A photocurable silicon-based ceramic precursor and its preparation method and application

Abstract

The present invention belongs to the technical field of photocurable materials, silicon-based ceramic precursors and silicon-based ceramics, and specifically relates to a photocurable silicon-based ceramic precursor and a preparation method and application thereof. The photocurable silicon-based ceramic precursor provided by the present invention can be used as a silicon-based ceramic precursor resin, and the ceramic yield of the cured product is high, and it shows great application prospects in the fields of preparing resin films / coatings, organic-inorganic hybrid material films / coatings, ceramic films / coatings, ceramic fibers, ceramic-based composite materials, and 3D printing to prepare ceramic parts.

Description

[0001] The invention belongs to the technical field of photocurable materials, silicon-based ceramic precursors and silicon-based ceramics, and in particular relates to a photocurable silicon-based ceramic precursor and a preparation method and application thereof. Background Art

[0002] Photosensitive silicon-based ceramic precursors show great application prospects in the preparation of ceramic coatings, ceramic-based composite materials, stereolithography, ceramic micro-electromechanical systems and other fields. Among them, the use of stereolithography technology, that is, photocuring 3D printing technology, to prepare complex structure ceramic parts is a ceramic part preparation technology with great development potential. Compared with photocuring ceramic slurries, photocuring silicon-based ceramic precursor polymers have several advantages in 3D printing. First, silicon-based ceramic precursors can be in liquid phase, and there is no agglomeration and light scattering effect. Secondly, the ceramic composition can be regulated by the precursor structure composition, which makes it easy to print more precise ceramic parts with fewer impurities.

[0003] At present, there is a serious lack of various types of photocurable silicon-based ceramic precursor products in the commercial market. The only photocurable polysiloxane with the brand name TEGO RC 711 from Evonik of Germany has a ceramic yield of only 7.4wt% after photocuring (1000℃, N 2 ). In current research, a common method for preparing photocurable polyoxane is to obtain photocurable polysiloxane by hydrolyzing and condensing a silane coupling agent containing a photosensitive group (such as KH-570). The photosensitive group content and product viscosity of the photocurable polysiloxane obtained by this method are difficult to control, and the ceramic yield is low, with the highest reported value being only 51.2wt%. There are fewer studies on the photocuring of silicon-based ceramic precursors such as polycarbosilane, polysilazane, and polysilicon boron nitrogen, and there are no commercial products. Therefore, the development of photocurable silicon-based ceramic precursors has important applications and commercial value.

[0004] In terms of silicon-based ceramic precursor products, there are currently many commercial products in China, such as our unit's polysiloxane-based ceramic precursors, polysilazane-based ceramic precursors, polycarbosilane-based ceramic precursors or polyborosilazane ceramic precursors. For example, polysiloxane-based ceramic precursors (such as brand KH-PSO-1), liquid polycarbosilane (such as brand KH-VHPCS-1, KH-AHPCS-1); polysilazane (such as brand KH-PSN1, KH-PSN2); polyborosilazane (such as brand KH-PSNB), etc. The above-mentioned liquid polycarbosilane, polysilazane, and polyborosilazane are all products suitable for thermal curing in the prior art and have been used in high-tech fields such as aerospace. However, the above-mentioned products are designed and synthesized for the molecular structure required for thermal curing processes, and their photocuring properties cannot meet typical application requirements. Summary of the invention

[0005] In order to overcome the deficiencies in the prior art, the present invention provides a novel structured silicon-based ceramic precursor that can be photocured at room temperature, and a preparation method and application thereof.

[0006] The present invention provides the following technical solutions:

[0007] A photocurable silicon-based ceramic precursor having a segment structure as shown in formula M or N:

[0008]

[0009]

[0010] Wherein, R, R' are the same or different and are independently selected from H, unsubstituted, or optionally substituted by one, two or more Ra: 1-20 Alkyl or C 1-20 Alkoxy; Ra is selected from hydroxy, halogen, amino or C 1-20 alkyl;

[0011] Y are the same or different and are independently selected from the following groups which are unsubstituted or optionally substituted by one, two or more Rb: C 2-10 Alkenyl or C 2-10 Alkynyl;

[0012] Rb is selected from hydroxy, halogen, amino or C 1-20 alkyl;

[0013] X are the same or different and are independently selected from the photosensitive reaction group Rg, wherein the photosensitive reaction group Rg is a group that undergoes polymerization reaction under the conditions of light and the presence of a photoinitiator;

[0014] The photosensitive reaction group Rg is a carbonyl group, a carboxyl group, a peroxide group and a group containing an unsaturated bond, and the photosensitive reaction group is preferably an acrylate group, a vinyl ether group or an epoxy group;

[0015] x=0.01~0.9, y=0.00~0.9, z=0.00~0.9, x+y+z=0.01~0.9.

[0016] Preferably, x is 0.05 to 0.50, y is 0 to 0.5, z is 0 to 0.5; x+y+z=0.1 to 0.8.

[0017] For example, x is 0.1, 0.2, 0.4; y is 0, 0.1, 0.5; and z is 0, 0.1, 0.3.

[0018] It should be clear that although the chain segments of the photocurable silicon-based ceramic precursor of the present invention are shown as M or N, it does not mean that the chain segments represented by x, y, z and (1-xyz) in its structure are arranged in this order. Due to the influence of factors such as chemical steric hindrance and reaction site activity, X and Y can be substituted at any position of the main chain.

[0019] According to an embodiment of the present invention, R is H, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Hydroxyl substituted C 1-4 Alkyl or halogenated C 1-4 Alkyl, preferably H or C 1-4 alkyl.

[0020] According to an embodiment of the present invention, R' is H, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Hydroxyl substituted C 1-4 Alkyl or halogenated C 1-4 Alkyl, preferably H or C 1-4 alkyl.

[0021] According to an embodiment of the present invention, the weight average molecular weight M of the photocurable silicon-based ceramic precursor is w 600-100000, number average molecular weight M n For example, the weight average molecular weight M of the photocurable silicon-based ceramic precursor is w 1000-40000, number average molecular weight M n 500-10000.

[0022] According to an embodiment of the present invention, Y is CH 2 =CH-, CH 2 =CHCH 2 -, CH 2 =C(CH 3 )-,CH 3 CH=CH-, HC≡C-, HC≡C-CH 2 - or cyclopropyl-(CH 2 ) 2 CH-, preferably CH 2 =CH- or CH 2 =CHCH 2 -.

[0023] According to an embodiment of the present invention, the acrylate group is selected from -A-OOC-C(R 1 )=CH 2 , wherein A is selected from absent or -O(CH 2) a -, when A does not exist, -OOC-C(R 1 )=CH 2 The O in -OOC- is connected to Si. When present, -O(CH 2 ) a -, O is connected to Si, a is an integer of 1-6 (e.g., an integer of 2-4), R 1 Selected from H, C 1-6 Alkyl; Also specifically, the acrylate group is selected from -OOC-CH=CH 2 ,-OOC-C(CH 3 )=CH 2 ,-O(CH 2 ) 2 OOC-CH=CH 2 ,-O(CH 2 ) 3 OOC-CH=CH 2 ,-O(CH 2 ) 2 OOC-C(CH 3 )=CH 2 ,-O(CH 2 ) 3 OOC-C(CH 3 )=CH 2 wait.

[0024] According to an embodiment of the present invention, the vinyl ether group is selected from the group represented by formula (2):

[0025] -O-(CH 2 ) m1 -O-(CH 2 ) m2 -C(R 2 )=CH(R 3 ) Formula (2)

[0026] Wherein, m1 is an integer of 1-6 (for example, an integer of 1-4), m2 is an integer of 0-6 (for example, 0 or 1), R 2 is selected from H, methyl or ethyl, R 3 Select from H or C 1-6 alkyl.

[0027] Also specifically, the vinyl ether group is selected from -OCH 2 -O-CH=CH 2 ,-O(CH 2 ) 2 -O-CH=CH 2 , -OCH 2 -O-CH=CH-CH 3, -OCH 2 -O-CH=CH-C 2 H 5 , -OCH 2 -O-CH=CH-C 3 H 7 ,-O(CH 2 ) 3 -O-CH=CH 2 ,-O(CH 2 ) 4 -O-CH=CH 2 ,-O(CH 2 ) 5 -O-CH=CH 2 ,-O(CH 2 ) 6 -O-CH=CH 2 , -OCH 2 -O-CH 2 -CH=CH 2 ,-O(CH 2 ) 2 -O-CH 2 -CH=CH 2 ,-O(CH 2 ) 3 -O-CH 2 -CH=CH 2 ,-O(CH 2 ) 4 -O-CH 2 -CH=CH 2 ,-O(CH 2 ) 5 -O-CH 2 -CH=CH 2 ,-O(CH 2 ) 6 -O-CH 2 -CH=CH 2 wait.

[0028] According to an embodiment of the present invention, the epoxy group is selected from -O(CH 2 ) n1 -R 4 , where n1 is an integer from 1 to 6, R 4 Selected from substituted or unsubstituted C 2-12 Epoxyalkyl, substituted or unsubstituted epoxy C 3-12 Cycloalkyl, when substituted, the substituent is C 1-6 Alkyl (e.g. C 1-3 For example, R 4 Selected from substituted or unsubstituted C 2-5Epoxyalkyl, substituted or unsubstituted epoxy C 3-8 Cycloalkyl, substituted by 1-6 Alkyl (e.g. C 1-3 For example, R 4 is selected from substituted or unsubstituted ethylene oxide, substituted or unsubstituted propylene oxide, substituted or unsubstituted butylene oxide, substituted or unsubstituted cyclobutylene oxide, substituted or unsubstituted cyclopentyl oxide, substituted or unsubstituted cyclohexyl oxide, the substituent being C 1-3 For example, R 4 Selected from ● is the connection site.

[0029] According to an exemplary embodiment of the present invention, the photocurable silicon-based ceramic precursor has a structure shown in any one of the following formulas M1 to M7 and N1 to N6:

[0030]

[0031]

[0032]

[0033] According to an embodiment of the present invention, the TGA ceramic yield of the photocurable silicon-based ceramic precursor at 1000° C. is 40-90%, such as 45-85%.

[0034] According to the embodiment of the present invention, the TGA ceramic yield of the photocurable silicon-based ceramic precursor after cross-linking and curing under the action of a catalyst is 50-85.0%.

[0035] According to an embodiment of the present invention, the photocurable silicon-based ceramic precursor is sealed and stored at room temperature (0-40° C.) for 1-3 months, and the viscosity change thereof is less than 10%.

[0036] The present invention also provides a method for preparing the above-mentioned photocurable silicon-based ceramic precursor, comprising the following steps: using a silicon-based ceramic precursor resin containing a silicon-hydrogen bond and a hydroxyl-containing photosensitive monomer Rg-H as raw materials, and performing a catalytic reaction in the presence of a dehydrogenation coupling catalyst;

[0037] In Rg-H, Rg has the same meaning as described above.

[0038] According to an embodiment of the present invention, the silicon-based ceramic precursor resin containing silicon-hydrogen bonds is selected from polysiloxane (for example, KH-PSO-1, KH-PSO-2, KH-PSO-3 or KH-PSO-4), liquid polycarbosilane (for example, grades KH-VHPCS-1, KH-AHPCS-1, KH-AHPCS-2, KH-VHPCS-2, KH-HPCS-1); polysilazane (for example, grades KH-PSN1, KH-PSN2); polyborosilazane (for example, grade KH-PSNB), etc.

[0039] Preferably, the liquid silicon-based ceramic precursor resin containing silicon-hydrogen bonds is polysiloxane (KH-PSO-1) or polycarbosilane (KH-VHPCS-1, KH-AHPCS-1, KH-AHPCS-2, KH-VHPCS-2).

[0040] According to an embodiment of the present invention, the photosensitive monomer Rg-H containing -OH is an acrylate monomer containing -OH, a vinyl ether monomer containing -OH or an epoxy monomer containing -OH.

[0041] According to an embodiment of the present invention, the structural formula of the acrylic ester monomer containing -OH is HA-OOC-C(R 1 )=CH 2 , where A and R 1 Having the definitions as above;

[0042] Preferably, the -OH-containing acrylic ester monomer is selected from HOOC-CH=CH 2 , HOOC-C(CH 3 )=CH 2 , HO(CH 2 ) 2 OOC-CH=CH 2 , HO(CH 2 ) 3 OOC-CH=CH, HO(CH 2 ) 2 OOC-C(CH 3 )=CH 2 or HO(CH 2 ) 3 OOC-C(CH 3 )=CH 2 .

[0043] According to an embodiment of the present invention, the structural formula of the -OH-containing vinyl ether monomer is HO(CH 2 ) m1 -O-(CH 2 ) m2 -C(R 2)=CH(R 3 ), wherein m1, m2, R 2 and R 3 Having the definitions as above;

[0044] Preferably, the -OH-containing vinyl ether monomer is HOCH 2 -O-CH=CH 2 , HO(CH 2 ) 2 -O-CH=CH 2 , HO(CH 2 ) 3 -O-CH=CH 2 , HO(CH 2 ) 4 -O-CH=CH 2 , HO(CH 2 ) 5 -O-CH=CH 2 , HO(CH 2 ) 6 -O-CH=CH 2 , HOCH 2 -O-CH 2 -CH=CH 2 , HO(CH 2 ) 2 -O-CH 2 -CH=CH 2 , HO(CH 2 ) 3 -O-CH 2 -CH=CH 2 , HO(CH 2 ) 4 -O-CH 2 -CH=CH 2 , HO(CH 2 ) 5 -O-CH 2 -CH=CH 2 or HO(CH 2 ) 6 -O-CH 2 -CH=CH 2 .

[0045] According to an embodiment of the present invention, the structural formula of the epoxy monomer containing -OH is HO(CH 2 ) n1 -R 4 , the n1 and R 4 Has the same definition as above.

[0046] Preferably, the -OH-containing epoxy monomer is selected from the following structures:

[0047]

[0048] According to an embodiment of the present invention, the solvent is selected from benzene-containing solvents, ether solvents, low-boiling point alkane solvents, and the like.

[0049] For example, the benzene-containing solvent is one, two or more of toluene, xylene, trimethylbenzene, etc.; preferably, it is toluene.

[0050] For example, the ether solvent is one, two or more of diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, methyl tert-butyl ether, methyl tert-amyl ether, and cyclopentyl methyl ether; preferably, it is one, two or more of tetrahydrofuran, 2-methyltetrahydrofuran, methyl tert-butyl ether, and methyl tert-amyl ether.

[0051] For example, the low boiling point alkane solvent is one, two or more of pentane, cyclopentane, hexane and petroleum ether (30-120° C.); preferably, it is a mixture of hexane and petroleum ether (60-90° C.).

[0052] According to an embodiment of the present invention, the dehydrogenation coupling catalyst is selected from transition metal catalysts, alkali metal catalysts, metal-free organic catalysts, and the like.

[0053] For example, the transition metal catalyst is selected from the fourth group metallocene complex catalyst, Cp 2 MR 2 (M=Ti, Zr, Hf;R=alkyl,Ph,H;Cp=η 5 -cyclopentadienyl or its alkyl substituted derivatives) or Cp 2 MX 2 / n-BuLi(M=Ti,Zr,Hf; X=Cl,OAr),Ti IV ,Mn II ,Re IV ,Fe II ,Ru II ,Rh II ,Ir II ,Ni II ,Cu II ,Au I ,Pt II and Zn II Homogeneous metal complexes with multiple valence states; lanthanide metallocenes; one, two or more of palladium chloride and nickel chloride; preferably, Cp 2 Ti(CH 3 )2 , palladium chloride, nickel chloride, one, two or three.

[0054] For example, the alkali metal catalyst is a fluoride salt KF, a strong base NaOH, KOH, an alkali gold salt [MN(SiMe 3 ) 2 ](M=Li,Na,K), one, two or more of sodium tri(sec-butyl)borohydride, potassium tri(sec-butyl)borohydride, lithium tri(sec-butyl)borohydride; preferably, NaOH, [NaN(SiMe 3 ) 2 ], one, two or more of sodium tri(sec-butyl)borohydride.

[0055] For example, the metal-free organic catalyst is one, two or more of tri(pentafluorophenyl)borane, N-heterocyclic carbene (NHCs), N,N-diethylhydroxylamine, and tetrabutylammonium fluoride; preferably, it is at least one of N,N-diethylhydroxylamine and tri(pentafluorophenyl)borane.

[0056] According to an embodiment of the present invention, the molar ratio of Si-H in the silicon-based ceramic precursor resin containing silicon-hydrogen bonds to -OH in the photosensitive monomer containing -OH is 1:(0.01-1), preferably 1:(0.1-1).

[0057] According to an embodiment of the present invention, the molar ratio of the dehydrogenation coupling catalyst to the -OH-containing photosensitive monomer is 1:(1-1000000), preferably 1:(0.1-1000).

[0058] According to an embodiment of the present invention, the volume ratio of the silicon-based ceramic precursor resin containing silicon-hydrogen bonds to the solvent is 1:1 to 1:100.

[0059] According to an embodiment of the present invention, the reaction temperature is 15°C to 90°C, preferably, the reaction temperature is 35°C to 70°C; the reaction time is 3h to 36h, preferably, the reaction time is 6h to 24h.

[0060] According to an embodiment of the present invention, the preparation method may further include post-treatment: removing the dehydrogenation coupling catalyst, and distilling the obtained photocurable silicon-based ceramic precursor to obtain a final product.

[0061] Preferably, a method for preparing a photocurable silicon-based ceramic precursor is provided, wherein the method comprises:

[0062] (1) Under stirring, a dehydrogenation coupling catalyst is added to a silicon-based ceramic precursor resin containing silicon-hydrogen bonds and a photosensitive monomer containing a hydroxyl group, and a catalytic reaction is carried out under suitable solvent and temperature conditions.

[0063] (2) adding an absorbent of the dehydrogenation coupling catalyst, removing the catalyst, and performing post-treatment such as filtering, centrifugation or adding water and low-boiling alkane for phase separation and distillation to obtain a purified final product, a photocurable silicon-based ceramic precursor.

[0064] The present invention also provides the application of the above-mentioned photocurable silicon-based ceramic precursor, which is used as a photocurable resin material or a photocurable ceramic precursor composition.

[0065] The present invention also provides a photocurable resin material, the raw materials of which include the above-mentioned photocurable silicon-based ceramic precursor, a photoinitiator and a stabilizer.

[0066] According to an embodiment of the present invention, the raw materials of the photocurable resin material include, by mass percentage, 95-99.9% of the above-mentioned photocurable silicon-based ceramic precursor, 0.1-5% of a photoinitiator, and 0-1% of a stabilizer.

[0067] Preferably, the raw materials of the photocurable material include, by mass percentage, 98-99.5% of the above-mentioned photocurable silicon-based ceramic precursor, 0.5-2% of a photoinitiator, and 0-0.2% of a stabilizer.

[0068] According to an embodiment of the present invention, the photoinitiator is a free radical photoinitiator and / or a cationic photoinitiator.

[0069] Preferably, the carbosilane photosensitive monomer containing an acrylate group adopts a free radical photoinitiator, the carbosilane photosensitive monomer containing an epoxy group adopts a cationic photoinitiator, and the carbosilane photosensitive monomer containing a vinyl ether group adopts a cationic photoinitiator and / or a free radical photoinitiator.

[0070] According to an embodiment of the present invention, the cationic photoinitiator includes an iodonium salt and a sulfonium salt, for example, at least one of diaryl iodonium hexafluorophosphate, diaryl iodonium hexafluoroarsenate, diaryl iodonium hexafluoroantimonate, triaryl sulfonium hexafluorophosphate, triaryl sulfonium hexafluoroarsenate or triaryl sulfonium hexafluoroantimonate, etc. Preferably, it is triaryl sulfonium hexafluoroantimonate.

[0071] According to an embodiment of the present invention, the free radical photoinitiator includes a free radical initiator that can initiate polymerization of all unsaturated monomers containing carbon double bonds. For example, it is selected from phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, 2,4,6-trimethylbenzoyl-ethoxy-phenyl phosphine oxide, 2-hydroxy-2-methyl-1-phenyl acetone, benzophenone, benzoin dimethyl ether, chlorinated benzophenone, 4-benzoyl-4'-2-2-hydroxy-2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxycyclohexyl benzophenone or 2,4-diethylthioxanthone, or a mixture of two or more thereof. Preferably, it is benzoin dimethyl ether or 1-hydroxycyclohexyl benzophenone.

[0072] According to an embodiment of the present invention, the stabilizer can be a free radical inhibitor, such as 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, butylated hydroxytoluene (BHT) or 2,2,6,6-tetramethylpiperidinoxide (TEMPO), etc.; the stabilizer can also include ultraviolet absorbers, such as hexamethylphosphoramide (HMPA), 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone or 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, etc.

[0073] The present invention also provides a photocuring method for the above-mentioned photocurable resin material, comprising the following steps:

[0074] A photoinitiator is added to the photocurable silicon-based ceramic precursor and the precursor is cured under light.

[0075] According to an embodiment of the present invention, ultraviolet light is used for irradiation, and the wavelength of the ultraviolet light is 254 to 405 nm; the irradiation time is 1 to 60 minutes.

[0076] The present invention also provides a photocurable ceramic precursor composition, which comprises: the above-mentioned photocurable silicon-based ceramic precursor, a photoinitiator, an optional organic oligomer, an optional stabilizer, and an optional inorganic filler.

[0077] The present invention also provides a method for preparing the above-mentioned photocurable ceramic precursor composition, the method comprising: adding a photoinitiator to the above-mentioned photocurable silicon-based ceramic precursor, optionally adding or not adding an organic oligomer, optionally adding or not adding a stabilizer, optionally adding or not adding an inorganic filler, and curing under light to prepare the photocurable ceramic precursor composition;

[0078] According to an embodiment of the present invention, the organic oligomer refers to a photosensitive resin with a relatively low molecular weight, having a group that can undergo a photocuring reaction, such as various unsaturated double bonds or epoxy groups, etc. For example, one, two or more selected from various acrylic resins, epoxy resins and vinyl ether resins.

[0079] According to an embodiment of the present invention, the inorganic filler includes but is not limited to typical oxide or non-oxide ceramic materials, such as silicon oxide, aluminum oxide, zirconium oxide, mullite, silicon carbide, zirconium carbide, boron nitride, silicon nitride, zirconium boride, zirconium silicide, titanium oxide, etc.

[0080] According to an embodiment of the present invention, the method for preparing the above-mentioned photocurable ceramic precursor material composition specifically includes: adding a photoinitiator, an organic oligomer, a stabilizer, and optionally an inorganic filler to the above-mentioned photocurable silicon-based ceramic precursor, curing under light, and preparing a photocurable ceramic precursor composition.

[0081] According to an embodiment of the present invention, the illumination is ultraviolet light illumination, the wavelength of the ultraviolet light is 172 to 470 nm, for example, 254 to 405 nm; the illumination time is 1 to 60 min.

[0082] According to an embodiment of the present invention, the method for preparing the above-mentioned photocurable ceramic precursor composition specifically comprises:

[0083] (S1) using α-hydroxyalkyl phenone free radical photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide or 1-hydroxycyclohexyl phenyl ketone as the initiator of the photocurable silicon-based ceramic precursor containing acrylate group; or using diaryl iodonium salt or triaryl sulfonium salt as the initiator of the photocurable silicon-based ceramic precursor containing epoxy group and vinyl ether group;

[0084] (S2) Initiating a photopolymerization reaction by ultraviolet light irradiation to prepare a photocurable ceramic precursor composition.

[0085] Among them, the curing degree of the photocurable ceramic precursor can be characterized by infrared, photocuring rheology, DSC and other methods.

[0086] The precursor system has the characteristic of being transformed into silicon-based non-oxide ceramics with a high yield at high temperature, and the precursor has a low viscosity (less than 500cp) and is suitable for 3D printing.

[0087] The present invention also provides an application of the above-mentioned photocurable ceramic precursor composition, which is used to prepare resin films / coatings, organic-inorganic hybrid material films / coatings, ceramic films / coatings, ceramic parts, ceramic fibers, ceramic-based composite materials, 3D-printed ceramic products or ceramic micro-electromechanical systems, etc., preferably for preparing 3D-printed ceramic products.

[0088] The present invention also provides a method for preparing the above-mentioned ceramic component, the method comprising:

[0089] The photocurable ceramic precursor composition is heated and pyrolyzed to prepare a ceramic product.

[0090] According to an embodiment of the present invention, the pyrolysis temperature is 800-1600° C. and the heating time is 0.5-10 h.

[0091] According to an embodiment of the present invention, the pyrolysis is carried out in air or an inert atmosphere, such as an argon or nitrogen atmosphere.

[0092] According to an embodiment of the present invention, before the photocurable ceramic precursor composition is pyrolyzed, the photocurable ceramic precursor composition may be subjected to a heat treatment at 100-300° C. to increase the curing degree or mechanical strength thereof.

[0093] According to an embodiment of the present invention, before the photocurable ceramic precursor composition is pyrolyzed, the photocurable ceramic precursor composition can be coated and then photocured to prepare a resin film or coating. The resin film or coating can be further pyrolyzed to prepare an organic-inorganic hybrid material or a ceramic material, wherein the pyrolysis temperature is 500-700°C for an organic-inorganic hybrid material, and the pyrolysis temperature is 800-1600°C for a ceramic material.

[0094] The present invention also provides a method for preparing the above-mentioned 3D printed ceramic product, the method comprising:

[0095] K1: Create a 3D model of a ceramic part;

[0096] K2: placing the above-mentioned photocurable ceramic precursor composition in a 3D printer, setting laser parameters, starting the 3D printer, and starting 3D printing to prepare a 3D printed ceramic primary product;

[0097] K3: Pyrolyze the primary 3D printed ceramic product to prepare 3D printed ceramic products.

[0098] In step K1 , the method of creating a three-dimensional model of the ceramic component is a common method in the prior art, such as computer-aided design (CAD).

[0099] Step K2 also includes post-processing the 3D printed ceramic primary product, such as cleaning the surface of the 3D printed ceramic product with a solvent to remove unreacted photocurable ceramic precursor, wherein the solvent is one of isopropanol, ethanol, n-hexane, acetone, etc.

[0100] Step K3 may also include post-curing treatment of the 3D printed ceramic product. The specific steps of the post-curing treatment are: curing the 3D printed ceramic product in a UV curing box for 0.5-3 hours, and then continuing to pyrolyze at 800-1300° C. to prepare the 3D printed ceramic product.

[0101] In step K3, pyrolysis is carried out under an inert atmosphere, and the pyrolysis time is 1-5 hours.

[0102] Preferably, during pyrolysis, the heating or cooling rate is 0.5-2°C / min, preferably 1°C / min.

[0103] In step K2, the wavelength of the laser is 254-405 nm, for example, 405 nm; the laser power is 100-400 mW, for example, 250 mW.

[0104] The wavelength of the ultraviolet light curing box in step K3 is 254-405 nm, for example, 405 nm.

[0105] Beneficial Effects

[0106] First, the method for preparing the photocurable silicon-based ceramic precursor provided by the present invention has the advantages of easy availability of raw materials, mild reaction conditions, and high yield;

[0107] Second, the method for preparing the photocurable silicon-based ceramic precursor provided by the present invention has the advantages of rich product variety, strong structural designability, controllable reaction and product viscosity, and can achieve low viscosity and good fluidity;

[0108] Thirdly, the photocurable silicon-based ceramic precursor provided by the present invention can be used as a silicon-based ceramic precursor resin, and the ceramic yield of the cured product is high.

[0109] Fourth, the photocurable silicon-based ceramic precursor and its composition provided by the present invention show great application prospects in the fields of preparing resin films / coatings, organic-inorganic hybrid material films / coatings, ceramic films / coatings, ceramic fibers, ceramic-based composite materials and 3D printing to prepare ceramic parts.

[0110] Terms and Definitions

[0111] When the numerical range described in the specification and claims of this application is defined as an "integer", it should be understood that the two endpoints of the range and each integer in the range are recorded. For example, "an integer from 1 to 5" should be understood as recording each integer of 1, 2, 3, 4 and 5.

[0112] The term "C 1-20 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably C 1-10 Alkyl. "C 1-10 The term “alkyl” is understood as meaning preferably a linear or branched, saturated, monovalent hydrocarbon radical having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. The alkyl radical is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, etc. or their isomers. In particular, the radical has 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms (“C 1-6 alkyl), for example methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly, the radical having 1, 2 or 3 carbon atoms (“C 1-3 alkyl"), for example methyl, ethyl, n-propyl or isopropyl.

[0113] The term "C 1-20 "Alkoxy" means -OC 1-20 Alkyl, where C 1-20 Alkyl has the above definition.

[0114] The term "C 2-10 "Alkenyl" is understood to mean a linear or branched, monovalent hydrocarbon radical containing one or more double bonds and having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, in particular 2 or 3 carbon atoms ("C 2-3"alkenyl"), it being understood that, in the case where the alkenyl contains more than one double bond, the double bonds may be separated from one another or conjugated. The alkenyl is, for example, vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, (E)-but-2-enyl, (Z)-but-2-enyl, (E)-but-1-enyl, (Z)-but-1-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)-pent-3-enyl, -enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)-pent-1-enyl, (Z)-pent-1-enyl, hex-5-enyl, (E)-hex-4-enyl, (Z)-hex-4-enyl, (E)-hex-3-enyl, (Z)-hex-3-enyl, (E)-hex-2-enyl, (Z)-hex-2-enyl, (E)-hex-1-enyl, (Z)-hex-1-enyl, isopropenyl, 2-hexenyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)-pent-1-enyl, (Z)-pent ...1-enyl, (Z)-pent-1-enyl, isopropenyl, 2-hexenyl, (E)-pent-2- -methylprop-2-enyl, 1-methylprop-2-enyl, 2-methylprop-1-enyl, (E)-1-methylprop-1-enyl, (Z)-1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E)-2-methylbut-2-enyl, (Z)-2-methylbut-2-enyl, (E)-1-methylbut-2-enyl 1-ethylprop-1-enyl, 1-propylvinyl, and 1-isopropylvinyl.

[0115] The term "C 2-10 "Alkynyl" is understood to mean a linear or branched, monovalent hydrocarbon radical containing one or more triple bonds and having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, in particular 2 or 3 carbon atoms ("C 2 -C 3-ynyl”). The alkynyl group is, for example, ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl, 1-methylprop-2-ynyl, 2-methylbut-3-ynyl, 1-methylbut-3-ynyl, 1-methylbut-2-ynyl, 3-methylbut-1-ynyl, 1-ethylprop-2-ynyl, 3-methylpent-4-ynyl, 2-methylpent-4-ynyl, 1-methylpent- In some embodiments, the alkynyl group is ethynyl, prop-1-ynyl or prop-2-ynyl.

[0116] The term "C 2-12 "Oxiranyl" is understood to mean a cycloalkane which contains 1 O atom and has 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, in particular 2 to 4 carbon atoms, and which is saturated. 2-12 "Oxiranyl" is, for example, ethylene oxide, propylene oxide, butylene oxide, pentylene oxide.

[0117] The term "epoxy C 3-12 The term "cycloalkyl" shall be understood to mean a ring formed by ethylene oxide and a cyclic alkane containing 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, wherein the 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms are not shared carbon atoms, and further, the cyclic alkane shall be saturated. 3-12 "Cycloalkyl" is, for example, BRIEF DESCRIPTION OF THE DRAWINGS

[0118] The drawings are only for the purpose of illustrating particular embodiments and are not to be construed as limiting the invention.

[0119] Figure 1 The photocurable polysiloxane ceramic precursor obtained in Example 1 1 H-NMR spectrum (the deuterated reagent is deuterated chloroform).

[0120] Figure 2The photocurable polysiloxane ceramic precursor obtained in Example 2 1 H-NMR spectrum (the deuterated reagent is deuterated chloroform).

[0121] Figure 3 This is a photocuring rheological characterization diagram of the photocurable polysiloxane ceramic precursor obtained in Example 2.

[0122] Figure 4 This is the infrared spectrum of the photocurable polysiloxane ceramic precursor obtained in Example 2 before and after photocuring.

[0123] Figure 5 The thermogravimetric graphs of the photocurable polysiloxane ceramic precursor obtained in Example 2 and the raw material KH-PSO-1 (the line represented by PSO).

[0124] Figure 6 Schematic diagram of the 3D printed ceramic product obtained in Example 2 before and after pyrolysis.

[0125] Figure 7 The photocurable polysiloxane ceramic precursor obtained in Example 3 1 H-NMR spectrum (the deuterated reagent is deuterated chloroform).

[0126] Figure 8 The photocurable polycarbosilane ceramic precursor obtained in Example 6 1 H-NMR spectrum (the deuterated reagent is deuterated chloroform).

[0127] Fig. 9 The photocurable polycarbosilane ceramic precursor obtained in Example 7 1 H-NMR spectrum (the deuterated reagent is deuterated chloroform).

[0128] Fig.10 The photocurable polycarbosilane ceramic precursor obtained in Example 8 1 H-NMR spectrum (the deuterated reagent is deuterated chloroform). DETAILED DESCRIPTION

[0129] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope that the present invention is intended to protect.

[0130] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0131] Example 1

[0132] A method for synthesizing a photocurable silicon-based ceramic precursor:

[0133] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide device, and a magnetron and a liquid polysiloxane ceramic precursor resin KH-PSO-1 (3.56g) containing a silicon-hydrogen bond were added. Under magnetic stirring, the mixture was vacuumed for 30 minutes, and then vacuumed and replaced with nitrogen three times. Under a nitrogen atmosphere, 80mL of dry toluene solvent, hydroxyl-containing photosensitive monomer hydroxyethyl acrylate (0.464g) were added to the reaction bottle in sequence, and then a mixed solution of catalyst N,N-diethylhydroxylamine (0.036g) and toluene (20mL) was added to the reaction bottle. After stirring evenly, the mixture was reacted at 60-65°C for 18h and the heating was stopped.

[0134] Under stirring, add the absorbent acidic ion exchange resin (10g) of the catalyst N,N-diethylhydroxylamine to the above system, continue stirring at room temperature for more than 6 hours, and remove the catalyst N,N-diethylhydroxylamine. After filtering, the solvent is removed by rotary evaporation to obtain the final product of the photocurable polysiloxane ceramic precursor, which is a colorless and transparent liquid with a yield of 95%. The product corresponds to the structure in formula M, wherein R is -CH 3 , R' is -CH 3 , x = 0.1, y = 0.5, z = 0 (confirmed by NMR spectrum), X is -O(CH 2 ) 2 OOC-CH=CH 2 , Y is -CH=CH 2 The specific structure is shown in formula M1. GPC test shows that its molecular weight Mw=22953, Mn=3022.

[0135]

[0136] The product was sealed and stored at room temperature for 3 months. The viscosity of the product was almost unchanged by the viscometer test, which was about 178 cP. 1 wt% of the photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone was used to cure under ultraviolet light of 365 nm (room temperature) for 5 min. The curing was complete. Under nitrogen atmosphere, the TGA ceramic yield of the cured product at 1000°C was 78%.

[0137] Figure 1 is the product M1 of Example 1 1 H-NMR spectrum. Figure 1 The peak at the chemical shift of 0-0.25 ppm can be attributed to Si-CH 3The peaks at chemical shifts of 3.92, 4.22, 6.14, 6.16, 6.39 and 6.43 ppm can be attributed to the photosensitive group -O(CH 2 ) 2 OOC-CH=CH 2 The resonance peak at the chemical shift of 4.71 ppm can be attributed to the Si-H group in the KH-PSO-1 structure, and the resonance peak at the chemical shift of 5.7 to 6.1 ppm can be attributed to the Si-CH=CH 2 Compared with the raw material KH-PSO-1, the Si-H peak is reduced and the newly generated photosensitive group -O(CH 2 ) 2 OOC-CH=CH 2 The peak of indicates that the photosensitive group was successfully introduced and a photocurable polysiloxane ceramic precursor was obtained.

[0138] Example 2

[0139] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide device, and a magnetron and a liquid polysiloxane ceramic precursor resin KH-PSO-1 (3.56g) containing a silicon-hydrogen bond were added. Under magnetic stirring and nitrogen atmosphere, 80mL of dry toluene solvent, hydroxyl-containing photosensitive monomer hydroxyethyl acrylate (0.928g) were added to the reaction bottle in sequence, and then a mixed solution of catalyst N, N-diethylhydroxylamine (0.036g) and toluene (20mL) was added to the reaction bottle. After stirring evenly, the mixture was reacted at 60-65°C for 24h and the heating was stopped.

[0140] Under stirring, add the absorbent acidic ion exchange resin (10g) of the catalyst N,N-diethylhydroxylamine to the above system, continue stirring at room temperature for more than 6 hours, and remove the catalyst N,N-diethylhydroxylamine. After filtering, the solvent is removed by rotary evaporation to obtain the final product of the photocurable polysiloxane ceramic precursor, which is a colorless and transparent liquid with a yield of 93%. The product corresponds to the structure in formula M, wherein R is -CH 3 , R' is -CH 3 , x = 0.2, y = 0.5, z = 0 (confirmed by NMR spectrum), X is -O(CH 2 ) 2 OOC-CH=CH 2 , Y is -CH=CH 2 The specific structure is shown in formula M2. GPC test shows that its molecular weight Mw=26539 and Mn=3478.

[0141]

[0142] The product was sealed and stored at room temperature for 3 months. The viscosity of the product was almost unchanged by viscometer test, which was about 306 cP. 1 wt% of photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone was used to cure under ultraviolet light of 365 nm wavelength (room temperature) for 5 min. The curing was complete. Under nitrogen atmosphere, the TGA ceramic yield of the cured product at 1000°C was 73%.

[0143] Figure 2 Example 2 reaction product M2 1 H-NMR spectrum, where the peak with a chemical shift of 0-0.25 ppm can be attributed to Si-CH 3 The peaks at chemical shifts of 3.92, 4.22, 6.14, 6.16, 6.39 and 6.43 ppm can be attributed to the photosensitive group -O(CH 2 ) 2 OOC-CH=CH 2 The resonance peak at the chemical shift of 4.71 ppm can be attributed to the Si-H group in the KH-PSO-1 structure, and the resonance peak at the chemical shift of 5.7 to 6.1 ppm can be attributed to the Si-CH=CH 2 Compared with the raw material KH-PSO-1, the Si-H peak is reduced and the newly generated photosensitive group -O(CH 2 ) 2 OOC-CH=CH 2 The peak of indicates that the photosensitive group was successfully introduced and a photocurable polysiloxane ceramic precursor was obtained.

[0144] Figure 3 This is the photocuring rheological curve of the reaction product M2 in Example 2. It can be seen that the storage modulus and the loss modulus intersect at 6 seconds of illumination, indicating that the photocurable material changes from liquid to solid and gels at this time. After 20 seconds of illumination, the storage modulus and the loss modulus tend to balance, indicating that the photocurable material has been completely cured.

[0145] Figure 4 : The infrared spectra of the reaction product M2 in Example 2 before and after photocuring (the solid line is the characterization result before curing, and the dotted line is the characterization result after curing). 2 ) 2 OOC-CH=CH 2 Vinyl peak (1635cm -1 ) was significantly reduced, indicating that the photosensitive groups were involved in the photocuring reaction.

[0146] Figure 5The thermogravimetric (TG) curves of the photocured reaction product M2 and the raw material KH-PSO-1 in Example 2. From the TG curves, it can be seen that the ceramic yield of the photocured product in a nitrogen atmosphere at 1000°C is 73%, while the ceramic yield of the thermally cured product of the raw material KH-PSO-1 in a nitrogen atmosphere at 1000°C is 83%.

[0147] Figure 6 This is a structural photograph of the ceramic precursor component prepared by 3D printing from the reaction product M2 in Example 2 before and after pyrolysis (1000°C). It can be seen from the figure that the shape of the pyrolysis product remains intact, there are no obvious cracks, and the shrinkage in all directions is uniform.

[0148] Example 3

[0149] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide device, and a magnetron and a liquid polysiloxane ceramic precursor resin KH-PSO-1 (3.56g) containing a silicon-hydrogen bond were added. Under magnetic stirring and nitrogen protection atmosphere, dry toluene solvent (80mL) and hydroxyl-containing photosensitive monomer hydroxyethyl acrylate (1.856g) were added to the reaction bottle in sequence, and then a mixed solution of catalyst N, N-diethylhydroxylamine (0.072g) and toluene (20mL) was added to the reaction bottle. After stirring evenly, the reaction was carried out at 60-65°C for 24h, and the heating was stopped.

[0150] Under stirring, add the absorbent acidic ion exchange resin (20g) of the catalyst N,N-diethylhydroxylamine to the above system, continue stirring at room temperature for more than 6 hours, and remove the catalyst N,N-diethylhydroxylamine. After filtering, the solvent is removed by rotary evaporation to obtain the final product of the photocurable polysiloxane ceramic precursor, which is a colorless and transparent liquid with a yield of 90%. The product corresponds to the structure in formula M, wherein R is -CH 3 , R' is -CH 3 , x = 0.4, y = 0.5, z = 0 (confirmed by NMR spectrum), X is -O(CH 2 ) 2 OOC-CH=CH 2 , Y is -CH=CH 2 The specific structure is shown in formula M3. GPC test shows that its molecular weight Mw=31256, Mn=4127.

[0151]

[0152] The product was sealed and stored at room temperature for 3 months, and the viscosity was almost unchanged by GPC test, which was about 465 cP. Using 1 wt% photoinitiator phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, it was cured under ultraviolet light of 405 nm wavelength (room temperature) for 5 min, and the curing was complete. Under nitrogen atmosphere, the TGA ceramic yield of the cured product at 1000 ° C was 57%.

[0153] Figure 7 Example 3 reaction product M3 1 H-NMR spectrum shows that the product has a reduced Si-H peak compared to the raw material KH-PSO-1, and a newly generated photosensitive group -O(CH 2 ) 2 OOC-CH=CH 2 The peak of indicates that the photosensitive group was successfully introduced and a photocurable polysiloxane ceramic precursor was obtained.

[0154] Example 4

[0155] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide device, and a magnetron and a liquid polysiloxane ceramic precursor resin KH-PSO-1 (3.56g) containing silicon-hydrogen bonds were added. Under magnetic stirring and nitrogen atmosphere, dry toluene solvent (80mL) and hydroxyl-containing photosensitive monomer 4-hydroxybutyl vinyl ether (1.392g) were added to the reaction bottle in sequence, and then a mixed solution of catalyst N, N-diethylhydroxylamine (0.054g) and toluene (20mL) was added to the reaction bottle. After stirring evenly, the reaction was carried out at 60-65°C for 24h, and the heating was stopped.

[0156] Under stirring, add the absorbent acidic ion exchange resin (15g) of the catalyst N,N-diethylhydroxylamine to the above system, continue stirring at room temperature for more than 6 hours, and remove the catalyst N,N-diethylhydroxylamine. After filtering, the solvent is removed by rotary evaporation to obtain the final product of the photocurable polysiloxane ceramic precursor, which is a colorless and transparent liquid with a yield of 92%. The product corresponds to the structure in formula M, wherein R is -CH 3 , R' is -CH 3 , x = 0.2, y = 0.5, z = 0 (confirmed by NMR spectrum), X is -O(CH 2 ) 4 -O-CH=CH 2 , Y is -CH=CH 2 The specific structure is shown in formula M4. GPC test shows that its molecular weight Mw=27317 and Mn=3615.

[0157]

[0158] The product was sealed and stored at room temperature for 3 months. The viscosity of the product was almost unchanged by the viscometer test, which was about 366 cP. 5 wt% of the photoinitiator triarylsulfonium hexafluoroantimonate was added and cured under ultraviolet light of 365 nm wavelength (room temperature) for 10 min. The product was completely cured under nitrogen atmosphere. The TGA ceramic yield of the cured product at 1000°C was 65%.

[0159] Example 5

[0160] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide device, and a magnetron and a liquid polysiloxane ceramic precursor resin KH-PSO-1 (3.56g) containing a silicon-hydrogen bond were added. Under magnetic stirring and a nitrogen atmosphere, toluene solvent (80mL) and hydroxyl-containing photosensitive monomer 1-hydroxymethyl-3-cyclohexene oxide (1.026g) were added to the reaction bottle in sequence, and then a mixed solution of catalyst N,N-diethylhydroxylamine (0.072g) and toluene (20mL) was added to the reaction bottle. After stirring evenly, the reaction was carried out at 60-65°C for 24h, and the heating was stopped.

[0161] Under stirring, add the absorbent acidic ion exchange resin (20g) of the catalyst N,N-diethylhydroxylamine to the above system, continue stirring at room temperature for more than 6 hours, and remove the catalyst N,N-diethylhydroxylamine. After filtering, the solvent is removed by rotary evaporation to obtain the final product of the photocurable polysiloxane ceramic precursor, which is a colorless and transparent liquid with a yield of 80%. The product corresponds to the structure in formula M, wherein R is -CH 3 , R' is -CH 3 , x = 0.2, y = 0.5, z = 0 (confirmed by NMR spectrum), X is Y is -CH=CH 2 The specific structure is shown in Formula M5. GPC test shows that its molecular weight Mw=27673, Mn=3748.

[0162]

[0163] The product was sealed and stored at room temperature for 3 months, and the viscosity of the product was almost unchanged by the viscometer test, which was about 178 cP. 5 wt% of the photoinitiator triarylsulfonium hexafluoroantimonate was added, and the product was cured under ultraviolet light of 365 nm for 15 min. The product was completely cured. In a nitrogen atmosphere, the TGA ceramic yield of the cured product at 1000°C was 57%.

[0164] Example 6

[0165] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide device, and a magnetron and a liquid polycarbosilane ceramic precursor resin KH-AHPCS-1 (1.10 g) containing a silicon-hydrogen bond were added. Under magnetic stirring and a nitrogen protective atmosphere, dry toluene solvent (80 mL), hydroxyl-containing photosensitive monomer hydroxyethyl acrylate (0.46 g) were added to the reaction bottle in sequence, and then a mixed solution of catalyst N, N-diethylhydroxylamine (0.045 g) and toluene (20 mL) was added to the reaction bottle. After stirring evenly, the reaction was carried out at 60-65°C for 18 hours, and the heating was stopped.

[0166] Under stirring, add the absorbent acidic ion exchange resin (10g) of the catalyst N,N-diethylhydroxylamine to the above system, continue stirring at room temperature for more than 6 hours, and remove the catalyst N,N-diethylhydroxylamine. After filtering, the solvent is removed by rotary evaporation to obtain the final product of the photocurable polysiloxane ceramic precursor. It is a colorless and transparent liquid with a yield of 95%. The product corresponds to the structure in formula N, wherein R is -H, R' is -H, x=0.2, y=0.1, z=0 (confirmed by NMR spectrum), and X is -O(CH 2 ) 2 OOC-CH=CH 2 , Y is -CH 2 -CH=CH 2 The specific structure is shown in Formula N1. GPC test shows that its molecular weight Mw=6845, Mn=966.

[0167]

[0168] The product has a viscosity of 236 cP at room temperature. 1 wt% of photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone was added and cured under ultraviolet light of 365 nm wavelength (room temperature) for 5 min. The product was completely cured under nitrogen atmosphere. The TGA ceramic yield of the cured product at 1000° C. was 74%.

[0169] Figure 8 Example 6 reaction product N1 1 H-NMR spectrum. It can be seen from the figure that the product is relatively 3 The peak intensity decreased significantly, and the newly generated photosensitive group -O(CH 2 ) 2 OOC-CH=CH 2 The resonance absorption peak of indicates that the photosensitive group was successfully introduced and a photocurable polycarbosilane ceramic precursor was obtained.

[0170] Example 7

[0171] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide device, and a magnetron and a liquid polycarbosilane ceramic precursor resin KH-VHPCS-1 (2.05g) containing a silicon-hydrogen bond were added. Under magnetic stirring, the mixture was vacuumed for 30 minutes, and then the nitrogen was replaced by vacuum three times. In a nitrogen atmosphere, dry toluene solvent (80mL), hydroxyl-containing photosensitive monomer hydroxyethyl acrylate (0.92g) were added to the reaction bottle in sequence, and then a mixed solution of catalyst N, N-diethylhydroxylamine (0.045g) and toluene (20mL) was added to the reaction bottle. After stirring evenly, the mixture was reacted at 60-65°C for 18h and the heating was stopped.

[0172] Under stirring, add the absorbent acidic ion exchange resin (10g) of the catalyst N,N-diethylhydroxylamine to the above system, continue stirring at room temperature for more than 6 hours, and remove the catalyst N,N-diethylhydroxylamine. After filtering, the solvent is removed by rotary evaporation to obtain the final product of the photocurable polycarbosilane ceramic precursor. It is a colorless and transparent liquid with a yield of 95%. The product corresponds to the structure in formula N, wherein R is -H, R' is H, x=0.2, y=0.1, z=0 (confirmed by NMR spectrum), and X is -O(CH 2 ) 2 OOC-CH=CH 2 , Y is -CH=CH 2 The specific structure is shown in formula N2. GPC test shows that its molecular weight Mw=6445, Mn=783.

[0173]

[0174] The product was sealed and stored at room temperature for 1 month. The viscosity of the product was almost unchanged by the viscometer test, which was about 459 cP. 1 wt% of the photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone was added and cured under ultraviolet light of 365 nm wavelength (room temperature) for 5 min. The product was completely cured. Under nitrogen atmosphere, the TGA ceramic yield of the cured product at 1000°C was 78%.

[0175] Fig. 9 Example 7 Reaction product N2 1 H-NMR spectrum. Fig. 9 It can be found that the product belongs to Si-H relative to the raw material KH-VHPCS-1. 3 The absorption peak intensity decreased significantly, and a new peak attributed to -O(CH 2 ) 2 OOC-CH=CH 2 The absorption peak of the photosensitive group indicates that the photosensitive group has been successfully introduced and a photocurable polycarbosilane ceramic precursor has been obtained.

[0176] Example 8

[0177] After drying, a 150mL three-necked round-bottom flask was connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide device, and a magnet and sodium hydroxide (0.16g) were added. The mixture was dried by vacuum heating at 50℃ for 30min, and then replaced with nitrogen. Under magnetic stirring, ultra-dry tetrahydrofuran solvent (80mL) was added to the reaction bottle in sequence, and then a mixed solution of liquid polycarbosilane ceramic precursor resin KH-AHPCS-2 (2.05g) containing silicon-hydrogen bonds and ultra-dry tetrahydrofuran (20mL) was added to the reaction bottle. After stirring evenly, hydroxyl-containing photosensitive monomer hydroxyethyl acrylate (1.38g) was added dropwise at 60-65℃, and the reaction was continued for 18h, and the heating was stopped.

[0178] Under stirring, 50mL of n-hexane was added to the reaction bottle. The above system was added to a hydrochloric acid aqueous solution (100ml, 0.03g / ml), mixed thoroughly in a separatory funnel, allowed to stand for stratification, and the upper organic phase was subjected to the above acid washing operation twice. After drying over anhydrous magnesium sulfate, filtering and then rotary evaporation to remove the solvent, the final product of the photocurable polycarbosilane ceramic precursor was obtained, which was a colorless and transparent liquid with a yield of 95%. The product corresponds to the structure in formula N, wherein R is -H, R' is -H, x=0.3, y=0.1, z=0 (confirmed by NMR spectrum), and X is -O(CH 2 ) 2 OOC-CH=CH 2 , Y is -CH=CH 2 The specific structure is shown in Formula N3. GPC test shows that its molecular weight Mw=6727, Mn=754.

[0179]

[0180] The product was sealed and stored at room temperature for 1 month. The viscosity of the product was almost unchanged by the viscometer test, which was about 270 cP. 1 wt% of the photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone was added and cured under ultraviolet light of 365 nm wavelength for 5 min. The curing was complete. Under nitrogen atmosphere, the TGA ceramic yield of the cured product at 1000°C was 78%.

[0181] Fig.10 Example 8 reaction product N3 1 H-NMR spectrum, from which we can see that the product is relatively different from the raw material KH-AHPCS-2, Si-H 3 The number of groups was significantly reduced, and a new photosensitive group -O(CH 2 ) 2 OOC-CH=CH 2 , indicating that the photosensitive group was successfully introduced and a photocurable polycarbosilane ceramic precursor was obtained.

[0182] Example 9

[0183] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide device, and a magnetron and a liquid polycarbosilane ceramic precursor resin KH-HPCS-1 (1.76g) containing a silicon-hydrogen bond were added. Under magnetic stirring, the mixture was vacuumed for 30 minutes, and then the nitrogen was replaced by vacuum three times. In a nitrogen atmosphere, dry toluene solvent (80mL), hydroxyl-containing photosensitive monomer hydroxyethyl acrylate (0.92g) were added to the reaction bottle in sequence, and then a mixed solution of catalyst N,N-diethylhydroxylamine (0.045g) and toluene (20mL) was added to the reaction bottle. After stirring evenly, the mixture was reacted at 60-65°C for 18h and the heating was stopped.

[0184] Under stirring, add the absorbent acidic ion exchange resin (10g) of the catalyst N,N-diethylhydroxylamine to the above system, continue stirring at room temperature for more than 6 hours, and remove the catalyst N,N-diethylhydroxylamine. After filtering, the solvent is removed by rotary evaporation to obtain the final product of the photocurable polycarbosilane ceramic precursor. It is a colorless and transparent liquid with a yield of 95%. The product corresponds to the structure in formula N, wherein R is -H, x=0.2, y=0, z=0 (confirmed by NMR spectrum), and X is -O(CH 2 ) 2 OOC-CH=CH, the specific structure is shown in formula N4. GPC test shows that its molecular weight Mw=5456, Mn=856.

[0185]

[0186] The product has a viscosity of 223 cP at room temperature. 1 wt% of photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone was added and cured under ultraviolet light of 365 nm wavelength (room temperature) for 5 min. The product was completely cured under nitrogen atmosphere. The TGA ceramic yield of the cured product at 1000° C. was 79%.

[0187] Example 10

[0188] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide, and a magnet and sodium hydroxide (0.16g) were added. Under heating conditions at 50°C, the mixture was vacuumed for 30min, and then the nitrogen was replaced by vacuum three times. Under magnetic stirring and nitrogen atmosphere, ultra-dry tetrahydrofuran solvent (80mL) was added to the reaction bottle in sequence, and then a mixed solution of liquid polycarbosilane ceramic precursor resin KH-VHPCS-1 (2.05g) containing silicon-hydrogen bonds and ultra-dry tetrahydrofuran (20mL) was added to the reaction bottle. After stirring evenly, 4-hydroxybutyl vinyl ether (0.92g), a hydroxyl-containing photosensitive monomer, was added dropwise at 60-65°C, and the reaction was continued for 18h, and the heating was stopped.

[0189] Under stirring, 50 mL of n-hexane was added to the reaction bottle. The above system was added to a hydrochloric acid aqueous solution (100 mL, 0.03 g / mL), mixed thoroughly in a separatory funnel, allowed to stand for stratification, and the upper organic phase was subjected to the above acid washing operation twice. After drying over anhydrous magnesium sulfate, filtering and then rotary evaporation to remove the solvent, the final product of the photocurable polycarbosilane ceramic precursor was obtained, which was a colorless and transparent liquid with a yield of 95%. The product corresponds to the structure in formula N, wherein R is -H, R' is -H, x=0.2, y=0.1, z=0 (confirmed by NMR spectrum), and X is -O(CH 2 ) 4 -O-CH=CH 2 , Y is -CH=CH 2 The specific structure is shown in Formula N5. GPC test shows that its molecular weight Mw=6872, Mn=869.

[0190]

[0191] The product has a viscosity of 340 cP at room temperature. 5 wt% of the photoinitiator triarylsulfonium hexafluoroantimonate was added and cured under ultraviolet light of 365 nm wavelength (room temperature) for 5 min. The product was completely cured. In a nitrogen atmosphere, the TGA ceramic yield of the cured product at 1000° C. was 78%.

[0192] Embodiment 11

[0193] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide, and a magnet and sodium hydroxide (0.16g) were added. The mixture was heated at 50℃ for 30min under vacuum, and then the nitrogen was replaced by vacuum three times. Under magnetic stirring and nitrogen atmosphere, ultra-dry tetrahydrofuran solvent (80mL) was added to the reaction bottle in sequence, and then a mixed solution of liquid polycarbosilane ceramic precursor resin KH-VHPCS-1 (2.05g) containing silicon-hydrogen bonds and ultra-dry tetrahydrofuran (20mL) was added to the reaction bottle. After stirring evenly, 1-hydroxymethyl-3-cyclohexene oxide (1.02g), a hydroxyl-containing photosensitive monomer, was added dropwise at 60-65℃, and the reaction was continued for 18h, and the heating was stopped.

[0194] Under stirring, add 50mL of n-hexane to the reaction bottle. Add the above system to a hydrochloric acid aqueous solution (100mL, 0.03g / ml), mix thoroughly in a separatory funnel, let stand to separate, and repeat the above acid washing operation twice for the upper organic phase. Dry with anhydrous magnesium sulfate, filter and evaporate to remove the solvent to obtain the final product of the photocurable polycarbosilane ceramic precursor, which is a colorless and transparent liquid with a yield of 95%. The product corresponds to the structure in formula N, wherein R is -H, R' is -H, x=0.2, y=0.1, z=0 (confirmed by NMR spectrum), and X is Y is -CH=CH 2 The specific structure is shown in Formula N6. GPC test shows that its molecular weight Mw=6851, Mn=827.

[0195]

[0196] The product has a viscosity of 628 cP at room temperature. 5 wt% of the photoinitiator triarylsulfonium hexafluoroantimonate was added and cured under ultraviolet light of 365 nm wavelength (room temperature) for 5 min. The product was completely cured. In a nitrogen atmosphere, the TGA ceramic yield of the cured product at 1000° C. was 78%.

[0197] Example 12

[0198] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide device, and a magnetron and a liquid polysiloxane ceramic precursor resin KH-PSO-4 (3.56g) containing a silicon-hydrogen bond were added. Under magnetic stirring, the mixture was vacuumed for 30 minutes, and then vacuumed and replaced with nitrogen three times. Under a nitrogen atmosphere, 80mL of dry toluene solvent, hydroxyl-containing photosensitive monomer hydroxyethyl acrylate (0.464g) were added to the reaction bottle in sequence, and then a mixed solution of catalyst N,N-diethylhydroxylamine (0.036g) and toluene (20mL) was added to the reaction bottle. After stirring evenly, the mixture was reacted at 60-65°C for 18h and the heating was stopped.

[0199] Under stirring, add the absorbent acidic ion exchange resin (10g) of the catalyst N,N-diethylhydroxylamine to the above system, continue stirring at room temperature for more than 6 hours, and remove the catalyst N,N-diethylhydroxylamine. After filtering, the solvent is removed by rotary evaporation to obtain the final product of the photocurable polysiloxane ceramic precursor, which is a colorless and transparent liquid with a yield of 95%. The product corresponds to the structure in formula M, wherein R is -CH 3 , R' is -CH 3 , x = 0.1, y = 0.45, z = 0.1 (confirmed by NMR spectrum), X is -O(CH 2 ) 2 OOC-CH=CH 2, Y is -CH=CH 2 The specific structure is shown in Formula M6. GPC test shows that its molecular weight Mw=21673, Mn=2988.

[0200]

[0201] The product was sealed and stored at room temperature for 3 months. The viscosity of the product was almost unchanged by the viscometer test, which was about 345 cP. 1 wt% of the photoinitiator 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide was used to cure under ultraviolet light of 405 nm wavelength (room temperature) for 5 minutes. The curing was complete. Under nitrogen atmosphere, the TGA ceramic yield of the cured product at 1000°C was 73%.

[0202] Embodiment 13

[0203] A 150mL three-necked round-bottom flask was dried, connected with a spherical condenser, a thermometer, a constant pressure dropping funnel and a gas guide device, and a magnetron and a liquid polysiloxane ceramic precursor resin KH-PSO-3 (3.56g) containing a silicon-hydrogen bond were added. Under magnetic stirring, the mixture was vacuumed for 30 minutes, and then vacuumed and replaced with nitrogen three times. Under a nitrogen atmosphere, 80mL of dry toluene solvent, hydroxyl-containing photosensitive monomer hydroxyethyl acrylate (0.464g) were added to the reaction bottle in sequence, and then a mixed solution of catalyst N,N-diethylhydroxylamine (0.036g) and toluene (20mL) was added to the reaction bottle. After stirring evenly, the mixture was reacted at 60-65°C for 18h and the heating was stopped.

[0204] Under stirring, add the absorbent acidic ion exchange resin (10g) of the catalyst N,N-diethylhydroxylamine to the above system, continue stirring at room temperature for more than 6 hours, and remove the catalyst N,N-diethylhydroxylamine. After filtering, the solvent is removed by rotary evaporation to obtain the final product of the photocurable polysiloxane ceramic precursor, which is a colorless and transparent liquid with a yield of 94%. The product corresponds to the structure in formula M, wherein R is -CH 3 , R' is -CH 3 , x = 0.1, y = 0.35, z = 0.3 (confirmed by NMR spectrum), X is -O(CH 2 ) 2 OOC-CH=CH 2 , Y is -CH=CH 2 The specific structure is shown in Formula M7. GPC test shows that its molecular weight Mw=22491, Mn=3519.

[0205]

[0206] The product was sealed and stored at room temperature for 3 months. The viscosity of the product was almost unchanged by the viscometer test, which was about 399 cP. 1 wt% of the photoinitiator 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide was used to cure under ultraviolet light of 405 nm (room temperature) for 5 min. The product was completely cured under nitrogen atmosphere. The TGA ceramic yield of the cured product at 1000°C was 71%.

[0207] Embodiment 14

[0208] A method for preparing a photocurable ceramic precursor system:

[0209] 40 g of the product M2 obtained in Example 2, 0.2 g of photoinitiator 2-hydroxy-2-methyl-1-phenylacetone, 0.2 g of photoinitiator phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.12 g of ultraviolet absorber hexamethylphosphoramide (HMPA) were added to a 150 mL single-mouth bottle, stirred with a magnetic stirrer for 2 h to mix evenly to prepare a photocurable ceramic precursor system for photocurable 3D printing, which was poured into a brown reagent bottle and stored away from light for later use.

[0210] A method for preparing a 3D printed ceramic part:

[0211] 3D printing was performed using CeraMatrix, a research-based ceramic material 3D printing system (developed by the Space Center). The wavelength of the UV laser was 405nm, the laser power was 250mw, and the layer thickness was set to 100 microns. The three-dimensional model was created through computer-aided design (CAD) and saved as an STL file; after 3D printing, the initial product of the 3D printed ceramic part was prepared.

[0212] The initial 3D printed ceramic product was cleaned with isopropyl alcohol to remove the uncured photosensitive polysiloxane ceramic precursor on the surface. The initial 3D printed ceramic product was then post-cured in a UV curing box (CL-1000L) for 30 minutes and weighed 1.418g. In order to convert the honeycomb structure parts into ceramics, the temperature was raised to 1000°C at 1°C / min and kept warm for 2 hours in a tubular furnace (Hefei Kejing, OTF-1200X-S) under the protection of flowing argon to obtain a 3D printed ceramic product. After pyrolysis, the ceramic parts weighed 1.04g, and the ceramic yield was 1.04 / 1.418*100%=73%. Schematic diagram of honeycomb structure parts before and after pyrolysis is shown in the figure. Figure 6 As shown by Figure 6 It can be seen that the precursor parts after printing have complete structure and high resolution. The ceramic parts after pyrolysis shrink evenly without obvious cracks and defects.

[0213] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A photocurable silicon-based ceramic precursor, characterized in that: It has a segment structure as shown in Formula M: Formula M; Wherein, R, R' are the same or different and are independently selected from H, unsubstituted, or optionally substituted by one, two or more Ra: 1-6 Alkyl or C 1-6 Alkoxy; Ra is selected from hydroxy, halogen, amino or C 1-6 alkyl; Y are the same or different and are independently selected from the following groups which are unsubstituted or optionally substituted by one, two or more Rb: C 2-6 Alkenyl or C 2-6 Alkynyl; Rb is selected from hydroxy, halogen, amino or C 1-6 alkyl; X are the same or different and are independently selected from the photosensitive reaction group Rg, wherein the photosensitive reaction group Rg is a group that undergoes polymerization reaction under the conditions of light and the presence of a photoinitiator; The photosensitive reaction group Rg is an acrylate group, a vinyl ether group or an epoxy group; The acrylate group is selected from -A-OOC-C(R1)=CH2, wherein A is selected from not existing or -O(CH2) a -, when A does not exist, O in -OOC-C(R1)=CH2 is connected to Si, when it exists, -O(CH2) a -O is connected to Si, a is an integer of 1-6, R1 is selected from H, C 1-6 alkyl; The vinyl ether group is selected from the group represented by formula (2): -O-(CH2) m1 -O-(CH2) m2 -C(R2)=CH(R3) Formula (2) wherein m1 is an integer of 1-6, m2 is an integer of 0-6, R2 is selected from H, methyl or ethyl, R3 is selected from H or C 1-6 alkyl; The epoxy group is selected from -O(CH2) n1 -R4, wherein n1 is an integer of 1-6, and R4 is selected from substituted or unsubstituted C 2-12 Epoxyalkyl, substituted or unsubstituted epoxy C 3-12 Cycloalkyl, when substituted, the substituent is C 1-6 alkyl; x=0.01~0.9, y=0.1~0.9, z=0.1~0.9, x+y+z=0.01~0.

9.

2. The photocurable silicon-based ceramic precursor according to claim 1, characterized in that: The R is H, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Hydroxyl substituted C 1-4 Alkyl or halogenated C 1-4 alkyl; The R' is H, C 1-4 Alkyl, C 1-4 Alkoxy, C 1-4 Hydroxyl substituted C 1-4 Alkyl or halogenated C 1-4 alkyl; Said Y is CH2=CH-, CH2=CHCH2-, CH2=C(CH3)-, CH3CH=CH-, HC≡C-, HC≡C-CH2- or cyclopropyl-(CH2)2CH-.

3. The photocurable silicon-based ceramic precursor according to claim 1, characterized in that: x is 0.05~0.50, y is 0.1~0.5, z is 0.1~0.5; x+y+z=0.1~0.

8.

4. The photocurable silicon-based ceramic precursor according to claim 1, characterized in that: The acrylate group is selected from -OOC-CH=CH2, -OOC-C(CH3)=CH2, -O(CH2)2OOC-CH=CH2, -O(CH2)3OOC-CH=CH2, -O(CH2)2OOC-C(CH3)=CH2, -O(CH2)3OOC-CH=CH2; The vinyl ether group is selected from -OCH2-O-CH=CH2, -O(CH2)2-O-CH=CH2, -OCH2-O-CH=CH-CH3, -OCH2-O-CH=CH-C2H5, -OCH2-O-CH=CH-C3H7, -O(CH2)3-O-CH=CH2, -O(CH2)4-O-CH=CH2, -O(CH2)5-O-CH=CH2, -O(CH2)6-O-CH=CH2, -OCH2-O-CH2-CH=CH2, -O(CH2)2-O-CH2-CH=CH2, -O(CH2)3-O-CH2-CH=CH2, -O(CH2)4-O-CH2-CH=CH2, -O(CH2)5-O-CH2-CH=CH2, -O(CH2)6-O-CH=CH2, -OCH2-O-CH2-CH=CH2, -O(CH2)2-O-CH2-CH=CH2, -O(CH2)3-O-CH2-CH=CH2, -O(CH2)4-O-CH2-CH=CH2, -O(CH2)5-O-CH2-CH=CH2, -O(CH2)6-O-CH2-CH=CH2; R4 is selected from , or , ● is the connection site.

5. The photocurable silicon-based ceramic precursor according to claim 1, characterized in that: The weight average molecular weight M of the photocurable silicon-based ceramic precursor w 600-100000, number average molecular weight M n It is 300-50000.

6. The photocurable silicon-based ceramic precursor according to any one of claims 1 to 5, characterized in that: The photocurable silicon-based ceramic precursor has a structure shown in any one of the following formulas M1 to M7: M1； M2； M3； M4； M5； M6； M7。 7. The method for preparing the photocurable silicon-based ceramic precursor according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: using a silicon-based ceramic precursor resin containing a silicon-hydrogen bond and a photosensitive monomer Rg-H containing a hydroxyl group as raw materials, and performing a catalytic reaction in the presence of a dehydrogenation coupling catalyst; In Rg-H, Rg is an acrylate group, a vinyl ether group or an epoxy group; The silicon-based ceramic precursor resin containing silicon-hydrogen bonds is selected from polysiloxane; The dehydrogenation coupling catalyst is selected from transition metal catalysts, alkali metal catalysts, and metal-free organic catalysts.

8. The preparation method according to claim 7, characterized in that: The reaction is carried out in a solvent, and the solvent includes a benzene-containing solvent, an ether solvent, and a low-boiling-point alkane solvent; The low boiling point alkane solvent is one, two or more of pentane, cyclopentane, hexane and petroleum ether.

9. The preparation method according to claim 7, characterized in that: The molar ratio of Si-H in the silicon-based ceramic precursor resin containing silicon-hydrogen bonds to -OH in the photosensitive monomer containing -OH is 1:(0.01-1).

10. The preparation method according to claim 7, characterized in that: The preparation method further comprises post-treatment: removing the dehydrogenation coupling catalyst, and distilling the obtained photocurable silicon-based ceramic precursor to obtain the final product.

11. Use of the photocurable silicon-based ceramic precursor according to any one of claims 1 to 6, characterized in that: It is used as a photocurable resin material or a photocurable ceramic precursor composition.

12. A photocurable resin material, characterized in that: The raw materials of the photocurable resin material include the photocurable silicon-based ceramic precursor according to any one of claims 1 to 6, a photoinitiator and a stabilizer.

13. A method for photocuring the photocurable resin material according to claim 12, characterized in that: The steps include: Add a photoinitiator to the photocurable silicon-based ceramic precursor according to any one of claims 1 to 6, and cure it under light.

14. A photocurable ceramic precursor composition, characterized in that: include: The photocurable silicon-based ceramic precursor according to any one of claims 1 to 6, a photoinitiator, an optional organic oligomer, an optional stabilizer, and an optional inorganic filler.

15. The method for preparing the photocurable ceramic precursor composition according to claim 14, characterized in that: The method comprises: adding a photoinitiator to the photocurable silicon-based ceramic precursor according to any one of claims 1 to 6, optionally adding or not adding an organic oligomer, optionally adding or not adding a stabilizer, optionally adding or not adding an inorganic filler, and curing under light to prepare a photocurable ceramic precursor composition.

16. Use of the photocurable ceramic precursor composition according to claim 14, characterized in that: The method is used for preparing organic-inorganic hybrid material films or coatings, ceramic films or coatings, and ceramic parts.

17. The use according to claim 16, characterized in that The ceramic component is selected from ceramic matrix composite materials, 3D printed ceramic products or ceramic micro-electromechanical systems.

18. A method for preparing a ceramic part, characterized in that: The method comprises: The photocurable ceramic precursor composition according to claim 14 is heated and pyrolyzed to prepare a ceramic part.

19. A method for preparing a 3D printed ceramic product, characterized in that: The method comprises: K1: Create a 3D model of a ceramic part; K2: placing the photocurable ceramic precursor composition according to claim 14 in a 3D printer, setting laser parameters, starting the 3D printer, and starting 3D printing to prepare a 3D printed ceramic primary product; K3: Pyrolyze the primary 3D printed ceramic product to prepare 3D printed ceramic products.

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