High-strength and high-elasticity organic silicon light-cured 3D printing material and preparation method thereof

Abstract

The invention relates to a high-strength and high-elasticity organic silicon light-cured 3D printing material and a preparation method thereof.The preparation method comprises the steps that multi-arm vinyl silicone oil with macrocyclic phenyl siloxane as a core, a polysiloxane polymer containing silicon-hydrogen groups, filler and auxiliaries are mixed and stirred to be uniform according to the mass percent, then a photoinitiator is added, the mixture is stirred to be uniform, and the high-strength and high-elasticity organic silicon light-cured 3D printing material is obtained; the organic silicon photosensitive resin material is prepared. According to the preparation method, the ultraviolet light is adopted to initiate local short-time curing of the addition type organic silicon material, rapid curing forming of the organic silicon material in the photocuring 3D printing process is achieved, and a formed part is colorless and transparent and has good mechanical performance. Vinyl silicone oil used in the process method is multi-arm vinyl silicone oil, has the characteristics of excellent thermal stability, good mechanical property, low dielectric constant, excellent biocompatibility and the like, has a three-dimensional and regular structure and high surface functional group density, and can increase crosslinking sites of hydrosilylation reaction to form a compact crosslinked network structure; the mechanical property of the material is improved.

Description

Technical Field

[0001] The invention relates to a high-strength and high-elasticity organosilicon light-curing 3D printing material, a preparation method and an application thereof, and belongs to the field of curing materials. Background Art

[0002] With the continuous development of 3D printing technology, light-curing 3D printing has attracted wide attention due to its high precision, high efficiency and low cost. However, the curing resin materials currently used for 3D printing mainly include acrylic resin, polyurethane resin, epoxy resin, etc. These resins have the advantages of high strength and good adhesion, but the curing hardness is high and cannot be made into an ideal elastomeric material. In addition, the weather resistance and biocompatibility are poor, which limits their wide application in various fields.

[0003] Silicone polymer is a semi-inorganic and semi-organic macromolecular compound with silicon-oxygen bond as the main chain and silicon and organic groups as the side chain. The special structure gives it many excellent properties, such as high and low temperature resistance, weather resistance, aging resistance, corrosion resistance, low surface tension and physiological inertness, etc. It can be made into rubber elastomer with excellent performance. The combination of silicone material and light curing technology can not only expand the application of silicone material to new fields, but also add new and excellent types to light curing materials.

[0004] The curing mechanism of the hydrosilicone addition reaction type organosilicon system is that under the irradiation of ultraviolet light, the ultraviolet light-sensitive photoinitiator generates free radicals, which initiate the curing of the vinyl-containing organopolysiloxane and the silicon-hydrogen bond-containing organopolysiloxane. This system does not require the photosensitization modification of the organosiloxane, and can use the existing organosilicon resin in the presence of the photoinitiator to perform the photocuring reaction, which simplifies the reaction process and reduces costs.

[0005] Patent CN104559196A discloses a colorless and transparent light-curable 3D printing material, including organopolysiloxane containing vinyl groups, organopolysiloxane containing silicon-hydrogen bonds, photoinitiators, reinforcing fillers, and additives. However, the mechanical properties are much lower than those of addition silicone rubber, and the tensile strength and elongation at break are relatively poor.

[0006] In order to improve the hardness and elasticity of printed products, and to give them better functionality and wider application areas, this patent provides a preparation method and application of high-strength and high-elasticity silicone photocuring 3D printing materials. Summary of the invention

[0007] In view of the above problems existing in the prior art, the main purpose of the present invention is to provide a silicone photosensitive resin material using a metal complex photoinitiator, and to provide a method for preparing a colorless, transparent and elastic 3D printing material, so as to solve the problems of high brittleness and poor biocompatibility of photocurable printing materials, while making the printed parts have good mechanical properties and can be quickly formed.

[0008] In order to achieve the above object, the present invention provides the following technical solutions: Multi-arm vinyl silicone oil, multi-arm vinyl silicone oil with macrocyclic phenylsiloxane as the core, has the following structural formula: , wherein R includes any one of OSi(CH2CH2CH2CH3)2CH=CH2, R=OSi(Me)2(C=CH2CH3), and R=OSiMe(CH2CH2CH2CHCH3CH3)CH=CH2. In the structural formula, Vi is the abbreviation of CH=CH2, and the part OSiMe2Vi is R.

[0009] The viscosity of the multi-arm vinyl silicone oil is 1000-100000 mPa•S, and the vinyl content is 0.1-10.0wt%. The macrocyclic phenyl silsesquioxane with a stereoregular structure has a high surface functional group density, excellent thermal stability, good mechanical properties, low dielectric constant, excellent biocompatibility and the like.

[0010] The preparation method of the multi-arm vinyl silicone oil comprises the following steps: (1) A mixture of 1-butanol, phenyltri(butyloxy)silane, sodium hydroxide solution and water is stirred and refluxed at 110°C to 130°C, and then an anhydrous copper chloride alcohol solution is added dropwise. After reflux reaction, the blue crystals are filtered to obtain blue crystals. After drying, the blue crystals are stirred in a solvent, added dropwise to a hydrochloric acid solution, stirred and filtered to obtain a white crystalline solid, which is washed and dried to obtain a white crystalline product tri-cis-tri-trans-dodeca[(phenyl)(hydroxy)]cyclododecasiloxane [C6H5Si(O)OH] 12 ; (2) Dissolve tris-cis-tris-twelve [(phenyl) (hydroxy)] cyclododecyl siloxane in pyridine, add dimethylvinyl chlorosilane, stir and reflux at room temperature, cool after the reaction, add solvent and reflux at 110°C to 130°C, wash and dry after the reaction, and obtain a multi-arm vinyl silicone oil [PhSi(O)OSiMe2Vi] with a macrocyclic phenylsiloxane as the core. 12 .

[0011] The molar ratio of phenyltri(butoxy)silane, sodium hydroxide and anhydrous cupric chloride is 3-5:3-5:0.5-1.

[0012] The alcohol solution of anhydrous cupric chloride in step (1) is a 1-butanol solution of anhydrous cupric chloride.

[0013] The amount of water added is a trace amount, which promotes the reaction.

[0014] The solvent in step (1) is selected from a mixed solution of toluene and ethanol, and the volume ratio of the two is 3-10:1.

[0015] The hydrochloric acid solution in step (1) is a solution with a mass concentration of 5-10%.

[0016] The polysiloxane polymer containing silicon hydrogen groups in step (2) has a viscosity of 20-80 mPa•S and a hydrogen content of 0.05-1.5%, and includes one or more of single-end hydrogen-containing silicone oil, double-end hydrogen-containing silicone oil, and side hydrogen-containing silicone oil; The mass ratio of multi-arm vinyl silicone oil to polysiloxane polymer containing silicon hydrogen groups is 60-70:10-15.

[0017] The photoinitiator is an alcohol solution of chloroplatinic acid; The filler includes fumed silica and vinyl MQ resin, and has a specific surface area of ​​10-400 m 2 / g; The inhibitor is 1-ethynyl cyclohexanol.

[0018] The technical solution of the present invention prepares multi-arm vinyl silicone oils with viscosities of 5000, 20000, 60000 and 100000 cP respectively by changing the proportion of dimethylvinylchlorosilane.

[0019] The R=OSi(CH2CH2CH2CH3)2CH=CH2 can be introduced by dibutylvinylchlorosilane, or R=OSi(Me)2(C=CH2CH3) can be introduced by (1-methylvinyl)dimethylvinylchlorosilane, or R=OSiMe(CH2CH2CH2CHCH3CH3)CH=CH2 can be introduced by (4-methylpentyl)methylvinylchlorosilane, to achieve products with different multi-arm vinyl silicone oil structures.

[0020] Another technical solution of the present invention is to provide a method for preparing a high-strength and high-elasticity organosilicon photosensitive resin, comprising the following steps: (1) mixing the arm vinyl silicone oil, the polysiloxane polymer containing a silane group, the filler and the inhibitor according to mass percentage and stirring them uniformly; (2) Add a photoinitiator and stir evenly to obtain a photosensitive resin material.

[0021] The viscosity of the polysiloxane polymer containing silicon hydrogen groups is 20-80 mPa•S, the hydrogen content is 0.05-1.5%, and it includes one or more of single-end hydrogen-containing silicone oil, double-end hydrogen-containing silicone oil, and side hydrogen-containing silicone oil.

[0022] The relationship between the addition amount of multi-arm vinyl silicone oil and polysiloxane polymer containing silicon hydrogen groups is: 100 parts of multi-arm vinyl silicone oil with macrocyclic phenylsiloxane as the core 0.1-20 parts of polysiloxane polymer containing silicon hydrogen groups Photoinitiator 0.001-10 parts Filler 0-70 parts Inhibitor 0-30 parts.

[0023] The photoinitiator is an alcohol solution of chloroplatinic acid.

[0024] The filler includes fumed silica and vinyl MQ resin, and has a specific surface area of ​​10-400 m 2 / g; In some embodiments, the fumed silica is treated with a silane coupling agent to make it hydrophobic to obtain modified fumed silica.

[0025] The inhibitor is 1-ethynyl cyclohexanol. The addition reaction is inhibited by the low temperature of the alkynyl group, and the activity of the inhibitor is reduced under high temperature conditions, thereby achieving the function of the inhibitor.

[0026] The high-strength and high-elasticity organosilicon light-curing 3D printing material is prepared by using the high-strength and high-elasticity organosilicon photosensitive resin prepared by the method under ultraviolet light curing conditions.

[0027] A photocurable 3D printing material comprises the high-strength and high-elasticity organic silicon photocurable 3D printing material.

[0028] The UV curing 3D printing method comprises the following steps: S1: Stir the silicone photosensitive resin material evenly and load it into the barrel, install the barrel on the feed pump of the 3D printer, and connect the print head; the ultraviolet light source of the 3D printer is fixed at the bottom of the print head and moves synchronously with the print head. The light path is focused and collimated and acts on the glue outlet position of the print head for pre-curing the photosensitive material; S2: Under the control of the printing program, the high-strength and high-elasticity silicone light-curing 3D printing material is printed out into a tensile spline structure by the printing nozzle under the action of the feed pump; it is quickly cured under ultraviolet light for 0.1~30s to obtain the printed material.

[0029] The high-strength and high-elasticity organosilicon light-curing 3D printing material is prepared according to the method, has good fluidity, is uniform and has no obvious particles, and the photocuring 3D printing material made of the photosensitive resin has a tensile strength of 5.5-9.8MPa, an elongation at break of 700-1000%, and a tear strength of 20.9-35KN / m.

[0030] Further preferably, the photosensitive resin light-cured 3D printing material has a tensile strength of 8.5-9.5 MPa, an elongation at break of 840-980%, and a tear strength of 27.0-30.5 KN / m.

[0031] More preferably, the resilience of the silicone photocurable 3D printing material is 66-90%, more preferably 75-90%, and more preferably 75-85%.

[0032] Through the above technical solution, the present invention has the following technical effects: (1) The vinyl silicone oil used in the process method of the present invention is a multi-arm vinyl silicone oil, which has the characteristics of excellent thermal stability, good mechanical properties, low dielectric constant, excellent biocompatibility, etc. Its structure is three-dimensionally regular and the surface functional group density is high. It can increase the cross-linking sites of the hydrosilylation reaction, form a dense cross-linking network structure, and improve the mechanical properties of the material.

[0033] (2) Metal complex photoinitiators are used to initiate the hydrosilylation reaction, which results in a fast curing reaction speed and a wide wavelength range of curable light sources.

[0034] (3) The volume shrinkage is low, the cured product is colorless, transparent and elastic.

[0035] (4) No volatile solvents, all photosensitive resins are involved in curing, and there is no pollution. DETAILED DESCRIPTION

[0036] The present invention is further explained below with reference to the examples, but the examples do not limit the present invention in any form.

[0037] The preparation method of the multi-arm vinyl silicone oil comprises the following steps: (1) A mixture of 120 mL of 1-butanol, 14.6 g (45 mmol) of phenyltri(butyloxy)silane, 1.8 g (45 mol) of sodium hydroxide solution, and 0.81 mL of water was stirred and refluxed at 110°C to 130°C, and then 2.01 g (15 mmol) of anhydrous copper chloride / 1-butanol solution was dropped into it. After reflux reaction, it was filtered to obtain blue crystals. After drying, 8.4 g of the blue crystals were stirred in a mixed solution of toluene / ethanol (200:50 mL), and then dropped into a 8.7% concentrated hydrochloric acid solution. After stirring, it was filtered to obtain a white crystalline solid. The white crystalline product was washed and dried to obtain tri-cis-tri-trans-dodeca[(phenyl)(hydroxy)]cyclododecasiloxane [C6H5Si(O)OH] 12 ; (2) 4 g (14.5 mmol) of tris-cis-tris-dodecyl[(phenyl)(hydroxy)]cyclododecylsiloxane was dissolved in 13.74 g (87 mmol) of pyridine, and then added to 20.96 g (87 mmol) of dimethylvinylsilyl chloride. The mixture was stirred at room temperature and refluxed for an exothermic reaction. After cooling, 130 mL of toluene was added and the mixture was refluxed at 110°C to 130°C for 1 h. After the reaction was completed, the mixture was washed and dried to obtain 5000 cP of multi-arm vinyl silicone oil [PhSi(O)OSiMe2Vi] with a macrocyclic phenylsiloxane core. 12 . Multi-arm vinyl silicone oil [PhSi(O)OSiMe2Vi] 12 The structural formula is as follows: , where R=OSi(Me)2CH=CH2.

[0038] By using the above-mentioned preparation method, when the molar ratio of tris-cis-tris-dodeca[(phenyl)(hydroxy)]cyclododecylsiloxane:pyridine:dimethylvinylchlorosilane is 1:26:26 (14.5 mmol, 377 mmol, 377 mmol), a multi-arm vinyl silicone oil with a macrocyclic phenylsiloxane as the core and a viscosity of 20000 cP is obtained.

[0039] By using the above-mentioned preparation method, when the molar ratio of tris-cis-tris-dodeca[(phenyl)(hydroxy)]cyclododecylsiloxane:pyridine:dimethylvinylchlorosilane is 1:114:114 (14.5 mmol, 1653 mmol, 1653 mmol), a multi-arm vinyl silicone oil with a macrocyclic phenylsiloxane as the core and a viscosity of 60000 cP is obtained.

[0040] By using the above-mentioned preparation method, when the molar ratio of tris-cis-tris-dodeca[(phenyl)(hydroxy)]cyclododecylsiloxane:pyridine:dimethylvinylchlorosilane is 1:187:187 (14.5 mmol, 2711.5 mmol, 2711.5 mmol), a multi-arm vinyl silicone oil with a macrocyclic phenylsiloxane as the core and a viscosity of 100000 cP is obtained.

[0041] The following test was conducted on the multi-arm vinyl silicone oils with macrocyclic phenylsiloxane as the core and the viscosities of 5000, 20000, 60000 and 100000 cP obtained above.

[0042] Based on this, using the same preparation method as above, when dimethylvinylchlorosilane was replaced by dibutylvinylchlorosilane, a multi-arm vinyl silicone oil in which R was OSi(CH2CH2CH2CH3)2CH=CH2 was obtained.

[0043] Based on this, the same preparation method as above was used to obtain a multi-arm vinyl silicone oil in which R=OSi(Me)2(C=CH2CH3) when dimethylvinylchlorosilane was replaced by (1-methylvinyl)dimethylvinylchlorosilane.

[0044] Based on this, using the same preparation method as above, when dimethylvinylchlorosilane was replaced by (4-methylpentyl)methylvinylchlorosilane, a multi-arm vinyl silicone oil with R=OSiMe(CH2CH2CH2CHCH3CH3)CH=CH2 was obtained.

[0045] Example 1 A method for preparing a high-strength and high-elasticity organosilicon light-curing 3D printing material, wherein the preparation process of the organosilicon photosensitive resin material is as follows: (1) 70 g of a multi-arm vinyl silicone oil with a viscosity of 5000 cP and a macrocyclic phenylsiloxane core, 12 g of a single-end hydrogenated silicone oil, 8 g of 1-ethynylcyclohexanol, and 7 g of fumed silica are mixed and stirred uniformly; (2) 3 g of a chloroplatinic acid isopropanol solution (in terms of Pt metal, 10 ppm based on the total mass of the photosensitive resin) is added to the mixture obtained in (1), and the mixture is stirred and mixed uniformly to obtain a transparent photosensitive resin material, i.e., a high-strength and high-elasticity organosilicon light-curing 3D printing material.

[0046] Example 2 A method for preparing a high-strength and high-elasticity organosilicon light-curing 3D printing material, wherein the preparation process of the organosilicon photosensitive resin material is as follows: (1) 70g of a multi-arm vinyl silicone oil with a macrocyclic phenylsiloxane core having a viscosity of 20,000 cP, 12g of a single-end hydrogenated silicone oil, 8g of 1-ethynylcyclohexanol, and 7g of fumed silica; (2) 3g of a chloroplatinic acid isopropanol solution (calculated as Pt metal, 10ppm based on the total mass of the photosensitive resin) is added to the mixture obtained in (1), and the mixture is stirred and mixed to obtain a transparent photosensitive resin material, i.e., a high-strength and high-elasticity organosilicon light-curing 3D printing material.

[0047] Example 3 A method for preparing a high-strength and high-elasticity organosilicon light-curing 3D printing material, wherein the preparation process of the organosilicon photosensitive resin material is as follows: (1) 70 g of a multi-arm vinyl silicone oil with a viscosity of 60,000 cP and a macrocyclic phenylsiloxane core, 12 g of a single-end hydrogenated silicone oil, 8 g of 1-ethynylcyclohexanol, and 7 g of fumed silica; (2) adding 3 g of chloroplatinic acid isopropanol solution (calculated as Pt metal, based on 10 ppm of the total photosensitive resin mass) to the mixture obtained in (1), stirring and mixing evenly, to obtain a transparent photosensitive resin material, i.e., a high-strength and high-elasticity organosilicon light-curing 3D printing material.

[0048] Example 4 A method for preparing a high-strength and high-elasticity organosilicon light-curing 3D printing material, wherein the preparation process of the organosilicon photosensitive resin material is as follows: (1) 70g of a multi-arm vinyl silicone oil with a viscosity of 100,000 cP and a macrocyclic phenylsiloxane core, 12g of a single-end hydrogenated silicone oil, 8g of 1-ethynylcyclohexanol, and 7g of fumed silica; (2) adding 3g of chloroplatinic acid isopropanol solution (calculated as Pt metal, based on 10ppm of the total photosensitive resin mass) to the mixture obtained in (1), stirring and mixing evenly, to obtain a transparent photosensitive resin material, i.e., a high-strength and high-elasticity organosilicon light-curing 3D printing material.

[0049] Example 5 A method for preparing a high-strength and high-elasticity organosilicon light-curing 3D printing material, wherein the preparation process of the organosilicon photosensitive resin material is as follows: (1) 70g of a multi-arm vinyl silicone oil with a viscosity of 60000cP and a macrocyclic phenylsiloxane core, 12g of a double-ended hydrogenated silicone oil, 8g of 1-ethynylcyclohexanol, and 7g of fumed silica; (2) adding 3g of chloroplatinic acid isopropanol solution (calculated as Pt metal, based on 10ppm of the total photosensitive resin mass) to the mixture obtained in (1), stirring and mixing evenly, to obtain a transparent photosensitive resin material, i.e., a high-strength and high-elasticity organosilicon light-curing 3D printing material.

[0050] Example 6 A method for preparing a high-strength and high-elasticity organosilicon light-curing 3D printing material, wherein the preparation process of the organosilicon photosensitive resin material is as follows: (1) 70g of a multi-arm vinyl silicone oil with a viscosity of 60000cP and a macrocyclic phenylsiloxane as a core, 6g of a double-end hydrogenated silicone oil, 6g of a side hydrogenated silicone oil, 8g of 1-ethynylcyclohexanol, and 7g of fumed silica; (2) 3g of a chloroplatinic acid isopropanol solution (calculated as Pt metal, 10ppm based on the total mass of the photosensitive resin) is added to the mixture obtained in (1), and the mixture is stirred and mixed to obtain a transparent photosensitive resin material, i.e., a high-strength and high-elasticity organosilicon light-curing 3D printing material.

[0051] Example 7 A method for preparing a high-strength and high-elasticity organosilicon light-curing 3D printing material, wherein the preparation process of the organosilicon photosensitive resin material is as follows: (1) 70g of a multi-arm vinyl silicone oil with a viscosity of 60000cP and a macrocyclic phenylsiloxane core, 6g of a double-end hydrogenated silicone oil, 6g of a side hydrogenated silicone oil, 8g of 1-ethynylcyclohexanol, and 7g of a vinyl MQ resin; (2) 3g of a chloroplatinic acid isopropanol solution (calculated as Pt metal, based on 10ppm of the total photosensitive resin mass) is added to the mixture obtained in (1), and the mixture is stirred and mixed to obtain a transparent photosensitive resin material, i.e., a high-strength and high-elasticity organosilicon light-curing 3D printing material.

[0052] Example 8 The method and steps are the same as those of Example 6, except that the multi-arm vinyl silicone oil with macrocyclic phenylsiloxane as the core is replaced by a multi-arm vinyl silicone oil in which R is OSi(CH2CH2CH2CH3)2CH=CH2.

[0053] Example 9 The method and steps are the same as those in Example 6, except that the multi-arm vinyl silicone oil with macrocyclic phenylsiloxane as the core is replaced by a multi-arm vinyl silicone oil with R=OSi(Me)2(C=CH2CH3).

[0054] Comparative Example 1 In this comparative case, the multi-arm vinyl silicone oil was replaced with an equal amount of dimethylvinylsiloxy-terminated dimethylpolysiloxane, and the remaining conditions were the same as in Example 3.

[0055] Comparative Example 2 In this comparative case, the multi-arm vinyl silicone oil was replaced with an equal amount of dimethylvinylsiloxy-terminated four-arm star polysiloxane, and the other conditions were the same as those in Example 3.

[0056] The preparation steps of four-arm star polysiloxane are as follows: (1) A mixture of 60 mL 1-butanol, 12.56 g (38.7 mmol) phenyltri(butoxy)silane, 1.55 g (38.7 mol) sodium hydroxide solution, and 0.7 mL water is stirred and refluxed at 110°C to 130°C, cooled and filtered to obtain white needle-shaped crystals. After drying, 9.5 g of white crystals are stirred in a toluene / ethanol (60:35 mL) mixed solution, added dropwise to a 1% hydrochloric acid solution, washed and filtered, and the obtained white crystalline solid is washed and dried to obtain a white crystalline product [C6H5Si(O)OH]4; (2) Dissolve 2.07 g (3.5 mmol) of [C6H5Si(O)OH]4 in 50.9 g (900 mmol) of pyridine, add 77.9 g (644 mmol) of dimethylvinylsilyl chloride, stir at room temperature, and reflux for reaction. The reaction is exothermic. After cooling, add 700 mL of toluene and reflux at 110°C~130°C for 1 h. After the reaction is completed, wash and dry to obtain 60,000 cP of four-arm vinyl silicone oil [PhSi(O)OSiMe2Vi]4.

[0057] Comparative Example 3 In this comparative case, the multi-arm vinyl silicone oil is replaced with an equal amount of dimethylvinylsiloxy-terminated six-arm star polysiloxane, and the other conditions are the same as those in Example 3. The preparation steps of the six-arm star polysiloxane are as follows: (1) A mixture of 130 mL of 1-butanol, 12.8 g (39 mmol) of phenyltri(butoxy)silane, 1.8 g (45 mol) of sodium hydroxide solution, and 0.7 mL of water is stirred and refluxed at 110°C to 130°C, and then 3.01 g (13 mmol) of hexaamminenickel chloride is dropped in. After reflux reaction, the mixture is filtered to obtain orange crystals. After drying, 5.6 g of the orange crystals are stirred in a mixed solution of toluene / ethanol (100:50 mL), and then dropped into a 7.4% hydrochloric acid solution. After stirring, the mixture is washed and filtered to obtain a white crystalline solid. The white crystalline product [C6H5Si(O)OH]6 is obtained by washing and drying. (2) Dissolve 4 g (4.5 mmol) of [C6H5Si(O)OH]6 in 53.3 g (675 mmol) of pyridine, add 81.8 g (675 mmol) of dimethylvinylsilyl chloride, stir at room temperature, and reflux for reaction. The reaction is exothermic. After cooling, add 1000 mL of toluene and reflux at 110°C~130°C for 1 h. After the reaction is completed, wash and dry to obtain 60000 cP six-arm vinyl silicone oil [PhSi(O)OSiMe2Vi]6.

[0058] The photosensitive resin materials prepared in the above embodiments and comparative examples were applied to a UV-curable 3D printer, and a printing test was conducted at 25° C. The printing method included the following steps: (1) Before use, stir the silicone photosensitive resin material evenly and load it into the barrel, install the barrel on the feed pump of the 3D printer, and connect the print head; the ultraviolet light source of the 3D printer is fixed at the bottom of the print head and moves synchronously with the print head. After focusing and collimating, the light path acts on the glue outlet position of the print head for pre-curing of the photosensitive material; (2) Under the control of the printing program, the photosensitive resin is printed out into a tensile spline structure by the printing nozzle under the action of the feed pump; it is rapidly cured under 325nm~400nm ultraviolet light for 0.1-10 s; and then a conventional post-curing treatment is carried out, using a portable hand-held ultraviolet lamp for 10 min-3 h.

[0059] The prepared silicone photocurable 3D printing materials were scored for their application performance. The pre-curing time (the shortest time required for the silicone material to change from liquid to immovable solid) and the transparency of the molded parts (3 points: almost transparent; 2 points: translucent; 1 point: opaque) were measured by 3D printer printing. The tensile strength, elongation at break, tear strength, hardness, rebound rate and other properties of the printed materials were measured according to GB / T528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber. The results are shown in Table 1: Table 1 Test data of photosensitive resin molded products Test items Pre-curing time / s Transparency of molded parts Tensile strength / MPa Elongation at break / % <![CDATA[Tear strength / KN·m -1 > Hardness / HA Rebound rate / % Volume shrinkage / % Example 1 10 2 5.5 702 21.9 35 71 2.0 Example 2 8 2 6.0 741 23.5 40 70 1.8 Example 3 5 2 7.6 798 25.6 43 68 1.5 Example 4 2 2 7.4 788 25.8 44 66 1.6 Example 5 4.2 2 8.5 839 27.0 45 75 1.2 Example 6 3.5 2 9.0 950 28.9 48 80 1.2 Example 7 3.3 2 9.3 980 30.5 50 82 0.9 Example 8 3.6 2 9.1 957 29.4 49 81 1.0 Example 9 3.5 2 9.3 976 30.1 50 80 1.1 Comparative Example 1 30 2 1.5 186 5.3 12 55 4.5 Comparative Example 2 24 1 2.2 242 8.2 19 52 3.8 Comparative Example 3 19 1 3.6 517 10.1 24 51 3.2 As can be seen from Table 1, it can be seen from Example 3 and Comparative Examples 1-3 that compared with the photosensitive resin prepared by vinyl silicone oil with fewer linear or cross-linking sites, the curing rate of the photosensitive resin material prepared by the present invention is significantly faster, the mechanical properties of the photocurable 3D printing material are greatly enhanced, and the hardness and rebound rate are improved; it can be seen from Examples 1-4 that when the multi-arm vinyl silicone oil with a viscosity of 1000-100000 mPa•S is added, there are more cross-linking sites, the cross-linking network is more dense, the mechanical properties of the photocurable 3D printing material are good, and the volume shrinkage rate is small; by comparing Examples 3, 5, and 6, it can be seen that when double-ended hydrogenated silicone oil is added, the chain length can be increased, and when side hydrogenated silicone oil is added, the cross-linking network is denser, which can improve the mechanical properties of the photocurable 3D printing material; by comparing Examples 6 and 7, it can be seen that the vinyl MQ resin is a good reinforcing filler, which can improve the mechanical properties of the photocurable 3D printing material. In summary, the tensile strength of the photocurable 3D printing material prepared from multi-arm vinyl silicone oil can be increased to 5.5-9.3MPa, the elongation at break can be increased to 702-980%, the tear strength can be increased to 20.9-30.5KN / m, the rebound rate can be increased to 66-82%, the hardness is increased, and the volume shrinkage is reduced. It can be seen from Examples 8 and 9 that the R group can be replaced with R=OSi(CH2CH2CH2CH3)2CH=CH2, R=OSi(Me)2(C=CH2CH3), etc., to achieve products with different multi-arm vinyl silicone oil structures, which can improve the mechanical properties of photocurable 3D printing materials.

[0060] The present invention uses ultraviolet light to initiate the local short-time curing of the addition-type organosilicon material, and realizes the rapid curing and molding of the organosilicon material in the process of photocuring 3D printing. The molded parts are colorless and transparent and have good mechanical properties, good hardness and elasticity, which solves the problems of large brittleness and poor biocompatibility of photocuring printing materials. The vinyl silicone oil used in the process method of the present invention is a multi-arm vinyl silicone oil, which has the characteristics of excellent thermal stability, good mechanical properties, low dielectric constant, excellent biocompatibility, etc. Its structure is three-dimensionally regular, and the surface functional group density is high. It can increase the cross-linking sites of the silane addition reaction, form a dense cross-linked network structure, and improve the mechanical properties of the material; the metal complex photoinitiator is used to initiate the silane addition reaction, the curing reaction speed is fast, and the wavelength range of the curable light source is large; the volume shrinkage rate is low, the cured product is colorless, transparent, and elastic; there is no volatile solvent, and all photosensitive resins participate in the curing, and there is no pollution.

[0061] The specific implementation of the present invention described above does not constitute a limitation on the protection scope of the present invention. Any other corresponding changes and modifications made based on the technical concept of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. Multi-arm vinyl silicone oil, characterized in that: Multi-arm vinyl silicone oil with macrocyclic phenylsiloxane as the core has the following structural formula: , wherein R includes any one of OSi(CH2CH2CH2CH3)2CH=CH2, R=OSi(Me)2(C=CH2CH3), and R=OSiMe(CH2CH2CH2CHCH3CH3)CH=CH2.

2. The multi-arm vinyl silicone oil according to claim 1, characterized in that The multi-arm vinyl silicone oil is a macrocyclic phenyl silsesquioxane with a stereoregular structure, a viscosity of 1000-100000 mPa•S, and a vinyl content of 0.1-10.0 wt%.

3. The method for preparing multi-arm vinyl silicone oil according to claim 1 or 2, characterized in that, The steps include: (1) A mixture of 1-butanol, phenyltri(butyloxy)silane, sodium hydroxide solution and water is stirred and refluxed at 110°C to 130°C, and then an anhydrous copper chloride alcohol solution is added dropwise. After reflux reaction, the blue crystals are filtered to obtain blue crystals. After drying, the blue crystals are stirred in a solvent, added dropwise to a hydrochloric acid solution, stirred and filtered to obtain a white crystalline solid, which is washed and dried to obtain a white crystalline product tri-cis-tri-trans-dodeca[(phenyl)(hydroxy)]cyclododecasiloxane [C6H5Si(O)OH] 12 ; (2) Dissolve tris-cis-tris-twelve [(phenyl) (hydroxy)] cyclododecyl siloxane in pyridine, add dimethylvinyl chlorosilane, stir and reflux at room temperature, cool after the reaction, add solvent and reflux at 110°C to 130°C, wash and dry after the reaction, and obtain a multi-arm vinyl silicone oil [PhSi(O)OSiMe2Vi] with a macrocyclic phenylsiloxane as the core. 12 .

4. The method for preparing the arm vinyl silicone oil according to claim 3, characterized in that: In step (2), the molar ratio of tris-cis-tris-dodeca[(phenyl)(hydroxy)]cyclododecylsiloxane:pyridine:dimethylvinylchlorosilane is 1:6-10:5-10, and the solvent comprises toluene.

5. A method for preparing a high-strength and high-elasticity organosilicon photosensitive resin, characterized in that: The steps include: (1) Mix the multi-arm vinyl silicone oil according to claim 1 or 2, the polysiloxane polymer containing silane groups, the filler and the inhibitor according to mass percentage and stir them uniformly; (2) Add a photoinitiator and stir evenly to obtain a photosensitive resin material.

6. The method for preparing the high-strength and high-elasticity organosilicon photosensitive resin according to claim 5, characterized in that: The polysiloxane polymer containing silicon hydrogen groups has a viscosity of 20-80 mPa•S and a hydrogen content of 0.05-1.5%, and includes one or more of single-end hydrogen-containing silicone oil, double-end hydrogen-containing silicone oil, and side hydrogen-containing silicone oil.

7. The method for preparing the high-strength and high-elasticity organosilicon photosensitive resin according to claim 5, characterized in that: The photoinitiator is an alcohol solution of chloroplatinic acid; The filler includes fumed silica and vinyl MQ resin, and has a specific surface area of ​​10-400 m 2 / g; The inhibitor is 1-ethynyl cyclohexanol.

8. High-strength and high-elasticity silicone light-curing 3D printing material, characterized by: The high-strength and high-elasticity organosilicon photosensitive resin prepared by the method described in any one of claims 5 to 7 is prepared under ultraviolet light curing conditions.

9. A UV-curing 3D printing method for high-strength and high-elasticity silicone photocurable 3D printing material, characterized in that: The steps include: S1: The high-strength and high-elasticity organosilicon photosensitive resin prepared by the method described in any one of claims 5 to 7 is stirred evenly and loaded into a barrel, the barrel is installed on a feed pump of a 3D printer, and connected to a print nozzle; the ultraviolet light source of the 3D printer is fixed at the bottom of the print nozzle and moves synchronously with the print nozzle, and the light path is focused and collimated and acts on the glue outlet position of the print nozzle for pre-curing the photosensitive material; S2: Under the control of the printing program, the high-strength and high-elasticity silicone light-curing 3D printing material is printed out into a tensile spline structure by the printing nozzle under the action of the feed pump; it is quickly cured under ultraviolet light for 0.1~30 s to obtain the printed material.

10. A high-strength and high-elasticity silicone light-curing 3D printing material, characterized in that: The organosilicon light-curing 3D printing material prepared according to the method of claim 9 has good fluidity, high strength and high elasticity, and the light-curing 3D printing material made of photosensitive resin has a tensile strength of 5.5-9.8 MPa, an elongation at break of 700-1000%, and a tear strength of 20.9-35 KN / m.

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