PEGYLATED THIOXANTHONE PHOTOINITIATOR AND PHOTOSENSITIVE RESIN COMPOSITION

• US 20200131147A1
• Filed: 12/30/2019
• Published: 04/30/2020
• Est. Priority Date: 06/29/2017
• Status: Active Grant

• Current Assignee: Jenkem Technology Co., Ltd. (Tanjin)
• Original Assignee: Jenkem Technology Co., Ltd. (Tanjin)
• Inventors: ZHU, HUI, LIN, MEINA, ZHAO, XUAN
• Granted Patent: US 11,174,239 B2
• Time in Patent Office: Days
• CPC Class Codes: C07D 335/16 Oxygen atoms, e.g. thioxanthones
• CPC Class Codes: C08G 65/3344 containing oxygen in addition to sulfur
• CPC Class Codes: C08G 65/3346 having sulfur bound to carbon and oxygen
• CPC Class Codes: C08K 5/18 with aromatically bound amino groups
• CPC Class Codes: G03F 7/0037 Production of three-dimensional images
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/031 Organic compounds not covered by group G03F7/029

Abstract

The present invention discloses a PEGylated thioxanthone photoinitiator and a photosensitive resin composition, the PEGylated thioxanthone compound is eco-friendly and has low toxicity, high initiation efficiency and good thermal stability, meanwhile, as a kind of photoinitiator, the compound has a small amount of fragment residue after cured, and may improve the compatibility of the photoinitiator and photosensitive resin composition system. The photosensitive resin composition provided by the present invention has reasonable allocation of ingredients and content in the components thereof, capable of 3D-printing a hydrogel having a specific structure; the hydrogel has lower cytotoxicity and better biocompatibility, and may applied in bioengineering fields, e.g., 3D cell culture.

Claims

1. A PEGylated thioxanthone compound, comprising a structure shown in the formula I,

2. The compound according to claim 1, wherein in the R_1-8, the alkyl is a C_1-6 alkyl;

and/or,

the alkoxy is a C_1-6 alkoxy; and

/or,

the halogen is F, Cl or Br; and

/or,

the aryl is selected from;

phenyl, naphthyl, anthryl, phenanthryl, indenyl and pyrenyl; and

/or,

the heterocyclyl is a nitroge-containing 5-membered ring or a nitroge-containing 6-membered ring; and

/or,

the X is selected from any one or a combination of two or more of the group consisting of;

the above —

(CH₂)_i—

, —

(CH₂)_iO—

, —

(CH₂)_iS—

, —

(CH₂)_iCO—

, —

(CH₂)_iNH— and

—

(CH₂)_iCONH—

; and

/or,

i is an integer of 0 to 5.

3. The compound according to claim 1, wherein the PEG is a linear polyethylene glycol residue and has a structure shown in the general formula II:

4. The compound according to claim 1, wherein the PEG is a linear polyethylene glycol residue and has a structure shown in the general formula II;

and/or, the X is a single bond.

5. The compound according to claim 1, wherein the molecular weight of PEG ranges from 500 Da to 80000 Da.

6. The compound according to claim 1, wherein the R₂ and/or R₄ is —

X-PEG.

7. The compound according to claim 1, wherein the compound has a structure shown in the formula VI-VIII:

8. A photoinitiator, comprising the PEGylated thioxanthone compound according to claim 1.

9. A photosensitive resin composition, comprising a photosensitizer, wherein the photosensitizer comprises the photoinitiator according to claim 8;

preferably, the composition further comprises an active component (such as 8-armed polyethylene glycol acrylate) and a diluent;

more preferably, content of the active component in the composition ranges from 1% to 40%, preferably 10% to 30%; and

/or,

content of the diluent in the composition ranges from 40% to 90%, preferably 60% to 85%; and

/or,

content of the photoinitiator in the composition ranges from 0.1%, preferably 0.5% to 5%.

10. The photosensitive resin composition according to claim 9, wherein the active component is selected from:

one or more of PEG acrylate, PEG epoxy ether, monodispersed polyethylene glycol acrylate, monodispersed polyethylene glycol epoxy ether, diol diacrylate and diol dialkylene oxide.

11. The photosensitive resin composition according to claim 10, wherein the PEG acrylate is PEG diacrylate or PEG acrylate with 3-8 arms;

and/or,

the PEG epoxy ether is PEG diepoxy ether or PEG epoxy ether with 3-8 arms; and

/or,

the monodispersed polyethylene glycol acrylate is monodispersed polyethylene glycol diacrylate; and

/or,

the monodispersed polyethylene glycol epoxy ether is monodispersed polyethylene glycol diepoxy ether; and

/or,

the diol is selected from;

ethylene glycol, propylene glycol and butylene glycol.

12. The photosensitive resin composition according to claim 9, wherein the diluent comprises an inactive diluent and/or an active diluent;

preferably, the inactive diluent is solvent, and selected from;

water, buffer solution, ethanol, isopropanol, DMSO, DMF, dioxane and THF; and

/or,

the active diluent is selected from;

one or more of ethyl acrylate, butyl acrylate, isobutyl acrylate, epoxy propyl acrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, epoxypropyl methacrylate, allyl methacrylate, monomethoxyl PEG acrylate, monomethoxyl PEG epoxy ether, monomethoxyl monodispersed polyethylene glycol acrylate and monomethoxyl monodispersed polyethylene glycol epoxy ether.

13. The photosensitive resin composition according to claim 10, wherein the molecular weight of PEG ranges from 500 Da to 80000 Da;

and/or, polymerization degree of the ethylene glycol in the monodispersed polyethylene glycol is 2-50.

14. The photosensitive resin composition according to claim 9, wherein the photosensitive resin composition further comprises an auxiliary additive;

the auxiliary additive is selected from;

one or more of co-initiator, antifoaming agent, flatting agent, polymerization inhibitor, antioxidant, antisettling agent, pigment, fluorescent agent, filler, wetting dispersant, flexibilizer and cross-linking agent;

content of the auxiliary additive in the composition ranges from 0% to 10%;

preferably,

the auxiliary additive comprises a co-initiator;

the co-initiator is selected from;

one or more of triethanolamine, N,N-dimethyl benzylamine, N,N-dimethylaniline and triethylamine;

content of the co-initiator in the photosensitive resin composition ranges from 0% to 5%;

and/or,

the auxiliary additive comprises a polymerization inhibitor;

the polymerization inhibitor is selected from;

one or more of phenolic polymerization inhibitors, quinone polymerization inhibitors, aromatic nitro-compound polymerization inhibitors and inorganic compound polymerization inhibitors;

content of the polymerization inhibitor in the photosensitive resin composition ranges from 0% to 1%.

15. The photosensitive resin composition according to claim 9, wherein the composition further comprises an auxiliary functional component;

preferably, content of the auxiliary functional component in the composition ranges from 0% to 20%, preferably, 0.1% to 20.0%, more preferably, 0.1% to 10.0%.

16. The photosensitive resin composition according to claim 15, wherein the auxiliary functional component comprises any one or a combination of two or more of the group consisting of:

gelatin and acrylic acid-derived gelatin, hyaluronic acid and acrylic acid-derived hyaluronic acid, chitosan and modified chitosan, cellulose and carboxymethyl cellulose, alginate and modified alginate, collagen, agarose and cell nutrient solution, and/or, a block polymer of multi-armed or linear polyethylene glycol polyester whose terminal group is modified by acrylate.

17. The photosensitive resin composition according to claim 16, wherein in the block polymer of multi-armed or linear polyethylene glycol polyester, the polyester chain portion is selected from any one or a combination of two or more of the group consisting of:

polylactide, polyglycollide, glycolide, lactide copolymer and polycaprolactone; and

/or,

molecular weight of the polyester chain portion ranges from 800 Da to 80000 Da; and

/or,

molecular weight of the PEG chain portion ranges from 800 Da to 80000 Da; and

/or,

in the block polymer of the multi-armed polyethylene glycol polyester, the number of arms ranges from 3 to 8.

18. The photosensitive resin composition according to claim 15, wherein the auxiliary functional component is acrylic acid-derived hyaluronic acid, acrylic acid-derived gelatin or a block polymer of multi-armed polyethylene glycol polycaprolactone whose terminal group is modified by acrylate.

19. A hydrogel obtained by 3D-printing the photosensitive resin composition according to claim 9.