3D printed cartilage carving model and manufacturing method thereof

Abstract

The present invention relates to a silicone composition which can be cured by an addition reaction and which comprises: (A) at least one alkenyl-containing organopolysiloxane A which comprises, per molecule, at least two alkenyl groups attached to a silicon atom, preferably C2-C12, more preferably C2-C6 alkenyl groups, (B) at least one organohydrogen-containing polysiloxane B comprising, per molecule, at least one hydrogen atom attached to the same or different silicon atoms, (C) at least one catalyst C comprising at least one metal selected from the platinum group or a compound thereof, (E) gt, based on the total weight of the composition; 12% by weight of at least one silica reinforcing filler E, and (G) at least one thixotropic agent G. In addition, the invention also relates to a cartilage sculpture model obtained by a method comprising additive manufacturing with the above organosilicon composition, and a method for preparing the cartilage sculpture model by additive manufacturing.

Description

Technical Field

[0001] The present invention relates to a cartilage sculpture model made by material addition using an organic silicon composition and a method for making such a cartilage sculpture model. Background of the Invention

[0003] Cartilage, such as rib cartilage, is a commonly used tissue material in plastic surgery, and is often used in operations such as ear reconstruction and rhinoplasty. In these operations, the cartilage needs to be carved, and whether the carving effect is beautiful depends on the surgical skills and experience of the plastic surgeon. There are large individual differences in the commonly used rib cartilage. The properties and size of rib cartilage vary greatly between different ages, genders, and individuals, which increases the difficulty of carving rib cartilage.

[0004] In order to improve the carving effect of these cartilages, doctors need to practice and train on cartilage materials for many years. Existing carving materials include animal cartilage, cadaver cartilage and hard materials (such as soap, carrots, etc.), as well as silicone models made by casting.

[0005] However, animal cartilage is closer to real cartilage in terms of mechanics and subjective carving experience, but its appearance is quite different from human cartilage, and there is a risk of spreading diseases; while human cadaver cartilage is difficult to obtain and there are ethical risks. As for simulated materials such as soap and carrots, although there is no risk of spreading diseases or ethical risks, they are far from natural cartilage in terms of mechanics, subjective carving experience and appearance.

[0006] In addition, the models made by casting can achieve a certain degree of appearance and subjective carving experience close to human cartilage, but the casting method is suitable for large-scale repeated production of teaching aids with exactly the same shape and size. For costal cartilage with large variations in shape and size, personalized customization and preoperative simulation cannot be achieved.

[0007] In addition, there are also some technical solutions for 3D printing to make cartilage models in the prior art. For example, CN111671978A discloses a 3D printing bio-ink based on rib cartilage, which includes rib cartilage powder, photocurable hydrogel and phenyl-2,4,6-trimethylbenzoylphosphonate lithium. The rib cartilage powder is autologous rib cartilage powder, and the photocurable hydrogel is one or more of methacrylated gelatin, methacrylated hyaluronic acid, methacrylated silk fibroin, and methacrylated chitosan.

[0008] Typically, these models are not accurate enough, the printed models may have large errors from the original CAD models, and the carving feel is often lacking.

[0009] Therefore, in view of these existing technologies, there is an urgent need to develop a material that can be suitable for 3D printing to make cartilage models, so that cartilage models can be manufactured at low cost and customized, and the cartilage model should highly restore the performance of rib cartilage in terms of mechanical properties, have improved carving feel and shape accuracy, thereby facilitating doctors' daily carving training. SUMMARY OF THE INVENTION

[0011] The object of the present invention is to provide a cartilage sculpture model made by additive manufacturing using an organosilicon composition and a method for manufacturing such a cartilage sculpture model. The above-mentioned invention objects can be achieved using the cartilage sculpture model and the manufacturing method of the present invention.

[0012] It has been found that this object can be achieved by the cartilage sculpture model and its manufacturing method as described below. DETAILED DESCRIPTION OF THE INVENTION

[0014] In a first aspect, the present invention relates to an organosilicon composition which is curable by an addition reaction and comprises:

[0015] (A) at least one alkenyl-containing organopolysiloxane A, each molecule of which contains at least two alkenyl groups attached to silicon atoms, preferably C2-C 12 , more preferably C2-C6 alkenyl,

[0016] (B) at least one organic hydrogen-containing polysiloxane B comprising, per molecule, at least one hydrogen atom bonded to the same or different silicon atoms,

[0017] (C) at least one catalyst C comprising at least one metal selected from the platinum group or a compound thereof,

[0018] (E) >12 wt. %, preferably >15 wt. % or more preferably >20 wt. %, based on the total weight of the composition, of at least one silica reinforcing filler E, and

[0019] (G) at least one thixotropic agent G;

[0020] The prerequisite is that at least one of the following conditions is met:

[0021] (1) in the organohydrogenpolysiloxane B, the molar ratio of the Si-H bonds at the chain ends to the total Si-H bonds of the component (B) is less than 40%, preferably less than 30%, more preferably less than 10%, and

[0022] (2) The composition comprises at least two alkenyl-containing organopolysiloxanes A, wherein at least one alkenyl-containing organopolysiloxane A is a polyalkenylpolysiloxane A' having at least 3, more preferably at least 4 alkenyl groups per molecule.

[0023] The inventors of the present application have discovered that the above prerequisites are very important for obtaining a cartilage sculpture model that is very close to a real rib, especially having the desired very good sculpture feel and ideal mechanical properties.

[0024] The inventors have found that the silicone composition described above is particularly suitable for obtaining a cartilage (especially costal cartilage) sculpture model by an additive manufacturing method, and the cartilage sculpture model obtained in this way has a hardness range very close to that of the real rib, that is, the Shore A hardness is in the range of 60-95, such as 62-92 or 60-85, and at the same time has a very good carving feel and ideal mechanical properties, such as a tear strength in the range of 7-50N / mm, a tensile strength of 4-15MPa and an elongation at break of 15-500% or 85-170%.

[0025] In a second aspect, the present invention relates to a cartilage sculpture model obtained by a method comprising additive manufacturing with a silicone composition, wherein the silicone composition is as described above.

[0026] In a third aspect, the present invention relates to a method for additively manufacturing the cartilage sculpture model, comprising the following steps: (1) collecting shape information of the cartilage to be carved, (2) establishing a digital model, and (3) using a 3D printing device to additively manufacture the cartilage sculpture model using the silicone composition described above.

[0027] In the step of additive manufacturing, the first layer of the silicone composition can be printed on a substrate so that the layer is formed on the substrate. The substrate is not limited and can be any substrate. The substrate can support the 3D article during the manufacturing method of the 3D article, for example as a substrate plate of a 3D printer. The substrate can be rigid or flexible and can be continuous or discontinuous. The substrate itself can be supported, for example by a substrate table or plate, so that the substrate does not need to have rigidity. It can also be removable from the 3D article. Alternatively, the substrate can be physically or chemically bonded to the 3D article. In one embodiment, the substrate can be silicone.

[0028] Subsequently, a subsequent layer is formed by printing a silicone composition onto the above-mentioned first layer using a 3D printer.

[0029] In this document, the term "layer" may refer to a layer at any stage of the process, the first layer or preceding layer or a subsequent layer. The layers may each have various dimensions, including thickness and width. The thickness of the layers may be uniform or may vary. The average thickness is related to the thickness of the layer just after printing.

[0030] In a fourth aspect, the present invention relates to the use of the silicone composition as described above for preparing a cartilage sculpture model by a method including additive manufacturing.

[0031] 3D Printing Content

[0032] 3D printing is often associated with a number of related technologies for manufacturing physical objects from computer-generated (such as computer-aided design (CAD)) data sources.

[0033] This disclosure is generally incorporated into ASTM Designation F2792-12a, “Standard Terminology for Additive Manufacturing Technologies Under this ASTM standard.”

[0034] A “3D printer” is defined as “a machine used for 3D printing” and “3D printing” is defined as “the production of objects by deposition of material using a print head, nozzle or other printer technology”.

[0035] "Additive Manufacturing (AM)" is defined as "the process of joining materials from 3D modal data, typically layer by layer, to produce an object, as opposed to subtractive manufacturing techniques". Synonyms related to and covered by 3D printing include additive manufacturing, additive process, additive technology, additive layer manufacturing, layer manufacturing, and freeform manufacturing. Additive Manufacturing (AM) may also be referred to as Rapid Prototyping (RP). As used herein, "3D Printing" is generally interchangeable with "Additive Manufacturing" and vice versa.

[0036] "Printing" is defined as depositing a material (here, the silicone composition) using a print head, nozzle, or other printer technology.

[0037] In this disclosure, "3D or three-dimensional article, object or component" refers to an article, object or component obtained by additive manufacturing or 3D printing as disclosed above.

[0038] Generally, all 3D printing processes have a common starting point, which is a computer-generated data source or program that can describe the object. In the present invention, this means that information such as the shape of the cartilage to be sculpted can be collected by methods such as CT scanning, and then a digital model of the cartilage can be built by computer software such as CAD modeling software.

[0039] A computer-generated data source or program is typically converted to a Standard Tessellation Language (STL) file format; however, other file formats may be used or used in addition. The file is typically read into 3D printing software, which takes the file and optional user input information to divide it into hundreds, thousands, or even more "slices." Machine instructions are transmitted to the 3D printer, which then builds the object layer by layer based on this slice information in the form of machine instructions. The thickness of these slices can vary.

[0040] An extrusion 3D printer is a 3D printer in which material is extruded through a nozzle, syringe, or orifice during the additive manufacturing process. Material extrusion is typically performed by extruding material through a nozzle, syringe, or orifice to print one cross-section of an object, which may be repeated for each subsequent layer. The extruded material bonds to the layer below it during the curing of the material.

[0041] In a preferred embodiment, the method for additively manufacturing a three-dimensional silicone elastomer article uses an extrusion 3D printer. The silicone composition is extruded through a nozzle. The nozzle can be heated to help distribute the addition-crosslinkable silicone composition.

[0042] Typically, a 3D printer uses a dispenser, such as a nozzle or print head, for printing a specific curable silicone composition. Optionally, the dispenser can be heated before, during, and after dispensing the silicone composition. More than one dispenser can be used, each with independently selected properties.

[0043] In one embodiment, such methods can use support materials to build the object. If support materials are used to print the object, they are typically removed after the printing process is complete, leaving the finished object.

[0044] Silicone composition

[0045] The organic silicone composition according to the present invention is an organic silicone composition that can be cured by an addition reaction.

[0046] 1. Organopolysiloxane A containing alkenyl groups

[0047] The alkenyl-containing organopolysiloxane A according to the present invention comprises at least two alkenyl groups connected to silicon atoms per molecule, preferably C2-C 12 , more preferably C2-C6 alkenyl, preferably vinyl.

[0048] According to a particularly advantageous manner, the alkenyl-containing organopolysiloxane A containing at least two alkenyl groups bonded to a silicon atom per molecule comprises:

[0049] (i) at least two siloxane units (A.1), which may be identical or different and have the following formula:

[0050]

[0051] in:

[0052] - a = 1 or 2, b = 0, 1 or 2 and a + b = 1, 2 or 3;

[0053] - the symbols W may be identical or different and represent a linear or branched C2-C6 alkenyl group, and

[0054] - the symbols Z may identically or differently represent a monovalent straight-chain, branched or cyclic alkyl group containing 1 to 30 carbon atoms, preferably 1 to 8 carbon atoms, which may be unsubstituted or substituted by one or more halogen atoms, such as fluorine, chlorine and bromine atoms and / or by one or more aryl groups, for example phenyl, and even more preferably are selected from methyl, ethyl, propyl, 3,3,3-trifluoropropyl, and

[0055] (ii) optionally at least one siloxane unit having the formula:

[0056]

[0057] in:

[0058] -c=0, 1, 2 or 3,

[0059] -Symbol Z 1 may identically or differently represent a monovalent straight-chain, branched or cyclic alkyl group containing 1 to 30 carbon atoms, preferably 1 to 8 carbon atoms, which may be unsubstituted or substituted by one or more halogen atoms, such as fluorine, chlorine and bromine atoms and / or by one or more aryl groups, for example phenyl, and even more preferably is selected from methyl, ethyl, propyl, 3,3,3-trifluoropropyl.

[0060] Advantageously, Z and Z 1 R is selected from methyl, ethyl and propyl, and W is selected from the group consisting of vinyl, propenyl, 3-butenyl, 5-hexenyl, 9-decenyl, 10-undecenyl, 5,9-decadienyl and 6,11-dodecadienyl, and preferably W is vinyl.

[0061] In a preferred embodiment, in formula (A.1) a=1 and a+b=2 or 3 and in formula (A.2) c=2 or 3.

[0062] These alkenyl-containing organopolysiloxanes A may have a linear or branched chain, a cyclic structure, or a three-dimensional network structure. When the organopolysiloxane A has a three-dimensional network structure, it is also generally referred to as a polysiloxane resin.

[0063] When they are linear polymers, they are mainly formed of siloxane units "D" and siloxane units "M", wherein the siloxane units "D" are selected from siloxane units W2SiO 2 / 2 、WZSiO 2 / 2 and Z 1 2SiO 2 / 2 , and the siloxane unit "M" is selected from the siloxane unit W3SiO 1 / 2 、WZ2SiO 1 / 2、W2ZSiO 1 / 2 and Z 1 3SiO 1 / 2 . Symbols W, Z and Z 1 As mentioned above.

[0064] As examples of the terminal unit "M", mention may be made of a trimethylsiloxy group, a dimethylvinylsiloxy group or a dimethylhexenylsiloxy group.

[0065] As examples of the unit "D", mention may be made of a dimethylsiloxy group, a methylvinylsiloxy group, a methylbutenylsiloxy group, a methylhexenylsiloxy group, a methyldecenylsiloxy group or a methyldecadienylsiloxy group.

[0066] The alkenyl-containing organopolysiloxane A may have a dynamic viscosity of about 1 to 10,000,000 mPa.s at 25°C, and typically has a dynamic viscosity of about 200 to 1,000,000 mPa.s at 25°C.

[0067] The viscosity considered in this description corresponds to the amount of "Newtonian" dynamic viscosity at 25° C., ie the dynamic viscosity measured in a manner known per se using a Brookfield viscometer at a sufficiently low shear rate gradient that the measured viscosity is independent of the rate gradient.

[0068] When they are cyclic alkenyl-containing organopolysiloxanes, they are formed from siloxane units "D" having the formula: W2SiO 2 / 2 , Z 1 2SiO 2 / 2 or WZSiO 2 / 2 , which may be of dialkylsiloxy, alkylvinylsiloxy or alkylsiloxy type. Examples of such siloxane units have been mentioned above. The cyclic organopolysiloxane A may have a viscosity of, for example, about 1-5000 mPa.s at 25°C.

[0069] In one embodiment, the alkenyl-containing organopolysiloxane A may be a polymer comprising at least two different siloxane units selected from the formula R3SiO 1 / 2 The siloxane unit M of formula R2SiO 2 / 2 The siloxane unit D of formula RSiO 3 / 2 The siloxane unit T and the formula SiO 4 / 2 Siloxane units Q wherein R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, with the proviso that at least one of these siloxane units is a siloxane unit T or Q and at least one of the siloxane units M, D and T contains an alkenyl group.

[0070] For the siloxane unit M (MVi As the alkenyl-containing organopolysiloxane having a unit), a polysiloxane resin selected from the following organopolysiloxane resins can be used (in the above and below, when referring to the unit T, Q or D, the unit with the superscript "Vi" indicates the unit containing an alkenyl group):

[0071] -Formula M Vi Q's organopolysiloxane resin, which consists essentially of the following units:

[0072] Formula R'R2SiO 1 / 2 The monovalent siloxane unit M Vi ,and

[0073] Formula SiO 4 / 2 of tetravalent siloxane units Q, and

[0074] -Form MM Vi Q's organopolysiloxane resin, which consists essentially of the following units:

[0075] Formula R3SiO 1 / 2 of monovalent siloxane units M, and

[0076] Formula R'R2SiO 1 / 2 , the monovalent siloxane unit M Vi ,and

[0077] Formula SiO 4 / 2 of tetravalent siloxane units Q, and

[0078] -Formula M Vi T Vi Q's organopolysiloxane resin, which consists essentially of the following units:

[0079] (a) Formula R'R2SiO 1 / 2 The monovalent siloxane unit M Vi ,

[0080] (b) Formula R'SiO 3 / 2 The trivalent siloxane unit T Vi ,and

[0081] (c) Formula SiO 4 / 2 The tetravalent siloxane unit Q,

[0082] -Formula M Vi TQ organopolysiloxane resin, which consists essentially of the following units:

[0083] RSiO 3 / 2 trivalent siloxane unit T;

[0084] Formula R'R2SiO 1 / 2 The monovalent siloxane unit M Vi ,and

[0085] Formula SiO 4 / 2 of tetravalent siloxane units Q, and

[0086] -Formula M Vi DQ organopolysiloxane resin, which is essentially composed of the following units:

[0087] Formula R2SiO 2 / 2 The divalent siloxane unit D,

[0088] Formula R'R2SiO 1 / 2 The monovalent siloxane unit M Vi ,and

[0089] Formula SiO 4 / 2 The tetravalent siloxane unit Q,

[0090] wherein R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a monovalent aliphatic or aromatic hydrocarbon group having preferably 1 to 12, more preferably 1 to 8 carbon atoms, and

[0091] R' represents an alkenyl group, preferably an alkenyl group having 2 to 12, more preferably 2 to 6 carbon atoms, in particular a vinyl group or an allyl group, and most preferably a vinyl group.

[0092] For the siloxane unit D (D Vi The alkenyl-containing organopolysiloxane having a unit) can be a polysiloxane resin selected from the following:

[0093] -MD Vi Q's organopolysiloxane resin, which consists essentially of the following units:

[0094] Formula R2SiO 2 / 2 A divalent siloxane unit M;

[0095] Formula R'R2SiO 1 / 2 The monovalent siloxane unit D Vi ,and

[0096] Formula SiO 4 / 2 The tetravalent siloxane unit Q,

[0097] wherein R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a monovalent aliphatic or aromatic hydrocarbon group having preferably 1 to 12, more preferably 1 to 8 carbon atoms, and

[0098] R' represents an alkenyl group, preferably an alkenyl group having 2 to 12, more preferably 2 to 6 carbon atoms, in particular a vinyl group or an allyl group, and most preferably a vinyl group.

[0099] In addition, the siloxane unit D (DVi The organopolysiloxane resin of the unit) can also be selected from the formula MD Vi TQ organopolysiloxane resin.

[0100] In an advantageous embodiment, the alkenyl-containing organopolysiloxane may be selected from the group consisting of: Vi Q and / or MD Vi Q's organopolysiloxane resin.

[0101] In one embodiment according to the present invention, the silicone composition may contain 10-85wt%, preferably 15-80wt%, more preferably 25-75wt%, such as 50-75wt% of the alkenyl-containing organopolysiloxane A, based on the total weight of the silicone composition.

[0102] In one embodiment according to the present invention, as alkenyl-containing organopolysiloxane A, at least one chain-like, such as straight-chain or branched, alkenyl-containing organopolysiloxane, cyclic alkenyl-containing organopolysiloxane, or a mixture thereof and at least one alkenyl-containing organopolysiloxane resin may be used. In such a mixture, the alkenyl-containing organopolysiloxane resin may be present in a proportion of, for example, 0.4 wt % to 20 wt %, such as 0.4 wt % to 10 wt %, or such as 0.5 wt % to 5 wt %, based on the weight of the entire composition.

[0103] As described above, in order to achieve the excellent effects of the present invention, a very favorable premise is that the composition contains at least two, for example, three, alkenyl group-containing organopolysiloxanes A, wherein at least one alkenyl group-containing organopolysiloxane A is a polyalkenyl polysiloxane A' having at least 3, more preferably at least 4 alkenyl groups per molecule. Here, the alkenyl group of the polyalkenyl polysiloxane A' is preferably C2-C 12 , more preferably C2-C6 alkenyl, such as vinyl.

[0104] Such polyalkenyl polysiloxane A' is linear, branched or cyclic, preferably cyclic polysiloxane. The alkenyl group in the polyalkenyl polysiloxane A' is preferably vinyl, and thus examples of such polyalkenyl polysiloxane A' include tetramethyltetravinylcyclotetrasiloxane, such as 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane. In particular, such polyalkenyl polysiloxane A' is not a resin or does not have a three-dimensional network structure.

[0105] It has been found to be very advantageous that the amount of polyalkenyl polysiloxane A' in the silicone composition is 0.05 wt % to 12.0 wt %, preferably 0.1 wt % to 10.0 wt %, for example 0.1 wt % to 8 wt % or 0.1 wt % to 6.5 wt %, for example 0.5 to 4.0 wt %, relative to the total weight of the silicone composition.

[0106] 2. Organic hydrogen-containing polysiloxane B

[0107] The organohydrogen-containing polysiloxane B according to the present invention contains at least one, for example at least 2, 3, 4, 5 or more hydrogen atoms connected to the same or different silicon atoms, i.e., Si-H bonds, per molecule. Such Si-H bonds may be located at any position of the polysiloxane compound B.

[0108] Advantageously, the organohydrogenpolysiloxane B is an organopolysiloxane comprising:

[0109] (i) at least two siloxane units having the formula and preferably at least three siloxane units having the formula:

[0110]

[0111] in:

[0112] - d = 1 or 2, e = 0, 1 or 2 and d + e = 1, 2 or 3,

[0113] -Symbol Z 3 may identically or differently represent a monovalent straight-chain, branched or cyclic alkyl group containing 1 to 30 carbon atoms, preferably 1 to 8 carbon atoms, which may be unsubstituted or substituted by one or more halogen atoms, such as fluorine, chlorine and bromine atoms and / or by one or more aryl groups, for example phenyl, and is even more preferably selected from methyl, ethyl, propyl, 3,3,3-trifluoropropyl, and

[0114] (ii) optionally at least one siloxane unit having the formula:

[0115]

[0116] in:

[0117] -c=0, 1, 2 or 3,

[0118] -Symbol Z 2 may identically or differently represent a monovalent straight-chain, branched or cyclic alkyl group containing 1 to 30 carbon atoms, preferably 1 to 8 carbon atoms, which may be unsubstituted or substituted by one or more halogen atoms, such as fluorine, chlorine and bromine atoms and / or by one or more aryl groups, for example phenyl, and even more preferably is selected from methyl, ethyl, propyl, 3,3,3-trifluoropropyl.

[0119] The organohydrogenpolysiloxane B may consist only of siloxane units of the formula (B.1) or may also contain units of the formula (B.2).

[0120] The organohydrogen-containing polysiloxane B may have a linear, branched, cyclic or three-dimensional network structure. When the organohydrogen-containing polysiloxane B presents a three-dimensional network structure, it is also generally referred to as a hydrogen-containing polysiloxane resin. Accordingly, the Si-H bonds in the organohydrogen-containing polysiloxane B may be located within the chain and / or at the chain end (when it is, for example, a linear or branched structure), or in the case of a cyclic structure, on the cyclic chain, or may also be located at any position in the three-dimensional network structure.

[0121] In the context of the present invention, the "chain-terminal Si-H bond" refers to the Si-H bond located at the end of the chain structure in a linear or branched organic hydrogen-containing polysiloxane. For example, a linear organic hydrogen-containing polysiloxane may have Si-H bonds at up to two chain ends. In a preferred embodiment of the present invention, the organic hydrogen-containing polysiloxane B does not have a chain-terminal Si-H bond.

[0122] Examples of siloxane units of formula (B.1) are in particular the following units: H(CH3)2SiO 1 / 2 and HCH3SiO 2 / 2 .

[0123] When they are linear polymers, they are formed primarily from:

[0124] - is selected from the group consisting of Z 2 2SiO 2 / 2 or Z 3 HSiO 2 / 2 units of siloxane units "D", and

[0125] - is selected from the group consisting of Z 2 3SiO 1 / 2 or Z 3 2HSiO 1 / 2 The siloxane unit "M" is composed of 1,2-dimethylsiloxane units.

[0126] These linear organopolysiloxanes may have a dynamic viscosity of about 1-1,000,000 mPa.s at 25°C, typically about 10-500,000 mPa.s at 25°C, or preferably about 50-10,000 or 5,000 mPa.s at 25°C, or a molecular weight of about 1,000,000 mPa.s or more at 25°C.

[0127] When they are cyclic organopolysiloxanes, they are composed of compounds having the formula Z 2 2SiO 2 / 2 and Z 3 HSiO 2 / 2 The siloxane units "D" are formed, which may be of the dialkylsiloxy type or only the units Z 3 HSiO 2 / 2They then have a viscosity of about 1 to 5000 mPa.s.

[0128] Examples of the linear organohydrogenpolysiloxane B are: dimethylpolysiloxane with hydrodimethylsilyl terminal groups, dimethylhydrogenmethylpolysiloxane with trimethylsilyl terminal groups, dimethylhydrogenmethylpolysiloxane with hydrodimethylsilyl terminal groups, hydromethylpolysiloxane with trimethylsilyl terminal groups.

[0129] Oligomers and polymers corresponding to the general formula (B.3) are particularly preferred as organohydrogenpolysiloxanes B:

[0130]

[0131] in:

[0132] - x and y are integers between 0 and 10000,

[0133] -Symbol R 1 Can be the same or different and independently represent:

[0134] A straight-chain or branched alkyl group containing 1 to 8 carbon atoms, which is optionally substituted by at least one halogen, preferably fluorine, the alkyl group being preferably methyl, ethyl, propyl, octyl and 3,3,3-trifluoropropyl, or

[0135] Cycloalkyl groups containing 5 to 8 ring carbon atoms.

[0136] Aralkyl groups having an alkyl moiety containing 5 to 14 carbon atoms and an aryl moiety containing 6 to 12 carbon atoms.

[0137] The following compounds are particularly suitable for use as organohydrogenpolysiloxane B in the present invention:

[0138]

[0139] where a', b', c', d' and e' are defined as follows:

[0140] - In the polymer of formula S1:

[0141] - 0≤a'≤150, preferably 0≤a'≤100, and more particularly 0≤a'≤20, and

[0142] - 1≤b'≤90, preferably 10≤b'≤80 and more particularly 30≤b'≤70,

[0143] - In the polymer of formula S2: 0≤c'≤15

[0144] - in the polymer of formula S3: 5≤d'≤200, preferably 20≤d'≤100, and

[0145] 2≤e'≤90, preferably 10≤e'≤70.

[0146] In one embodiment, the organohydrogen-containing polysiloxane B may be a polymer as follows:

[0147] a) contains at least two different siloxy units selected from the following: formula R3SiO 1 / 2 The siloxane unit M of formula R2SiO 2 / 2 The siloxane unit D of formula RSiO 3 / 2 The siloxane unit T and the formula SiO 4 / 2 A siloxane unit Q, wherein R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and

[0148] b) with the proviso that at least one of the siloxane units is a siloxane unit T or Q and at least one of the siloxane units M, D or T comprises a Si-H group.

[0149] According to one embodiment, the organohydrogenpolysiloxane B may be an organohydrogenpolysiloxane resin selected from the following group:

[0150] - an organopolysiloxane resin of formula M'Q, which is essentially formed by the following units:

[0151] (a) Formula R2HSiO 1 / 2 A monovalent siloxy unit M'; and

[0152] (b) Formula SiO 4 / 2 A tetravalent siloxy unit Q; and

[0153] - an organopolysiloxane resin of formula MD'Q, which is essentially formed by the following units:

[0154] (a) Formula RHSiO 2 / 2 Divalent siloxy units D';

[0155] (b) Formula R3SiO 1 / 2 A monovalent siloxy unit M; and

[0156] (c) Formula SiO 4 / 2 A tetravalent siloxy unit Q;

[0157] wherein R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a monovalent aliphatic or aromatic hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms.

[0158] In one embodiment of the present invention, as the organohydrogenpolysiloxane B, at least one linear or branched organohydrogenpolysiloxane containing at least one of Si—H bonds located within the chain and Si—H bonds located at the chain ends, a cyclic organohydrogenpolysiloxane, or at least one organohydrogenpolysiloxane resin, or a mixture thereof can be used.

[0159] As described above, in order to achieve the excellent effects of the present invention, a very favorable premise is that in the organic hydrogen-containing polysiloxane B, the molar ratio of the Si-H bonds at the chain ends to the total Si-H bonds of the component (B) is less than 40%, preferably less than 35%, more preferably less than 30% or 25% or 20%, for example less than 10% or even 5% and 2%.

[0160] 3. Catalyst C

[0161] Catalysts C containing at least one metal from the platinum group or a compound thereof are well known. The metals of the platinum group are those known by the name platinoids, a term which includes, in addition to platinum, ruthenium, rhodium, palladium, osmium and iridium. Here, the compounds include complexes or compounds formed by the respective elements. Therefore, in the present invention, it is preferred to use platinum and rhodium compounds, for example, a complex of platinum and an organic product with 1,3-divinyltetramethyldisiloxane, a complex of a silicone resin powder containing the aforementioned catalyst, a rhodium compound, for example, those represented by the following formula: RhCl(Ph3P)3, RhCl3[S(C4H9)2]3, etc.; tetrakis(triphenyl)palladium, a mixture of palladium black and triphenylphosphine, etc.

[0162] The platinum catalyst should preferably be used in a catalytically sufficient amount to allow sufficiently rapid crosslinking at room temperature. Typically, 1-10000 ppm by weight of catalyst is used, preferably 1-100 ppm by weight, more preferably 1-50 ppm by weight, based on the amount of Pt metal, relative to the total silicone composition.

[0163] 4. Silica reinforced filler E

[0164] In order to obtain sufficiently high mechanical strength, the addition-crosslinkable silicone composition advantageously comprises >12 wt. %, preferably >15 wt. % or more preferably >20 wt. % of silica particles as reinforcing filler E, based on the total weight of the composition. Preferably, the silica particles are at least partially surface treated. Precipitated and fumed silicas and mixtures thereof can be used. The specific surface area of ​​these active reinforcing fillers should be at least 50 m 2 / g, preferably 100-400m 2 / g, as determined by the BET method. Such active reinforcing fillers are very well known materials in the field of silicone rubbers. The silica filler can be hydrophilic or can be hydrophobized by known methods. Advantageously, the silica reinforcing filler is subjected to an overall surface treatment. This means that at least 50%, more preferably at least 80% or at least 90% or especially preferably the entire surface of the silica reinforcing filler is preferably hydrophobized.

[0165] In a preferred embodiment, the silica reinforcing filler is fumed silica having a specific surface area of ​​at least 50 m 2 / g, and preferably 100-400m 2 / g, as measured by the BET method. Hydrophobic surface treated fumed silica may be used. In those cases, if hydrophobic surface treated fumed silica is used, fumed silica with a preliminary hydrophobic surface treatment may be used, or a surface treatment agent may be added during the mixing of the fumed silica with the organopolysiloxane A so as to treat the fumed silica in situ.

[0166] The surface treatment agent may be selected from any conventionally used agent, such as alkylalkoxysilanes, alkylchlorosilanes, alkylsilazanes, silane coupling agents, titanate-based treatment agents, and fatty acid esters, and a single treatment agent may be used or two or more treatment agents may be used in combination, either simultaneously or at different times.

[0167] The amount of silica reinforcing filler E in the silicone composition of the present invention is preferably 12.1 wt% to 40 wt%, more preferably 15 wt% to 40 wt%, more preferably 15 wt% to 35 wt%, and more preferably 20 wt% to 30 wt% of the total composition weight.

[0168] 5. Cross-linking inhibitor F

[0169] At least one crosslinking inhibitor F may optionally be included in the silicone composition of the invention in an amount of >0 wt. % and <4.5 wt. %, based on the total weight of the composition.

[0170] Crosslinking inhibitors are generally used in addition-crosslinking silicone compositions to slow down the curing of the composition at ambient temperature. The crosslinking inhibitor F may be selected from the following compounds:

[0171] - acetylenic alcohols, such as ethynyl cyclohexanol,

[0172] - pyridine,

[0173] - organic phosphines and phosphites,

[0174] - unsaturated amides, and

[0175] -Alkyl maleates.

[0176] These acetylenic alcohols (see FR-B-1 528 464 and FR-A-2 372 874) are preferred heat retarders for hydrosilylation reactions and have the following formula:

[0177] (R')(R")(OH)CC≡CH

[0178] wherein: R' is a linear or branched alkyl group, or a phenyl group; and -R" is H or a linear or branched alkyl group, or a phenyl group; the groups R' and R" and the carbon atom α to the triple bond may form a ring.

[0179] The total number of carbon atoms contained in R' and R" is at least 5 and preferably 9-20. As for the alkynol, examples that may be mentioned include:

[0180] -1-ethynyl-1-cyclohexanol;

[0181] -3-methyl-1-dodecyne-3-ol;

[0182] -3,7,11-trimethyl-1-dodecyne-3-ol;

[0183] -1,1-diphenyl-2-propyn-1-ol;

[0184] -3-ethyl-6-ethyl-1-nonyn-3-ol;

[0185] -2-methyl-3-butyn-2-ol;

[0186] -3-methyl-1-pentadecyn-3-ol; and

[0187] - diallyl maleate or a diallyl maleate derivative.

[0188] In a preferred embodiment, the crosslinking inhibitor F is selected from 1-ethynyl-1-cyclohexanol.

[0189] Advantageously, the amount of crosslinking inhibitor F in the addition-crosslinkable silicone composition is 0.01 to 4.0% by weight, preferably 0.09% by weight or 0.5 to 3.0% by weight, relative to the total weight of the silicone composition.

[0190] 6. Other components

[0191] The silicone composition according to the invention may also contain other additives, such as standard semi-reinforcing or filling fillers, other functional silicone resins such as silicone resins with epoxy groups, non-reactive methylpolysiloxanes, pigments or adhesion promoters.

[0192] Non-siliceous minerals that may be included as semi-reinforcing or filling mineral fillers may be selected from: carbon black, titanium dioxide, alumina, hydrated alumina, calcium carbonate, ground quartz, diatomaceous earth, zinc oxide, mica, talc, iron oxide, barium sulfate and slaked lime.

[0193] However, in the embodiment of the present invention, the organosilicon composition contains a thixotropic agent G as an essential component. The thixotropic agent of the present invention can be selected from compounds containing aromatic groups such as phenyl groups, compounds containing epoxy groups, compounds containing ester groups, compounds containing ether groups, etc. These compounds can be connected to polysiloxane or hydrocarbon groups, and can be small molecular compounds or polymers.

[0194] Such a thixotropic agent G preferably comprises an organopolysiloxane G' having an aryl group. The organopolysiloxane E having an aryl group is an organopolysiloxane containing at least one siloxane unit, which carries an aryl group directly bonded to a Si atom.

[0195] In a preferred embodiment, the organopolysiloxane G' having an aryl group is an organopolysiloxane containing a siloxane unit of formula (G-1):

[0196] [R 5 p R 6 q SiO (4-p-q) / 2 ] n (G-1)

[0197] in

[0198] R 5 and R 6 independently of one another selected from hydrocarbon-based groups containing 1 to 30 carbon atoms and hydrogen;

[0199] in

[0200] n is an integer greater than or equal to 1;

[0201] p and q are independently 0, 1, 2 or 3; and

[0202] p+q=1, 2 or 3;

[0203] Provided that the organopolysiloxane G' having an aryl group contains at least one aryl group directly bonded to a Si atom.

[0204] In a preferred embodiment, the organopolysiloxane G' consists essentially of siloxane units of formula (G-1).

[0205] In a preferred embodiment, the hydrocarbon-based group contains 1-24, preferably 1-18, more preferably 1-12, for example 2-8 carbon atoms. The hydrocarbon-based group may include a linear, branched or cyclic alkyl or alkenyl group, which is unsubstituted or substituted with one or more halogen and aryl groups, and an aryl group, which is unsubstituted or substituted with one or more halogen and C1-C6-alkyl and contains 6-12 carbon atoms.

[0206] The organopolysiloxane G' is a linear, branched or cyclic structure, and is preferably a linear one. In a linear or branched structure, the organopolysiloxane G may be terminated by -R or -SiR3 groups, wherein R has independently of each other a 5 and R 6 The person skilled in the art will understand that the aryl groups may be present sideways on the main chain of the organopolysiloxane G or at the ends of the chain as end-capping groups R or contained in end-capping groups -SiR3.

[0207] In a preferred embodiment, the aryl groups may be unsubstituted or substituted by one or more halogens and C1-C6-alkyl groups and contain 6 to 12 carbon atoms. More preferably, they are selected from xylyl, tolyl and phenyl groups, most preferably phenyl.

[0208] In a preferred embodiment, in the above formula (G-1):

[0209] n is an integer greater than or equal to 2.

[0210] In a preferred embodiment, in the above formula (G-1):

[0211] p and q are 1 or 2 independently of each other.

[0212] In a preferred embodiment, in the above formula (G-1):

[0213] Group R 5 and R 6 At least one of the groups is an aryl group and the rest are selected from an alkyl group containing 1 to 8 carbon atoms, preferably a methyl group or an ethyl group, and an alkenyl group containing 2 to 6 carbon atoms, preferably a vinyl group.

[0214] In another preferred embodiment, the organopolysiloxane G′ having aromatic groups, for example of formula (G-1), contains at least one aromatic group, preferably a phenyl group, and at least one alkenyl group, preferably a vinyl group.

[0215] In another preferred embodiment, the organopolysiloxane G′ having aromatic groups, for example of the formula (G-1), contains at least one aromatic group, preferably a phenyl group, and at least one SiH group.

[0216] In another preferred embodiment, the organopolysiloxane G′ having aromatic groups, for example of formula (G-1), contains at least one aromatic group, preferably a phenyl group, at least one alkenyl group, preferably a vinyl group, and at least one SiH group.

[0217] In one advantageous embodiment, the organopolysiloxane G′ having aryl groups contains or consists of an organopolysiloxane which consists of siloxane units of the abovementioned formula (G-1) which are terminated by groups —R or —SiR 3 .

[0218] As useful examples of organopolysiloxanes G' having aryl groups, mention may be made of compounds of the following formula:

[0219]

[0220]

[0221] Methods for preparing organopolysiloxanes having aryl groups and preferably alkenyl groups are well known in the art, for example in CN105778102A, CN 108329475A, CN106977723A, CN105778102A, CN101885845A, CN104403105A and CN103012797A.

[0222] In a preferred embodiment, the silicone composition according to the present invention comprises an organopolysiloxane containing vinyl and phenyl groups, such as a vinyl-containing diphenyldimethylpolysiloxane (eg, having the formula (GV)) as the organopolysiloxane G′ having an aromatic group.

[0223] In the present invention, the silicone composition comprises 0.01-20 wt%, such as 0.1-20 wt%, preferably 0.3-15 wt%, preferably 0.8-10 wt%, more preferably 1.0-7.0 or 1.0-5.0 wt% of at least one organopolysiloxane G' having an aromatic group, relative to the total weight of the silicone composition.

[0224] Furthermore, advantageously, the organopolysiloxane G' having aromatic groups has a viscosity of 3 to 10,000,000 mPas, preferably 10 to 200,000 mPas, for example 50 to 100,000 mPas and 100 to 10,000 mPas; and / or the amount of aromatic groups is 2 to 70 wt %, preferably 5 to 62 wt %, and for example 10 to 58 wt %, based on the total weight of the organopolysiloxane G' having aromatic groups.

[0225] In another preferred embodiment, the organic silicon composition according to the present invention may contain epoxy-containing polydimethylsiloxane or polyether grafted polysiloxane G", for example, in an amount of 0.01 wt % to 5 wt %, such as 0.1 to 3 wt %.

[0226] In the context of the present invention, the molar ratio of hydrogen atoms bonded to silicon (Si-H) to alkenyl groups bonded to silicon (e.g. Si-CH=CH2) in the entire composition is from 0.2 to 20, preferably between 0.5 and 15, more preferably between 0.5 and 10, and even more preferably between 0.5 and 5.

[0227] In a preferred embodiment X1, the silicone composition of the present invention comprises, relative to 100 wt % of the silicone composition:

[0228] - 15-80 wt%, such as 25-75 wt%, of at least one linear or branched alkenyl-containing organopolysiloxane A;

[0229] -optionally at least one alkenyl-containing organopolysiloxane resin A', preferably 0.4 wt% to 10 wt%, such as 0.5 wt% to 5 wt% of at least one alkenyl-containing organopolysiloxane resin A';

[0230] - 0.1-40 wt%, such as 1-25 wt% or such as 2-20 wt% of at least one organic hydrogen-containing polysiloxane B;

[0231] - 15-35 wt %, such as 20-30 wt %, of at least one optionally at least partially surface-treated silica reinforcing filler E;

[0232] - 0.0002% to 0.05 wt%, such as 0.0008 to 0.03 wt%, of a catalyst C, such as a platinum compound; and

[0233] - 0.01-20.0 wt%, such as 0.1-7.0 wt%, of a thixotropic agent G; and

[0234] - 0.1 to 10.0% by weight of polyalkenylpolysiloxane A'.

[0235] In another preferred embodiment X2, the silicone composition of the present invention comprises, relative to 100 wt % of the silicone composition:

[0236] - 15-80 wt%, such as 25-75 wt%, of at least one alkenyl-containing organopolysiloxane A;

[0237] - 0.1-40 wt%, such as 1-25 wt% or 2-20 wt% of at least one organic hydrogen-containing polysiloxane B, which is at least one linear or branched organic hydrogen-containing polysiloxane containing at least one of Si-H bonds located in the chain and Si-H bonds located at the chain ends, a cyclic organic hydrogen-containing polysiloxane, or at least one organic hydrogen-containing polysiloxane resin, or a mixture thereof, wherein the molar proportion of Si-H bonds located at the chain ends to all Si-H bonds of the component (B) is less than 40%, preferably less than 30%, more preferably less than 10%;

[0238] - 15-35 wt %, such as 20-30 wt %, of at least one at least partially surface-treated silica reinforcing filler E;

[0239] - 0.0002% to 0.05 wt%, such as 0.0008 to 0.03 wt%, of a catalyst C, such as a platinum compound; and

[0240] - 0.01-20.0 wt%, such as 0.1-7.0 wt%, of a thixotropic agent G.

[0241] In the above-mentioned embodiment X2, more preferably, the organosilicon composition further comprises, relative to 100 wt % of the organosilicon composition:

[0242] - 0.1 to 10.0% by weight of said polyalkenylpolysiloxane A'.

[0243] In the above-mentioned embodiment X2, more preferably, component B is 0.1-20wt%, for example 0.1-10wt%, and also for example 1-6wt% of at least one linear or branched organic hydrogen-containing polysiloxane, which contains at least one of Si-H bonds located in the chain and Si-H bonds located at the chain ends, and 1-30wt%, for example 2-20wt% of at least one organic hydrogen-containing polysiloxane resin, wherein the molar ratio of Si-H bonds located at the chain ends to all Si-H bonds of the component (B) is less than 40%, preferably less than 30%, and more preferably less than 10%.

[0244] It should be noted that the amounts described in the above two preferred embodiments and in the above ranges in this application are exemplary only, and therefore each of them can be combined in any manner known to those skilled in the art. At the same time, the above two exemplary preferred formulations can also include other components as described above in listed amounts or preferred amounts.

[0245] The following examples are intended to illustrate but not to limit the present invention. Example

[0246] In the following examples, the raw materials listed in Table 1 were used.

[0247] Table 1

[0248]

[0249]

[0250] Preparation and testing of examples and comparative examples

[0251] All the raw materials shown in Table 2 below are mixed in the indicated weight ratios. In this process, the indicated amount of the vinyl-terminated polysiloxane and the vinyl silicone resin as component A are first mixed with the indicated amount of components A'-1 and F-2. Then the treated white carbon black component E is added and then fully mixed. Then the organic hydrogen-containing polysiloxane component B and the catalyst component C are added and stirred in sequence, and finally 2.5 parts of the component G are added and fully mixed to obtain the sample of the embodiment or comparative example.

[0252] Examples 1-7 and Comparative Examples 1-2 were prepared according to the general procedure described above.

[0253] The properties of the prepared samples were tested according to the following methods and the test results are summarized in Table 2 below.

[0254] Viscosity test: According to ASTM D445, the viscosity of the sample mixture is tested at 23°C, and the test conditions are detailed in Table 2. For example, the expression (7#, 2rpm) means that the viscosity is measured using spindle 7 at 2rpm, and so on.

[0255] Thixotropic index: A thixotropic fluid has low viscosity when stirred at high speed and high viscosity when stirred at low speed. The thixotropic index is obtained by measuring the viscosity at two speeds that differ by a factor of 10 (e.g. 0.2 and 2 rpm) at room temperature. Here, the ratio between viscosity-0.2 and viscosity-2, i.e. (viscosity-0.2 / viscosity-2), defines the degree to which the fluid hangs or resists sagging under the influence of gravity. When at rest, the fluid will not flow or will flow very little, but when subjected to shear or pressure, it will flow easily. The higher the thixotropic ratio, the more thixotropic the non-Newtonian fluid.

[0256] Hardness test: The hardness of the cured sample was measured according to ASTM D2240 at 23° C. The test sample was obtained by press curing at 150° C. for 2 hours.

[0257] Tensile strength and elongation at break test: The tensile strength and elongation at break of the cured samples were measured according to ASTM D412 at 23° C. The test samples were obtained by press-curing at 150° C. for 2 hours.

[0258] Tear Strength Test: The tear strength of the cured samples was measured according to ASTM D624 at 23° C. The test samples were obtained by press-curing at 150° C. for 2 hours.

[0259] Carving feel: The tested silicone composition was prepared as described below. Preparation of costal cartilage carving model After the rib cartilage sculpture model was made by 3D printing using the method described above, it was evaluated according to the method described in the following literature:

[0260] Pensalfini,M.,Meneghello,S.,Lintas,V.,Bircher,K.,Ehret,AE,Mazza,E.The suture retention test,revisited and revised.Journal of the MechanicalBehavior of Biomedical Materials 2018;77:711-717

[0261] The scores obtained according to this test method are used as the basis for judging whether the engraving feel is good or bad: scores above 8 points are evaluated as "good", and scores below this value are evaluated as "bad".

[0262]

[0263]

[0264]

[0265] Preparation of costal cartilage carving model

[0266] Patients who are scheduled to undergo costal cartilage removal surgery will undergo a chest CT scan before surgery to assess whether they are suitable for costal cartilage removal surgery, and the CT data will be used as imaging data for three-dimensional reconstruction.

[0267] Use 3D reconstruction software such as Mimics to perform 3D reconstruction on the CT data of the patient's costal cartilage that needs to be removed and save the reconstructed CAD model in STL format. Use software to slice the STL model of the costal cartilage and plan the printing path.

[0268] The formula of Example 3 was used as the main material to manufacture the rib cartilage teaching aids on the silicone 3D printer S300. The 3D printing equipment is liquid extrusion molding, has a dual-nozzle extrusion printing function, and is equipped with an automatic cutoff system, which can print the main body and auxiliary support materials; the printer extrusion nozzle has a Z-axis avoidance function. Here, a 0.4mm extrusion nozzle and appropriate process parameters are selected for parametric slicing.

[0269] The key process parameters are as follows: scanning speed is 15 mm / s, layer thickness is 0.2 mm, filling rate is 100%, and material supply rate is 80%.

[0270] After printing is completed, the printed silicone rib cartilage is placed in an 80°C oven for heating and curing for 30-60 minutes, and then heated to 120°C for heating and curing for 15 minutes to complete the curing and molding of the product. Finally, the cured product is taken out for support removal, water washing, and drying to obtain the final product.

[0271] The printing accuracy of the printed rib cartilage teaching aids was evaluated according to the following tests:

[0272] The printed rib cartilage teaching aids were CT scanned for 3D reconstruction, and then the resulting STL model was put into the software together with the initial STL model for 3D comparison to obtain accuracy comparison data. After multiple tests, the accuracy of the silicone 3D printed rib cartilage model was about 95%.

Claims

1. A silicone composition which is curable by an addition reaction and comprises: (A) at least one alkenyl-containing organopolysiloxane A, each molecule of which contains at least two alkenyl groups attached to silicon atoms, preferably C2-C 12 , more preferably C2-C6 alkenyl, (B) at least one organic hydrogen-containing polysiloxane B comprising, per molecule, at least one hydrogen atom bonded to the same or different silicon atoms, (C) at least one catalyst C comprising at least one metal selected from the platinum group or a compound thereof, (E) > 12 wt. %, based on the total weight of the composition, of at least one silica reinforcing filler E, and (G) at least one thixotropic agent G; The prerequisite is that at least one of the following conditions (1) and (2) is met: (1) in the organohydrogenpolysiloxane B, the molar ratio of the Si-H bonds at the chain ends to the total Si-H bonds of the component (B) is less than 40%, preferably less than 30%, more preferably less than 10%, and (2) The composition comprises at least two alkenyl-containing organopolysiloxanes A, wherein at least one alkenyl-containing organopolysiloxane A is a polyalkenylpolysiloxane A' having at least 3, more preferably at least 4 alkenyl groups per molecule.

2. The organosilicon composition according to claim 1, characterized in that The amount of the silica reinforcing filler E is 15 wt % to 40 wt %, preferably 20 wt % to 30 wt % based on the weight of the total composition.

3. The organosilicon composition according to any one of the preceding claims, characterized in that The polyalkenyl polysiloxane A' is linear, branched or cyclic, preferably cyclic, such as tetramethyltetravinylcyclotetrasiloxane, such as 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane.

4. The organosilicon composition according to any one of the preceding claims, characterized in that The amount of the polyalkenyl polysiloxane A' is 0.05 to 12.0 wt%, preferably 0.1 to 6.5 wt%, for example 0.5 to 4.0 wt%, relative to the total weight of the silicone composition.

5. The silicone composition according to any one of the preceding claims, characterized in that The thixotropic agent G in the silicone composition is selected from compounds containing aromatic groups such as phenyl groups, compounds containing epoxy groups, compounds containing ester groups, and compounds containing ether groups; preferably, the organopolysiloxane G' having an aromatic group, more preferably, the organopolysiloxane containing vinyl and phenyl groups, such as vinyl-containing diphenyldimethylpolysiloxane.

6. The organosilicon composition according to claim 5, characterized in that The silicone composition comprises 0.3-15 wt %, preferably 0.8-10 wt %, more preferably 1.0-5.0 wt % of at least one organopolysiloxane G' having an aromatic group, relative to the total weight of the silicone composition.

7. The silicone composition according to any one of the preceding claims, characterized in that The silicone composition comprises epoxy-containing polydimethylsiloxane or polyether grafted polysiloxane G" as a thixotropic agent G, for example, the content thereof is 0.01 wt% to 5 wt%, such as 0.1 to 3 wt%.

8. The organosilicon composition according to any one of the preceding claims, characterized in that In the entire composition, the molar ratio of hydrogen atoms bonded to silicon (Si-H) to alkenyl groups bonded to silicon (e.g., Si-CH=CH2) is 0.2 to 20, preferably between 0.5 and 15, more preferably between 0.5 and 10, and even more preferably between 0.5 and 5.

9. The organosilicon composition according to any one of the preceding claims, characterized in that The organosilicon composition comprises, relative to 100 wt % of the organosilicon composition: - 15-80 wt%, such as 25-75 wt%, of at least one chain, such as a straight chain or branched chain, or a cyclic alkenyl-containing organopolysiloxane A; -optionally at least one alkenyl-containing organopolysiloxane resin A', preferably 0.4 wt% to 10 wt%, such as 0.5 wt% to 5 wt% of at least one alkenyl-containing organopolysiloxane resin A'; - 0.1-40 wt%, such as 1-25 wt% or such as 2-20 wt% of at least one organic hydrogen-containing polysiloxane B; - 15-35 wt %, such as 20-30 wt %, of at least one optionally at least partially surface-treated silica reinforcing filler E; - 0.0002%-0.05wt%, such as 0.0008-0.03wt% of catalyst C, for example a platinum compound; - 0.01-20.0wt%, such as 0.1-7.0wt% of thixotropic agent G; and - 0.1 to 10.0% by weight of said polyalkenylpolysiloxane A'.

10. The organosilicon composition according to any one of claims 1 to 8, characterized in that The organosilicon composition comprises, relative to 100 wt % of the organosilicon composition: - 15-80 wt%, such as 25-75 wt%, of at least one alkenyl-containing organopolysiloxane A; - 0.1-40 wt%, such as 1-25 wt% or such as 2-20 wt% of at least one organohydrogenpolysiloxane B, which is at least one linear or branched organohydrogenpolysiloxane containing at least one of Si-H bonds located in the chain and Si-H bonds located at the chain ends, a cyclic organohydrogenpolysiloxane, or at least one organohydrogenpolysiloxane resin, or a mixture thereof, wherein the molar proportion of Si-H bonds located at the chain ends to all Si-H bonds of the component (B) is less than 40%, preferably less than 30%, more preferably less than 10%; - 15-35 wt %, such as 20-30 wt %, of at least one at least partially surface-treated silica reinforcing filler E; - 0.0002%-0.05wt%, such as 0.0008-0.03wt% of catalyst C, for example a platinum compound; and - 0.01-20.0 wt%, such as 0.1-7.0 wt%, of a thixotropic agent G.

11. The organosilicon composition according to claim 10, characterized in that The organosilicon composition further comprises, relative to 100 wt % of the organosilicon composition: - 0.1 to 10.0% by weight of said polyalkenylpolysiloxane A'.

12. The silicone composition according to claim 10, characterized in that Component B is 0.1-20wt%, for example 0.1-10wt% or 1-6wt% of at least one linear or branched organic hydrogen-containing polysiloxane containing at least one of Si-H bonds located in the chain and Si-H bonds located at the chain ends, and 1-30wt%, for example 2-20wt% of at least one organic hydrogen-containing polysiloxane resin, wherein the molar proportion of Si-H bonds located at the chain ends to all Si-H bonds of the component (B) is less than 40%, preferably less than 30%, and more preferably less than 10%.

13. The silicone composition according to claim 1, characterized in that The organohydrogenpolysiloxane B has no Si—H bond at the chain end.

14. A cartilage sculpture model obtained by a method comprising additive manufacturing with a silicone composition, wherein the silicone composition is as claimed in any one of claims 1 to 13.

15. The cartilage sculpture model according to claim 14, characterized in that The cartilage is costal cartilage.

16. The cartilage sculpture model according to claim 14 or 15, characterized in that The cartilage sculpture model has a Shore A hardness in the range of 60-95, such as 62-92 or 60-85, a tear strength in the range of 7-50 N / mm, a tensile strength of 4-15 MPa and an elongation at break of 15-500% or 85-170%.

17. A method for additively manufacturing a cartilage sculpture model using the silicone composition as described in any one of claims 1 to 13, comprising the following steps: (1) collecting shape information of the cartilage to be carved, (2) establishing a digital model, and (3) using a 3D printing device to additively manufacture the cartilage sculpture model using the silicone composition as described in any one of claims 1 to 13 as the main material.

18. Use of the organosilicon composition according to any one of claims 1 to 13 for preparing a cartilage sculpture model by a method comprising additive manufacturing.

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