CN114656583A - Preparation method of functionalized liquid 1,2-polybutadiene rubber - Google Patents

Preparation method of functionalized liquid 1,2-polybutadiene rubber Download PDF

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CN114656583A
CN114656583A CN202210252547.5A CN202210252547A CN114656583A CN 114656583 A CN114656583 A CN 114656583A CN 202210252547 A CN202210252547 A CN 202210252547A CN 114656583 A CN114656583 A CN 114656583A
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polybutadiene rubber
catalyst
functionalized liquid
butadiene
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华静
刘金慧
耿洁婷
张文静
胡鹏程
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Qingdao University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C2019/09—Metathese

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  • Medicinal Chemistry (AREA)
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Abstract

The invention relates to a preparation method of liquid rubber, in particular to a preparation method of bio-based functionalized liquid 1,2-polybutadiene rubber. The method comprises the following steps: under the catalysis of a coordination catalyst, butadiene is synthesized into 1,2-polybutadiene rubber at a certain polymerization temperature by a solution method; after polymerizing for a period of time, adjusting the polymerization temperature and adding a bio-based polar small molecule additive and an olefin metathesis catalyst to obtain the functionalized liquid 1,2-polybutadiene rubber; the bio-based polar small molecule additive is one of cardanol, anacardic acid, pineapple ester, soybean oil, palm oil, algal oil or rapeseed oil; the molar ratio of the butadiene to the polar small molecular additive is 0.2-1: 1. The 1,2-polybutadiene rubber of the functionalized liquid prepared by the invention has 65-95% of adjustable 1, 2-structure, 0.2-6 ten thousand number average molecular weight and contains ester group/carboxyl/phenolic hydroxyl functional groups.

Description

Preparation method of functionalized liquid 1,2-polybutadiene rubber
Technical Field
The invention relates to a preparation method of liquid rubber, in particular to a preparation method of functionalized liquid 1,2-polybutadiene rubber.
Background
Liquid rubbers, known as "future rubbers", have good flow properties and are easy to process. At present, the industrial production method of polybutadiene liquid rubber is mainly free radical polymerization and anion polymerization, and the 1, 4-structure accounts for 75-95%, and the 1, 2-structure accounts for 5-25%. The liquid 1,2-polybutadiene (liquid 1,2-PB) is superior to the high 1, 4-polybutadiene in color wettability, flex resistance, aging resistance, etc., and has high hardness, no streaks when coated, and excellent chemical corrosion resistance. After the liquid 1,2-PB is functionalized, groups such as carboxyl, amino, epoxy and the like can be introduced, and the liquid has wide application prospects in the fields of adhesives, electrophoretic paints, water-based coatings, casting elastomers, rubber compatilizers and the like. The functional liquid 1,2-PB can be prepared by an anion method, but the preparation of the liquid 1,2-PB with the 1, 2-structure content higher than 90% usually needs ultralow temperature polymerization, the temperature is lower than-80 ℃, the industrialization difficulty is high, the cost is high, and the development of the liquid 1,2-PB is limited. At present, a small amount of functionalized liquid 1,2-PB is sold in Japan Cao, the content of the 1, 2-structure is about 80 percent, the price is high, the product brand is few, and the requirement of domestic and foreign markets for the functionalized liquid 1,2-PB cannot be met.
The preparation method comprises the steps of degrading a high molecular weight rubber product into low molecular weight liquid rubber by using an olefin metathesis technology, introducing a functional group by adding a polar small molecule, adding a functional small molecule with a double bond into a solution of styrene butadiene rubber and nitrile butadiene rubber by using China oil and gas resources Co., Ltd, and preparing a series of multifunctional plasticizers such as a reinforcing plasticizer (CN 201610833899.4), an anti-aging plasticizer (CN 201610835755.2), a flame-retardant softener (CN 201610474132.7, CN 201610476260.5) and the like by using a cross olefin metathesis reaction.
MARCINICE et al (catalysis of 1,2-polybutadiene by ruthenium complex catalyzed coupling with vinylisms. Polymer Vol.38No.20, pp.5169-5172,1997) use a ruthenium complex to catalyze the reaction of vinylsilane with syndiotactic 1,2-PB (1, 2-structure content 85%, Mn 1000) to introduce a silyl group into 1,2-PB to produce a silyl group 1,2-PB having Mn 1000. CHAPALA et al (Synthesis of 3, 4-dihydroxyphe)nyl-containing polymeric materials from 1,2-polybutadiene and eugenin via thiol-ene addition, Russ. chem. Bull., int.Ed., Vol.65, No.4, pp.1061-1066,2016) syndiotactic 1,2-polybutadiene from JSR (1, 2-structure content 93%, Mw 195 × 10)3) Metathesis with triethylsilyl-protected eugenol produced phenolic hydroxyl-modified 1,2-PB with Mw ═ 2000. The olefin double decomposition reaction is obtained by re-dissolving the obtained rubber finished product and then reacting under the anhydrous and oxygen-free conditions, and the dried rubber has low solubility, long consumed time and poor environmental protection property when being re-dissolved, and is not beneficial to industrial production. In addition, the current 1,2-PB has limited variety and yield, narrow adjustable range of 1, 2-structure and lower initial molecular weight, which results in small adjustable range of 1, 2-structure and lower molecular weight of the product.
Therefore, the preparation of the functionalized liquid 1,2-PB industrial product with multiple microstructures and adjustable molecular weight in a wide range has certain difficulty.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a functionalized liquid 1,2-polybutadiene rubber which is simple and environment-friendly in process, adjustable in 1, 2-structure by 65-95%, 0.2-6 ten thousand in number average molecular weight and contains ester group/carboxyl group/phenolic hydroxyl functional groups.
On the basis of preparing 1,2-PB by a molybdenum catalyst, 1,2-PB with a microstructure capable of being adjusted in a wide range is synthesized by adjusting a catalytic system and a polymerization process, an olefin metathesis reaction catalyst and a double-bond-containing bio-based polar additive are simultaneously added to continue an olefin metathesis reaction, functional groups are grafted on a 1,2-PB molecular chain while the molecular weight of the 1,2-PB is reduced, and the functionalized liquid 1,2-PB is synthesized by a monomer polymerization-cross metathesis (polymerization-grafting) 'one-pot method', so that the processes of rubber condensation, drying and redissolution in the middle are omitted, the method is simple and environment-friendly, the rubber synthesis technology is closely combined, and the product structure can be adjusted in a certain range.
The invention is realized by the following technical scheme:
the preparation method of the functionalized liquid 1,2-polybutadiene rubber is a polymerization-grafting one-pot method, and specifically comprises the following steps: under the catalysis of a coordination catalyst, butadiene is synthesized into 1,2-polybutadiene rubber at a certain polymerization temperature by a solution method; after polymerizing for a period of time, adjusting the polymerization temperature and adding a polar small molecule additive and an olefin double decomposition catalyst to obtain the functionalized liquid 1,2-polybutadiene rubber;
the polar small molecular additive is one of cardanol, anacardic acid, pineapple ester, soybean oil, palm oil, seaweed oil or rapeseed oil. The molar ratio of the butadiene to the polar small molecular additive is 0.2-1: 1;
the 1,2-polybutadiene rubber of the functional liquid has 65-95% of adjustable 1, 2-structure, 0.2-6 ten thousand number average molecular weight and contains ester group/carboxyl group/phenolic hydroxyl functional group.
The method mainly comprises two processes, namely a polymerization process and an olefin metathesis process, and specifically comprises the following steps:
1) the polymerization process comprises the following steps:
the concentration of the butadiene is 0.10-0.16 g/mL.
The coordination catalyst is a molybdenum-based catalyst system capable of catalyzing butadiene to directionally polymerize 1,2-polybutadiene and consists of a main catalyst and a cocatalyst.
The main catalyst is a complex of a molybdenum compound and phosphate, the molybdenum compound is molybdenum pentachloride, and the phosphate is triethyl phosphate, tributyl phosphate, di (2-ethylhexyl) phosphate or triisopropylphenyl phosphate; the molar ratio of the main catalyst to the butadiene is 0.5-10 multiplied by 10-41, preferably 1 to 5X 10-41, wherein the main catalyst is calculated by Mo.
The cocatalyst is a complex of aluminum alkyl and a phenolic compound, the aluminum alkyl is triisobutylaluminum, and the phenolic compound is m-cresol; the molar ratio of the cocatalyst to the main catalyst is 6-20: 1, wherein the cocatalyst is calculated by Al, and the main catalyst is calculated by Mo.
The solvent used in the solution method is a solvent which does not contain alkene and can dissolve polybutadiene rubber, and n-hexane or cyclohexane is preferred.
The certain polymerization temperature is 40-130 ℃.
2) Olefin metathesis process
The polymerization time is 10-240 min.
And the polymerization temperature is adjusted to be 30-80 ℃.
The olefin metathesis catalyst is a metal carbene catalyst with an olefin metathesis function, preferably one or a combination of Grubbs 1st, Grubbs 2nd, Grubbs 3rd, Hoveyda-Grubbs 1st or Hoveyda-Grubbs 2nd catalyst, preferably one of Grubbs 2nd, Grubbs 3rd or Hoveyda-Grubbs 2 nd; the molar ratio of the butadiene to the olefin metathesis catalyst is 500: 1-20000: 1, wherein the olefin metathesis catalyst is calculated by Ru.
Preferably, the preparation method of the functionalized liquid 1,2-polybutadiene rubber specifically comprises the following steps:
adding a normal hexane solution of butadiene (Bd) into a reaction bottle under the protection of nitrogen, heating to 60 ℃, adding a molybdenum-based main catalyst and a molybdenum-based cocatalyst, polymerizing for 20-80 min, sequentially adding a polar small-molecule additive and a double decomposition catalyst, and continuing to react for 3-6 hours. The reaction was stopped by the addition of terminator 264. The polymer was precipitated with ethanol and dried to constant volume in a vacuum oven at constant temperature of 60 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, by reasonable design, an olefin metathesis catalyst and a polar small molecule additive are added in the butadiene polymerization process, and the low molecular weight 1,2-PB containing polar functions is prepared by a polymerization-olefin metathesis one-pot method, all solvents are nontoxic alkane solvents, and the method has mild reaction conditions, is economic and environment-friendly, and is easy for industrial production.
2. The polar micromolecular additives adopted by the invention are all bio-based additives, and have the advantages of environmental protection, no toxicity and sustainable development.
3. The product of the invention has a molecular weight of 0.2-6 ten thousand, a grafting ratio of 0.5-2%, a 1, 2-structure content of 65-95%, and a molecular weight and a microstructure which can be adjusted in a wide range, and is suitable for various application places.
Detailed Description
The following further describes embodiments of the present invention with reference to examples.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the specific techniques or conditions are not indicated in the examples, and the techniques or conditions are described in the literature in the field or according to the product specification; the reagents and materials, both of which are analytically pure reagents, are commercially available without specific reference.
The manufacturers of some of the raw materials used in the examples are shown in Table 1.
Table 1 the manufacturers of some of the raw materials used in the examples
Figure BDA0003547394520000041
The test methods used in the examples and comparative examples are illustrated below:
1. the microstructure content is calculated by Fourier infrared spectroscopy (FTIR) spectrum area integration method, and an infrared spectrometer produced by Germany Bruker company and a total reflection mode are adopted.
2. The grafting rate is measured by NMR (hydrogen nuclear magnetic resonance)1H NMR), experiment in CCl3D is solvent, resonance frequency is 202.456MHz, N2Protection was measured using AV-500 NMR spectrometer, BRUKER.
3. The molecular weight and molecular weight distribution were measured by Gel Permeation Chromatography (GPC) using a high performance liquid chromatography pump model 1515 gel permeation chromatograph manufactured by waters technologies, Inc. of America. Tetrahydrofuran is used as a mobile phase, the temperature of a chromatographic column is 40 ℃, the flow rate is 0.35mL/min, and a standard polystyrene is used as a standard sample to prepare a calibration curve.
Preparation of the main catalyst 1:
0.2g of molybdenum pentachloride (Mo) and 0.4mL of triethyl phosphate (P1) are introduced under nitrogen into a 20mL ampoule, P1/Mo 3, 14.2mL of n-hexane are added and the mixture is aged at 60 ℃ for 24 hours.
Preparation of the main catalyst 2:
0.2g of molybdenum pentachloride (Mo) and 0.6mL of tributyl phosphate (P2) are introduced under nitrogen into a 20mL ampoule, P2/Mo.3, 14.0mL of n-hexane are added and the mixture is aged at 60 ℃ for 24 hours.
Preparation of the main catalyst 3:
0.2g of molybdenum pentachloride (Mo) and 0.7mL of di (2-ethylhexyl) phosphate (P3) are introduced under nitrogen into a 20mL ampoule, and 13.9mL of n-hexane are added thereto, with P3/Mo being 3, and the mixture is aged at 60 ℃ for 24 hours.
Preparation of the main catalyst 4:
0.2g of molybdenum pentachloride (Mo) and 0.4mL of triisopropylphenyl phosphate (P4) were introduced under nitrogen into a 20mL ampoule, and 14.2mL of n-hexane were added thereto and the mixture was aged at 60 ℃ for 24 hours, with P3/Mo being 3.
Preparation of the cocatalyst:
50mL of 6.88X 10-5mol/mL Al (i-Bu)3And 0.37mL of m-cresol in a reaction flask under nitrogen, stirred at 0-5 ℃ for 6 hours.
Comparative example 1
300mL of a 0.13g/mL butadiene n-hexane solution was added to a 500mL reaction flask under nitrogen, heated to 60 ℃ and 16.7mL of a 6.88X 10 solution was added-5mol/mL of cocatalyst and 2.9mL of 5X 10-5mol/mL of Main catalyst 1 (molar ratio of cocatalyst to Main catalyst 8, molar ratio of Main catalyst to butadiene 2X 10)-4) Heating to 120 ℃ after 10min, polymerizing for 230min, cooling, adding 5mL of ethanol solution with 1 wt% of antioxidant 264 to terminate the reaction, pouring the glue solution into boiling water, boiling for 20min to separate out the glue solution into glue blocks, shearing the glue blocks, air-drying for 24 hours, and drying in a constant-temperature vacuum drying oven at 80 ℃ for 4 hours to obtain 1,2-PB with Mn of 24.8 ten thousand and 1, 2-structure content of 65%.
Dissolving 31.2g of the 1,2-PB in 1.2L of n-hexane under nitrogen protection, dissolving at 40 deg.C for 24 hr, sequentially adding 12mL of cardanol additive and 1mL of cardanol additive with concentration of 5.8 × 10-5Reacting for 2 hours with Grubbs 2nd double decomposition catalyst of mol/mL, adding 5mL ethanol solution with 1 wt% of age resister 264 to terminate the reaction, then precipitating the polymer with ethanol, and placing at 60 ℃ for constant temperatureDrying in a warm vacuum drying oven to constant volume. Obtaining the functionalized liquid 1,2-PB product with Mn of 1.6 ten thousand, phenolic hydroxyl grafting rate of 1 percent and 1, 2-structure content of 65 percent.
Example 1
300mL of a 0.13g/mL butadiene n-hexane solution was added to a 500mL reaction flask under nitrogen, heated to 60 ℃ and 16.7mL of a 6.88X 10 concentration solution-5mol/mL of cocatalyst and 2.9mL of 5X 10-5Heating to 120 deg.C after 1/mL main catalyst for 10min, polymerizing for 60min, cooling to 60 deg.C, sequentially adding 70mL cardanol additive and 1mL cardanol additive with concentration of 5.8 × 10-5And (3) continuing the reaction for 3 hours by using the Grubbs 2nd double decomposition catalyst in mol/mL, adding 5mL of ethanol solution with the age inhibitor 264 concentration of 1 wt% to terminate the reaction, then precipitating the polymer by using ethanol, and drying the polymer in a constant-temperature vacuum drying oven at the temperature of 60 ℃ to a constant amount. Obtaining the functionalized liquid 1,2-PB product with Mn of 1.2 ten thousand, phenolic hydroxyl grafting rate of 1 percent and 1, 2-structure content of 65 percent. Wherein the molar ratio of polybutadiene to olefin metathesis catalyst is 1000:1, the molar ratio of cardanol to polybutadiene is 0.5:1, and the mass of polybutadiene is calculated as 80% of conversion.
Example 2
Prepared by the same method as in example 1 except that the main catalyst 1 was changed to the main catalyst 2, the molar ratio of the cocatalyst to the main catalyst was 15, and the molar ratio of the main catalyst to butadiene was 1X 10-4Heating to 100 ℃ after 10min, polymerizing for 60min, cooling to 60 ℃, and then sequentially adding 70mL of cardanol additive and 1mL of cardanol additive with the concentration of 5.8 multiplied by 10-5The reaction was continued for 3 hours using a molar/mL Grubbs 2nd metathesis catalyst, the subsequent preparation being identical to example 1. Obtaining the functionalized liquid 1,2-PB product with Mn of 1.6 ten thousand, phenolic hydroxyl grafting rate of 1 percent and 1, 2-structure content of 75 percent.
Example 3
Prepared by the same method as example 1, except that the normal hexane solution of butadiene was changed to cyclohexane solution, the main catalyst 1 was changed to main catalyst 3, the molar ratio of the cocatalyst to the main catalyst was 10, and the molar ratio of the main catalyst to butadiene was 3X 10-4，10mKeeping 60 deg.C after in for polymerization for 60min, sequentially adding 70mL cardanol additive and 1mL cardanol additive with concentration of 5.8 × 10-5mol/mL Grubbs 2nd metathesis catalyst, and the reaction was continued for 3 hours. The latter post-treatment method was the same as in example 1. Obtaining the functionalized liquid 1,2-PB product with Mn of 2.4 ten thousand, phenolic hydroxyl grafting rate of 1 percent and 1, 2-structure content of 85 percent.
Example 4
Prepared by the same method as example 1, except that the normal hexane solution of butadiene was changed to cyclohexane solution, the main catalyst 1 was changed to main catalyst 4, the molar ratio of the cocatalyst to the main catalyst was 8, and the molar ratio of the main catalyst to butadiene was 5X 10-4Cooling to 40 ℃ after 10min, polymerizing for 120min, and then sequentially adding 70mL of cardanol additive and 1mL of cardanol additive with the concentration of 5.8 multiplied by 10-5mol/mL Grubbs 2nd metathesis catalyst, and the reaction was continued for 3 hours. The latter post-treatment method was the same as in example 1. Obtaining the functionalized liquid 1,2-PB product with Mn of 2.1 ten thousand, phenolic hydroxyl grafting rate of 1 percent and 1, 2-structure content of 95 percent.
Example 5
Prepared by the same method as example 2, except that the olefin metathesis catalyst was 2mL of Grubbs 3 rd. Obtaining the functionalized liquid 1,2-PB product with Mn of 2.3 ten thousand, phenolic hydroxyl grafting rate of 1 percent and 1, 2-structure content of 75 percent.
Example 6
Prepared in the same manner as in example 2, except that 2mL of Grubbs 2nd metathesis catalyst was added. Obtaining the functionalized liquid 1,2-PB product with Mn of 1.2 ten thousand, phenolic hydroxyl grafting rate of 1 percent and 1, 2-structure content of 75 percent.
Example 7
Prepared in the same manner as in example 2 except that the amount of cardanol added was 105 mL. Obtaining the functionalized liquid 1,2-PB product with Mn of 2.2 ten thousand, phenolic hydroxyl grafting rate of 1.5 percent and 1, 2-structure content of 75 percent.
Example 8
Prepared in the same manner as in example 1, except that the amount of Hoveyda-Grubbs 2nd metathesis catalyst added was 4 mL. Obtaining the functional liquid 1,2-PB product with Mn of 0.2 ten thousand, phenolic hydroxyl grafting rate of 2 percent and 1, 2-structure content of 65 percent.
Example 9
Prepared in the same manner as in example 4, except that Grubbs 2nd metathesis catalyst was added in an amount of 0.5 mL. Obtaining the functionalized liquid 1,2-PB product with Mn of 6 ten thousand, phenolic hydroxyl grafting rate of 1 percent and 1, 2-structure content of 95 percent.
Examples 10-15 are the effects of additive type on product structure, and the specific results are shown in Table 2
Table 2 additive types versus product structure
Examples Polar additive/amount Polar group Graft ratio (%)
1 Cardanol/0.5: 1 Phenolic hydroxyl group 1
10 Rapeseed oil/1: 1 Ester group 1.1
11 Soybean oil/0.5: 1 Ester group 0.8
12 Palm oil/0.5: 1 Ester group 0.9
13 Algae oil/1: 1 Ester group 1
14 Pineapple ester/0.5: 1 Ester group 1.2
15 Anacardic acid/0.5: 1 Carboxyl group 0.6

Claims (10)

1. A preparation method of functionalized liquid 1,2-polybutadiene rubber is characterized by comprising the following steps: the method comprises the following steps: under the catalysis of a coordination catalyst, butadiene is synthesized into 1,2-polybutadiene rubber at a certain polymerization temperature by a solution method; after polymerizing for a period of time, adjusting the polymerization temperature and adding a polar small molecule additive and an olefin double decomposition catalyst to obtain the functionalized liquid 1,2-polybutadiene rubber;
the polar small molecular additive is one of cardanol, anacardic acid, pineapple ester, soybean oil, palm oil, seaweed oil or rapeseed oil; the molar ratio of the butadiene to the polar small molecular additive is 0.2-1: 1;
the 1,2-polybutadiene rubber of the functional liquid has 65-95% of adjustable 1, 2-structure, 0.2-6 ten thousand number average molecular weight and contains ester group/carboxyl group/phenolic hydroxyl functional group.
2. The method for preparing a functionalized liquid 1,2-polybutadiene rubber according to claim 1, wherein: the concentration of the butadiene is 0.10-0.16 g/mL.
3. The method for preparing a functionalized liquid 1,2-polybutadiene rubber according to claim 1, wherein: the coordination catalyst is a molybdenum-based catalyst system capable of catalyzing butadiene to directionally polymerize 1,2-polybutadiene and consists of a main catalyst and a cocatalyst.
4. The method for preparing a functionalized liquid 1,2-polybutadiene rubber according to claim 3, wherein: the main catalyst is a complex of a molybdenum compound and phosphate, the molybdenum compound is molybdenum pentachloride, and the phosphate is triethyl phosphate, tributyl phosphate, di (2-ethylhexyl) phosphate or triisopropylphenyl phosphate; the molar ratio of the main catalyst to the butadiene is 0.5-10 multiplied by 10-41, wherein the main catalyst is calculated by Mo.
5. The method of preparing functionalized liquid 1,2-polybutadiene rubber according to claim 3, wherein: the cocatalyst is a complex of aluminum alkyl and a phenolic compound, the aluminum alkyl is triisobutyl aluminum, and the phenolic compound is m-cresol; the molar ratio of the cocatalyst to the main catalyst is 6-20: 1, wherein the cocatalyst is calculated by Al, and the main catalyst is calculated by Mo.
6. The method of preparing functionalized liquid 1,2-polybutadiene rubber according to claim 1, characterized in that: the solvent used in the solution method is n-hexane or cyclohexane.
7. The method for preparing a functionalized liquid 1,2-polybutadiene rubber according to claim 1, wherein: the certain polymerization temperature is 40-130 ℃.
8. The method for preparing a functionalized liquid 1,2-polybutadiene rubber according to claim 1, wherein: the polymerization time is 10-240 min.
9. The method of preparing functionalized liquid 1,2-polybutadiene rubber according to claim 1, characterized in that: and the polymerization temperature is adjusted to be 30-80 ℃.
10. The method of preparing functionalized liquid 1,2-polybutadiene rubber according to claim 1, characterized in that: the olefin metathesis catalyst is one or the combination of Grubbs 1st, Grubbs 2nd, Grubbs 3rd, Hoveyda-Grubbs 1st or Hoveyda-Grubbs 2nd catalyst; the molar ratio of the butadiene to the olefin metathesis catalyst is 500: 1-20000: 1, wherein the olefin metathesis catalyst is calculated by Ru.
CN202210252547.5A 2022-03-15 2022-03-15 Preparation method of functionalized liquid 1,2-polybutadiene rubber Pending CN114656583A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115181197A (en) * 2022-06-30 2022-10-14 海南天然橡胶产业集团股份有限公司 End group functionalized liquid natural rubber and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115181197A (en) * 2022-06-30 2022-10-14 海南天然橡胶产业集团股份有限公司 End group functionalized liquid natural rubber and preparation method and application thereof
CN115181197B (en) * 2022-06-30 2024-04-02 海南天然橡胶产业集团股份有限公司 End group functionalized liquid natural rubber and preparation method and application thereof

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