A modified silicone rubber, a method of preparation and use in hybrid membranes and gas separation

Abstract

The application discloses a modified silicone rubber, a preparation method and application in a hybrid membrane and gas separation, and the modified silicone rubber is obtained by simultaneously dissolving or dispersing a siloxane monomer containing methyl hydrogen, a mono-olefin modifier, a di-olefin crosslinking agent, a catalyst and a hybrid agent in a solvent, and a structural formula of the modified silicone rubber is shown as formula I: The method provided by the application can conveniently and quickly prepare various modified silicone rubbers and film materials thereof, improve the selectivity, and further dope the modified silicone rubbers according to requirements to improve the performance, and the prepared film can be used for gas separation.

Description

Technical Field

[0001] This application relates to a modified silicone rubber, its preparation method, and its application in hybrid membranes and gas separation, belonging to the field of silicone rubber technology. Background Technology

[0002] Organosilicon products contain both "organic" groups and "inorganic" structures. This unique structure gives them characteristics of both organic and inorganic substances, resulting in properties such as temperature resistance and inertness. PDMS silicone rubber is a widely used organosilicon product. Its molecular chains have a helical structure, very weak intermolecular forces, good mobility of molecular chain segments, and a high free volume within the molecule, thus exhibiting excellent gas permeability. However, due to the low cohesive energy density between molecular chains, its selectivity is also low, with an O2 / N2 selectivity of approximately 2.0–2.1 (Journal of Polymer Science: Part B: Polymer Physics, Vol. 38, 415–434 (2000); Journal of Membrane Science 175 (2000) 285–288).

[0003] To address the aforementioned issues, PDMS needs to be modified to improve selectivity. Modification is mainly divided into two types: main-chain modification and side-chain modification. Side-chain modification involves introducing larger or polar groups onto the side chain to increase cohesive energy and thus improve selectivity. Currently, the most researched methods for side-chain modification are multi-step and two-step methods. The multi-step method mainly involves reacting methylhydrochlorosilane or methylhydroalkoxysilane with α-olefins via hydrosilylation to obtain long-chain methyl alkylchlorosilanes or alkoxysilanes, followed by hydrolysis and condensation to obtain the corresponding siloxane intermediates. These intermediates are then equilibrated using conventional methods to obtain copolymerized long-chain alkylsiloxanes, which are then crosslinked. The two-step method is mainly divided into two categories: one involves first performing ring-opening ionic polymerization of cyclosiloxanes, followed by chemical crosslinking of the extracted products; the other involves synthesizing α-olefins and polymethylhydrosiloxanes via hydrosilylation, followed by further crosslinking of the extracted polyalkylmethylsiloxanes with tetraethoxy or tetramethoxysilanes. The above methods have drawbacks such as long preparation process and complex operation steps. Summary of the Invention

[0004] Based on the above background technology, this invention provides a simple and convenient method for preparing modified silicone rubber, and also provides a method for preparing a modified silicone rubber gas separation membrane, which can achieve better separation performance. Furthermore, based on modified silicone rubber, a method for preparing its hybrid membrane is proposed.

[0005] The one-pot method for preparing modified silicone rubber and its hybrid films proposed in this invention involves simultaneously dissolving or dispersing monomers, modifiers, crosslinking agents, catalysts, and hybrid agents in a solvent, allowing the modification and pre-crosslinking reactions of the silicone rubber to proceed concurrently. Following a simple post-treatment, the modification, crosslinking, and film formation of the silicone rubber are then completed in an integrated manner.

[0006] In one aspect, the present invention provides a modified silicone rubber, the modified silicone rubber having the structural formula shown in Formula I:

[0007]

[0008] Wherein, the molar content m = 0.005~1, n+p = 0~0.995, 0 <r / m≤0.96,n≥0,p≥0;

[0009] R1, R2, R3, R4, and R5 are independently selected from -C x H y X z Hydrocarbon group, wherein X is selected from one or more of O, N, S, and halogens, x = 1 to 20, y = 2 to 41, z = 0 to 10;

[0010] The hydrocarbon group is C. 1-20 At least one of the following: alkane group, olefin group, aromatic group, or alkane group, olefin group, or aromatic group containing heteroatom X;

[0011] R6 is C a H b+1 M d The C a H b+1 M d From compound C a H b M d The compound C a H b M d It is at least one of α-olefins and aromatics; wherein M is selected from one or more of O, N, S, and halogens, a = 2 to 25, b = 3 to 50, and d = 0 to 10;

[0012] R7 is C e-4 H f-6 Y g Where Y is one or more of O, N, S, and halogens, e = 4–20, f = 6–38, and g = 0–32;

[0013] The compound C a H b M d When it is an aromatic hydrocarbon, C a H b M d Selected from C2-25 Aromatic hydrocarbons or C containing heteroatoms M 2-25 At least one of aromatic hydrocarbon derivatives;

[0014] The compound C a H b M d When it is the α-olefin, C a HbM d Selected from C 2-25 Chain monoolefins or C containing heteroatoms M 2-25 At least one of the chain-like monoolefin derivatives.

[0015] Among them, olefins include chain olefins, cyclic olefins, aromatic olefins, as well as substituted chain olefins, substituted cyclic olefins, and substituted aromatic olefins.

[0016] Optionally, the C containing heteroatom M 2-25 Aromatic derivatives are selected from CH2=CH(CH2). 0-J NH(CH2) 0-K C6H5, CH2=CH(CH2) 0～17 At least one of C6H4F, J+K≤17;

[0017] Optionally, the C containing heteroatom M 2-25 The aromatic derivative is selected from at least one of CH2=CH-CH2NHC6H5, CH2=CHCH2NHCH2C6H5, CH2=CHC6H4F, and CH2=CHCH2C6H4F;

[0018] The structural formula of CH2=CH-CH2NHC6H5 is shown in Formula III;

[0019]

[0020] Optionally, the C 2-25 The chain-like monoolefin is selected from CH2=CH(CH2). 0～23 At least one of H;

[0021] Optionally, when M consists of two elements M1 and M2, d(M1):d(M2) = 1:1 to 1:6;

[0022] Optionally, the C containing heteroatom M 2-25 The chain-like monoolefin derivative is selected from at least one of haloalkenes, nitrogen-containing monoolefin derivatives, oxygen-containing monoolefin derivatives, and sulfur-containing monoolefin derivatives;

[0023] Optionally, the nitrogen-containing functional group of the nitrogen-containing monoolefin derivative is selected from at least one of amino, amide, and cyano groups;

[0024] Optionally, the oxygen-containing functional group of the oxygen-containing monoolefin derivative is selected from at least one of carboxyl, hydroxyl, ester, ether, and carbonyl groups;

[0025] Optionally, the sulfur-containing functional group of the sulfur-containing monoolefin derivative is selected from at least one of thioesters, thioethers, and mercapto groups;

[0026] Optionally, the haloalkene is selected from CH2=CH(CH2). 0～23 At least one of M'; M' is selected from F, Cl or Br;

[0027] Optionally, the C containing heteroatom M 2-25 Chain-like monoolefin derivatives are in It is a functional group containing heteroatoms M;

[0028] Optionally, the haloalkene is selected from CH2=CHF, CH2=CHCl, CH2=CHBr, CH2=CHI, and CH2=CH(CH2). 0～15 CH2Cl, CH2=CH(CH2) 0～15 CH2Br, CH2=CH(CH2) 0～15 At least one of CH2I;

[0029] Optionally, the nitrogen-containing monoolefin derivative is selected from CH2=CH(CH2). 0～22 CN, CH2=CH(CH2) 0-J NH(CH2) 0-K CH3, CH2=CH(CH2) 0-J CHNH2(CH2) 0-K CH3, CH2=CH(CH2) 0-J CONH(CH2) 0-K At least one of CH3, J+K≤22;

[0030] Optionally, the nitrogen-containing monoolefin derivative is selected from at least one of CH2=CH-CH2NHCH3, CH2=CHCH2CH2CN, CH2=CHCONH(CH2)2CH3, and CH2=CH-CH2CH2CHNH2CH3;

[0031] Optionally, the oxygen-containing monoolefin derivative is selected from CH2=CH(CH2). 0～22 CH2OH, CH2=CH(CH2) 0～ 22 COOH, CH2=CH(CH2) 0-J CHOH(CH2) 0-K CH3, CH2=CH(CH2) 0-JCO(CH2) 0-K CH3, CH2=CH(CH2) 0-J O(CH2) 0-K CH3, CH2=CH(CH2) 0-J COO(CH2) 0-K At least one of CH3, J+K≤22;

[0032] Optionally, the oxygen-containing monoolefin derivative is selected from CH2=CHCH2COOH and CH2=CH-(CH2). 0～8 CH2OH, CH2=CH(CH2) 1～2 CHOH(CH2) 0～4 CH3, CH2=CH-(CH2) 0～14 COOCH3, CH2=CH-CH2OCO(CH2)4CH3, CH2=CH-CH2CH2COCH3, CH2=CHCH2O(CH2) 0-3 CH3, CH2=CHO(CH2) 1-15 At least one of CH3;

[0033] Optionally, the sulfur-containing monoolefin derivative is selected from CH2=CH(CH2). 0-J S(CH2) 0-K At least one of CH3 and CH2=CHCH2SH, J+K≤22;

[0034] Optionally, the sulfur-containing monoolefin derivative is selected from CH2=CH-CH2S(CH2). 0-2 At least one of CH3 and CH2=CHCH2SH;

[0035] Optionally, when the C containing heteroatom M... 2-25 When M in a chain-like monoolefin derivative is two or more of O, N, S, and halogens, the C containing the heteroatom M... 2-25 The chain-like monoolefin derivatives are selected from CH2=CH(CH2). 0-J SCO(CH2) 0- K CH3, CH2=CH(CH2) 0-J O(CH2) 0-K M', CH2=CH(CH2) 0-J COO(CH2) 0-K M', CH2=CH(CH2) 0-J NHCO(CH2) 0-K CH2M', CH2=CH(CH2) 0-J CO(CH2) 0-K M', CH2=CH(CH2)0-J OCO(CH2) 0-K T(T=M',-NH2,-CF3), CH2=CH(CH2) 0-J CONH(CH2) 0-K OH, CH2=CH(CH2) 0-J CONH(CH2) 0-K CH3, CH2=CH(CH2) 0-J’ CO(CH2) 0-k’ COO(CH2) 0-L CH3, CH2=CH(CH2) 0-J’ COO(CH2) 0-k’ OCONH(CH2) 0-L At least one of CH3, J+K≤23, J'+K'+L≤20;

[0036] Optionally, the C containing heteroatom M 2-25 The chain-like monoolefin derivative is selected from at least one of CH2=CH(CH2)9SCOCH3, CH2=CHO(CH2)2Cl, CH2=CHCOO(CH2)2Cl, CH2=CH(CH2)9NHCOCH2Cl, CH2=CH(CH2)8COCl, CH2=CH(CH2)2COCl, CH2=CHCH2OCOCH2Cl, CH2=CHOCOCH2Cl, CH2=CHCH2OCONH2, CH2=CHCH2OCOCF3, CH2=CHCONHCH2OH, CH2=CHCONHCH2CH2OH, CH2=CHCONH(CH2)3OCH3, CH2=CH(CH2)2COCH2COOC2H5, and CH2=CHCOO(CH2)2OCONH(CH2)3CH3.

[0037] Optionally, the C 1-20 The hydrocarbon group is -(CH2). 1～18 At least one of H, -C6H5, and -CH=CH2;

[0038] Optionally, when X consists of two elements, the molar ratio of the two elements is 1:1 to 1:6;

[0039] Optionally, the hydrocarbon group containing heteroatom X is selected from halogenated, nitrogen-containing, oxygen-containing, and sulfur-containing C groups. 1-20 At least one of alkane group, olefin group, and aromatic group;

[0040] Optionally, the nitrogen-containing functional group of the nitrogen-containing hydrocarbon group is selected from at least one of amino, amide, and cyano groups;

[0041] Optionally, the oxygen-containing functional group of the oxygen-containing hydrocarbon group is selected from at least one of carboxyl, hydroxyl, ester, ether, and carbonyl groups;

[0042] Optionally, the sulfur-containing functional group of the sulfur-containing hydrocarbon group is selected from at least one of mercapto and sulfone groups;

[0043] Optionally, the haloalkyl group is selected from -(CH2). 0-h (CA2) 0-i (CH2) 0-q At least one of X'; X' is selected from F, Cl or Br, h+i+q≤20;

[0044] Optionally, the haloalkyl group is selected from -(CH2). 1～17 CX'3, -(CH2)2(CX'2)3CX'3, -(CH2) 1～17 CH2X';

[0045] Optionally, the haloalkyl group is selected from -(CH2). 1～17 CF3, -(CH2)2(CF2)3CF3, -(CH2) 1～17 At least one of CH2Cl;

[0046] Optionally, the nitrogen-containing hydrocarbon group is selected from -(CH2). 1～20 NH2、-(CH2) 0-h NH(CH2) 0-i CH3, -(CH2) 0-h NH(CH2) 0-i NH2、-(CH2) 0-h CONH(CH2) 0-i CH3, -(CH2) 0-h NHCO(CH2) 0-i CH3, -(CH2) 0-19 CONH2、-(CH2) 0- 19 At least one of CN, h+i≤20;

[0047] Optionally, the nitrogen-containing hydrocarbon group is selected from -(CH2). 2～10 NH2, -(CH2)3NHCH2CH2NH2, -(CH2)3CONH(CH2)2CH3, -(CH2)3NHCOCH2CH3, -(CH2) 2-6 CN;

[0048] Optionally, the oxygen-containing hydrocarbon group is selected from (CH2). 1～9 O(CH2CH2O) 1～5 CH3, -(CH2) 1～10 O(CH2CH2O)1～5 H, -(CH2) 1～10 (OCH2CH2) 1～5 OH, -(CH2) 1～20 OH, -(CH2) 1～17 At least one of OCOC = CH2;

[0049] Optionally, the oxygen-containing hydrocarbon group is selected from (CH2). 1～3 O(CH2CH2O) 1～2 CH3, -(CH2) 1～2 O(CH2CH2O) 1～3 H, -(CH2) 1～4 (OCH2CH2) 1～4 OH, -(CH2) 1～10 OH, -(CH2) 1～10 At least one of OCOC = CH2;

[0050] Optionally, the sulfur-containing hydrocarbon group is selected from -(CH2). 0-h SO2(CH2) 0-i H、-(CH2) 1～20 SH must be at least one, and h+i≤20;

[0051] Optionally, the sulfur-containing hydrocarbon group is selected from -(CH2). 1-4 SO2(CH2) 1-6 H、-(CH2) 1～10 SH.

[0052] In another aspect of this application, a method for preparing the above-mentioned modified silicone rubber is provided, wherein raw materials containing polysiloxane monomer, modifier, crosslinking agent and catalyst are mixed with solvent, and modified silicone rubber is obtained after reaction.

[0053] The polysiloxane monomer is a siloxane polymer containing methyl hydrogen with a structure of Formula II;

[0054]

[0055] R1, R2, R3, R4, and R5 are independently selected from -C. x H y X z The molar content is m = 0.005~1, n+p = 0~0.995, n≥0, p≥0, and the molecular weight is 800~50000.

[0056] The modifier, crosslinking agent, and hybrid agent are added in pure substance or solution form. The crosslinking agent and hybrid agent can be added at the beginning of the reaction or after a certain period of reaction.

[0057] Optionally, the modifier is the C a H b M d , which is a terminal monoolefin or its derivative;

[0058] Optionally, the crosslinking agent is a hydrocarbon compound containing at least two double bonds;

[0059] Optionally, the crosslinking agent is an olefin or its derivative containing double bonds at both ends. e H f Y g After removing the double bonds at both ends, its molecular formula is R7, where Y is one or more of O, N, S, and halogens, e = 4 to 20, f = 6 to 38, and g = 0 to 32.

[0060] Optionally, when Y consists of two elements, the molar ratio of the two elements is 1:1 to 1:6;

[0061] Optionally, the crosslinking agent is selected from C 4-20 Chain-like terminal dienes or C containing heteroatoms Y 4-20 At least one of the chain-like terminal diene derivatives;

[0062] Optionally, the chain-like terminal diene is selected from at least one of 1,5-hexadiene, 1,7-octadiene, (1,13-tetradecadiene), 1,9-decadiene, and 3-methyl-1,4-pentadiene.

[0063] Optionally, the C containing heteroatoms Y 4-20 The chain-like terminal diene derivative is selected from at least one of halodienes, oxygen-containing diene derivatives, nitrogen-containing diene derivatives, and sulfur-containing diene derivatives;

[0064] Optionally, the oxygen-containing functional group of the oxygen-containing diene derivative is selected from at least one of carboxyl, hydroxyl, ester, ether, and carbonyl groups;

[0065] Optionally, the nitrogen-containing functional group of the nitrogen-containing diene derivative is selected from at least one of amino, amide, and cyano groups;

[0066] Optionally, the sulfur-containing functional group of the sulfur-containing diene derivative is selected from at least one of thioesters and thioethers;

[0067] Optionally, the halodiene is selected from at least one of 3,3,4,4-tetrafluoro-1,5-hexadiene and 1,6-divinylperfluorohexane;

[0068] Optionally, the oxygen-containing diene derivative is selected from at least one of diallyl carbonate, 1,6-heptadien-4-ol, 1,5-hexadien-3-ol, diallyl maleate, allyl ether, diethylene glycol divinyl ether, and neopentyl glycol diacrylate.

[0069] Optionally, the nitrogen-containing diene derivative is selected from at least one of diallylamine, N-methyldiallylamine, and N,N'-methylenebisacrylamide;

[0070] Optionally, the sulfur-containing diene derivative is selected from at least one of diallyl trisulfide and allyl disulfide;

[0071] Optionally, when the C containing heteroatom Y 4-20 When the Y in the chain-like terminal diene derivative is two or more of O, N, S, and halogen, the C containing the heteroatom Y... 4-20 The chain-terminated diene derivative is selected from at least one of allyl oxychloride, 4-aminomethyl-hept-1,6-dien-4-ol, and dichloropropeneamine.

[0072] Optionally, the catalyst is a transition metal catalyst;

[0073] Optionally, the catalyst is at least one selected from platinum group compounds, palladium group compounds, rhodium group compounds, and nickel group compounds;

[0074] Optionally, the catalyst is selected from at least one of chloroplatinic acid, karsted, Pd(PPh3)4, PdCl2(Ph3P)2, PdCl2(PhCN)2, [RhCl(CO)2]2, (Ph3P)2(CO)RhCl, (Et3P)2(CO)RhCl, and (Ph3P)2NiCl2.

[0075] Optionally, the raw material also includes a hybrid agent. In order to further regulate the properties of silicone rubber, it can be doped with a hybrid agent. The hybrid agent is a substance that can improve its mechanical properties or separation properties. The hybrid agent is selected from at least one of carbon materials, quantum dots, metal oxides, metal-organic frameworks, glass fibers, and silicon dioxide.

[0076] Optionally, the carbon material is selected from at least one of graphite, graphene, graphene oxide, carbon nitride, and nanotubes;

[0077] Optionally, the metal oxide is selected from at least one of titanium dioxide, zinc oxide, and aluminum oxide;

[0078] Optionally, the solvent is selected from C5 to C6. 12 One of the following: saturated alkanes, benzene, toluene, tetrahydrofuran, gasoline, and dimethyl sulfoxide;

[0079] Optionally, the mass concentration of the polysiloxane monomer is 1-10% relative to the solvent, and the concentration of the catalyst is 0.4-5 mg / g solvent;

[0080] Optionally, the molar ratio of the modifier to the polysiloxane monomer is ≤0.96;

[0081] Optionally, the molar ratio of the modifier to the polysiloxane monomer is 0.1 to 0.95;

[0082] Optionally, the upper limit of the molar ratio of the modifier to the polysiloxane monomer can be independently selected from 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, and 0.95; the lower limit can be independently selected from 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, and 0.8.

[0083] Optionally, the total molar amount of the crosslinking agent and modifier is ≤1 / 2 molar ratio of the polysiloxane monomer;

[0084] Optionally, the total molar amount of the crosslinking agent and the modifier is in a molar ratio of 0.2 to 1 with that of the polysiloxane monomer;

[0085] Optionally, the upper limit of the total molar amount of the crosslinking agent and modifier and the molar ratio of the polysiloxane monomer can be independently selected from 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and 1; and the lower limit can be independently selected from 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, and 0.9.

[0086] Optionally, the mass ratio of the hybrid agent to the polysiloxane monomer is ≤20%;

[0087] Optionally, the mass ratio of the hybrid agent to the polysiloxane monomer is 2% to 10%.

[0088] Optionally, the upper limit of the mass ratio of the hybrid agent to the polysiloxane monomer can be independently selected from 4%, 5%, 6%, 7%, 8%, 9%, and 10%; the lower limit can be independently selected from 2%, 3%, 4%, 5%, 6%, 7%, and 8%.

[0089] Optionally, the reaction is cooled and refluxed at a temperature close to the solvent boiling point for 1–24 h.

[0090] In this application, the near-solvent boiling point temperature refers to the range of (solvent boiling point - 15) °C to (solvent boiling point - 5) °C.

[0091] In another aspect of this application, a hybrid membrane casting solution is provided, the hybrid membrane casting solution comprising the modified silicone rubber described above or the modified silicone rubber prepared according to the preparation method described above.

[0092] Another aspect of this application provides a method for preparing a hybrid membrane, wherein the hybrid membrane casting solution obtained above is attached to a support by at least one of the following methods: dip coating, casting, or coating, to obtain the hybrid membrane.

[0093] Optionally, the support is selected from at least one of a supporting base film, a glass plate, and a PTFE plate;

[0094] Optionally, the supporting substrate is selected from at least one of polysulfone, polyethersulfone, polyacrylonitrile, polyetherimide, polyimide, polyvinylidene fluoride, and polyarylethersulfone ketone.

[0095] Optionally, the method further includes heat treatment;

[0096] Optionally, the heat treatment temperature is 30–90°C, and the treatment time is 2–120 h.

[0097] Optionally, the upper limit of the heat treatment temperature can be independently selected from 40℃, 50℃, 60℃, 70℃, 80℃, and 90℃, and the lower limit can be independently selected from 30℃, 40℃, 50℃, 60℃, 70℃, and 80℃.

[0098] Optionally, the upper limit of the processing time can be independently selected from 4h, 6h, 12h, 24h, 48h, 96h, and 120h, and the lower limit can be independently selected from 2h, 4h, 6h, 12h, 24h, 48h, and 96h.

[0099] Another aspect of this application provides an application of a hybrid membrane in gas separation, wherein the hybrid membrane is a hybrid membrane prepared by the above-described preparation method;

[0100] Preferably, the gas separation is selected from one of O2 / N2 and CO2 / N2.

[0101] The beneficial effects that this application can produce include:

[0102] (1) The method provided in this application can prepare modified silicone rubber in one pot, and the modification and pre-crosslinking occur in one step, avoiding the multi-step operation in the traditional method, and can conveniently and quickly prepare the desired target product. At the same time, the modification, crosslinking and film formation of silicone rubber can be completed in one integrated process after simple post-treatment.

[0103] (2) The method provided in this application can be used to prepare a variety of modified silicone rubber and its film materials, improve their selectivity, and further dope them to improve their performance as needed. The O2 / N2 and CO2 / N2 selectivity can be improved by 40% and 37% respectively compared with PDMS. Detailed Implementation

[0104] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0105] Unless otherwise specified, the raw materials used in the embodiments of this application were all purchased commercially. The molecular weight of polymethylhydrosiloxane is 1700-3200 g / mol, the equivalent weight of methylhydrosiloxane-octylmethylsiloxane copolymer (HAM-301) is 440-480, the equivalent weight of methylhydrosiloxane-octylmethylsiloxane-dimethylsiloxane trimer (HAM-3012) is 280-320, and the equivalent weight of methylhydrosiloxane-phenylmethylsiloxane copolymer (HPM-502) is 160-170.

[0106] The properties of the modified silicone rubber and its hybrid membrane of this invention were determined using the constant pressure variable volume method on the permeate side, employing a soap bubble flow meter. The test conditions were 35℃ and 0.3 MPa. The test gas was pure gas, and the membrane performance was characterized by gas permeability and separation selectivity α.

[0107] The units for gas permeation flux J and permeability coefficient P are GPU and Barrer, respectively, and the relationship between them is J = P / l, where l is the film thickness in cm, and 1 GPU = 1 × 10⁻⁶. -6 cm 3 (STP) / cm 2 ·s·cmHg, 1 Barrer = 1×10 -10 cm 3 (STP)·cm / cm 2 ·s·cmHg.

[0108] Example 1

[0109] 0.56 g of 1-octene in n-hexane (15 wt%) and 50 μL of karsted catalyst were added to a 1.5 g n-hexane solution of polymethylhydrosiloxane (3 wt%). The mixture was refluxed at 55 °C and stirred for 2 h. Then, a 2.2 g n-hexane solution of 1,7-octadiene (10 wt%) was added. The mixture was then heated to 65 °C and refluxed for another 1 h to obtain a polymethyloctylsiloxane solution.

[0110] The above solution was coated onto a polyacrylonitrile (PAN) substrate by dip coating and dried at 50°C for 48 hours to obtain a polymethyl octylsiloxane gas separation membrane.

[0111] The above membrane was used for O2 and N2 gas permeation performance testing.

[0112] Example 2

[0113] A hexane solution containing 4 g of 1-octene and 0.2 g of 1,7-octadiene was added to a hexane solution containing 2.6 g of polymethylhydrosiloxane, followed by the addition of a hexane solution containing 145 mg of catalyst karsted. The mixture was then refluxed at 60 °C for 3 h to obtain a solution of polymethyloctylsiloxane.

[0114] The above solution was coated onto a polyacrylonitrile (PAN) substrate and dried at 60°C for 48 hours to obtain a polymethyl octylsiloxane gas separation membrane.

[0115] The above membrane was used for O2 and N2 gas permeation performance testing.

[0116] Example 3

[0117] A hexane solution containing 3.6 g of 1-octene and 0.88 g of 1,7-octadiene was added to a hexane solution containing 2.4 g of polymethylhydrosiloxane, followed by the addition of a hexane solution containing 136 mg of karsted catalyst. The mixture was then refluxed at 60 °C for 3 h to obtain a solution of polymethyloctylsiloxane.

[0118] The above solution was coated onto a polyacrylonitrile (PAN) substrate and dried at 70°C for 6 hours to obtain a polymethyl octylsiloxane gas separation membrane.

[0119] The above membrane was used for O2 and N2 gas permeation performance testing.

[0120] Example 4

[0121] 3.8 g of 1-octene and 0.19 g of 1,7-octadiene were added to a 2.4 g isooctane solution of polymethylhydrosiloxane (3 wt%), and then 136 mg isooctane solution of catalyst karsted was added. The mixture was refluxed at 90 °C and stirred for 12 h to obtain a polymethyldecylsiloxane solution.

[0122] The above solution was cast onto a glass plate and dried at 70°C for 48 hours to obtain a polymethyldecylsiloxane gas separation membrane.

[0123] The above membrane was used for O2 and N2 gas permeation performance testing.

[0124] Example 5

[0125] A solution of polymethyldecylsiloxane was obtained by adding 4g of 1-decene, 0.16g of 1,7-octadiene and 76mg of karsted catalyst to a 2g hexane solution (3wt%) of polymethylhydrosiloxane and stirring under reflux at 60°C for 20h.

[0126] The above solution was cast onto a PTFE plate and dried at 65°C for 96 hours to obtain a polymethyldecylsiloxane gas separation membrane.

[0127] The above membrane was used for O2 and N2 gas permeation performance testing.

[0128] Example 6

[0129] A hexane solution containing 7.2 g of 1-octene and 1.76 g of 1,7-octadiene was added to a hexane solution containing 4.8 g of polymethylhydrosiloxane, followed by the addition of a hexane solution containing 160 mg of karsted catalyst. The mixture was then refluxed at 60 °C and stirred for 6 h to obtain a solution of polymethyloctylsiloxane.

[0130] The above solution was impregnated and coated onto a PAN substrate, and dried at 65°C for 6 hours to obtain a polymethyl octylsiloxane gas separation membrane.

[0131] The above membrane was used for gas permeation performance testing of O2, N2, and CO2.

[0132] Example 7

[0133] A solution of 10.8 g of 1-octene and 2.64 g of 1,7-octadiene in isooctane was added to a solution of 7.2 g of polymethylhydrosiloxane in isooctane, followed by the addition of 240 mg of karsted catalyst in isooctane. The mixture was then prepared into a mixed solution containing 5 wt% polymethylhydrosiloxane. The solution was refluxed at 90 °C and stirred for 6 h to obtain a solution of polymethyloctylsiloxane.

[0134] The above solution was impregnated and coated onto a polyetherimide (PEI) substrate, and dried at 65°C for 4 hours to obtain a polymethyl octylsiloxane gas separation membrane.

[0135] The above membrane was used for gas permeation performance testing of O2, N2, and CO2.

[0136] Example 8

[0137] 0.69 g of 1,7-octadiene in n-hexane was added to 2.9 g of HAM-301 in n-hexane, and then 176 mg of catalyst karsted in n-hexane was added to prepare a mixed solution containing 3 wt% HAM-301. The solution was refluxed at 60 °C and stirred for 3 h to obtain the HAM-301 solution.

[0138] The above solution was impregnated and coated onto a polyacrylonitrile (PAN) substrate membrane, and dried at 60°C for 24 hours to obtain the HAM-301 gas separation membrane.

[0139] The above membrane was used for O2 and N2 gas permeation performance testing.

[0140] Example 9

[0141] 0.28 g of 1,7-octadiene in n-hexane was added to 3.4 g of HAM-3012 in n-hexane, and then 197 mg of catalyst karsted in n-hexane was added to prepare a mixed solution containing 3 wt% HAM-3012. The solution was refluxed at 60 °C and stirred for 3 h to obtain the HAM-3012 solution.

[0142] The above solution was impregnated and coated onto a polyacrylonitrile (PAN) substrate membrane, and dried at 60°C for 24 hours to obtain the HAM-3012 gas separation membrane.

[0143] The above membrane was used for O2 and N2 gas permeation performance testing.

[0144] Example 10

[0145] 5.28 g of 11-chloro-1-undecene and 1.32 g of 1,7-octadiene were added to a tetrahydrofuran solution (8 wt%) of 2.4 g of polymethylhydrosiloxane, and then 82.8 mg of catalyst PdCl2(Ph3P)2 was added. The mixture was refluxed at 55 °C and stirred for 10 h to obtain a solution of polymethyl11-chloro-1-undecenesiloxane.

[0146] The above solution was impregnated and coated onto a polyacrylonitrile (PAN) substrate, and dried at 30°C for 48 hours to obtain a modified silicone rubber gas separation membrane.

[0147] The above membrane was used for gas permeation performance testing of O2, N2, and CO2.

[0148] Example 11

[0149] 2.97 g of 1-hexene-5-amine and 3.16 g of diethylene glycol divinyl ether were added to a 3 g toluene solution (2 wt%) of polymethylhydrosiloxane, and then 661.5 mg of catalyst (Ph3P)2(CO)RhCl was added. The mixture was refluxed at 100 °C and stirred for 8 h to obtain a solution of polymethyl5-amine-hexylsiloxane.

[0150] The above solution was impregnated and coated onto a polyimide (PI) substrate, and dried at 60°C for 48 hours to obtain a modified silicone rubber gas separation membrane.

[0151] The above membrane was used for gas permeation performance testing of O2, N2, and CO2.

[0152] Example 12

[0153] 5.13 g of allyl butyl ether and 0.89 g of diallyl trisulfide were added to a 3 g solution of polymethylhydrosiloxane in dimethyl sulfoxide (DMSO) (3 wt%), and then 194 mg of chloroplatinic acid catalyst was added. The mixture was refluxed at 175 °C and stirred for 8 h to obtain a solution of polymethylpropyl butyl ether siloxane.

[0154] The above solution was impregnated and coated onto a polysulfone Psf substrate, and dried at 80°C for 96 hours to obtain a modified silicone rubber gas separation membrane.

[0155] The above membrane was used for gas permeation performance testing of O2, N2, and CO2.

[0156] Example 13

[0157] A solution of 1.76 g of allyl methyl sulfide in isooctane and a solution of 0.77 g of 3,3,4,4-tetrafluoro-1,5-hexadiene in isooctane were added to a solution of 10 g of HPM-502 in isooctane. Then, a solution of 281.8 mg of catalyst (Ph3P)2NiCl2 in isooctane was added to prepare a mixed solution containing 8 wt% HPM-502. The solution was refluxed at 90 °C and stirred for 12 h to obtain a solution of modified silicone rubber.

[0158] The above solution was impregnated and coated onto a polysulfone Psf substrate, and dried at 60°C for 48 hours to obtain a modified silicone rubber gas separation membrane.

[0159] The above membrane was used for gas permeation performance testing of O2, N2, and CO2.

[0160] Example 14

[0161] A solution of 10.8 g of 1-octene and 2.64 g of 1,7-octadiene in isooctane was added to a solution of 7.2 g of polymethylhydrosiloxane in isooctane, followed by the addition of 240 mg of karsted catalyst in isooctane, resulting in a mixed solution containing 5 wt% polymethylhydrosiloxane. The solution was refluxed at 90 °C and stirred for 3 h, followed by the addition of 0.36 g of SiO2 and stirring for another 3 h to obtain a solution of SiO2-doped polymethyloctylsiloxane.

[0162] The above solution was impregnated and coated onto a polyetherimide (PEI) substrate, and dried at 60°C for 48 hours to obtain a SiO2-doped polymethyl octylsiloxane gas separation membrane.

[0163] The above membrane was used for gas permeation performance testing of O2, N2, and CO2.

[0164] Example 15

[0165] 2.97 g of 1-hexene-5-amine and 3.16 g of diethylene glycol divinyl ether were added to a 3 g toluene solution (2 wt%) of polymethylhydrosiloxane, followed by the addition of 661.5 mg of catalyst (Ph3P)2(CO)RhCl. The mixture was refluxed at 100 °C and stirred for 5 h. Then, 0.24 g of MIL-101-NH2 was added and the mixture was refluxed and stirred for another 5 h to obtain a solution of MIL-101-NH2-doped polymethyl5-amine-hexylsiloxane.

[0166] The above solution was impregnated and coated onto a polyimide (PI) substrate, and dried at 60°C for 12 hours to obtain a modified silicone rubber gas separation membrane.

[0167] The above membrane was used for gas permeation performance testing of O2, N2, and CO2.

[0168] Example 16

[0169] 5.13 g of allyl butyl ether and 0.89 g of diallyl trisulfide were added to a 3 g solution of polymethylhydrosiloxane in dimethyl sulfoxide (DMSO) (3 wt%), followed by the addition of 194 mg of chloroplatinic acid catalyst. The mixture was refluxed at 175 °C and stirred for 3 h, and then 0.06 g of carbon nanotubes were added and the mixture was refluxed and stirred for another 6 h to obtain a solution of nanotube-doped polymethylpropyl butyl ether siloxane.

[0170] The above solution was impregnated and coated onto a polysulfone Psf substrate, and dried at 80°C for 96 hours to obtain a nanotube-doped modified silicone rubber gas separation membrane.

[0171] The above membrane was used for gas permeation performance testing of O2, N2, and CO2.

[0172] Example 17

[0173] 0.9 g N-n-propylacrylamide and 0.31 g N,N-methylenebisacrylamide were added to 10 g of HAM-3012 in isooctane solution (5 wt%), then 377 mg of catalyst karsted was added, the mixture was refluxed at 90 °C and stirred for 5 h, and then 0.5 g of aminated carbon quantum dots were added and the mixture was refluxed and stirred for another 5 h to obtain a carbon quantum dot-doped polymethylpropylacrylamide-methyloctyl-dimethylsiloxane solution.

[0174] The above solution was impregnated and coated onto a polyacrylonitrile (PAN) substrate, and dried at 60°C for 12 hours to obtain a modified silicone rubber gas separation membrane.

[0175] The above membrane was used for gas permeation performance testing of O2, N2, and CO2.

[0176] Comparative Example 1

[0177] 11 g of 1,7-octadiene was added to a 6 g solution of polymethylhydrosiloxane in isooctane (5 wt%), and then 200 mg of karsted catalyst in isooctane was added. The mixture was refluxed at 90 °C and stirred for 12 h to obtain a polysiloxane solution.

[0178] The above solution was impregnated and coated onto a polyacrylonitrile (PAN) substrate, and dried at 60–70°C for 48 hours to obtain a polymethyldecylsiloxane gas separation membrane.

[0179] The above membrane was used for gas permeation performance testing of O2, N2, and CO2.

[0180] The O2 / N2 selectivity of the silicone rubber material prepared by this invention is above 2.2, reaching as high as 2.8, and the CO2 / N2 selectivity is greater than 10.5, reaching 13. Compared with PDMS, which has an O2 / N2 selectivity of about 2 and a CO2 / N2 selectivity of 9.5 (Journal of Polymer Science: Part B: Polymer Physics, Vol. 38, 415–434 (2000)), this invention obtains a silicone rubber material with higher selectivity by modifying the side chain and main chain.

[0181] Compared with Examples 3 and 7, the introduction of the modifier Cl element in Example 10 increased the cohesive energy of the molecule, reduced the free volume within the molecule, decreased the flux, and increased the selectivity.

[0182] Compared to Examples 3 and 7, Example 11 uses a branched modifier and an ether-based crosslinking agent with stronger chain segment mobility, resulting in increased free volume and flux of the material. Simultaneously, the introduction of amino and ether oxygen groups improves CO2 / N2 selectivity while slightly decreasing O2 / N2 selectivity.

[0183] Compared with Examples 3 and 7, Example 12 shows that the introduction of flexible ether radical groups in the modifier increases the free volume and flux, while slightly decreasing the O2 / N2 selectivity. The introduction of ether groups improves the CO2 / N2 selectivity.

[0184] Compared with Examples 3 and 7, Example 13 shows that the large group structure of the benzene ring in the monomer increases the free volume, and at the same time, due to its rigid structure, the mobility is reduced, which improves the permeability and selectivity of the material.

[0185] Compared with Example 11, the addition of functionalized MOF in Example 15 can further improve the permeability and selectivity of the material.

[0186] Compared with Example 12, the addition of carbon nanotubes in Example 16 can further improve the permeability of the material without affecting selectivity.

[0187] Comparative Example 1 uses monomers without side chain modification for direct crosslinking. Compared with Examples 6 and 7, its permeability decreased sharply, while its selectivity increased. It can be seen that the present invention has a very significant effect on improving membrane performance.

[0188] As can be seen from the above embodiments, different monomers, modifiers, crosslinking agents, etc., can be selected according to the target product. Simultaneously, by dissolving or dispersing the monomers, modifiers, crosslinking agents, catalysts, and hybrid agents in a solvent, the modification, pre-crosslinking, and doping processes of siloxanes can be achieved in one step. Then, a simple heat treatment further integrates the modification, crosslinking, and film formation of silicone rubber, facilitating the convenient and rapid preparation of the desired modified silicone rubber film. The prepared modified silicone rubber film exhibits higher selectivity.

[0189] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing modified silicone rubber, characterized in that, A raw material containing polysiloxane monomer, modifier, crosslinking agent, and catalyst is mixed with a solvent, and modified silicone rubber is obtained after reaction. The polysiloxane monomer is a siloxane polymer containing methyl hydrogen with a structure of Formula II; Formula II; R1, R2, R3, R4, and R5 are independently selected from -C x H y X z Hydrocarbon group; in Formula II, m = 0.005~1, n+p = 0~0.995, n≥0, p≥0, molecular weight 800~50000; Where X is selected from one or more of O, N, S, and halogens, x=1~20, y=2~41, z=0~10; The hydrocarbon group is C. 1-20 The modifier is at least one of alkane group, olefin group, aromatic group, or alkane group, olefin group, or aromatic group containing heteroatom X; the modifier is C a H b M d The compound C a H b M d It is at least one of α-olefins and aromatics; wherein M is selected from one or more of O, N, S, and halogens, a=2~25, b=3~50, d=0~10, and d is not 0; The compound C a H b M d When it is an aromatic hydrocarbon, C a H b M d Selected from C containing heteroatom M 2-25 At least one of aromatic hydrocarbon derivatives; The compound C a H b M d When it is an α-olefin, C a H b M d Selected from C containing heteroatom M 2-25 At least one of the chain-like monoolefin derivatives; The crosslinking agent is an olefin derivative C containing double bonds at both ends. e H f Y g Where Y is one or more of O, N, S, and halogens, e=4~20, f=6~38, g=0~32, and g is not 0; The raw materials also include hybrid agents; The hybrid agent is selected from at least one of carbon nanotubes, aminated carbon quantum dots, MIL-101-NH2, and silicon dioxide; The mass ratio of the hybrid agent to the polysiloxane monomer is 2-10%. The molar ratio of the modifier to the polysiloxane monomer is 0.1~0.95; The total molar amount of the crosslinking agent and modifier and the molar ratio of the polysiloxane monomer are 0.2~1.

2. The preparation method according to claim 1, characterized in that, The C containing heteroatom M 2-25 Aromatic derivatives are selected from CH2=CH(CH2). 0-J NH(CH2) 0-K C6H5, CH2=CH(CH2) 0~ 17 At least one of C6H4F, J+K≤17.

3. The preparation method according to claim 1, characterized in that, The C containing heteroatom M 2-25 The aromatic derivative is selected from at least one of CH2=CHCH2NHC6H5, CH2=CHCH2NHCH2C6H5, CH2=CHC6H4F, and CH2=CHCH2C6H4F.

4. The preparation method according to claim 1, characterized in that, When M consists of two elements, the ratio of the two elements is 1:1 to 1:

6.

5. The preparation method according to claim 1, characterized in that, The C containing heteroatom M 2-25 The chain-like monoolefin derivative is selected from at least one of haloalkenes, nitrogen-containing monoolefin derivatives, oxygen-containing monoolefin derivatives, and sulfur-containing monoolefin derivatives.

6. The preparation method according to claim 5, characterized in that, The nitrogen-containing functional group of the nitrogen-containing monoolefin derivative is selected from at least one of amino, amide, and cyano groups; The oxygen-containing functional group of the oxygen-containing monoolefin derivative is selected from at least one of carboxyl, hydroxyl, ester, ether, and carbonyl groups; The sulfur-containing functional group of the sulfur-containing monoolefin derivative is selected from at least one of thioesters, thioethers, and mercapto groups. The haloalkene is selected from CH2=CH(CH2). 0~23 At least one of M'; M' is selected from F, Cl or Br.

7. The preparation method according to claim 1, characterized in that, The C containing heteroatom M 2-25 The chain-like monoolefin derivative is CH2=CH(CH2). 0~J (CH2) 0~k (CH3) 0~1 , where M is a functional group containing heteroatoms.

8. The preparation method according to claim 6, characterized in that, The haloalkene is selected from CH2=CHF, CH2=CHCl, CH2=CHBr, CH2=CHI, and CH2=CH(CH2). 0~15 CH2Cl, CH2=CH(CH2) 0~15 CH2Br, CH2=CH(CH2) 0~15 At least one of CH2I; The nitrogen-containing monoolefin derivative is selected from CH2=CH(CH2). 0~22 CN, CH2=CH(CH2) 0-J NH(CH2) 0-K CH3, CH2=CH(CH2) 0-J CHNH2(CH2) 0-K CH3, CH2=CH(CH2) 0-J CONH(CH2) 0-K At least one of CH3, J+K≤22.

9. The preparation method according to claim 8, characterized in that, The nitrogen-containing monoolefin derivative is selected from at least one of CH2=CH-CH2NHCH3, CH2=CHCH2CH2CN, CH2=CHCONH(CH2)2CH3, and CH2=CH-CH2CH2CHNH2CH3.

10. The preparation method according to claim 6, characterized in that, The oxygen-containing monoolefin derivative is selected from CH2=CH(CH2). 0~22 CH2OH, CH2=CH(CH2) 0~22 COOH, CH2=CH(CH2) 0-J CHOH(CH2) 0-K CH3, CH2=CH(CH2) 0-J CO(CH2) 0-K CH3, CH2=CH(CH2) 0-J O(CH2) 0-K CH3, CH2=CH(CH2) 0-J COO(CH2) 0-K At least one of CH3, J+K≤22.

11. The preparation method according to claim 10, characterized in that, The oxygen-containing monoolefin derivatives are selected from CH2=CHCH2COOH and CH2=CH-(CH2). 0~8 CH2OH, CH2=CH(CH2) 1~2 CHOH(CH2) 0~4 CH3, CH2=CH-(CH2) 0~14 COOCH3, CH2=CH-CH2OCO(CH2)4CH3, CH2=CH-CH2CH2COCH3, CH2=CHCH2O(CH2) 0-3 CH3, CH2=CHO(CH2) 1-15 At least one of CH3.

12. The preparation method according to claim 6, characterized in that, The sulfur-containing monoolefin derivative is selected from CH2=CH(CH2). 0-J S(CH2) 0-K At least one of CH3 and CH2=CHCH2SH, J+K≤22.

13. The preparation method according to claim 12, characterized in that, The sulfur-containing monoolefin derivative is selected from CH2=CH-CH2S(CH2). 0-2 At least one of CH3 and CH2=CHCH2SH.

14. The preparation method according to claim 1, characterized in that, When the C containing heteroatom M 2-25 When M in a chain-like monoolefin derivative is two or more of O, N, S, and halogens, the C containing the heteroatom M... 2-25 The chain-like monoolefin derivatives are selected from CH2=CH(CH2). 0-J SCO(CH2) 0-K CH3, CH2=CH(CH2) 0-J O(CH2) 0-K M', CH2=CH(CH2) 0-J COO(CH2) 0- K M', CH2=CH(CH2) 0-J NHCO(CH2) 0-K CH2M', CH2=CH(CH2) 0-J CO(CH2) 0-K M', CH2=CH(CH2) 0-J OCO(CH2) 0-K T (T=M', -NH2, -CF3), CH2=CH(CH2) 0-J CONH(CH2) 0-K OH, CH2=CH(CH2) 0-J CONH(CH2) 0- K CH3, CH2=CH(CH2) 0-J’ CO(CH2) 0-k’ COO(CH2) 0-L CH3, CH2=CH(CH2) 0-J’ COO(CH2) 0-k’ OCONH(CH2) 0- L At least one of CH3, wherein J+K≤23, J'+K'+L≤20.

15. The preparation method according to claim 1, characterized in that, The C containing heteroatom M 2-25 The chain-like monoolefin derivative is selected from at least one of CH2=CH(CH2)9SCOCH3, CH2=CHO(CH2)2Cl, CH2=CHCOO(CH2)2Cl, CH2=CH(CH2)9NHCOCH2Cl, CH2=CH(CH2)8COCl, CH2=CH(CH2)2COCl, CH2=CHCH2OCOCH2Cl, CH2=CHOCOCH2Cl, CH2=CHCH2OCONH2, CH2=CHCH2OCOCF3, CH2=CHCONHCH2OH, CH2=CHCONHCH2CH2OH, CH2=CHCONH(CH2)3OCH3, CH2=CH(CH2)2COCH2COOC2H5, and CH2=CHCOO(CH2)2OCONH(CH2)3CH3.

16. The preparation method according to claim 1, characterized in that, The C 1-20 The hydrocarbon group is -(CH2). 1~18 At least one of H, -C6H5, and -CH=CH2; When X consists of two elements, the molar ratio of the two elements is 1:1 to 1:6; The hydrocarbon group containing heteroatom X is selected from halogenated, nitrogen-containing, oxygen-containing, and sulfur-containing C groups. 1-20 At least one of alkane group, olefin group, and aromatic group; The nitrogen-containing functional group of the nitrogen-containing hydrocarbon group is selected from at least one of amino, amide, and cyano groups; The oxygen-containing functional group of the oxygen-containing hydrocarbon group is selected from at least one of carboxyl, hydroxyl, ester, ether, and carbonyl groups; The sulfur-containing functional group of the sulfur-containing hydrocarbon group is selected from at least one of mercapto and sulfone groups; The haloalkyl group is selected from -(CH2). 0-h (CA2) 0-i (CH2) 0-q At least one of X'; X' is selected from F, Cl or Br, and h+i+q≤20.

17. The preparation method according to claim 16, characterized in that, The haloalkyl group is selected from -(CH2). 1~17 CX'3, -(CH2)2(CX'2)3CX'3, -(CH2) 1~17 CH2X'; The nitrogen-containing hydrocarbon group is selected from -(CH2). 1~20 NH2、-(CH2) 0-h NH(CH2) 0-i CH3, -(CH2) 0-h NH(CH2) 0-i NH2、-(CH2) 0-h CONH(CH2) 0-i CH3, -(CH2) 0-h NHCO(CH2) 0-i CH3, -(CH2) 0-19 CONH2、-(CH2) 0-19 At least one of CN, h+i≤20; The oxygen-containing hydrocarbon group is selected from (CH2). 1~9 O(CH2CH2O) 1~5 CH3, -(CH2) 1~10 O(CH2CH2O) 1~5 H、-(CH2) 1~10 (OCH2CH2) 1~5 OH, -(CH2) 1~20 OH, -(CH2) 1~17 At least one of OCOC=CH2; The sulfur-containing hydrocarbon group is selected from -(CH2). 0-h SO2(CH2) 0-i H、-(CH2) 1~20 SH must be at least one, and h+i≤20.

18. The preparation method according to claim 17, characterized in that, The haloalkyl group is selected from -(CH2). 1~17 CF3, -(CH2)2(CF2)3CF3, -(CH2) 1~17 At least one of CH2Cl; The nitrogen-containing hydrocarbon group is selected from -(CH2). 2~10 NH2, -(CH2)3NHCH2CH2NH2, -(CH2)3CONH(CH2)2CH3, -(CH2)3NHCOCH2CH3, -(CH2) 2-6 CN; The oxygen-containing hydrocarbon group is selected from (CH2). 1~3 O(CH2CH2O) 1~2 CH3, -(CH2) 1~2 O(CH2CH2O) 1~3 H、-(CH2) 1~4 (OCH2CH2) 1~4 OH, -(CH2) 1~10 OH, -(CH2) 1~10 At least one of OCOC=CH2; the sulfur-containing hydrocarbon group is selected from -(CH2). 1- 4SO2(CH2) 1-6 H、-(CH2) 1~10 SH.

19. The preparation method according to claim 1, characterized in that, When Y consists of two elements, the molar ratio of the two elements is 1:1 to 1:

6.

20. The preparation method according to claim 1, characterized in that, The crosslinking agent is selected from C containing heteroatoms Y. 4-20 At least one of the chain-like terminal diene derivatives.

21. The preparation method according to claim 20, characterized in that, The C containing heteroatom Y 4-20 The chain-like terminal diene derivative is selected from at least one of halodienes, oxygen-containing diene derivatives, nitrogen-containing diene derivatives, and sulfur-containing diene derivatives; The oxygen-containing functional group of the oxygen-containing diene derivative is selected from at least one of carboxyl, hydroxyl, ester, ether, and carbonyl groups; The nitrogen-containing functional group of the nitrogen-containing diene derivative is selected from at least one of amino, amide, and cyano groups; The sulfur-containing functional group of the sulfur-containing diene derivative is selected from at least one of thioesters and thioethers. The halodiene is selected from at least one of 3,3,4,4-tetrafluoro-1,5-hexadiene and 1,6-divinylperfluorohexane.

22. The preparation method according to claim 21, characterized in that, The oxygen-containing diene derivative is selected from at least one of diallyl carbonate, 1,6-heptadien-4-ol, 1,5-hexadien-3-ol, diallyl maleate, allyl ether, diethylene glycol divinyl ether, and neopentyl glycol diacrylate. The nitrogen-containing diene derivative is selected from at least one of diallylamine, N-methyldiallylamine, and N,N'-methylenebisacrylamide; The sulfur-containing diene derivative is selected from at least one of diallyl trisulfide and allyl disulfide.

23. The preparation method according to claim 20, characterized in that, When the C containing heteroatom Y 4-20 When the Y in the chain-like terminal diene derivative is two or more of O, N, S, and halogen, the C containing the heteroatom Y... 4-20 The chain-terminated diene derivative is selected from at least one of allyl oxychloride, 4-aminomethyl-hept-1,6-dien-4-ol, and dichloropropeneamine.

24. The preparation method according to claim 1, characterized in that, The catalyst is a transition metal catalyst; The catalyst is at least one of platinum group compounds, palladium group compounds, rhodium group compounds, and nickel group compounds.

25. The preparation method according to claim 24, characterized in that, The catalyst is selected from at least one of chloroplatinic acid, karsted, Pd(PPh3)4, PdCl2(Ph3P)2, PdCl2(PhCN)2, [RhCl(CO)2]2, (Ph3P)2(CO)RhCl, (Et3P)2(CO)RhCl, and (Ph3P)2NiCl2.

26. The preparation method according to claim 1, characterized in that, The solvent is selected from C5~C6. 12 At least one of saturated alkanes, benzene, toluene, tetrahydrofuran, gasoline, and dimethyl sulfoxide.

27. The preparation method according to claim 1, characterized in that, The mass concentration of the polysiloxane monomer relative to the solvent is 1-10%, and the concentration of the catalyst is 0.4-5 mg / g solvent.

28. The preparation method according to claim 1, characterized in that, The reaction was cooled and refluxed at near the solvent boiling point for 1–24 h.

29. A hybrid membrane casting solution, characterized in that, The hybrid film casting solution comprises modified silicone rubber prepared according to the preparation method according to any one of claims 1 to 28.

30. A method for preparing a hybrid membrane, characterized in that, The hybrid membrane is prepared by attaching the casting solution of the hybrid membrane prepared according to claim 29 onto a support using at least one of the following methods: dip coating, casting, or coating.

31. The preparation method according to claim 30, characterized in that, The support is selected from at least one of the following: a supporting base film, a glass plate, and a PTFE plate; The supporting substrate is selected from at least one of polysulfone, polyethersulfone, polyacrylonitrile, polyimide, polyvinylidene fluoride, and polyarylethersulfone ketone. The method also includes heat treatment; The heat treatment temperature is 30~90℃, and the treatment time is 2~120h.

32. An application of a hybrid membrane in gas separation, characterized in that, The hybrid membrane is prepared by the preparation method according to any one of claims 30 to 31.

33. The application according to claim 32, characterized in that, The gas separation is selected from one of O2 / N2 and CO2 / N2.

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