A UV-curable polymer material that can be repeatedly shaped

Abstract

The application discloses a UV light-cured polymer material capable of repeated shaping, which comprises a photosensitive resin monomer or oligomer, a disulfide compound, a disulfide bond exchange promoter and a photoinitiator. The photosensitive resin can be easily polymerized in an ultraviolet light environment, and UV curing can be achieved. Meanwhile, a dynamic disulfide bond and a structure for promoting disulfide bond exchange are introduced into the system, and the dynamic disulfide bond can be quickly exchanged under certain conditions, so that the prepared orthopedic material has the repeated shaping capability. The polymer material can be used in the field of medical devices.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a UV-curable polymer material that can be repeatedly shaped and its raw material composition. Background Technology

[0002] In recent years, the number of patients with physical deformities has continued to increase both domestically and internationally, leading to a sustained increase in market demand for orthopedic braces as an effective medical device for correcting physical deformities. 3D printing technology is a rapid prototyping technology that uses discrete / accumulated materials to create solid models. It differs significantly from traditional material removal processes and is a comprehensive processing technology that integrates numerous cutting-edge technologies and knowledge. 3D printing offers advantages such as short manufacturing cycles, ease of forming complex structures, and material and energy savings. In particular, it breaks through the limitations of traditional parts in terms of shape design and processing technology, theoretically capable of producing parts of any shape. Its deep integration with information network technology has brought transformative changes to traditional manufacturing, making it one of the landmark technologies of the new industrial revolution. It has been widely applied in fields such as medicine, scientific research, cultural relics, manufacturing, automobiles, jewelry, toys, clothing, and construction. Especially in the field of orthopedic braces, because everyone's body size and degree of deformity are different, orthopedic braces manufactured using 3D printing technology can better fit the patient's body, resulting in greater patient comfort. Therefore, 3D-printed orthopedic braces are gradually replacing traditional plaster cast orthopedic braces, becoming one of the most promising new products in the orthopedic brace market. Compared with other types of 3D printing technologies, UV curing 3D printing technology has higher precision, lower printing temperature, and shorter printing time, hence its rapid development in recent years. However, because the patient's body changes continuously during the orthopedic process, conventional 3D-printed orthopedic braces no longer fit the patient's body after a period of use, requiring reprinting, which increases treatment costs and limits treatment effectiveness.

[0003] Orthopedic braces require high stiffness under normal conditions to ensure their orthopedic effect, while maintaining lower stiffness during reshaping. Therefore, only variable stiffness materials can achieve this effect. Variable stiffness materials are a new type of adaptive material whose stiffness reversibly changes with external environmental changes. Although some temperature-sensitive plastics have similar effects, their molding methods mainly rely on hot-melting and then cooling using molds. This method cannot achieve the high efficiency and precision of photopolymer 3D printing, nor can it achieve the most accurate body fit. Combining materials with excellent variable stiffness properties with photopolymer 3D printing technology can produce new deformable orthopedic braces. These orthopedic braces can deform locally during use, adapting to the continuous changes in the body during orthopedic procedures and maintaining a close fit. This not only eliminates the need for repeated printing but also improves the orthopedic effect.

[0004] However, obtaining photopolymer-cured variable stiffness materials for 3D printing is difficult because during the 3D printing process, photosensitive groups react rapidly to form a highly dense cross-linked network. This structure restricts the movement of polymer chains and related chemical units. Variable stiffness materials, in essence, change the molecular chain structure under certain stimuli, such as by raising the temperature, causing the polymer chains to change from a frozen state to a fluid state, thereby achieving a change from high stiffness to low stiffness. Therefore, solving the problem of internal molecular mobility is crucial for 3D printing variable stiffness materials.

[0005] Introducing dynamic bonds is effective in non-3D printing molding methods, and also has some effect in 3D printing soft materials because the movement of molecular chains within soft materials is less restricted. However, in 3D printing rigid orthopedic braces, dynamic bonds alone are insufficient; methods to promote the action of dynamic bonds are necessary to enable them to exert their dynamic effects and thus fundamentally solve the problem. Summary of the Invention

[0006] This invention addresses the shortcomings of existing technologies by introducing dynamic bonds (disulfide bonds) into photosensitive resins based on photopolymerization and 3D printing technologies. It also enhances the exchange efficiency through a disulfide bond accelerator. Under the action of the disulfide bond exchange accelerator, dynamic disulfide bonds can be exchanged efficiently, overcoming the problem of severe restriction of dynamic bonds in highly dense cross-linked networks. The polymer material obtained by photopolymerization has the ability to be repeatedly molded.

[0007] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0008] A photocurable polymer material raw material composition, comprising the following components in parts by weight:

[0009] 1 to 99 parts of photosensitive resin monomer or oligomer, preferably 20 to 80 parts, more preferably 30 to 70 parts;

[0010] 1 to 99 parts of disulfide compound, preferably 10 to 60 parts, more preferably 20 to 40 parts;

[0011] 1 to 99 parts of disulfide bond exchange promoter, preferably 5 to 60 parts, more preferably 10 to 30 parts;

[0012] The photoinitiator is 1 to 30 parts, preferably 1 to 20 parts, and more preferably 2 to 10 parts.

[0013] The disulfide compound is selected from propylthioamine disulfide, ammonium disulfide, 5,5'-dithiobis(2-nitrobenzoic acid), tetraethylthiuram disulfide, 4,4'-dinitrodiphenyl disulfide, 4,4'-dithiodimorpholine, xanthate disulfide, diethyl disulfide, 2,2'-dithiodibenzoic acid, dibenzothiazole disulfide, dibenzyl disulfide, L-4,4'-dithiobis(2-aminobutyric acid), dimethyl disulfide, dipropyl disulfide, and 4,4'-dithiodiphenyl disulfide. One or more of the following: amine, 3,3'-dithiodipropionylmethylamine, 2,2'-diaminodiphenyl disulfide, 2,2'-dinitrodiphenyl disulfide, 2,2'-dipyridyl disulfide, diallyl disulfide, methyl allyl disulfide, propyl propylene disulfide, methyl propyl disulfide, cyclohexyl disulfide, 4,4'-dipyridyl disulfide, diisobutylthiuram disulfide, difurfuryl disulfide, disec-butyl disulfide, bis(2-thienyl) disulfide, disulfide dichloride, and polysulfide rubber;

[0014] The disulfide compound is preferably one or more of tetraethylthiuram disulfide, 4,4'-dinitrodiphenyl disulfide, 4,4'-dithiodimorpholine, diethyl disulfide, 2,2'-dithiodibenzoic acid, dimethyl disulfide, dipropyl disulfide, 4,4'-dithiodiphenylamine, methyl allyl disulfide, methyl propyl disulfide, 4,4'-dipyridine disulfide, diisobutylthiuram bis(2-thienyl) disulfide, and polysulfide rubber; more preferably one or more of tetraethylthiuram disulfide, 4,4'-dinitrodiphenyl disulfide, 4,4'-dithiodimorpholine, diethyl disulfide, methyl allyl disulfide, and polysulfide rubber.

[0015] When the disulfide compound is two or more of the specific selections mentioned above, the present invention does not impose any special limitation on the ratio of the specific substances, and they can be mixed in any ratio. The disulfide bond exchange promoter is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol, lauryl dimethyl tertiary amine, 1,8-diazabicycloundec-7-ene, dodecyl mercaptan, hexadecyl dimethyl tertiary amine, hexamethylene mercaptan, dimethyltetradecylamine, 1-methylimidazolium-2-thiol, octadecyl dimethyl tertiary amine, isopropanethiol, N,N-dimethyldecylamine, tert-butanethiol, dioctadecyl methyl tertiary amine, dioctylmethylamine, propanethiol, oleyl dimethyl tertiary amine, alkyl tertiary amine, 2-diethylaminoethanethiol, butanethiol, 1,3-propanedithiol, dodecyl mercaptan, dithiothreitol, pentylenetetrol, hexamethylene mercaptan, and octyl mercaptan.

[0016] The preferred disulfide bond exchange promoter is one or more of the following: 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicycloundec-7-ene, dodecyl mercaptan, dimethyltetradecylamine, 1-methylimidazol-2-thiol, octadecyldimethyl tertiary amine, oleyldimethyl tertiary amine, butyl mercaptan, 1,3-propanedithiol, dodecyl mercaptan, dithiothreitol, and octyl mercaptan; more preferably, it is one or more of the following: 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicycloundec-7-ene, dodecyl mercaptan, oleyldimethyl tertiary amine, butyl mercaptan, dithiothreitol, and octyl mercaptan. When the disulfide bond exchange promoter is two or more of the above-mentioned specific selections, the present invention does not impose any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0017] The monomers of the photosensitive resin monomers or oligomers are selected from one or more of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, epoxy acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, polyurethane acrylate, polyurethane methacrylate, polyester acrylate, polyether acrylate, tetrahydrofuran acrylate, lauryl acrylate, lauryl methacrylate, isobornyl acrylate, acryloylmorpholine, cyclohexyl acrylate, cyclohexyl methacrylate, 2-phenoxyethyl acrylate, 1,6-hexanediol diacrylate, ethoxyethyl acrylate, and 1,3-propanediol monoacrylate.

[0018] The photosensitive resin or oligomer is preferably acrylic acid, methyl methacrylate, epoxy acrylate, polyurethane acrylate, polyurethane methacrylate, lauryl acrylate, tetrahydrofuran acrylate, isobornyl acrylate, acryloylmorpholine, ethoxyethyl acrylate, and 1,6-hexanediol diacrylate; more preferably, it is one or more of methyl methacrylate, epoxy acrylate, polyurethane acrylate, polyurethane methacrylate, isobornyl acrylate, and acryloylmorpholine.

[0019] When the photosensitive resin or oligomer is two or more of the above-mentioned specific selections, the present invention does not impose any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0020] The photoinitiator is a free radical photoinitiator and / or a cationic photoinitiator. The free radical photoinitiator is selected from one or more of benzoin and its derivatives, benzoyl derivatives, dialkoxyacetophenone, α-hydroxyalkyl phenyl ketone, α-aminealkyl phenyl ketone, acylphosphine oxide, benzophenone and its derivatives, thioxanthones, anthraquinones, co-initiators such as aliphatic tertiary amines, ethanolamine tertiary amines, tertiary amine benzoates, and active amines. The cationic photoinitiator is selected from one or more of diaryliodomonium salts, triarylthiomonium salts, and arylferrocene salts.

[0021] The initiator is preferably one or more of benzoin and its derivatives, benzoyl derivatives, α-hydroxyalkyl phenyl ketones, α-aminealkyl phenyl ketones, acylphosphine oxides, benzophenones and their derivatives, thioxanthones, anthraquinones, aliphatic tertiary amines, diaryliodomonium salts, triarylthiomonium salts, and arylferrocene salts; more preferably one or more of benzoyl derivatives, α-aminealkyl phenyl ketones, benzophenones and their derivatives, thioxanthones, diaryliodomonium salts, and triarylthiomonium salts.

[0022] When the photoinitiator is two or more of the specific choices mentioned above, the present invention does not impose any special limitation on the ratio of the specific substances mentioned above, and they can be mixed in any ratio.

[0023] In a preferred embodiment of the present invention, the photocurable polymer material raw material composition comprises the following components in parts by weight:

[0024] 30-70 parts of photosensitive resin monomer or oligomer;

[0025] 20-40 parts of disulfide compounds;

[0026] 10-30 parts of disulfide bond exchange promoter;

[0027] 2-10 parts of photoinitiator.

[0028] The disulfide compound is selected from one or more of tetraethylthiuram disulfide, 4,4'-dinitrodiphenyl disulfide, 4,4'-dithiodimorpholine, diethyl disulfide, methyl allyl disulfide, and polysulfide rubber.

[0029] The disulfide bond exchange promoter is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicycloundec-7-ene, dodecanethiol, oleyl dimethyl tertiary amine, butanethiol, dithiothreitol, and octylthiol.

[0030] The photosensitive resin monomer or oligomer is selected from one or more of methyl methacrylate, epoxy acrylate, polyurethane acrylate, polyurethane methacrylate, isobornyl acrylate, and acryloylmorpholine. The photoinitiator is selected from one or more of benzoyl derivatives, α-amine alkyl phenyl ketones, benzophenones and their derivatives, thioxanthones, diaryliodomonium salts, and triarylthiomonium salts.

[0031] The photocurable polymer material raw material composition of the present invention further includes 1 to 99 parts of other additives, preferably 10 to 80 parts, more preferably 15 to 60 parts, wherein the other additives are selected from one or more of diluents, toughening agents, plasticizers, inorganic fillers, anti-aging agents, dyes, and solvents.

[0032] The diluent is preferably one or more selected from dodecyl glycidyl ether, ethylene glycol diglycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, and polyhydroxy polyether. When the diluent is two or more of the above-mentioned specific selections, the present invention does not impose any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0033] The toughening agent is preferably one or more of the following: ethylene propylene rubber type toughening agent, polybutadiene rubber type toughening agent, butyl rubber type toughening agent, nitrile rubber type toughening agent, styrene-butadiene rubber type toughening agent, styrene-butadiene thermoplastic elastomer type toughening agent, methyl methacrylate-butadiene-styrene terpolymer type toughening agent, acrylonitrile-butadiene-styrene copolymer type toughening agent, chlorinated polyethylene type toughening agent, ethylene-vinyl acetate copolymer type toughening agent, liquid polysulfide polymer type toughening agent, and reactive polyurethane type epoxy toughening agent. When the toughening agent is two or more of the above-mentioned specific selections, the present invention does not have any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0034] The plasticizer is preferably one or more of phthalate plasticizers (PAEs), chlorinated paraffin, epoxidized soybean oil, and dioctyl adipate. The phthalate plasticizer is preferably one or more of di-n-octyl phthalate (DNOP or DnOP), butyl benzyl phthalate (BBP), di-sec-octyl phthalate (DCP), dicyclohexyl phthalate (DCHP), dibutyl phthalate (DBP), diisobutyl phthalate (DIBP), dimethyl phthalate (DMP), diethyl phthalate (DEP), diisononyl phthalate (DINP), and diisodecyl phthalate (DIDP). When two or more of the above-mentioned plasticizers are used, the present invention does not impose any special limitation on the ratio of the above-mentioned substances; they can be mixed in any ratio.

[0035] The inorganic filler is preferably one or more of the following: clay, fiber, silica, carbon black, graphene, carbon nanotubes, titanium dioxide, barium titanate, alumina, silicon oxide, boron nitride, calcium carbonate, and silicon nitride. When the inorganic filler is two or more of the above-mentioned specific selections, the present invention does not impose any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0036] In this invention, the inorganic filler is used to adjust viscosity, mechanical properties, appearance, reduce costs, and impart certain functions.

[0037] In this invention, the anti-aging agent is preferably an antioxidant and / or a radiation protectant. The antioxidant is preferably a primary antioxidant and a secondary antioxidant. The primary antioxidant is preferably a hindered phenolic antioxidant. The function of the primary antioxidant is to capture peroxide free radicals. The secondary antioxidant is preferably a phosphite and / or a thioester. The function of the secondary antioxidant is to assist in enhancing antioxidant capacity. The radiation protectant is preferably one or more of salicylate radiation absorbers, benzophenone radiation absorbers, benzotriazole radiation absorbers, substituted acrylonitrile radiation absorbers, and triazine radiation absorbers. When the anti-aging agent is two or more of the above-mentioned specific selections, this invention does not have any special limitation on the ratio of the above-mentioned specific substances; they can be mixed in any ratio.

[0038] In this invention, the dyeing agent is preferably an inorganic color additive and / or an organic color additive; the inorganic color additive is preferably one or more of the following: soot black, chalk, cinnabar, red clay, realgar, natural iron oxide, wollastonite, barite powder, talc powder, mica powder, kaolin, titanium dioxide, zinc barium white, lead chromate yellow, and iron blue. The organic color additive is preferably one or more of the following: gamboge, alizarin red, indigo, scarlet powder, pale yellow, phthalocyanine blue, and quinacridone. When the dyeing agent is two or more of the above-mentioned specific selections, this invention does not have any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio.

[0039] In this invention, the solvent is preferably one or more of the following: benzene, toluene, xylene, styrene, pentane, hexane, octane, cyclohexane, cyclohexanone, methylbenzene, dichlorobenzene, dichloromethane, chloroform, perchloroethylene, trichloroethylene, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, ethylene glycol ether, methyl acetate, ethyl acetate, propyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, benzyl alcohol, diethanolamine, tetrahydrofuran, and acetonitrile. Ethanol or acetone is more preferred. When the solvent is two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the ratio of the above-mentioned substances; they can be mixed in any ratio.

[0040] This invention also provides a photocurable polymer material, which is formed by UV curing of the photocurable polymer material raw material composition described in this invention. Specifically:

[0041] After uniformly mixing photosensitive resin monomers or oligomers, disulfide compounds, disulfide bond exchange promoters, photoinitiators and other additives, the mixture is cured using 3D printing equipment or UV curing equipment.

[0042] The present invention does not impose any special limitations on the mixing method; any mixing method known to those skilled in the art can be used.

[0043] The photocurable polymer material described in this invention possesses the ability to be repeatedly molded, primarily by altering its temperature, including photothermal, water bath, oil bath, hot air, and other heat conduction methods. At relatively high temperatures, the polymer material exhibits variable stiffness characteristics due to the activity of disulfide bonds (dynamic bonds). It can then be reshaped through bending, extrusion, and twisting, and its shape is fixed until the temperature drops to a lower level. At this point, the polymer material is in a glassy state, a new stable rigid state, capable of meeting further shaping requirements. This process can be repeated, thus possessing the ability to be repeatedly molded.

[0044] The present invention also provides the application of the aforementioned photocurable polymer material raw material composition or photocurable polymer material in the preparation of 3D printing materials.

[0045] The present invention also provides the application of the aforementioned photocurable polymer material raw material composition or photocurable polymer material in the preparation of medical devices.

[0046] In a preferred embodiment, the medical device is an orthotic brace.

[0047] Advantages of this invention:

[0048] This invention addresses the shortcomings of existing technologies by introducing dynamic bonds (disulfide bonds) into photosensitive resins based on photopolymerization and 3D printing technologies. A disulfide bond exchange promoter is used to enhance the exchange efficiency, thereby overcoming the problem of severely restricted dynamic bonds in highly dense cross-linked networks. The resulting photopolymerized polymer material exhibits the ability to be repeatedly molded. This solves the problem of existing technologies' difficulty in preparing 3D-printed variable stiffness materials using photopolymerization. Attached Figure Description

[0049] Figure 1 The storage modulus of the 3D printing material prepared in Example 5 was tested using a TA rheometer as a function of temperature.

[0050] Figure 2The storage modulus of the 3D printing materials prepared in Comparative Examples 2-4 and Example 11 was tested using a TA rheometer as a function of temperature.

[0051] Figure 3 The diagram shows the structural changes of the orthopedic brace 3D printed from components of Example 5 after being heated to 80°C for arbitrary shaping and then cooled to 25°C for final shaping. Detailed Implementation

[0052] The following detailed description, in conjunction with embodiments, illustrates a repeatedly shapeable 3D-printed orthopedic brace, its preparation method, and its applications, but these descriptions should not be construed as limiting the scope of protection of this invention.

[0053] A method for preparing a repeatedly shapeable 3D-printed orthopedic brace as described in Examples 1-15:

[0054] Photosensitive resin, disulfide compounds, disulfide bond exchange promoters, photoinitiators, and other additives are mixed evenly and then molded using a photopolymerization 3D printer. The printing process varies depending on the resin's activity. The printed material then possesses the ability to be repeatedly shaped.

[0055] Test method: The modulus as a function of temperature was measured using a TA rheometer.

[0056] Example 1

[0057] The photosensitive resin monomer is methyl methacrylate.

[0058] The disulfide compound is: diethyl disulfide.

[0059] The disulfide bond exchange promoter is dodecyl mercaptan; the photoinitiator is benzophenone.

[0060] Other additives include: calcium carbonate.

[0061] The proportions of the above ingredients are as follows:

[0062] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 60 50 3 20 50

[0063] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 10s.

[0064] Example 2

[0065] The photosensitive resin monomer is methyl methacrylate.

[0066] The disulfide compound is: diethyl disulfide.

[0067] The disulfide bond exchange promoter is: dodecanethiol.

[0068] The photoinitiator is benzophenone.

[0069] Other additives include: calcium carbonate.

[0070] The proportions of the above ingredients are as follows:

[0071]

[0072]

[0073] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 15s.

[0074] Example 3

[0075] The photosensitive resin monomer is methyl methacrylate.

[0076] The disulfide compound is: diethyl disulfide.

[0077] The disulfide bond exchange promoter is: dodecanethiol.

[0078] The photoinitiator is benzophenone.

[0079] Other additives include: calcium carbonate.

[0080] The proportions of the above ingredients are as follows:

[0081] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 60 50 15 20 50

[0082] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 17s.

[0083] Example 4

[0084] The photosensitive resin monomer is: epoxy acrylate.

[0085] Disulfide compounds include: polysulfide rubber.

[0086] The disulfide bond exchange promoter is: oleyl dimethyl tertiary amine

[0087] Photoinitiators are: thioxanthones

[0088] Other additives include: nitrile rubber.

[0089] The proportions of the above ingredients are as follows:

[0090] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 48 50 50 5 10

[0091] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 10s.

[0092] Example 5

[0093] The photosensitive resin oligomer is: polyurethane acrylate.

[0094] The disulfide compound is: propylpropene disulfide.

[0095] The disulfide bond exchange promoter is: octyl mercaptan.

[0096] The photoinitiator is: triarylsulfonium salt

[0097] Other additives include: glass fiber.

[0098] The proportions of the above ingredients are as follows:

[0099] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 80 20 16 10 3

[0100] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 8s.

[0101] Example 6

[0102] The photosensitive resin oligomer is: polyurethane methacrylate.

[0103] The disulfide compound is: diisobutylthiuram disulfide

[0104] The disulfide bond exchange promoter is: octadecyl dimethyl tertiary amine

[0105] The photoinitiator is: benzoyl derivative

[0106] Other additives include: Phthalocyanine Blue

[0107] The proportions of the above ingredients are as follows:

[0108] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 75 10 10 15 1

[0109] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 12s.

[0110] Example 7

[0111] The photosensitive resin monomer is: isobornyl acrylate

[0112] The disulfide compound is: cyclohexyl disulfide.

[0113] The disulfide bond exchange promoter is: alkyl tertiary amine.

[0114] The photoinitiator is: thioxanthone

[0115] Other additives include: titanium dioxide.

[0116] The proportions of the above ingredients are as follows:

[0117] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 65 5 5 10 8

[0118] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 13s.

[0119] Example 8

[0120] The photosensitive resin monomer is: acrylomorpholine

[0121] The disulfide compound is: 2,2'-diaminodiphenyl disulfide

[0122] The disulfide bond exchange promoter is hexamethylenetetramine.

[0123] The photoinitiator is: α-amine alkyl phenyl ketone

[0124] Other additives include talc powder. The proportions of the above ingredients are as follows:

[0125] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 77 12 12 7 30

[0126] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 15s.

[0127] Example 9

[0128] The photosensitive resin oligomer is: polyurethane methacrylate.

[0129] The disulfide compound is: 2,2'-diaminodiphenyl disulfide

[0130] The disulfide bond exchange promoter is: 1,8-diazabicycloundec-7-ene.

[0131] The photoinitiator is benzophenone.

[0132] Other additives include: diisodecyl phthalate

[0133] The proportions of the above ingredients are as follows:

[0134] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 65 20 20 10 15

[0135] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 12s.

[0136] Example 10

[0137] The photosensitive resin oligomer is: polyurethane acrylate.

[0138] The disulfide compound is a 1:1 mixture of methyl allyl disulfide and disec-butyl disulfide.

[0139] The disulfide bond exchange promoter is: dioctylmethylamine

[0140] The photoinitiator is: triarylsulfonium salt

[0141] Other additives include: liquid polysulfide polymer.

[0142] The proportions of the above ingredients are as follows:

[0143] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 45 13 12 7 30

[0144] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 8s.

[0145] Example 11

[0146] The photosensitive resin oligomer is: polyurethane acrylate.

[0147] The disulfide compound is: tetraethylthiuram disulfide.

[0148] The disulfide bond exchange promoter is: octyl mercaptan.

[0149] The photoinitiator is benzophenone.

[0150] Other additives include: nitrile rubber.

[0151] The proportions of the above ingredients are as follows:

[0152] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 45 13 12 7 30

[0153] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 11s.

[0154] Example 12

[0155] The photosensitive resin monomer is: hydroxyethyl acrylate.

[0156] The disulfide compound is: tetraethylthiuram disulfide.

[0157] The disulfide bond exchange promoter is: octyl mercaptan.

[0158] The photoinitiator is benzophenone.

[0159] Other additives include: nitrile rubber.

[0160] The proportions of the above ingredients are as follows:

[0161] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 33 10 10 8 30

[0162] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 13s.

[0163] Example 13

[0164] The photosensitive resin monomer is: acrylomorpholine

[0165] The disulfide compound is: tetraethylthiuram disulfide.

[0166] The disulfide bond exchange promoter is: dodecanethiol.

[0167] The photoinitiator is benzophenone.

[0168] Other additives include: silica.

[0169] The proportions of the above ingredients are as follows:

[0170] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 33 13 6 8 22

[0171] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 12s.

[0172] Example 14

[0173] The photosensitive resin oligomer is: polyurethane acrylate.

[0174] The disulfide compound is: tetraethylthiuram disulfide.

[0175] The disulfide bond exchange promoter is: oleyl dimethyl tertiary amine

[0176] The photoinitiator is benzophenone.

[0177] Other additives include: silica powder

[0178] The proportions of the above ingredients are as follows:

[0179] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 38 11 6 8 21

[0180] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 7s.

[0181] Example 15

[0182] The photosensitive resin oligomer is: polyether acrylate.

[0183] The disulfide compound is: tetraethylthiuram disulfide.

[0184] The disulfide bond exchange promoter is: butanethiol.

[0185] The photoinitiator is: dialkoxyacetophenone

[0186] Other additives include: talc.

[0187] The proportions of the above ingredients are as follows:

[0188] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 28 5 5 11 3

[0189] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 9s.

[0190] Comparative Example 1: The disulfide bond exchange promoter in Example 1 was removed.

[0191] The photosensitive resin monomer is methyl methacrylate.

[0192] The disulfide compound is: tetraethylthiuram disulfide.

[0193] The photoinitiator is benzophenone.

[0194] Other additives include: calcium carbonate.

[0195] The proportions of the above ingredients are as follows:

[0196] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 60 50 0 20 50

[0197] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 15s.

[0198] Comparative Example 2: Contains no disulfide compounds or disulfide bond exchange promoters

[0199] The photosensitive resin oligomer is: polyurethane acrylate.

[0200] The photoinitiator is benzophenone.

[0201] Other additives include: nitrile rubber.

[0202] The proportions of the above ingredients are as follows:

[0203] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 45 0 0 7 30

[0204] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 10s.

[0205] Comparative Example 3: Contains disulfide bond promoters but no disulfide compounds

[0206] Photosensitive resin is: polyurethane acrylate

[0207] The disulfide bond exchange promoter is: octyl mercaptan.

[0208] The photoinitiator is benzophenone.

[0209] Other additives include: nitrile rubber.

[0210] The proportions of the above ingredients are as follows:

[0211] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 45 0 12 7 30

[0212] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2 The layer thickness is 0.05mm and the exposure time is 12s.

[0213] Comparative Example 4: Contains disulfide compounds but lacks disulfide bond promoters

[0214] Photosensitive resin is: polyurethane acrylate

[0215] The disulfide compound is: tetraethylthiuram disulfide.

[0216] The photoinitiator is benzophenone.

[0217] Other additives include: nitrile rubber.

[0218] The proportions of the above ingredients are as follows:

[0219] Photosensitive resin disulfide compounds Disulfide bond exchange promoter Photoinitiator Other additives Number of weights 45 13 0 7 30

[0220] Printing method: DLP printer, printing parameters: wavelength 405nm, UV light power 10mW / cm² 2The layer thickness is 0.05mm and the exposure time is 11s.

[0221] The 3D printing process, key indicators, and minimum forming temperature of the statistical examples and comparative examples are shown in Table 1.

[0222] Table 1

[0223]

[0224] Figure 1 The storage modulus of the 3D printing material prepared in Example 5 was tested using a TA rheometer as a function of temperature. The results show that its storage modulus decreases sharply with increasing temperature.

[0225] Figure 2 The storage modulus of the 3D printing materials prepared in Comparative Examples 2-4 and Example 11 was tested using a TA rheometer as a function of temperature. The results show that only when both dynamic bonds and exchange promoters are present can a faster modulus change occur.

[0226] Figure 3 The diagram shows the structural changes of the orthopedic brace 3D printed from components of Example 5 after being heated to 80°C for arbitrary shaping and then cooled to 25°C for final shaping.

[0227] By comparing the embodiments and comparative examples, it was found that reshaping can be achieved at different temperatures using the method of the present invention. However, the comparative examples showed that dynamic bonds or disulfide bond exchange promoters alone cannot achieve both stiffness variation and reshaping; only the simultaneous presence of dynamic bonds and exchange promoters can achieve the purpose of reshaping. Furthermore, it was found that with the presence of dynamic bonds, the stiffness variation effect is more significant with increasing amounts of exchange promoters, and the shaping temperature is lower.

[0228] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. Use of a photocurable polymer material raw material composition in the production of a polymer material which can be reshaped, characterized in that The composition comprises the following components by weight: photosensitive resin monomer or oligomer 20~80 parts disulfide compound 10~60 parts disulfide bond exchange promoter 5~60 parts photoinitiator 1~20 parts The disulfide compound is selected from one or more of propylthiuram disulfide, thiamine disulfide, 5,5'-dithiobis(2-nitrobenzoic acid), tetraethylthiuram disulfide, 4,4'-dinitrodiphenyl disulfide, 4,4'-dithiodimorpholine, xanthate disulfide, diethyl disulfide, 2,2'-dithiodibenzoic acid, dithiobis(thiazoline), dibenzyl disulfide, L-4,4'-dithiobis(2-aminobutyric acid), dimethyl disulfide, dipropyl disulfide, 4,4'-dithiodianiline, 3,3'-dithiodipropionamide, 2,2'-diaminodiphenyl disulfide, 2,2'-dinitrodiphenyl disulfide, 2,2'-dipyridyl disulfide, diallyl disulfide, methylallyl disulfide, propylallyl disulfide, methylpropyl disulfide, cyclohexyl disulfide, 4,4'-dipyridyl disulfide, diisobutylthiuram disulfide, difurfuryl disulfide, di-sec-butyl disulfide, bis(2-thienyl) disulfide, dichloro disulfide, and polythiourethane rubber. The disulfide bond exchange promoter is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol, lauryldimethyl tertiary amine, 1,8-diazabicycloundec-7-ene, cetyl dimethyl tertiary amine, dimethyl tetradecyl amine, 1-methylimidazole-2-thiol, octadecyl dimethyl tertiary amine, isopropyl mercaptan, N,N-dimethyl decyl amine, tert-butyl mercaptan, dioctadecyl methyl tertiary amine, dioctyl methyl amine, propyl mercaptan, oleyl dimethyl tertiary amine, 2-diethylaminoethyl mercaptan, butyl mercaptan, 1,3-propanedithiol, dodecanethiol, dithiothreitol, pentanethiol, hexanethiol, octanethiol.

2. Use according to claim 1, wherein The monomer of the photosensitive resin monomer or oligomer is selected from one or more of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, epoxy acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, polyurethane acrylate, polyurethane methacrylate, polyester acrylate, polyether acrylate, tetrahydrofuran acrylate, lauryl acrylate, lauryl methacrylate, isobornyl acrylate, acryloyl morpholine, cyclohexyl acrylate, cyclohexyl methacrylate, 2-phenoxyethyl acrylate, 1,6-hexanediol diacrylate, ethoxyethyl acrylate, and 1,3-propanediol monoacrylate.

3. The use according to claim 1, wherein The photoinitiator is a free radical photoinitiator and / or a cationic photoinitiator, the free radical photoinitiator is selected from one or more of benzoin and its derivatives, benzoin ether derivatives, dialkoxyacetophenone, α-hydroxyalkyl phenone, α-amine alkyl phenone, acyl phosphine oxide, benzophenone and its derivatives, thioxanthone, anthraquinone, and the cationic photoinitiator is selected from one or more of diaryliodonium salt, triarylsulfonium salt, and aryl ferrocene salt.

4. The use according to claim 1, wherein The monomer of the photosensitive resin monomer or oligomer is selected from acrylic acid, methyl methacrylate, epoxy acrylate, polyurethane acrylate, polyurethane methacrylate, lauryl acrylate, tetrahydrofuran acrylate, isobornyl acrylate, acryloyl morpholine, ethoxyethyl acrylate or 1,6-hexanediol diacrylate; the disulfide compound is selected from one or more of tetraethylthiuram disulfide, 4,4'-dinitrodiphenyl disulfide, 4,4'-dithiodimorpholine, diethyl disulfide, 2,2'-dithiodibenzoic acid, dimethyl disulfide, dipropyl disulfide, 4,4'-dithiodianiline, methyl allyl disulfide, methyl propyl disulfide, 4,4'-dipyridyl disulfide, diisobutylthiuram disulfide bis(2-thienyl) disulfide, and polythiourethane rubber; The disulfide bond exchange promoter is selected from one or more of 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicycloundec-7-ene, dimethyltetradecylamine, 1-methylimidazole-2-thiol, octadecyldimethyl tertiary amine, oleyl dimethyl tertiary amine, butanethiol, 1,3-propanedithiol, dodecanethiol, dithiothreitol, octanethiol; The initiator is selected from one or more of benzoin and its derivatives, benzoin derivatives, alpha-hydroxyalkyl phenones, alpha-amine alkyl phenones, acyl phosphine oxides, benzophenone and its derivatives, thioxanthone, anthraquinone, aliphatic tertiary amine, diaryliodonium salt, triarylsulfonium salt, and aryl ferrocene salt.

5. The use according to claim 1, characterized in that The light-curable polymer material raw material composition further comprises one or more of a diluent, a toughening agent, a plasticizer, an inorganic filler, an anti-aging agent, a dyeing agent, and a solvent, in an amount of 1-50 parts by weight.

6. The use according to claim 5, wherein The diluent is selected from one or more of dodecyl glycidyl ether, ethylene glycol diglycidyl ether, benzyl glycidyl ether, phenyl glycidyl ether, and polyhydroxy polyether; The toughening agent is selected from one or more of ethylene-propylene rubber type toughening agent, polybutadiene rubber type toughening agent, butyl rubber type toughening agent, nitrile rubber type toughening agent, styrene-butadiene rubber type toughening agent, styrene-butadiene thermoplastic elastomer type toughening agent, methyl methacrylate-butadiene-styrene terpolymer type toughening agent, acrylonitrile-butadiene-styrene copolymer type toughening agent, chlorinated polyethylene type toughening agent, ethylene-vinyl acetate copolymer type toughening agent, liquid polysulfide polymer type toughening agent, and active polyurethane type epoxy toughening agent; The plasticizer is selected from one or more of phthalate plasticizer, chlorinated paraffin, epoxy soybean oil, and dioctyl adipate; The inorganic filler is selected from one or more of clay, fiber, white carbon black, carbon black, graphene, carbon nanotube, titanium dioxide, barium titanate, aluminum oxide, silicon oxide, boron nitride, calcium carbonate, and silicon nitride. The anti-aging agent is an antioxidant and / or an anti-irradiation agent, the antioxidant is a primary antioxidant and a secondary antioxidant, the primary antioxidant is a hindered phenol antioxidant, the secondary antioxidant is a phosphite and / or a thioester, and the anti-irradiation agent is one or more of a salicylate irradiation absorber, a benzophenone irradiation absorber, a benzotriazole irradiation absorber, a substituted acrylonitrile irradiation absorber, and a triazine irradiation absorber; The dyeing agent is an inorganic color additive and / or an organic color additive, the inorganic color additive is one or more of a smoke black, a chalk, a cinnabar, a red clay, a realgar, a natural iron oxide, a wollastonite, a barite powder, a talc powder, a mica powder, a kaolin, a titanium white, a zinc white, a lead chrome yellow, and an iron blue, and the organic color additive is one or more of a gamboge, an alizarin red, an indigo, a big red powder, a light yellow, a phthalocyanine blue, and a quinacridone; The solvent is one or more of benzene, toluene, xylene, styrene, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, perchloroethylene, trichloroethylene, methanol, ethanol, isopropyl alcohol, diethyl ether, propylene oxide, ethylene glycol ether, methyl acetate, ethyl acetate, propyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, benzyl alcohol, diethanolamine, tetrahydrofuran, and acetonitrile.

7. Use according to any one of claims 1 to 6, wherein The repeatedly shapeable high polymer material is formed by UV light curing of the light-curing high polymer material raw composition, and the repeatedly shapeable high polymer material is reshaped by bending, extruding, and twisting when the temperature is relatively high, and then the shape is fixed until the temperature is relatively low.

8. Use according to claim 7, wherein The light-curing high polymer material raw composition or the repeatedly shapeable high polymer material is used for preparing a 3D printing material.

9. The use according to claim 7, wherein The light-curing high polymer material raw composition or the repeatedly shapeable high polymer material is used for preparing a medical device.

10. The use according to claim 9, wherein The medical device is an orthopedic brace.

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