CN113831459A - Low-temperature-resistant flexible photosensitive resin composition for photocuring 3D printing and preparation method thereof - Google Patents

Low-temperature-resistant flexible photosensitive resin composition for photocuring 3D printing and preparation method thereof Download PDF

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CN113831459A
CN113831459A CN202111143356.7A CN202111143356A CN113831459A CN 113831459 A CN113831459 A CN 113831459A CN 202111143356 A CN202111143356 A CN 202111143356A CN 113831459 A CN113831459 A CN 113831459A
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CN113831459B (en
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陈少云
卓东贤
罗永强
黄慧玲
瞿波
王睿
郑燕玉
刘小英
李文杰
陈苗苗
许一昊
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Quanzhou Normal University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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Abstract

The invention discloses a low-temperature-resistant flexible photosensitive resin composition for photocuring 3D printing and a preparation method thereof. The composition comprises the following raw materials in parts by weight: 5-40 parts of acrylic group-terminated silicon chain-containing polyurethane prepolymer, 20-60 parts of acrylic group-terminated flexible polyurethane prepolymer, 5-10 parts of polyurethane acrylate resin, 20-70 parts of reactive diluent, 1.0-5.0 parts of photoinitiator and 0.1-1.0 part of antioxidant. The low-temperature-resistant flexible photosensitive resin composition for photocuring 3D printing has high reactivity, and can be used for conventional desktop-level 3D printing equipment such as SLA and DLP. Meanwhile, the printed product contains silicon chains, has good low temperature resistance, small shrinkage rate, is not easy to yellow and has excellent mechanical properties.

Description

Low-temperature-resistant flexible photosensitive resin composition for photocuring 3D printing and preparation method thereof
Technical Field
The application belongs to the technical field of chemical industry, and particularly relates to a low-temperature-resistant flexible photosensitive resin composition for photocuring 3D printing and a preparation method thereof.
Background
With popularization and application of SLA technology and DLP technology, 3D printing consumables are required to be more and more diversified in the market, and photosensitive resin is required to have different systems and different performances. With the development of some medical models and artware designs, the demand for flexible resin materials is increasing, so that the development of flexible resin meeting the requirements has great promotion effect on promoting the application of SLA and DLP technologies.
The photocuring organic silicon material has been researched and applied in a plurality of fields by virtue of excellent physical and chemical properties, and a new way is opened for solving the wide application of the flexible material in 3D printing. In particular, the organosilicon material has a series of excellent characteristics of good temperature resistance, oxidation resistance, hydrophobicity, flexibility, permeability, aging resistance, high transparency, physiological inertia, no adhesion with human tissues and blood, good biocompatibility, no toxicity, no odor, no carcinogenesis and the like. And the excellent low-temperature resistance of the silicone rubber can well solve the problem of low-temperature resistance of the 3D printing material. But the existing domestic and foreign researches are rarely related to the performance.
Silicone rubbers used for 3D printing are relatively rare and are mainly associated with the complexity of the formulation of the rubber and the limitations of the curing regime. These resins are also synthetic and high viscosity resins based on silicone acrylate resins, requiring further dilution with monomers. Based on this, Andrew j. boydston team reports a series of photo-resins suitable for DLP elastomer production, which use monofunctional acrylate monomer, bifunctional acrylate cross-linking agent monomer and acrylate-modified polysiloxane as main raw materials, and by adjusting the contents of the components, a series of elastomers with different mechanical properties can be obtained. The Kurary publication in japan proposes a photocurable elastomer having both curability and flexibility. By controlling the relative molecular mass and arrangement of the elastomer portion and the photocurable portion, it achieves both curability and flexibility, and can be used as an adhesive, a coating material, and a molding material. Kai Parthy has derived a 3D printing material that can be used for the sole, still can improve its elasticity and shock attenuation effect through intelligent design and section technique. German invention patent application Hochviskose silicone gum sheet, wherein the Horhviskose silicone gum sheet, the Holtellung elastomerer, the femto titels balistischer generator, the Verfahren (publication number WO 2017089496A1) discloses a method for 3D printing of high-viscosity silicone rubber, and silicon hydrogen addition liquid silicone rubber is used as a raw material, and a large amount of filler can be added to ensure the mechanical property; the photosensitive platinum catalyst with a special structure is adopted, and printing and curing are carried out under the irradiation of ultraviolet light. The method combines a photosensitive catalyst with the existing silicone rubber to realize DIW3D printing of the silicone rubber, can adapt to higher viscosity, and allows filling of a large amount of fillers. However, this method requires the use of an expensive platinum catalyst and is unstable during storage of the raw material.
In summary, the main problems of the photocuring 3D printing flexible material in the currently reported method are: most materials are thermosetting resins, not true rubber materials; the photosensitive platinum catalyst with a special structure is expensive; the synthesis method of the acrylic organosilicon material is complex, and the problem of oxygen inhibition also exists in the curing process; the compatibility problem of the acrylate and the organic silicon exists, the mechanical property of the product is lower, and the elasticity is poorer; the high and low temperature resistance of the silicon rubber can be greatly reduced by the acrylic acid, epoxy resin modified organic silicon and other structures; the material system is limited by the printing method and cannot achieve ideal mechanical properties. In addition, related products are not really pushed out about the flexible body material for 3D printing in China, and at present, few research reports about the flexible body material for 3D printing are reported, and the low-temperature resistant flexible body material for 3D printing is needless to say. Therefore, the flexible body material which has good flexibility, mechanical property and high and low temperature resistance, simple process and quick curing is researched and developed, is suitable for photocuring 3D printing, can reduce the material use cost of equipment, breaks the technical monopoly of foreign materials, and promotes the quick development of domestic photocuring 3D materials, thereby laying a certain foundation for the wide development of photocuring 3D printing in the industrial field.
Disclosure of Invention
Aiming at the condition of the prior art, the invention provides the low-temperature-resistant flexible photosensitive resin composition for the photocuring 3D printing, which is low in cost and excellent in mechanical property, and the preparation method thereof. The photosensitive resin composition has the advantages of low cost, wide applicability and cold resistance, is used for 3D printing technology, effectively solves the problems of high price of 3D printing resin, improvement on mechanical properties based on the flexible polyurethane photosensitive resin composition and the like, and lays a foundation for large-scale application of the 3D printing technology.
In order to achieve the purpose, the invention adopts the technical scheme that:
the flexible photosensitive resin composition for the low-temperature-resistant photocuring 3D printing comprises the following raw materials in parts by weight:
Figure BDA0003284826230000031
the structural formula of the acrylic acid group-terminated silicon chain polyurethane prepolymer is as follows:
Figure BDA0003284826230000032
in the above formula, R1，R2Not limited to the listed categories;
the structural formula of the acrylic group-terminated flexible polyurethane prepolymer is as follows:
Figure BDA0003284826230000041
in the above formula, R1，R2Not limited to the listed categories.
The preparation method of the low-temperature-resistant flexible photosensitive resin composition for the photocuring 3D printing comprises the following steps:
(1) continuously dropwise adding metered hydroxyl silicone oil into a round-bottom flask containing diisocyanate through a separating funnel, reacting for 3-6 hours under the protection of nitrogen and at the temperature of 80-100 ℃, then adding metered hydroxyl-containing acrylic acid monomer, continuously reacting for 2-3 hours, and vacuumizing and defoaming a product after reaction to obtain an acrylic acid group-terminated silicon-chain polyurethane photosensitive prepolymer;
wherein, the diisocyanate is one or more of toluene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate; the hydroxyl silicone oil is one or more of hydroxyl silicone oils with molecular weight of 20000 (hydroxyl content of 0.2%), 2000 (hydroxyl content of 2%), 1800 (hydroxyl content of 1.8%), 500 (hydroxyl content of 8%) and the like; the acrylic monomer containing hydroxyl is one or the combination of hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like; the input ratio of the diisocyanate to the hydroxyl silicone oil to the hydroxyl-containing acrylic monomer is as follows: the amount of-OH species is calculated as 1: 1.
(2) Continuously dropwise adding metered hydroxyl-containing acrylic monomers into a round-bottom flask filled with polyester or polyether with an isocyanate group end capping through a separating funnel, and reacting for 0.1-7.0 h under the protection of nitrogen and at the temperature of 50-100 ℃; vacuumizing and defoaming the product after reaction to obtain the acrylic group-terminated flexible polyurethane photosensitive prepolymer;
wherein, the polyester or polyether blocked by the isocyanate group is one or the combination of aliphatic polyester or polyether blocked by the isocyanate group (NCO content is 0.1-6.0%), alicyclic polyester or polyether blocked by the isocyanate group (NCO content is 0.1-4.0%), and aromatic polyester or polyether blocked by the isocyanate group (NCO content is 0.1-5.0%); the acrylic monomer containing hydroxyl is one or the combination of hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like; the isocyanate group-terminated polyester or polyether and the hydroxyl-containing acrylic monomer are added according to the proportion of-NCO: the amount of-OH species is calculated as 1: 1.
(3) According to the weight, 5-40 parts of acrylic group-terminated silicon chain polyurethane photosensitive prepolymer, 20-60 parts of acrylic group-terminated flexible polyurethane prepolymer, 5-10 parts of polyurethane acrylate resin, 20-70 parts of reactive diluent, 1.0-5.0 parts of photoinitiator and 0.1-1.0 part of antioxidant are mixed and heated to 30-80 ℃, and the mixture is stirred and mixed uniformly to obtain the low-temperature-resistant photocuring flexible photosensitive resin composition for 3D printing.
Preferably, the urethane acrylate resin is selected from one of aliphatic urethane acrylate oligomer, aromatic urethane acrylate oligomer, urethane diacrylate, and dimethyl urethane acrylate resin or a combination thereof.
Preferably, the reactive diluent is selected from one or a combination of glycerol propylene oxide triacrylate, ethoxylated pentaerythritol tetraacrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, isobornyl acrylate and cyclotrimethylolpropane formal acrylate.
Preferably, the photoinitiator is selected from one of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone or a combination thereof.
Preferably, the antioxidant is selected from one or a combination of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate and 2, 6-di-tert-butyl-4-methylphenol.
The invention has the beneficial effects that:
(1) according to the low-temperature-resistant flexible photosensitive resin composition for photocuring 3D printing, provided by the invention, the silicon chain is subjected to photosensitive modification and is connected into a structural system of photosensitive resin, so that a flexible material which is suitable for photocuring 3D printing and has excellent mechanical property and low-temperature resistance is developed.
(2) The photosensitive resin composition has the advantages of simple process, quick curing and the like, can reduce the material use cost of equipment, break through the technical monopoly of foreign materials, promote the quick development of domestic photocuring 3D materials, expand the application range of photocuring 3D printing, and is particularly applied to the shoe and clothes industry.
Drawings
Fig. 1 is a product printed by a desktop-level photocuring 3D printer from a low-temperature-resistant flexible photosensitive resin composition for photocuring 3D printing prepared in an example of the present invention.
Detailed Description
In the examples, the sources of the raw materials used and the abbreviations in the examples are as follows:
acrylic group-terminated silicon chain-containing polyurethane prepolymer
13.38g of toluene diisocyanate was added into a round-bottom flask, 72.57g of hydroxy silicone oil was continuously added dropwise through a separating funnel, and the reaction was stirred for 5 hours under the protection of nitrogen at 90 ℃. Adding 10g of hydroxyethyl methacrylate, and continuously stirring and reacting for 2 hours under the conditions of nitrogen protection and 90 ℃ to obtain an acrylic group-terminated silicon-chain-containing polyurethane photosensitive prepolymer, which is abbreviated as A-1;
12.07g of toluene diisocyanate was added into a round bottom flask, 65.51g of hydroxy silicone oil was continuously added dropwise through a separating funnel, and the mixture was stirred and reacted for 5 hours under the protection of nitrogen at 90 ℃. Adding 10g of hydroxypropyl methacrylate, and continuously stirring and reacting for 2h under the protection of nitrogen and at the temperature of 90 ℃ to obtain the acrylic group-terminated silicon-chain-containing polyurethane photosensitive prepolymer, which is abbreviated as A2.
Acrylic group-terminated flexible polyurethane prepolymer
In a round-bottom flask containing isocyanate group terminated polyester (ether), metered acrylic monomers with hydroxyl and C ═ C are added dropwise continuously through a separating funnel, and the mixture is reacted for 0 to 5 hours under the protection of nitrogen and at the temperature of 50 to 100 ℃. Vacuumizing and defoaming the product after reaction to obtain an isocyanate group-terminated flexible polyurethane photosensitive prepolymer, which is abbreviated as B-1;
urethane acrylate resin
Aliphatic urethane acrylate: purchased from sandoma corporation, product number CN9010, abbreviated as C-1;
aliphatic urethane acrylate: purchased from sandoma corporation under product number CN991, abbreviated as C-2;
reactive diluent
Hydroxyethyl methacrylate: purchased from Aladdin reagent (Shanghai) Co., Ltd, abbreviated as D-1;
hydroxypropyl methacrylate: purchased from Aladdin reagent (Shanghai) Co., Ltd, abbreviated as D-2;
cyclotrimethylolpropane formal acrylate (CTFA): purchased from sandoma corporation, abbreviated as D-3;
photoinitiator
Phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide: purchased from Aladdin reagent (Shanghai) Inc., product number photoinitiator XBPO, abbreviated as E-1;
1-hydroxycyclohexyl phenyl ketone: available from Allantin reagents (Shanghai) Inc., product number photoinitiator 184, abbreviated as E-2;
antioxidant agent
2, 6-di-tert-butyl-4-methylphenol: available from Allantin reagent (Shanghai) Inc., product number antioxidant BHT, abbreviated as F-1;
pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate: purchased from Kyon chemical Co., Ltd, Guangzhou, antioxidant 1010, abbreviated as F-2.
Examples 1 to 6 (preparation of sample No. 1 to sample No. 6)
According to parts by weight, 5-40 parts of silicon chain polyurethane photosensitive prepolymer terminated by acrylic groups, 20-60 parts of flexible polyurethane prepolymer terminated by acrylic groups, 5-10 parts of polyurethane acrylate resin, 20-70 parts of reactive diluent, 1.0-5.0 parts of photoinitiator and 0.1-1.0 part of antioxidant are mixed and heated to 30-80 ℃, and the mixture is stirred and mixed uniformly to obtain the low-temperature-resistant flexible photosensitive resin composition for photocuring 3D printing. The relationship between the sample number and the types and ratios of the components is shown in Table 1.
TABLE 1
Figure BDA0003284826230000081
Figure BDA0003284826230000091
Application of product prepared by embodiment in photocuring 3D printer
And introducing the prepared photosensitive resin composition into a photocuring 3D printer, and performing computer modeling, composition and molding after printing. For the products obtained in the above examples, the photosensitive resin compositions were evaluated by curing and observing the appearance of the cured products, and the results are shown in table 2 below:
TABLE 2
Figure BDA0003284826230000092

Claims (9)

1. The low-temperature-resistant flexible photosensitive resin composition for the photocuring 3D printing is characterized by comprising the following raw materials in parts by weight:
Figure FDA0003284826220000011
the structural formula of the acrylic acid group-terminated silicon chain polyurethane prepolymer is as follows:
Figure FDA0003284826220000012
in the above formula, R1，R2Is one of the listed categories;
the structural formula of the acrylic group-terminated flexible polyurethane prepolymer is as follows:
Figure FDA0003284826220000021
in the above formula, R1，R2Is one of the listed categories.
2. The method for preparing the flexible photosensitive resin composition for low temperature resistant photocuring 3D printing according to claim 1, comprising the steps of:
(1) continuously dropwise adding metered hydroxyl silicone oil into a round-bottom flask containing diisocyanate through a separating funnel, reacting for 3-6 hours under the protection of nitrogen and at the temperature of 80-100 ℃, then adding metered hydroxyl-containing acrylic acid monomer, continuously reacting for 2-3 hours, and vacuumizing and defoaming a product after reaction to obtain an acrylic acid group-terminated silicon-chain polyurethane photosensitive prepolymer;
(2) continuously dropwise adding metered hydroxyl-containing acrylic monomers into a round-bottom flask filled with polyester or polyether with an isocyanate group end capping through a separating funnel, and reacting for 0.1-7.0 h under the protection of nitrogen and at the temperature of 50-100 ℃; vacuumizing and defoaming the product after reaction to obtain the acrylic group-terminated flexible polyurethane photosensitive prepolymer;
(3) according to the weight, 5-40 parts of acrylic group-terminated silicon chain polyurethane photosensitive prepolymer, 20-60 parts of acrylic group-terminated flexible polyurethane prepolymer, 5-10 parts of polyurethane acrylate resin, 20-70 parts of reactive diluent, 1.0-5.0 parts of photoinitiator and 0.1-1.0 part of antioxidant are mixed and heated to 30-80 ℃, and the mixture is stirred and mixed uniformly to obtain the low-temperature-resistant photocuring flexible photosensitive resin composition for 3D printing.
3. The method for preparing the flexible photosensitive resin composition for low temperature resistant photocuring 3D printing according to claim 2, characterized in that in the step (1), the diisocyanate is one or more of toluene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate; the hydroxyl silicone oil is one or more of hydroxyl silicone oils with molecular weights of 20000, 2000, 1800 and 500; the acrylic monomer containing hydroxyl is one or the combination of hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like; the input ratio of the diisocyanate to the hydroxyl silicone oil to the hydroxyl-containing acrylic monomer is as follows: the amount of-OH species is calculated as 1: 1.
4. The method for preparing the flexible photosensitive resin composition for low temperature resistant photocuring 3D printing according to claim 2, wherein in the step (2), the isocyanate group-terminated polyester or polyether is one or a combination of isocyanate group-terminated aliphatic polyester or polyether, isocyanate group-terminated alicyclic polyester or polyether, and isocyanate group-terminated aromatic polyester or polyether; the acrylic monomer containing hydroxyl is one or the combination of hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate and dipentaerythritol pentaacrylate; the isocyanate group-terminated polyester or polyether and the hydroxyl-containing acrylic monomer are added according to the proportion of-NCO: the amount of-OH species is calculated as 1: 1.
5. The method for preparing the flexible photosensitive resin composition for low temperature resistant photo-curing 3D printing according to claim 2, wherein the urethane acrylate resin is selected from one or a combination of aliphatic urethane acrylate oligomer, aromatic urethane acrylate oligomer, urethane diacrylate and dimethyl urethane acrylate resin.
6. The method of claim 2, wherein the reactive diluent is selected from one or a combination of glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate, hydroxypropyl methacrylate, hydroxyethyl methacrylate, trimethylolpropane triacrylate, isobornyl acrylate and cyclotrimethylolpropane formal acrylate.
7. The method for preparing the low temperature resistant photo-curing flexible photosensitive resin composition for 3D printing according to claim 2, wherein the photo-initiator is selected from one of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone or a combination thereof.
8. The method of claim 2, wherein the antioxidant is selected from pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, phenyl tris (2, 4-di-tert-butyl) phosphite, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, 2, 6-di-tert-butyl-4-methylphenol, or a combination thereof.
9. Use of the photosensitive resin composition obtained by the production method according to any one of claims 2 to 8 for photocuring 3D printing.
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