reactions can be understood further by the examples that illustrate some of the processes by which these compounds are prepared or used. It will be appreciated, however, that these examples do not limit the invention. Variations of the invention, now known or further developed, are considered to fall within the scope of the present invention as described herein and as hereinafter claimed.

Summary:

Metal complexes e.g. ruthenium [1, 2] or iridium [3-8] complexes have been successfully used in photoinitiating systems (PISs) [9] for polymer synthesis as they possess excellent photochemical properties (e.g. intense visible light absorption, long lived excited states and suitable redox potentials) and can work through either an oxidation or a reduction cycle to produce reactive species e.g. radicals or cations. [10-15] Recently, copper complexes are attracting increasing attentions in the photopolymerization area due to their comparative cost advantage. Copper complexes with suitable ligands exhibit long excited- state lifetimes [16] when subjected to intense light radiation (outside of the visible range and middle-to-near UV range) which could endow them with potential for various applications such as organic light- emitting diode (OLED) [17-19] or light mediated photochemical reactions. [20-23] Interestingly, copper complexes have been reported for the light induced atom transfer radical polymerization (ATRP) in the presence [24, 25] or absence of common organic photoinitiators or dyes. [26, 27] But again, it involved intense light radiation, beyond the visible range and middle-to-near UV range. However, to the best of our knowledge, no attempt has been made to use copper complexes in the PISs for both cationic and radical photopolymerizations under mild light irradiations.

In what follows, three copper complexes have been incorporated into PISs (containing iodonium salt and optionally another additive) to photochemically generate reactive species (i.e. radicals and cations) which have been studied using cyclic voltammetry, electron spin resonance spin trapping, steady state photolysis, and laser flash photolysis techniques. The photoinitiation ability of the copper complexes based PISs for the radical or cationic photopolymerization has been investigated and compared to the reference camphorquinone (CQ) based PISs. The investigated copper complexes (El , Gl and G2) and other chemical compounds are shown in Schemes 1 and 2.

Scheme 1. Chemical structures of the studied copper complexes (El, Gl and G2).

Materials and methods

All reagents and solvents were purchased from Aldrich or Alfa Aesar and used as received without any further purification. Mass spectroscopy was performed by the Spectropole of Aix-Marseille University. ESI mass spectral analyses were recorded with a 3200 QTRAP (Applied Biosystems SCIEX) mass spectrometer. The HRMS mass spectral analysis was performed with a QStar Elite (Applied Biosystems SCIEX) mass spectrometer. Elemental analyses were recorded with a Thermo Finnigan EA 1 1 12 elemental analysis apparatus driven by the Eager 300 software. ^l H and ¹³ C NMR spectra were determined at room temperature in 5 mm o.d. tubes on a Broker Avance 400 spectrometer of the Spectropole: ^l H (400 MHz) and ¹³ C (100 MHz). The ^l H chemical shifts were referenced to the solvent peak DMSO-d6 (2.49 ppm) and the ¹³ C chemical shifts were referenced to the solvent peak DMSO-d6 (39.5 ppm). Complexes Gl and G2 were prepared by adapting a literature procedure. [33] [Methyl-4-phenyl(methyl-l -ethyl)-4-phenyl] iodonium tetrakis (penta fluorophenyl) borate (Iodl) [28, 29] was obtained from Bluestar Silicones-France. Diphenyliodonium hexafluorophosphate (Iod2), tris(trimethylsilyl)silane ((TMS^Si-H), N-vinylcarbazole (NVK) and solvents were purchased from Sigma-Aldrich or Alfa Aesar and used as received without further purification. Trimethylolpropane triacrylate (TMPTA) and (3,4- epoxycyclohexane)methyl 3,4-epoxycyclohexylcarboxylate (EPOX) were obtained from Cytec and used as benchmark monomers for radical and cationic photopolymerization.

Irradiation Sources

Different visible lights were used for the irradiation of photocurable samples: polychromatic light from the halogen lamp (Fiber-Lite, DC-950; incident light intensity: ~12 mW cm ^"2 in the 370-800 nm range), purple laser diode at 405 nm (~8 mW cm ^"2 ) or blue laser diode at 457 nm (~80 mW cm ^"2 ). LEDs at 405 or 455 nm were also used (Thorlabs ; ~80 mW cm ^"2 ). The emission spectrum of the halogen lamp is provided in Figure 1 1.

Redox Potentials

The oxidation potentials (E _ox vs SCE) of the studied copper complexes were measured in acetonitrile by cyclic voltammetry with tetrabutylammonium hexafluorophosphate (0.1 M) as a supporting electrolyte (Voltalab 6 Radiometer). The working electrode was a platinum disk and the reference electrode was a saturated calomel electrode (SCE). Ferrocene was used as a standard, and the potentials determined from the half peak potential were referred to the reversible formal potential of this compound (+0.44 V/SCE). The free energy change AG for an electron transfer between the studied copper complexes and iodonium salt can be calculated from the classical Rehm-Weller equation: AG = E _ox - E _ied - E _s + C; where E _ox , E _md , E _s , and C are the oxidation potential of the studied copper complexes, the reduction potential of iodonium salt, the excited state energy of the studied copper complexes, and the electrostatic interaction energy for the initially formed ion pair, generally considered as negligible in polar solvents. [30]

ESR Spin Trapping (ESR-ST) Experiment ESR-ST experiment was carried out using an X-Band spectrometer (MS 400 Magnettech). The radicals were generated at room temperature upon the halogen lamp exposure under N ₂ and trapped by phenyl-N-tert-butylnitrone (PBN) according to a procedure [31] described elsewhere in detail. The ESR spectra simulations were carried out using the WINSIM software.

Steady State Photolysis Experiments

The copper complex (and optionally iodonium salt) solutions were irradiated with the laser diode at 405 nm, and the UV-vis spectra were recorded using a JASCO V-530 UV/vis spectrophotometer at different irradiation time.

Laser Flash Photolysis

Nanosecond laser flash photolysis (LFP) experiments were carried out using a Q- switched nanosecond Nd/YAG laser ( _exc = 355 nm, 9 ns pulses; energy reduced down to 10 mJ) from Continuum (Minilite) and an analyzing system consisted of a ceramic xenon lamp, a monochromator, a fast photomultiplier and a transient digitizer (Luzchem LFP 212). [2]

Photopolymerization Experiments

For photopolymerization experiments, the conditions are given in the figure captions.

The photosensitive formulations were deposited on a BaF ₂ pellet under air or in laminate (25 μιη thick) for irradiation with different lights. The evolution of the double bond content of TMPTA and the epoxy group content of EPOX were continuously followed by real time FTIR spectroscopy (JASCO FTIR 4100) [8, 32] at about 1630 cm ¹ and 790 cm ^"1 , respectively.

The investigated copper complexes (El , Gl and G2) and other chemical compounds are shown in Schemes 1 and 2. El , Gl and G2 were prepared according to synthetic examples 1 -4.

Example 1 : Synthesis of 5,5'-6/s((9H-carbazol-9-yl)methyl)-2,2'-bipyridine

To 9H-carbazole (1.08 g, 5.98 mmol, 2.2 eq.) in 30 mL dry THF was added 0.3 g NaH (60% dispersion in mineral oil). After 20 min, 5,5'-^w(bromomethyl)-2,2'-bipyridine (1.0 g, 2.93 mmol) was added and the reaction mixture was heated at 60°C overnight. After cooling, the reaction mixture was quenched onto ice, and an insoluble precipitated formed. It was filtered and dried. It was used without any further purification (386 mg, 75% yield). ^l U NMR (CDC1 ₃ ) δ (ppm): 5.99 (s, 4H), 7.24-7.36 (8H), 7.38-7.48 (m, 8H), 8.13 (d, 2H, J = 7.6 Hz), 8.18 (d, 2H, J = 7.8 Hz), 8.54 (s, 2H); Anal. Calc. for C ₃₆ H ₂₆ N ₄ : C, 84.0; H, 5.1 ; N, 10.9; Found: C, 83.9; H, 5.4; N, 11.5%; HRMS (ESI MS) m/z: theor: 515.2230 found: 515.2233 ([M+H] ⁺ detected).

Example 2: Synthesis of fCufl py carbazole)q)PEphos)lBF. (El)

A mixture of [Cu(CH ₃ CN) ₄ ]BF ₄ (310 mg, 1 mmol) and to[2-(diphenylphosphino)phenyl] ether (540 mg, 1 mmol) in 200 mL of dichloromethane was stirred at 25°C for 2 h and then treated with a solution of 5,5'-^w((9H-carbazol-9-yl)methyl)-2,2'-bipyridine (515 mg, 1 mmol) in 50 mL of dichloromethane. The reaction mixture was stirred at room temperature during which time a precipitate formed. It was filtered off, washed with pentane and dried under vacuum (794 mg, 66% yield). ^l U NMR (CDC1 ₃ ) δ (ppm): 5.25 (s, 4H), 6.3(-6.37 (m, 2H), 6.48-6.57 (m, 4H), 6.60-6.80 (m, 8H), 6.80-7.10 (m, 16H), 7.20- 7.45 (m, 16H), 7.91-8.13 (m, 2H), 8.35-8.37 (m, 2H); ¹³ C NMR (CDC1 ₃ ) δ (ppm): 108.1, 110.8, 119.2, 119.7, 120.2, 120.3, 120.1, 123.3, 124.8-124.9 (m), 125.7, 126.2, 128.5 (t, J = 4.9 Hz), 129.0 (t, J = 4.7 Hz), 129.8 (t, J = 3.9 Hz), 130.6, 131.9 (t, J = 8.1 Hz), 132.7 (t, J = 8.1 Hz), 133.7 (t, J = 4.7 Hz), 134.3, 139.6, 140.2; ³¹ P NMR (CDC1 ₃ ) δ (ppm): - 11.23; HRMS (ESI MS) m/z: theor: 1115.3063 found: 1115.3066 (M ⁺ - detected)

Example 3: Synthesis of rCu(neo)q)PEphos)lBF. (Gl).

A mixture of [Cu(CH ₃ CN) ₄ ]BF ₄ (310 mg, 1 mmol) and to[2-(diphenylphosphino)phenyl] ether (540 mg, 1 mmol) in 200 mL of dichloromethane was stirred at 25 °C for 2 h and then treated with a solution of neocuproine (208 mg, 1 mmol) in 50 mL of dichloromethane. This reaction mixture was stirred at room temperature overnight and the solution was concentrated to ca. 15 rriL. Addition of pentane precipitated the complex which was filtered off, washed several times with pentane and dried under vacuum. The title complex was isolated as a light yellow solid in 86% yield (772 mg). ^l U NMR (CDC1 ₃ ) δ (ppm): 2.45 (s, 6H), 6.94-7.05 (m, 18H), 7.17-7.22 (m, 8H), 7.34 (td, 2H, J = 6.5 Hz, J = 1.8 Hz), 7.63 (d, 2H, J = 8.3 Hz), 7.86 (s, 2H), 8.40 (d, 2H, J = 8.3 Hz); ¹³ C NMR (CDC1 ₃ ) δ (ppm): 26.9, 120.0, 125.0-125.2 (m), 125.4, 125.9, 127.5, 128.4 (t, J = 4.6 Hz), 129.7, 131.5 (t, J = 16.3 Hz), 132.1, 132.6 (t, J = 7.8 Hz), 133.6, 137.9, 142.8 (t, J = 1.7 Hz), 158.2 (t, J = 6.1 Hz), 158.8; ³¹ P NMR (CDC1 ₃ ) δ (ppm): -12.93; HRMS (ESI MS) m/z: theor: 809.1906 found: 809.1606 (M ⁺ - detected).

Example 4: Synthesis of G2.

Copper complex G2 was prepared according to Example 3, by replacing bis[2- (diphenylphosphino)phenyl] ether with Xantphos (9,9-dimethyl-9H-xanthene-4,5- diyl)bis(diphenylphosphane).

Xantphos: (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane)

Example 5: Synthesis of rCu(diBu-phen)(OPEphos)lBF..

In a round bottom flask was added [Cu(CH ₃ CN) ₄ ]BF ₄ (93 mg, 0.4 mmol) and Xantphos (214 mg, 0.4 mmol) dissolved in THF (75 mL). The solution was allowed to stir at room temperature for lh and a solution of 2,9-dibutyl-l,10-phenanthroline (117 mg, 0.4 mmol) in THF (9 mL) was added. The resulting solution was stirred at room temperature overnight. The solution was concentrated to the third of its initial volume and addition of pentane precipitated the solid which was filtered off, washed with pentane and dried under vacuum (302 mg, 74% yield). ^l U NMR (CDC1 ₃ ) δ (ppm): 0.88 (t, 6H, J = 7.6 Hz, CH ₃ ), 1.26-1.30 (m, 4H, CH ₂ CH ₃ ), 1.79 (s, 6H), 1.91 (quint, 4H, J = 7.6 Hz, ArCH ₂ CH ₂ ), 3.19 (t, 4H, J = 7.6 Hz, ArCH ₂ ), 6.94-6.98 (m, 2H), 6.99-7.02 (m, 14H), 7.18-7.33 (m, 6H), 7.51 (d, 2H, J = 8.2 Hz), 7.57 (d, 2H, J = 8.4 Hz), 7.64 (d, 2H, J = 7.8 Hz), 7.84 (s, 2H), 8.41 (d, 2H, J = 8.4 Hz); ^1J C NMR (CDC1 ₃ ) δ (ppm): 13.7, 13.9, 14.0, 22.2, 30.3, 40.8, 67.8, 121.8 (t, J = 12.3 Hz), 122.4, 123.0, 124.8, 125.2, 127.0, 127.8, 128.4 (t, J = 9.8 Hz), 129.8, 130.2, 131.1 (t, J = 15.9 Hz), 132.7 (t, J = 7.7 Hz), 133.81-133.84 (m), 136.2, 138.0, 142.7 (t, J = 1.7 Hz), 145.2, 154.8 (t, J = 6.7 Hz), 161.5; ³¹ P NMR (CDC1 ₃ ) δ (ppm): -13.04; HRMS (ESI MS) mlz: theor: 933.3158 found: 933.3152 (M ⁺ - detected)

Example 6: Photopolymerization Experiments

For photopolymerization experiments, the conditions are given in the figure captions. The photosensitive formulations were deposited on a BaF ₂ pellet under air or in laminate (25 μιη thick) for irradiation with different lights. The evolution of the double bond content of TMPTA and the epoxy group content of EPOX were continuously followed by real time FTIR spectroscopy (JASCO FTIR 4100) at about 1630 cm ^"1 and 790 cm ^"1 , respectively [8 , 32].

Example 7: Light Absorption Properties of the Copper Complexes El, Gl, and H2

The absorption spectra of the investigated copper complexes (El, Gl and G2) in dichloromethane (DCM) are given in Figure 1 (a). For Gl and G2, the absorption maxima at 380 nm (ε ₃ 8ο„ ~ 3200 M ^"1 cm ^"1 ) and 383 nm (S383 nm ~ 2300 M ^"1 cm ^"1 ), respectively, correspond to a metal-to- ligand charge-transfer (MLCT) transition and more intense intraligand transitions appear at shorter wavelengths.— [33]

Interestingly, the light absorption of El, Gl and G2 allow efficient covering of the emission spectra of the laser diode at 405 nm (i.e. 8405„ ~ 2400, 2200 and 1800 M ^"1 cm ^"1 for El, Gl and G2, respectively). For the laser diode at 457 nm, the overlapping with El (8457 nm ~ 670 M ^"1 cm ^"1 ) is higher than that with Gl (8457 _nm ~ 70 M ^"1 cm ^"1 ) or G2 (8457 _nm ~ 70 M ^"1 cm ^"1 ). The light absorptions of the studied copper complexes also ensure good overlapping with the emission spectrum of the halogen lamp. The absorption spectrum of Gl was also studied in the more polar solvent acetonitrile (ACN), and the absorption spectra of Gl in DCM and ACN are compared in Figure 1 (b).

It can be seen that the MLCT maximum shifts from 380 nm in DCM to 374 nm in ACN, which is in agreement with the previous report that the maximum shifts toward shorter wavelengths in more polar solvents. [33]More interestingly, an absorption band at approx. 450 nm is observed in ACN, which could be attributed to the solvent-dependent ligand redistribution reactions of Gl in ACN. [33]

Furthermore, the UV-vis spectra of Gl in DCM and ACN after different irradiation (laser diode at 405 nm) time were shown in Figure 2. It can be clearly seen that the absorption band of Gl at 374 nm decreased and the absorption at -450 nm increased with the increasing of the irradiation time in ACN (Figure 2 (b)).

The appearance of absorption at -450 nm is probably due to the presence of Cu(dmp) ₂ complex (dmp = 2,9-dimethyl-l,10-phenanthroline) in the solution, [34] and the irradiation accelerated the generation of the Cu(dmp) ₂ complex. In the case of Gl in DCM, there was no change for the UV-vis spectra after the light irradiation (Figure 2 (a)), which indicates that Gl exhibits good photostability in DCM. [33] Similarly, El and G2 are also photostable in DCM (see Figure 12).

Example 8: Copper Complexes El, Gl, and G2 in Radical Initiating Systems It has been reported that radicals could be generated from the interaction between copper complexes and halides under visible light irradiation, [21] but to the best of our knowledge there was neither investigation on radical generation from the copper complexes/iodonium salts systems under visible light, nor on their application on photopolymerization. Herein, the mechanism of radical generation from the radical initiating systems including copper complexes and iodonium salts are investigated.

The free energy change of the El/Iodl electron transfer reaction AG = -1.72 eV (the oxidation potential of El, E _ox = 1.25 V was measured by cyclic voltammetry (see Figure 3); Es = 3.17 eV was evaluated from the average values of maximum absorption wavelength and maximum fluorescence emission wavelength of El ; and E _red = -0.20 V was used for Iodl [7]), which is highly negative and make the process favorable. For the Gl/lodl combination, AG = -1.17 eV (E _red = -0.20 V was used for Iodl, [7] E _ox = 1.35 V [33] or 1.36 V [35] reported previously was used for the oxidation potential of Gl, and Es = 2.72 eV was evaluated from the average values of maximum absorption wavelength and maximum fluorescence emission wavelength of Gl), also supporting the favorable electron transfer process.

In this case, the initiating radicals can be generated from the interaction between the copper complex excited state and iodonium salt. Upon the visible light (halogen lamp) irradiation of Gl/lodl, a signal of the PBN spin adduct is observed (hyperfine coupling constants: a _N = 14.2 G; <¾ = 2.2 G) in the ESR spin trapping experiment (see Figure 4); it is ascribed to the generation of phenyl radicals [1, 36] which could initiate the radical polymerization of TMPTA.

Furthermore, the generated phenyl radicals (Ph ^* ) can be converted to easily oxidizable radicals by an addition process onto the N-vinylcarbazole (NVK) double bond, and the newly generated NVK-based radicals can be further easily oxidized by an iodonium salt thereby leading to efficient initiating cations for the ring-opening cationic polymerization (ROP) of epoxides (Scheme 3). [37]

ROP of epox

Scheme 3. Conversion of easily oxidizable NVK-based radicals from phenyl radicals, and generation of initiating cations from the oxidization of NVK-based radicals by an iodonium salt.

The steady state photolysis of El/Iod2, Gl/Iod2 and G2/Iod2 in dichloromethane are given in Figure 5, (laser diode at 405 nm exposure under air). A very fast photolysis was observed for Gl (or G2)/Iod2 under the irradiation (Figure 5 (b) and (c)). More specifically, the absorption at 380 nm for Gl (or 383 nm for G2) decreased fast during the irradiation and the small shoulder peak at -450 nm appeared which was similar to that of Gl alone in ACN. It means that photochemical reaction between Gl (or G2) and Iod2 happened and the addition of Iod2 in the solution can accelerate the photolysis of Gl (or G2) in DCM, even though Gl (or G2) alone in DCM is quite photostable. On the other hand, very slow bleaching occurred in the El/Iod2 system (Figure 5 (a)), which supports the much lower efficiencies of these systems. This is in agreement with the relative photoinitiation ability of this system (see below).

Laser flash photolysis experiments were also carried out to better investigate the photochemical mechanism. For copper complex El , the short lifetime (xo < 6 ns) of the excited state (Figure 6) was unfavorable for the interaction between the excited state of El and iodonium salts: it thus led to low yield of radicals.

Following the laser excitation of Gl at 355 nm in dichloromethane, the luminescence at 600 nm exhibited a long lifetime (approx. 3 μ8) in the absence of lodl (Figure 7). The value measured here was different from the date (14.3 μ8) [33] reported previously, but both were in the microsecond range. On increasing the lodl amount, it was obvious that the luminescence was quenched and a very long-lived transient absorption was observed: it can be assigned to the newly generated photochemical products during the laser excitation of Gl/Iodl combination. Furthermore, the UV-vis absorption spectra of the sample were also measured before and after the laser flash photolysis experiment (Figure 13), it could be clearly seen that the absorption property changed after the laser excitation of LFP at 355 nm, also indicating that the new products were generated during the laser excitation.

Example 9: Photoinitiation ability of the investigated copper complexes El, Gl and G2 in Free Radical Photopolymerization of Acrylates

As investigated above, radicals could be generated during the interaction between the copper complexes and iodonium salts. Herein, the efficiencies of the copper complex based PISs for the FRP of TMPTA are studied. For the FRP of TMPTA in laminate upon the laser diode (405 nm or 457 nm), quite low conversions (< 30%) were obtained when using El/Iod2 (0.2%/2%, w/w) PIS (Figure 8 (a) and Table 1). This is in agreement with the slow steady state photolysis of El/Iod2 (Figure 5 (a)) and the LFP result (Figure 6) that the short lifetime (< 6 ns) for the excited state of El was unfavorable for the interaction between the El excited state and Iod2, and thus led to low efficiency for the generation of radicals to initiate the polymerization of TMPTA.

As to Gl/Iod2 system, it could more efficiently initiate the FRP of TMPTA than El/Iod2 and higher conversions (> 40%) were obtained under the laser diode at 405 nm or 457 nm, or the halogen lamp irradiation. With the addition of NVK, Gl/Iod2/NVK system was more efficient (i.e. higher photopolymerization rates and conversions 56%>) than the two- component system (e.g. in Figure 8 (b), curve 4 vs. curve 3; Table 1) upon the halogen lamp exposure. Gl/Iod2/NVK also worked under air for FRP (Figure 8 (b), curve 5) but with much lower photopolymerization rate and conversion due to the oxygen inhibition effect. Interestingly, Gl/Iod2 or Gl/Iod2/NVK exhibited better efficiency than the well- known CQ based PISs (Figure 8 (b) and Table 1) under the halogen lamp irradiation.

For the G2/Iod2 PIS (Figure 8 (c)), it was not as efficient as Gl/Iod2 system which could be ascribe to the better light absorption property (higher extinction coefficient) of Gl than that of G2 (Figure 1 (a)).

Table 2. TMPTA conversions obtained in laminate or under air upon exposure to different visible light sources for 500 s in the presence of El, Gl, or G2 based PISs (El, Gl, or G2: 0.2 wt%; Iod2: 2 wt%; NVK: 3 wt%); CQ/Iod (0.5%/2%, w/w) or CQ/MDEA (0.5%/2%, w/w) as references.

^a in laminate;

b under air;

c 400 s of light irradiation. Example 10: Photoinitiation ability of the investigated copper complexes El, Gl and G2 in Cationic Photopolymerization of Epoxides The cationic photopolymerization of EPOX in the presence of El (0.2%), El/Iodl (0.2%/2%, w/w) or El/(TMS) ₃ Si-H/Iodl (0.2%/3%/2%, w/w/w) under air were carried out using the laser diode (457 nm) or halogen lamp irradiation, but no polymerization was observed in all the case.

G2 based PISs (e.g. G2/Iodl or G2/Iodl/NVK) were ineffective for CP of EPOX either. Similarly, the well-known CQ based systems (i.e. CQ/Iod2 or CQ/Iod2/NVK) did not work either under the halogen lamp irradiation.

Remarkably, Gl/Iodl/NVK PIS exhibits good initiation ability for the polymerization of EPOX under air upon the halogen lamp exposure (Figure 9 (a)). During the photopolymerization, the epoxy group of EPOX (at 790 cm ^"1 , with the final conversion 61%) consumption was associated with the consumption of the double bond of NVK (at -1640 cm ^"1 , with final conversion 74%), and the concomitant formation of the polyether (at -1080 cm ^"1 ) and hydroxyl groups (at -3500 cm ^"1 ) (cf. Figure 9 (b)). The laser diode at 405 nm could also initiate the CP of EPOX (with the final conversion 32%>), but it was not as efficient as the halogen lamp. The initiation ability of Gl/Iodl PIS for the CP of EPOX was also studied under air upon the halogen lamp and laser diode at 405 nm exposure, but the polymerization conversions (the final conversion is 11%> and 13%> for halogen lamp and laser diode at 405 nm, respectively) were quite low. It means that the addition of NVK in the formulations could promote the CP of EPOX as previously reported. [37] Example 11: Photoinitiation ability of the investigated copper complexes El, Gl and G2 in IPN synthesis: Photopolymerization of EPOX/TMPTA Blends

The Gl/Iodl/NVK PIS allows the formation of interpenetrated polymer networks (IPNs) through concomitant cationic/radical photopolymerization of EPOX/TMPTA blend (50%)/50%> w/w) under air or in laminate upon the halogen lamp exposure (Figure 10). As elsewhere, [38-40] the polymerization conversion of TMPTA are higher in laminate than under air and the situation is opposite when considering the EPOX conversions (Table 2). It is attributed to the fact that the FRP of TMPTA is faster than FRPCP of EPOX and most of the free radicals are consumed to initiate the FRP when the oxygen inhibition effect is reduced by the laminated condition.

Table 2. EPOX and TMPTA conversions obtained in the photopolymerization of EPOX/TMPTA blend (50%/50%, w/w) under air or in laminate upon exposure to the halogen lamp (t = 800 s) in the presence of Gl/Iodl/NVK (0. l%/3%/5%, w/w/w).

EPOX conversion TMPTA conversion

Under air 45% 30%

In laminate 38% 74%

On the basis of the above studies, the photochemical mechanism of the cation formation is proposed in reactions 1-4:

Cu ¹ → "Cu ¹ (hu) (1)

*Cu ^r + Ph ₂ I ⁺ → Cu ¹¹ + Ph ₂ I ^* → Cu ¹¹ + Ph ^* + Ph-I (2)

Ph ^* + NVK→ Ph-NVK ^* (3)

Ph-NVK ^* + Ph ₂ I ⁺ → Ph-NVK ⁺ + Ph ^* + Ph-I (4)

The formed Cu ¹¹ in reaction 2 exhibited the slight efficiency to initiate the photopolymerization of EPOX with the low final conversion, this may be attributed to the fact that the active site (Cu ¹¹ ) was enveloped by the ligands and difficult to interact with epoxy groups in the formulation. After the conversion of phenyl radicals to more easily oxidizable NVK-based radicals (reaction 3), the NVK-based cations were then generated from the oxidation of NVK-based radicals by iodonium salts (reaction 4). And the NVK- based cations exhibited high efficiency to initiate photopolymerization of EPOX.

In conclusion, copper complexes Gl or G2 with iodonium salt (and optionally NVK) can work as the photoinitiating systems for the radical photopolymerization of TMPTA under different visible light irradiations (e.g. polychromatic visible light from halogen lamp, laser diodes at 405 nm or 457 nm). More interestingly, Gl/Iodl/NVK system exhibited good initiation ability for the cationic photopolymerization of EPOX under air upon the halogen lamp exposure. The El based system was not as efficient. The photochemical mechanism studies reveal that the ligands of the copper complexes play an important role for their properties (e.g. light absorption properties or luminescence lifetime) which could affect their photoinitiation ability.

Example 12: Polymer Analysis

The polymers synthesized according to the photopolymerization method of the invention can be characterized by various methods:

NMR data for confirmation of the chemical structure of the polymer.

Gel Permeation Chromatography (GPC) data for an assessment of chain-length and polymer dispersity. The Mn value can be routinely determined by GPC; GPC analyses may be performed on a GPC system equipped with a Shimadzu

RID10A refractometer detector and three 5-μ1 PL gel columns (300 x7.5 mm, Varian Corporation and Mixed-C porosity) in series, and using HPLC-grade THF as an eluent. The GPC columns may be eluted with THF at 45°C at 1 mL/min and were calibrated with polystyrene standards, specifically 23 monodisperse polystyrene standards. Analysis of the GPC data and calculation of the Mn and PDI values may be done with standard GPC software. Molecular weights and polydispersity indices (PDIs) may be calculated using polystyrene standards. In the case of molecular weight number values ( _n ), these may be corrected using by multiplying the experimental values (PS standard) by the correcting factor 0.58 (cf: Save et al., [46]). Accordingly, throughout this document, when Mn and DPI values are recited, they refer to measurements determined by GPC equipped with differential refractive index detectors, and polystyrene standard. Preferably, the measurements are done with THF as eluent, and at room temperature. Alternatively, or additionally, the Mn and DPI values could be determined by GPC equipped with light diffraction detectors, and polystyrene standard.

Differential scanning calorimetry (DSC) for melting point determination, and assessment of crystalline or semi-crystalline nature of the polymers.

Fourier transformed Infra red for monitoring the progress of the photopolymerization, or simultaneous free radical/cationic photopolymerization and assessment of homogenous character of the resulting interpenetrated polymer network.

In summary, three copper complexes (El, Gl and G2) with different ligands were used to generate aryl radicals in combination of iodonium salts (and another additive) upon visible light exposure. This approach can be worthwhile to initiate the free radical photopolymerization and ring-opening cationic photopolymerization under halogen lamp and laser diode, for example, or any visible light source. The photochemical mechanism of the production of initiating radicals was studied using ESR spin trapping, photolysis, luminescence, and laser flash photolysis techniques. As shown by the photopolymerization kinetics obtained from FTIR spectroscopy, Gl and G2 in the presence of iodonium salt (and another additive) exhibited good initiation polymerization abilities.

More generally, organometallic copper complexes with different ligands have been developed and used in polymerization photoinitiator systems for polymer synthesis under very mild conditions (ambient temperature, and even visible sunlight). As such, free radical and / or cationic polymerizations could be carried out. By effecting a selection of ligands, copper complexes were characterized by light absorption properties in different wavelength ranges in the visible range. These complexes proved to be veiy effective for different synthesis conditions (halogen lamp, LED, laser diode, sunlight etc ...). Under gentle irradiation conditions, free radicals could be produced by interaction between the copper complexes and iodonium salts. These bicomponent systems can very effectively initiate the polymerization of acrylic resins. High final conversions were reached a ter only 5 minutes of irradiation with a halogen lamp. Remarkably, the free radicals produced in these systems may be converted into cations (an oxidizing radical process) by the addition of an additive such as N-vinylcarbazole (NVK) while al lowing access to the cationic polymerization initiator (polymerization of epoxy, vinyl ether...). The use of these three-component systems (copper complexes / iodonium salt / NVK.) allows the simultaneous polymerization of mixtures of free radical and cationic monomers (e.g., acrylate epoxide) allowing access to the synthesis of hybrid polymer mixtures or interpenetrating interconnected polymers again under interesting synthetic conditions (room temperature, mild irradiation, the presence of ambient oxygen).

While we have described a number of embodiments of this invention, it is apparent that our basic examples may be altered to provide other embodiments that utilize the catalysts and methods of this invention. Therefore, it will be appreciated that the scope of this invention is to be defined by the appended claims rather than by the specific embodiments that have been represented by way of example. REFERENCES

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