A functionalized polybutadiene rubber in alkoxysilyl chains and a process for its preparation

Abstract

The application provides a kind of functionalized polybutadiene rubber in alkoxysilyl chain and its preparation method, belongs to polymer material technical field.The application utilizes rare earth-iron bimetallic catalytic system, using two-step silicon hydrogenation reaction strategy, by first step silicon hydrogenation reaction, introduces aryl silane group modification group to polybutadiene, by second step silicon oxidation reaction, again introduces alkoxysilyl group to aryl silane group modification group, successfully realizes the controlled, even chain functionalization of alkoxysilyl group in polymer molecular chain, both avoids the high cost of noble metal catalyst, and solves the problem of uneven distribution of functional groups in traditional modification method, poor reaction selectivity.The application has relatively mild reaction condition, simple preparation process, low cost and green environmental protection, has excellent compatibility to various silicon hydride reagents, can flexibly prepare functional group diversified alkoxysilyl modified polybutadiene product.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to a polybutadiene rubber with a functionalized alkoxysilane chain and its preparation method. Background Technology

[0002] Polydiolefin rubbers (such as polybutadiene and butadiene-styrene copolymers) possess excellent elasticity, abrasion resistance, and low-temperature resistance, and are widely used in tires, sealing materials, and shock-absorbing products. However, the molecular chains of traditional polydiolefin rubbers contain only carbon-carbon double bonds and aliphatic carbon chains, lacking polar groups, resulting in weak polarity and poor compatibility with fillers. To address these issues, functionalization modification is typically required. Introducing polar groups into the rubber molecular chain improves its interfacial compatibility with fillers, thereby promoting uniform dispersion of fillers in the polymer matrix and enhancing the overall mechanical properties of the resulting composite material. Among these, alkoxysilane groups, with their good surface compatibility and strong bonding with inorganic fillers, have become the preferred functional groups for polydiolefin rubber modification.

[0003] The preparation of existing alkoxysilane-functionalized rubber can be achieved by direct copolymerization of diene monomers with polar monomers containing alkoxysilane groups or by hydrosilylation of polydiene rubber molecular chains with siloxane reagents. However, in the first method, the alkoxysilane group poisons the catalyst, resulting in poor catalyst activity and a limited number of functional groups, making it difficult to achieve uniform distribution in the chain, thus limiting the interaction between the rubber and other materials. As Cui Dongmei et al. (Acta Polymerica Sinica, 2020, 51(1): 12-29) pointed out, polar monomers easily poison rare earth catalytic systems, resulting in low copolymerization activity, low content of functional groups and uneven distribution, making it difficult to achieve efficient functionalization of rubber. In the second method, the hydrosilylation catalysts used are mainly noble metals such as rhodium and platinum, which are expensive and sensitive to reaction conditions. These defects limit its large-scale application. For example, commonly used platinum-based Speier catalysts, Karstedt catalysts and rhodium-based Wilkinson catalysts, etc. Catal. Sci. Technol ., 2020, 10, 7240–7248; Polym. Degrad. and Stab .2025, 242, 111731; J. Catal. ,2019, 371, 27–34; Macromol. Chem. Phys (2008, 209, 675–684);) all suffer from drawbacks such as the high price of precious metals and the demanding requirements of reaction conditions. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a polybutadiene rubber with functionalized alkoxysilane chains and a method for preparing the same. This invention utilizes an inexpensive rare earth-iron bimetallic catalytic system to introduce alkoxysilane groups into polydiene rubber through a two-step hydrosilylation reaction, successfully achieving controllable and uniform in-chain functionalization of alkoxysilane groups in the polymer molecular chain. This avoids the high cost of precious metal catalysts and solves the problems of uneven functional group distribution and poor reaction selectivity in traditional modification methods.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a method for preparing polybutadiene rubber functionalized in an alkoxysilane chain, comprising the following steps: (1) Using rare earth complexes as a catalytic system, polybutadiene rubber is subjected to a first-step hydrosilylation reaction with arylsilane reagent to obtain arylsilane-modified polybutadiene rubber; The arylsilane reagent has the structure shown in formula a: HSiAr(R1)(R2) Equation a; In formula a, R1 and R2 are independently hydrogen atoms, deuterium atoms, aryl groups, alkyl groups, or alkoxy groups; Ar is an aromatic group or a substituted aromatic group; (2) Using an iron complex as a catalytic system, arylsilyl-modified polybutadiene rubber is subjected to a second hydrosilylation reaction with aryl aldehydes or aryl ketones to obtain polybutadiene rubber with functionalized alkoxysilyl chains. The aryl aldehyde has the structure shown in formula b, and the aryl ketone has the structure shown in formula c: Formula b; Formula c; In formulas b and c, R' is a hydrogen atom, alkyl, alkoxy, halogen, nitro, haloalkyl or haloalkoxy, and R" is an aryl or alkyl group.

[0006] Preferably, the polybutadiene-based rubber includes one or more of polybutadiene, butadiene / styrene copolymer, and butadiene / isoprene copolymer; the polybutadiene includes one or more of cis-1,4-structure, trans-1,4-structure, and 1,2-structure.

[0007] Preferably, the rare earth complex comprises an organic ligand in which a rare earth metal is coordinated with the rare earth metal; the rare earth metal comprises one or more of yttrium, lanthanum, samarium, scandium, lutetium, neodymium, ytterbium, cerium, and gadolinium. The rare earth complex has a structure shown in any one of formulas Ln1 to Ln9, where Ln represents a rare earth metal. ; The iron complex comprises iron and an organic ligand coordinated with the iron, wherein the iron has a divalent or trivalent valence, and the iron complex has a structure shown in any one of the formulas Fe1 to Fe12. .

[0008] Preferably, the first hydrosilylation reaction is carried out in an organic solvent, and after the first hydrosilylation reaction is completed, the product obtained from the first hydrosilylation reaction is directly used in the next step, the second hydrosilylation reaction. Alternatively, after the first hydrosilylation reaction is completed, the product obtained from the first hydrosilylation reaction is added to an alcohol solution for precipitation and drying to obtain arylsilyl-modified polybutadiene rubber. The arylsilyl-modified polybutadiene rubber is then used as a raw material for the subsequent second hydrosilylation reaction.

[0009] Preferably, in the polybutadiene rubber, the molar ratio of the double bond in the polybutadiene to the arylsilane reagent is 100:(0~50), and the amount of arylsilane reagent is not 0. The molar ratio of the double bond in polybutadiene to the rare earth complex is 100:(0.1~5).

[0010] Preferably, the temperature of the first step hydrosilylation reaction is 0~120℃ and the time is 0.5~5h.

[0011] Preferably, in the arylsilyl-modified polybutadiene rubber, the molar ratio of arylsilyl group to aryl aldehyde or aryl ketone is 1:(0.5~10), and the molar ratio of arylsilyl group to iron catalyst is 100:(0.1~10). The second step of hydrosilylation reaction is carried out at a temperature of 0~50℃ for 0.5~10h.

[0012] Preferably, before the second hydrosilylation reaction, the iron complex is further activated, the activation treatment including the following steps: The iron complex, trimethylsilylmethyllithium, and organic solvent were mixed to carry out an activation reaction; The molar ratio of the iron complex to trimethylsilylmethyllithium is 1:(1~5); The activation reaction is carried out at a temperature of 30-50°C for a time of 0.2-1 h.

[0013] This invention provides a polybutadiene-based rubber with a functionalized alkoxysilane chain prepared by the above-described method.

[0014] Preferably, the functionalization degree of the alkoxysilyl functional groups in the rubber is 0~50%, and not 0; The number-average molecular weight of the rubber is 0.1 × 10⁻⁶. 4 ~50×104 g / mol, with a molecular weight distribution index of 1.50~10.50.

[0015] This invention provides a method for preparing polybutadiene rubber with functionalized alkoxysilane chains, comprising the following steps: (1) using a rare earth complex as a catalytic system, the polybutadiene rubber is subjected to a first-step hydrosilylation reaction with an arylsilane reagent to obtain arylsilane-modified polybutadiene rubber; (2) using an iron complex as a catalytic system, the arylsilane-modified polybutadiene rubber is subjected to a second-step hydrosilylation reaction with an aryl aldehyde or aryl ketone to obtain polybutadiene rubber with functionalized alkoxysilane chains. This invention utilizes a rare earth-iron bimetallic catalytic system and adopts a two-step hydrosilylation reaction strategy. Through the first-step hydrosilylation reaction, arylsilane-modified groups are introduced into polybutadiene. Through the second-step siloxylation reaction, alkoxy groups are introduced into the arylsilane-modified groups. This successfully achieves controllable and uniform functionalization of siloxane groups in the polymer molecular chain, and the degree of functionalization can be adjusted within the range of 0-50%, with controllable product molecular weight. This invention can effectively control the functionalization degree by regulating the two-step hydrosilylation reaction, thereby achieving effective control over the content of functional groups. At the same time, the metal catalyst used is a combination of rare earth metals and iron catalysts, which is inexpensive. Therefore, it avoids the high cost of precious metal catalysts and solves the problems of uneven distribution of functional groups and poor reaction selectivity in traditional modification methods.

[0016] This invention can not only selectively catalyze the hydrosilylation reaction of vinyl carbon-carbon double bonds on polybutadiene molecular chains, but also simultaneously promote the subsequent siloxane modification process, ultimately achieving uniform distribution and controllable introduction of functional groups in the molecular chain, resulting in a chain-functionalized rubber product with excellent comprehensive performance.

[0017] The preparation method provided by this invention is mild, simple, economical, efficient, green and sustainable, and has excellent compatibility with various hydrosilylation reagents. It can flexibly prepare polybutadiene products with diverse functional groups of alkoxysilane-based modification, which has important theoretical and practical significance for enriching the range of silicon-based modified polymer materials and improving their industrial application value. Attached Figure Description

[0018] Figure 1 The 1H NMR spectrum of functionalized polybutadiene in Example 4; Figure 2 The carbon NMR spectrum of functionalized polybutadiene in Example 14; Figure 3 The 1H NMR spectra of functionalized polybutadiene from Examples 1, 11-14, and 18 are shown. Figure 4 The DSC spectra of functionalized polybutadiene are shown in Examples 11-14 and Example 16. Figure 5The 1H NMR spectra of functionalized polybutadiene in Examples 12, 45-49 are shown. Figure 6 The 1H NMR spectra of functionalized polybutadiene from Examples 12, 50-52 are shown. Figure 7 The 1H NMR spectra of functionalized polybutadiene in Examples 76-77 are shown. Detailed Implementation

[0019] This invention provides a method for preparing polybutadiene rubber functionalized in an alkoxysilane chain, comprising the following steps: (1) Using rare earth complexes as a catalytic system, polybutadiene rubber is subjected to a first-step hydrosilylation reaction with arylsilane reagent to obtain arylsilane-modified polybutadiene rubber; The arylsilane reagent has the structure shown in formula a: HSiAr(R1)(R2) Equation a; In formula a, R1 and R2 are independently hydrogen atoms, deuterium atoms, aryl groups, alkyl groups, or alkoxy groups; (2) Using an iron complex as a catalytic system, arylsilyl-modified polybutadiene rubber is subjected to a second hydrosilylation reaction with aryl aldehydes or aryl ketones to obtain polybutadiene rubber with functionalized alkoxysilyl chains. The aryl aldehyde has the structure shown in formula b, and the aryl ketone has the structure shown in formula c: Formula b; Formula c; In formulas b and c, R' is a hydrogen atom, alkyl, alkoxy, halogen, nitro, haloalkyl or haloalkoxy, and the substitution site can be ortho, meta or para of carbonyl; R" is an aryl or alkyl.

[0020] Unless otherwise specified, all raw materials used in this invention are commercially available.

[0021] This invention uses rare earth complexes as a catalytic system to perform a first-step hydrosilylation reaction between polybutadiene rubber and an arylsilane reagent to obtain arylsilyl-modified polybutadiene rubber. In this invention, the polybutadiene rubber preferably includes one or more of polybutadiene, butadiene / styrene copolymer, and butadiene / isoprene copolymer; the polybutadiene includes one or more of cis-1,4-structure, trans-1,4-structure, and 1,2-structure, i.e., one or more of vinyl polybutadiene, cis-polybutadiene, and trans-polybutadiene. In this invention, the molecular weight of the polybutadiene rubber is preferably 0.1 × 10⁻⁶. 4 ~50×10 4 g / mol, more preferably 1×10 g / mol 4 ~30×10 4g / mol, further preferably 5×10 g / mol 4 ~15×10 4 g / mol; the molecular weight distribution index (PDI) of the polybutadiene rubber is preferably 1.50~10.50, more preferably 2.50~8.50, and even more preferably 4.50~6.50.

[0022] In one specific embodiment of the present invention, the polybutadiene rubber is selected from medium-vinyl polybutadiene PB1 (1,2%=42.8%). M n =1.46×10 4 g / mol, PDI=1.09), high cis polybutadiene PB2 ( cis -1,4-%=98.7%, M n =0.86×10 4 g / mol, PDI=2.86) and high trans-polybutadiene PB3 ( trans -1,4-%=97.8%, M n =0.76×104 g / mol, PDI=1.17) or more of them.

[0023] In this invention, the rare earth complex comprises an organic ligand in which a rare earth metal is coordinated with the rare earth metal; the rare earth metal (abbreviated as Ln) includes one or more of yttrium (Y), lanthanum (La), samarium (Sm), scandium (Sc), lutetium (Lu), neodymium (Nd), ytterbium (Yb), cerium (Ce), and gadolinium (Gd), including but not limited to trimethylsilylmethyl rare earth complex Ln1 (according to literature). Organometallics. , 2020, 39, 3983-3991. Synthesis), mono(imidazoline-2-imine) rare earth complex Ln2 (according to literature) Organometallics. , 2020, 39, 3983-3991. Synthesis), Bis(imidazoline-2-imine) rare earth complex Ln3 (according to literature) Organometallics. Synthesis), N,N-bis(2,6-diisopropylphenyl)amidinyl rare earth complex Ln4 (according to literature) Angew. Chem. Int. Ed. , 2017, 56, 4560. Synthesis, (diisopropylaniline) β -Diketone diimine rare earth complex Ln5 (according to literature) Daiton Trans ., 2018, 47, 14985-14991. Synthesis), bis(pentamethylcyclopentadienyl) rare earth complex Ln6 (according to literature) Organometallics., 2018, 37, 2769-2777. Synthesis of (tetramethyltrimethylsilylcyclopentadienyl) rare earth complex Ln7 (according to literature) Molecules ., 2023, 28, 6792. Synthesis), mono(pentamethylcyclopentadienyl) rare earth complex Ln8 (according to literature) Molecules Synthesis), fluorene-based rare earth complex Ln9 (according to literature). Polymer. (2020, 187, 122105. Synthesis) one or more of the rare earth complexes, wherein the structure of the rare earth complex is preferably as shown in formulas Ln1 to Ln9: As a specific embodiment of the present invention, the rare earth complex is selected from one of the following formulas.

[0024] .

[0025] In this invention, the arylsilane reagent has the structure shown in formula a: HSiAr(R1)(R2) Equation a; In formula a, R1 and R2 are independently hydrogen atoms, deuterium atoms, aryl groups, alkyl groups, or alkoxy groups; the alkyl group is preferably C1-C6. 12 The alkyl group can be methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n-decyl; the aryl group is preferably phenyl, tolyl, methoxyphenyl, 1-naphthyl, or 2-naphthyl; the alkoxy group is preferably C1-C. 12The alkoxy group can specifically be methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, hexoxy, octoxy, decoxy, phenoxy, or benzyloxy; Ar is an aromatic group or a substituted aromatic group, preferably phenyl or naphthyl, and the substituent is preferably halogen or C1-C6 alkyl. Preferably, one of R1 and R2 is a hydrogen atom. As a specific embodiment of the present invention, the arylsilane reagent is preferably one or more of phenylsilane, 4-methoxy-phenylsilane, 4-methyl-phenylsilane, 3-methyl-phenylsilane, 2-methyl-phenylsilane, 4-chloro-phenylsilane, naphthylsilane, methylphenylsilane, diphenylsilane, triphenylsilane, ethylphenylsilane, and hexylphenylsilane. In the present invention, the purity of the arylsilane reagent is preferably ≥97%.

[0026] In this invention, the first step of hydrosilylation reaction is preferably carried out in an organic solvent, preferably one or more of toluene, n-hexane, cyclohexane and xylene, and the concentration of the polybutadiene rubber in the organic solvent is preferably 0.01~1 g / mL, more preferably 0.1~0.5 g / mL.

[0027] In this invention, the preferred process for the first step of hydrosilylation reaction is as follows: Polybutadiene rubber and organic solvent were stirred and mixed under an anhydrous and oxygen-free inert gas atmosphere to obtain a polybutadiene solution; Arylsilane reagent and rare earth complex are added to the polybutadiene solution to carry out the first step of hydrosilylation reaction, so as to obtain arylsilane-modified polybutadiene rubber.

[0028] In this invention, the anhydrous and oxygen-free inert atmosphere is preferably nitrogen and / or argon, and the stirring and mixing temperature is preferably room temperature. The molar ratio of the double bond in the polybutadiene to the arylsilane reagent is preferably 100:(0~50), and the amount of arylsilane reagent is not 0, more preferably 100:(0.5~35), further preferably 100:(5~30), and even more preferably 100:(10~20); the molar ratio of the double bond in the polybutadiene to the rare earth complex is preferably 100:(0.1~5), more preferably 100:(0.5~4), and even more preferably 100:(1~3).

[0029] In this invention, the temperature of the first step hydrosilylation reaction is preferably 0~120℃, more preferably 30~100℃, even more preferably 50~80℃, and the time is preferably 0.5~10h, more preferably 1~8h, and even more preferably 2~5h.

[0030] In this invention, the preferred structural formula of the arylsilyl-modified polybutadiene rubber is shown in Formula I: Formula I; In Formula I, x′:y′:z′=(0~100):(0~100):(0~50), and the values ​​of x′, y′, and z′ are not 0, x′+y′+z′=100; where x′ can be 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95, y′ can be 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 95, and z′ can be 5, 10, 20, 30, 40, or 45; R1 and R2 are independently hydrogen atoms, deuterium atoms, aryl, alkyl, or alkoxy groups, Ar is an aromatic group or a substituted aromatic group, wherein the aromatic group is preferably phenyl or naphthyl, and the substituent is preferably halogen or C1-C6 alkyl.

[0031] In this invention, the number-average molecular weight of the arylsilyl-modified polybutadiene rubber is... M n The preferred value is 1.50×10 4 ~25.5×10 4 The molecular weight distribution index (PDI) is preferably 1.20~5.80, and the degree of hydrosilylation is 0~30.5%, more preferably 0.5~20.5%, wherein the degree of hydrosilylation is calculated as the molar percentage of the total number of repeating units containing silicon groups to the total number of repeating units in the polymer.

[0032] In this invention, after the first hydrosilylation reaction is completed, the product obtained from the first hydrosilylation reaction is preferably used directly in the next hydrosilylation reaction, that is, a two-step hydrosilylation reaction is carried out in situ.

[0033] Alternatively, after the first hydrosilylation reaction is completed, the product obtained from the first hydrosilylation reaction is added to an alcohol solution for precipitation and drying to obtain arylsilyl-modified polybutadiene rubber. The arylsilyl-modified polybutadiene rubber is then used as a raw material for the subsequent second hydrosilylation reaction.

[0034] In this invention, the alcohol solvent is preferably ethanol. This invention does not have any special requirements for the drying method; any drying method well known to those skilled in the art can be used.

[0035] Using an iron complex as a catalytic system, arylsilyl-modified polybutadiene rubber is subjected to a second-step hydrosilylation reaction with aryl aldehydes or aryl ketones to obtain polybutadiene rubber with functionalized alkoxysilyl chains. The aryl aldehyde has the structure shown in formula b, and the aryl ketone has the structure shown in formula c: Formula b; Formula c.

[0036] In this invention, in formulas b and c, R' is a hydrogen atom, alkyl, alkoxy, halogen, nitro, haloalkyl, or haloalkoxy, and can be ortho, meta, or para of a carbonyl group; R" is an aryl or alkyl group; in this invention, the alkyl group is preferably C1-C1. 12 Alkyl groups, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n-decyl; the alkoxy group is preferably C1-C. 12 The alkoxy group can specifically be methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, hexoxy, octoxy, or decoxy; the halogen is preferably F, Cl, Br, or I. In this invention, the aryl group is preferably a substituted or unsubstituted phenyl or a substituted or unsubstituted naphthyl group, and the substituent is preferably a halogen or a C1-C6 alkyl group. In this invention, the purity of the aryl aldehyde or aryl ketone is preferably ≥97%.

[0037] As a specific embodiment of the present invention, the aryl aldehyde is preferably one or more of benzaldehyde, 3-methoxy-benzaldehyde, 4-methoxy-benzaldehyde, 4-methyl-benzaldehyde and 4-dimethylaminobenzaldehyde; the benzophenone is preferably one or more of 3-methoxy-acetophenone, 4-methoxy-acetophenone and 4-methyl-benzophenone.

[0038] In this invention, the iron complex preferably comprises iron and an organic ligand coordinated with the iron, wherein the iron has a divalent (II) or trivalent (III) valence, and the organic ligand preferably comprises... α -Imine functional groups, including but not limited to acenaphthoquinone groups α -Diimine iron complex Fe1 (II) ~Fe8 (II) and Fe1 (III) ~Fe8 (II) (According to the literature) Chin. J. Polym. Sci. , 2025, 43, 640-654.; Dalton Trans. (2023, 5217104-17108. Synthesis), glyoxal iron complex Fe9 (II) and Fe9 (III) (According to the literature) Macromolecules. (2007, 40, 7441-7452. Synthesis), Butanedione-based iron complex Fe10 (II) and Fe10 (III) (According to the literature) Polyhedron. (2021, 203, 115168. Synthesis), pyridine-2-imine iron complex Fe11 (II) and Fe11 (III) (According to the literature) Org . Chem. Front. (2014, 1, 1101-1106. Synthesis), Quinoline-2-iminoferric complex Fe12 (II) and Fe12 (III) (According to the literature) J. Organomet. Chem. 2011, 696, 3029-3035. Synthesis), its structural formula is shown in any one of the formulas Fe1~Fe12: .

[0039] In this invention, prior to the second hydrosilylation reaction, it is preferable to further include an activation treatment of the iron complex, wherein the activation treatment preferably includes the following steps: The iron complex, trimethylsilylmethyllithium, and organic solvent were mixed to carry out an activation reaction.

[0040] In this invention, the molar ratio of the iron complex to trimethylsilylmethyllithium is preferably 1:(1~5), more preferably 1:(2~4); the activation reaction is preferably carried out under an anhydrous and oxygen-free inert atmosphere, preferably nitrogen or argon; the activation reaction temperature is preferably 30~50℃, more preferably 30~40℃, and the time is preferably 0.2~1h, more preferably 0.5~0.8h. In this invention, the activator trimethylsilylmethyllithium functions to form an active center containing iron-carbon bonds.

[0041] As a specific embodiment of the present invention, the chemical formula of the iron complex is, for example, Fe1. (II) As shown: .

[0042] In this invention, in the arylsilyl-modified polybutadiene rubber, the molar ratio of the arylsilyl group to the aryl aldehyde or aryl ketone is preferably 1:(0.5~10), more preferably 1:(1~8), and even more preferably 1:(2~5); the molar ratio of the arylsilyl group to the iron catalyst is preferably 100:(0.1~10), more preferably 100:(1~8), and even more preferably 100:(3~5).

[0043] In this invention, the temperature of the first step hydrosilylation reaction is preferably 0~120℃, more preferably 30~100℃, even more preferably 50~80℃, and the time is preferably 0.5~10h, more preferably 1~8h, even more preferably 2~5h.

[0044] In this invention, when the product of the first step hydrosilylation reaction is directly used in the second step hydrosilylation reaction, the temperature of the second step hydrosilylation reaction is preferably 0~50℃, more preferably 30~50℃, and the time is preferably 0.5~10h, more preferably 1~8h, and even more preferably 3~5h.

[0045] In this invention, when arylsilyl-modified polybutadiene rubber is used as a raw material for the subsequent second-step hydrosilylation reaction, it is preferable to first dissolve the arylsilyl-modified polybutadiene rubber in an organic solvent before carrying out the second-step hydrosilylation reaction. In this invention, the organic solvent is preferably one or more of toluene, n-hexane, cyclohexane, and xylene.

[0046] Following the second hydrosilylation reaction, the present invention preferably adds the resulting product from the second hydrosilylation reaction to an alcohol solution for precipitation and drying to obtain a polybutadiene rubber with functionalized alkoxysilane chains. In this invention, the alcohol solvent is preferably ethanol. The present invention does not have special requirements for the drying method; any drying method well-known to those skilled in the art can be used.

[0047] This invention provides a polybutadiene rubber with an alkoxysilane-based functionalized chain prepared by the above-described method. In this invention, the polybutadiene rubber with the alkoxysilane-based functionalized chain preferably has the structure shown in Formula II: Formula II; In Formula I, m′:n′:p′:z′=(0~100):(0~100):(0~30):(0~30), and the values ​​of m′ and n′ are not 0, and m′+n′+p′+z′=100; wherein, the value of m′ can be 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 95, the value of n′ can be 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 or 95, the value of p′ can be 1, 5, 10, 15, 20, 25 or 30, and the value of z′ can be 1, 5, 10, 15, 20, 25 or 30. In this invention, Ar is an aromatic group or a substituted aromatic group, wherein the aromatic group is preferably phenyl or naphthyl, and the substituent is preferably halogen or C1-C6 alkyl. R' is a hydrogen atom, alkyl group, alkoxy group, halogen, nitro group, haloalkyl group, or haloalkoxy group, and can be ortho, meta, or para position of a carbonyl group; R" is an aryl group or alkyl group; in this invention, the alkyl group is preferably C1-C1. 12 Alkyl groups, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n-decyl; the alkoxy group is preferably C1-C. 12The alkoxy group can specifically be methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, hexoxy, octoxy, or decoxy; the halogen is preferably F, Cl, Br, or I. In this invention, the aryl group is preferably a substituted or unsubstituted phenyl or a substituted or unsubstituted naphthyl group, and the substituent is preferably a halogen or a C1-C6 alkyl group.

[0048] The functionalization degree of the alkoxysilyl functional groups in the rubber is 0-50%, and not 0; the hydrosilylation efficiency in the second step is 0-100%, more preferably 20-100%, and even more preferably 50-100%; the number-average molecular weight of the rubber is 0.1×10⁻⁶. 4 ~50×10 4 The molecular weight distribution index is 1.50~10.50 g / mol. In this invention, the degree of hydrosilylation is calculated as the molar percentage of the total number of repeating units containing alkoxysilane groups to the total number of repeating units in the polymer.

[0049] The following detailed description, in conjunction with embodiments, illustrates the functionalized polybutadiene rubber in the alkoxysilane chain provided by the present invention and its preparation method, but these descriptions should not be construed as limiting the scope of protection of the present invention.

[0050] Example 1 Under nitrogen protection, 0.1 g of polybutadiene substrate PB1 was dissolved in 2 mL of dry toluene solution to obtain reaction solution A. A phenylsilane and Y2 complex were added to solution A, with the ratio of C=C double bonds in the polybutadiene substrate to the phenylsilane and Y2 complex being 100:20:1, to obtain reaction solution B. Solution B was reacted at 50 °C for 2 hours, then poured into an ethanol solution. After precipitation and drying, polybutadiene rubber with functionalized phenylsilane chains was obtained. This example completes the first step of the hydrosilylation reaction.

[0051] Example 2 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst used was a Y1 complex. This example completes the first step of the hydrosilylation reaction.

[0052] Example 3 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst used was a Y3 complex. This example completes the first step of the hydrosilylation reaction.

[0053] Example 4 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the ratio of C=C double bonds to phenylsilane and Y2 in the polybutadiene substrate was 100:20:3. This example completes the first step of the hydrosilylation reaction.

[0054] Example 5 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst used was a Y1 complex, and the ratio of the C=C double bond in the polybutadiene substrate to phenylsilane and Y1 was 100:20:3. This example completes the first step of the hydrosilylation reaction.

[0055] Example 6 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst used was a Y3 complex, and the ratio of the C=C double bond in the polybutadiene substrate to phenylsilane and Y3 was 100:20:3. This example completes the first step of the hydrosilylation reaction.

[0056] Example 7 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the substrate chosen was high-cis polybutadiene PB2, and the ratio of C=C double bonds to phenylsilane and Y2 in the polybutadiene substrate was 100:20:3. This example completes the first step of the hydrosilylation reaction.

[0057] Example 8 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the substrate chosen was high-trans polybutadiene PB3, and the ratio of the C=C double bond to phenylsilane and Y2 in the polybutadiene substrate was 100:20:3. This example completes the first step of the hydrosilylation reaction.

[0058] Example 9 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the ratio of the C=C double bond in the polybutadiene substrate to the phenylsilane and Y2 complex was 100:20:2. This example completes the first step of the hydrosilylation reaction.

[0059] Example 10 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the ratio of the C=C double bond to the phenylsilane and Y2 complex in the polybutadiene substrate was 100:20:0.5. This example completes the first step of the hydrosilylation reaction.

[0060] Example 11 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the ratio of the C=C double bond to phenylsilane and Y2 in the polybutadiene substrate was 100:5:1. This example completes the first step of the hydrosilylation reaction.

[0061] Example 12 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the ratio of C=C double bonds to phenylsilane and Y2 in the polybutadiene substrate was 100:10:1. This example completes the first step of the hydrosilylation reaction.

[0062] Example 13 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the ratio of C=C double bonds to phenylsilane and Y2 in the polybutadiene substrate was 100:15:1. This example completes the first step of the hydrosilylation reaction.

[0063] Example 14 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the ratio of C=C double bonds to phenylsilane and Y2 in the polybutadiene substrate was 100:35:1. This example completes the first step of the hydrosilylation reaction.

[0064] Example 15 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the reaction temperature was 30 °C. This example completes the first step of the hydrosilylation reaction.

[0065] Example 16 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the reaction temperature was 80 °C. This example completes the first step of the hydrosilylation reaction.

[0066] Example 17 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the reaction temperature was 110 °C. This example completes the first step of the hydrosilylation reaction.

[0067] Example 18 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the hydrosilylation reagent was deuterated benzylsilane, and the ratio of the C=C double bond in the polybutadiene substrate to the deuterated benzylsilane and the Y2 complex was 100:10:1. This example completes the first step of the hydrosilylation reaction.

[0068] Example 19 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the hydrosilylation reagent used was 4-methylphenylsilane, and the ratio of the C=C double bond in the polybutadiene substrate to the silane and Y2 complex was 100:10:1. This example completes the first step of the hydrosilylation reaction.

[0069] Example 20 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the hydrosilylation reagent used was 4-chlorobenzenesilane, and the ratio of the C=C double bond in the polybutadiene substrate to the silane and Y2 complex was 100:10:1. This example completes the first step of the hydrosilylation reaction.

[0070] Example 21 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the hydrosilylation reagent used was 4-methoxyphenylsilane, and the ratio of the C=C double bond in the polybutadiene substrate to the silane and Y2 complex was 100:10:1. This example completes the first step of the hydrosilylation reaction.

[0071] Example 22 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the hydrosilylation reagent used was naphthylsilane, and the ratio of the C=C double bond in the polybutadiene substrate to the silane and Y2 complex was 100:10:1. This example completes the first step of the hydrosilylation reaction.

[0072] Example 23 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the hydrosilylation reagent used was methylphenylsilane. This example completes the first step of the hydrosilylation reaction.

[0073] Example 24 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the hydrosilylation reagent used was diphenylsilane. This example completes the first step of the hydrosilylation reaction.

[0074] Example 25 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln1, where Ln is Sc, denoted as the Sc1 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Sc1 complex is shown below: Example 26 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln2, where Ln is Sc, denoted as the Sc2 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Sc2 complex is shown below: Example 27 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln3, where Ln is Sc, denoted as the Sc3 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Sc3 complex is shown below: Example 28 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln4, where Ln is Nd, denoted as the Nd4 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Nd4 complex is shown below: Example 29 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln4, where Ln is Y, denoted as the Y4 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Y4 complex is shown below: Example 30 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln4, where Ln is Sc, denoted as the Sc4 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Sc4 complex is shown below: Example 31 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln5, where Ln is La, denoted as the La5 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the La5 complex is shown below: Example 32 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln5, where Ln is Sc, denoted as the Sc5 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Sc5 complex is shown below: Example 33 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln5, where Ln is Sm, denoted as the Sm5 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Sm5 complex is shown below: Example 34 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln6, where Ln is Lu, denoted as Lu6 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Lu6 complex is shown below: Example 35 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln6, where Ln is Yb, denoted as the Yb6 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Yb6 complex is shown below: Example 36 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln6, where Ln is Ce, denoted as Ce6 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Ce6 complex is shown below: Example 37 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln7, where Ln is Nd, denoted as the Nd7 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Nd7 complex is shown below: Example 38 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln7, where Ln is Sc, denoted as the Sc7 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Sc7 complex is shown below: Example 39 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln7, where Ln is Yb, denoted as the Yb7 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Yb7 complex is shown below: Example 40 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln8, where Ln is Ce, denoted as Ce8 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Ce8 complex is shown below: Example 41 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln8, where Ln is Sc, denoted as the Sc8 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Sc8 complex is shown below: Example 42 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln9, where Ln is Sm, denoted as the Sm9 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Sm9 complex is shown below: Example 43 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln9, where Ln is Ce, denoted as Ce9 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Ce9 complex is shown below: Example 44 As described in Example 1, all other conditions and preparation methods were exactly the same, except that the catalyst selected had the structure shown in Formula Ln9, where Ln is Gd, denoted as the Gd9 complex. This example completes the first step of the hydrosilylation reaction. The chemical formula of the Gd9 complex is shown below: The number-average molecular weight of the functionalized polybutadiene rubbers obtained in Examples 1-44 ( M n Molecular weight distribution index (PDI), arylsilane functionalization efficiency χ As shown in Table 1, the 1H NMR spectrum of the functionalized polybutadiene in Example 4 is as follows: Figure 1 As shown, the carbon NMR spectrum of the functionalized polybutadiene in Example 14 is as follows: Figure 2 As shown, the 1H NMR spectra of functionalized polybutadiene in Examples 1, 11-14, and 18 are as follows: Figure 3 As shown, the DSC spectra of functionalized polybutadiene in Examples 11-14 and Example 16 are as follows. Figure 4 As shown.

[0075] Table 1 Properties of the functionalized polybutadiene rubber in the chains of Examples 1-44

[0076] Depend on Figure 1 , 2 It can be seen that phenylsilane was successfully introduced into the polybutadiene backbone, resulting in in-chain functionalized polybutadiene rubber. Table 1 shows that the hydrosilylation efficiency of the vinyl-based polybutadiene rubber substrate is significantly higher than the other two types, indicating that the hydrosilylation reaction tends to occur at the side vinyl positions of the polymer chain. Furthermore, the Y2 catalyst with a single ligand structure exhibits the highest catalytic efficiency.

[0077] Example 45 Under nitrogen protection, 0.1 g of the phenylsilyl polybutadiene substrate obtained in Example 12 was dissolved in 2 mL of dry toluene solution to obtain reaction solution A; Fe1 (II) The complex and trimethylsilylmethyllithium were dissolved in 0.5 mL of toluene solution at a molar ratio of 1:2 and reacted at 30 °C for 0.5 hours to obtain reaction solution B. Benzaldehyde and reaction solution B were then added sequentially to reaction solution A to obtain reaction solution C. In this reaction, the molar ratio of silicon groups ([-Si-H-]) to benzaldehyde in the phenylsilyl polybutadiene substrate was 1:1, and [-Si-H-] and Fe1... (II) The molar ratio of the complex was 100:5. After reacting the above solution C at 30 °C for 5 hours, it was poured into an ethanol solution, and after precipitation and drying, polybutadiene rubber with functionalized alkoxysilane chains was obtained. This example completes the second step of the hydrosilylation reaction.

[0078] Example 46 As described in Example 45, all other conditions and preparation methods were exactly the same, except that the aryl aldehyde chosen was 3-methoxy-benzaldehyde. This example completes the second step of the hydrosilylation reaction.

[0079] Example 47 As described in Example 45, all other conditions and preparation methods were exactly the same, except that the aryl aldehyde chosen was 4-methoxy-benzaldehyde. This example completes the second step of the hydrosilylation reaction.

[0080] Example 48 As described in Example 45, all other conditions and preparation methods were exactly the same, except that the aryl aldehyde chosen was 4-methyl-benzaldehyde. This example completes the second step of the hydrosilylation reaction.

[0081] Example 49 As described in Example 45, all other conditions and preparation methods were exactly the same, except that the aryl aldehyde chosen was 4-dimethylaminobenzaldehyde. This example completes the second step of the hydrosilylation reaction.

[0082] Example 50 As described in Example 45, all other conditions and preparation methods were exactly the same, except that the aryl aldehyde chosen was 3-methoxy-acetophenone. This example completes the second step of the hydrosilylation reaction.

[0083] Example 51 As described in Example 45, all other conditions and preparation methods were exactly the same, except that the aryl aldehyde chosen was 4-methoxy-acetophenone. This example completes the second step of the hydrosilylation reaction.

[0084] Example 52 As described in Example 45, all other conditions and preparation methods were exactly the same, except that the aryl aldehyde chosen was 4-methyl-benzophenone. This example completes the second step of the hydrosilylation reaction.

[0085] Example 53 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe2+. (II) Complex. This embodiment completes the second step of the hydrosilylation reaction.

[0086] Example 54 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe3+. (II) Complex. This embodiment completes the second step of the hydrosilylation reaction.

[0087] Example 55 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe4+. (II) Complex. This embodiment completes the second step of the hydrosilylation reaction.

[0088] Example 56 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe5+. (II) Complex. This embodiment completes the second step of the hydrosilylation reaction.

[0089] Example 57 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe6+. (II) Complex. This embodiment completes the second step of the hydrosilylation reaction.

[0090] Example 58 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe7. (II) Complex. This embodiment completes the second step of the hydrosilylation reaction.

[0091] Example 59 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe8. (II) Complex. This embodiment completes the second step of the hydrosilylation reaction.

[0092] Example 60 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe9. (II) Complex. This embodiment completes the second step of the hydrosilylation reaction.

[0093] Example 61 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe10. (II) Complex. This embodiment completes the second step of the hydrosilylation reaction.

[0094] Example 62 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that Fe11 iron catalyst was selected. (II) Complex. This embodiment completes the second step of the hydrosilylation reaction.

[0095] Example 63 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that Fe12 iron catalyst was selected. (II) Complex. This embodiment completes the second step of the hydrosilylation reaction.

[0096] Example 64 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe1. (III) Complex, Fe1 (III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0097] Example 65 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe2+. (III) Complex, Fe2 (III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0098] Example 66 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe3+. (III) Complex, Fe3 (III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0099] Example 67 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe4+. (III) Complex, Fe4 (III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0100] Example 68 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe5+. (III) Complex, Fe5 (III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0101] Example 69 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe6+. (III) Complex, Fe6 (III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0102] Example 70 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe7. (III) Complex, Fe7 (III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0103] Example 71 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe8. (III) Complex, Fe8 (III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0104] Example 72 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe9. (III) Complex, Fe9(III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0105] Example 73 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that the iron catalyst selected was Fe10. (III) Complex, Fe10 (III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0106] Example 74 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that Fe11 iron catalyst was selected. (III) Complex, Fe11 (III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0107] Example 75 As described in Example 45, all other conditions and preparation methods were exactly the same, the only difference being that Fe12 iron catalyst was selected. (III) Complex, Fe12 (III) The complex and trimethylsilylmethyllithium were reacted in a molar ratio of 1:3. This example completes the second step of the hydrosilylation reaction.

[0108] The number-average molecular weight of the functionalized polybutadiene rubbers obtained in Examples 45-75 ( M n Molecular weight distribution index (PDI), siloxane functionalization efficiency f As shown in Table 2, the 1H NMR spectra of functionalized polybutadiene in Examples 12 and 45-49 are as follows: Figure 5 As shown, the 1H NMR spectra of functionalized polybutadiene in Examples 12, 50-52 are as follows: Figure 6 As shown.

[0109] Table 2 Properties of the chain-functionalized polybutadiene rubbers obtained in Examples 45-75

[0110] As shown in Table 2, in the second hydrosilylation reaction, this invention successfully prepared polybutadiene rubber with functionalized alkoxysilane chains. Among them, the aryl aldehyde substrate showed excellent reaction efficiency, approaching or even reaching 100%, and had good molecular weight distribution control, while the modification efficiency of the aryl ketone substrate was lower than that of the aryl aldehyde substrate.

[0111] Example 76 Under nitrogen protection, 0.1 g of polybutadiene substrate PB1 was dissolved in 2 mL of dry toluene solution to obtain reaction solution A. Phenylsilane and a Y2 complex were added to solution A, with the ratio of C=C double bonds in the polybutadiene substrate to the phenylsilane and Y2 complex being 100:3:0.5, to obtain reaction solution B. Reaction solution B was then reacted at 50 °C for 2 hours. Fe1 (II) The complex and trimethylsilylmethyllithium were dissolved in 0.5 mL of toluene solution at a molar ratio of 1:2 and reacted at 30 °C for 0.5 h to obtain reaction solution C. After 2 hours of reaction, 4-methoxybenzaldehyde and reaction solution C were added in situ to solution B to obtain reaction solution D. In this solution, the molar ratio of [-Si-H-] to benzaldehyde was 1:1, and [-Si-H-] and Fe1... (II) The molar ratio of the complex was 100:5. After reacting the above solution D at 30 °C for 5 hours, it was poured into an ethanol solution, and after precipitation and drying, polybutadiene rubber functionalized in the siloxane chain was obtained. In this example, the first and second hydrosilylation reactions were completed simultaneously.

[0112] Example 77 As described in Example 76, all other conditions and preparation methods were exactly the same, except that the ratio of the C=C double bond to the phenylsilane and Y2 complex in the polybutadiene substrate was 100:20:0.5. In this example, the first and second hydrosilylation reactions were completed simultaneously.

[0113] Comparative Example Under nitrogen protection, anionic polymerization was used to obtain a polybutadiene solution. Without quenching the reaction, 2 mL of polybutadiene gel (containing 0.1 g of polybutadiene substrate) was directly taken to obtain reaction solution A. Phenylsilane and Y2 complex were added to solution A. The ratio of C=C double bonds in the polybutadiene substrate to phenylsilane and Y2 complex was 100:20:0.5, resulting in reaction solution B. Solution B was reacted at 50 °C for 2 hours. Fe1 (II) The complex and trimethylsilylmethyllithium were dissolved in 0.5 mL of toluene solution at a molar ratio of 1:2 and reacted at 30 °C for 0.5 h to obtain reaction solution C. After 2 hours of reaction, 4-methoxybenzaldehyde and reaction solution C were added sequentially to solution B to obtain reaction solution D. In this solution, the molar ratio of [-Si-H-] to benzaldehyde was 1:1, and [-Si-H-] and Fe1... (II) The ratio of the complexes was 100:5. After reacting the above solution D at 30 °C for 5 hours, it was poured into an ethanol solution, and after precipitation and drying, polybutadiene rubber with functionalized siloxane chains was obtained. In this example, the first and second hydrosilylation reactions were completed simultaneously.

[0114] Examples 76-77, Number-average molecular weight of functionalized polybutadiene rubber in the chain obtained in the comparative example ( M n Molecular weight distribution index (PDI), siloxane functionalization efficiency f As shown in Table 3, the 1H NMR spectra of the functionalized polybutadiene in Examples 76-77 are as follows: Figure 7 As shown.

[0115] Table 3 Properties of the chain-functionalized polybutadiene rubbers obtained in Examples 76-77 and Comparative Examples

[0116] As can be seen from Table 3, the functionalization efficiency of the two tandem methods used in this invention both reached 100%, and the molecular weight and molecular weight distribution of the products were relatively stable. This indicates that both tandem methods can stably and efficiently achieve the functionalization modification of polybutadiene rubber.

[0117] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a polybutadiene-based rubber with functionalized alkoxysilane chains, characterized in that, Includes the following steps: (1) Using rare earth complexes as a catalytic system, polybutadiene rubber is subjected to a first-step hydrosilylation reaction with arylsilane reagent to obtain arylsilane-modified polybutadiene rubber. The arylsilane reagent has the structure shown in formula a: HSiAr(R1)(R2) Equation a; In formula a, R1 and R2 are independently hydrogen atoms, deuterium atoms, aryl groups, alkyl groups, or alkoxy groups; Ar is an aromatic group or a substituted aromatic group; (2) Using an iron complex as a catalytic system, arylsilyl-modified polybutadiene rubber is subjected to a second hydrosilylation reaction with aryl aldehydes or aryl ketones to obtain polybutadiene rubber with functionalized alkoxysilyl chains. The aryl aldehyde has the structure shown in formula b, and the aryl ketone has the structure shown in formula c: Formula b; Formula c; In formulas b and c, R' is a hydrogen atom, alkyl, alkoxy, halogen, nitro, haloalkyl or haloalkoxy, and R" is an aryl or alkyl group.

2. The preparation method according to claim 1, characterized in that, The polybutadiene-based rubber includes one or more of polybutadiene, butadiene / styrene copolymer, and butadiene / isoprene copolymer; the polybutadiene includes one or more of cis-1,4-structure, trans-1,4-structure, and 1,2-structure.

3. The preparation method according to claim 1 or 2, characterized in that, The rare earth complex comprises an organic ligand in which a rare earth metal is coordinated with the rare earth metal; the rare earth metal comprises one or more of yttrium, lanthanum, samarium, scandium, lutetium, neodymium, ytterbium, cerium, and gadolinium; The rare earth complex has a structure shown in any one of formulas Ln1 to Ln9, where Ln represents a rare earth metal. ； The iron complex comprises iron and an organic ligand coordinated with the iron, wherein the iron has a divalent or trivalent valence, and the iron complex has a structure shown in any one of the formulas Fe1 to Fe12. 。 4. The preparation method according to claim 1, characterized in that, The first step of hydrosilylation reaction is carried out in an organic solvent. After the first step of hydrosilylation reaction is completed, the product obtained from the first step of hydrosilylation reaction is directly used in the next step of the second step of hydrosilylation reaction. Alternatively, after the first hydrosilylation reaction is completed, the product obtained from the first hydrosilylation reaction is added to an alcohol solution for precipitation and drying to obtain arylsilyl-modified polybutadiene rubber. The arylsilyl-modified polybutadiene rubber is then used as a raw material for the subsequent second hydrosilylation reaction.

5. The preparation method according to claim 1, characterized in that, In the polybutadiene rubber, the molar ratio of the double bond in the polybutadiene to the arylsilane reagent is 100:(0~50), and the amount of arylsilane reagent is not 0. The molar ratio of the double bond in polybutadiene to the rare earth complex is 100:(0.1~5).

6. The preparation method according to claim 1 or 5, characterized in that, The temperature of the first step of hydrosilylation reaction is 0~120℃, and the time is 0.5~5h.

7. The preparation method according to claim 1, characterized in that, In the arylsilyl-modified polybutadiene rubber, the molar ratio of arylsilyl group to aryl aldehyde or aryl ketone is 1:(0.5~10), and the molar ratio of arylsilyl group to iron catalyst is 100:(0.1~10). The second step of hydrosilylation reaction is carried out at a temperature of 0~50℃ for 0.5~10h.

8. The preparation method according to claim 1, characterized in that, Before the second step of hydrosilylation, the iron complex is further activated, and the activation process includes the following steps: The iron complex, trimethylsilylmethyllithium, and organic solvent were mixed to carry out an activation reaction; The molar ratio of the iron complex to trimethylsilylmethyllithium is 1:(1~5); The activation reaction is carried out at a temperature of 30-50°C for a time of 0.2-1 h.

9. The polybutadiene-based rubber with functionalized alkoxysilane chains prepared by the preparation method according to any one of claims 1 to 8.

10. The polybutadiene-based rubber with functionalized alkoxysilane chains according to claim 9, characterized in that, The functionalization degree of the alkoxysilyl functional groups in the rubber is 0~50%, and not 0; The number-average molecular weight of the rubber is 0.1 × 10⁻⁶. 4 ~50×10 4 g / mol, with a molecular weight distribution index of 1.50~10.50.

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