CN115073666B - High molecular weight iron-based bio-based rubber, preparation method and application thereof, and rubber composition based on high molecular weight iron-based bio-based rubber - Google Patents
High molecular weight iron-based bio-based rubber, preparation method and application thereof, and rubber composition based on high molecular weight iron-based bio-based rubber Download PDFInfo
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Abstract
一种高分子量铁系生物基橡胶、其制备方法和应用、及基于它的橡胶组合物。本发明属于生物基橡胶及其制备领域。本发明的目的是为了解决现有生物基橡胶分子量低、玻璃化转变温度高以及现有制备方法成本高、效率低的技术问题。铁系生物基橡胶由石油基单体和生物基单体经铁系催化剂催化共聚而成，所述高分子量铁系生物基橡胶的数均分子量为5.0×105g/mol～20.0×105g/mol，分子量分布1.5～3.0，玻璃化转变温度Tg为‑100℃～‑20℃。方法：在无水无氧条件下，将生物基单体、石油基单体、铁系催化剂、溶剂、助催化剂加入到反应器中反应完全后淬灭反应，得到高分子量铁系生物基橡胶。应用：用于制造防化服、轮胎或鞋底。所述橡胶组合物包括高分子量铁系生物基橡胶，且具有较高机械性能。
A high molecular weight iron-based bio-based rubber, its preparation method and application, and a rubber composition based thereon. The invention belongs to the field of bio-based rubber and its preparation. The purpose of the invention is to solve the technical problems of low molecular weight, high glass transition temperature of existing bio-based rubber and high cost and low efficiency of existing preparation methods. Iron-based bio-based rubber is copolymerized by petroleum-based monomers and bio-based monomers catalyzed by iron-based catalysts. The number average molecular weight of the high molecular weight iron-based bio-based rubber is 5.0×10 5 g/mol ~ 20.0×10 5 g/mol, molecular weight distribution 1.5～3.0, glass transition temperature Tg ‑100℃～‑20℃. Method: Under anhydrous and oxygen-free conditions, add bio-based monomers, petroleum-based monomers, iron-based catalysts, solvents, and co-catalysts into the reactor and then quench the reaction after the reaction is complete to obtain high-molecular-weight iron-based bio-based rubber. Application: Used in the manufacture of chemical protective clothing, tires or shoe soles. The rubber composition includes high molecular weight iron-based bio-based rubber and has high mechanical properties.
Description
Technical Field
The invention belongs to the field of bio-based rubber and preparation thereof, and particularly relates to high molecular weight iron bio-based rubber, a preparation method and application thereof, and a rubber composition based on the high molecular weight iron bio-based rubber.
Background
Terpenes are one of the largest families of natural compounds synthesized by conifers and various plants. Among the bulky terpene-based monomers, β -myrcene having a unique conjugated diene structure is attracting increasing attention. After Johanson et al first reported on myrcene in 1948, scientists began to study myrcene polymers in different polymerization modes. In 1987, cawse et al used a free radical polymerization method with hydrogen peroxide as an initiator and n-butanol as a solvent to obtain low molecular weight (3100 g/mol to 4030 g/mol) polylaurene. But the selectivity of myrcene is not easy to be regulated. Meanwhile, due to the defect of the performance of the homopolymer of a single monomer, researchers start to study copolymers of myrcene and other monomers.
In 1993, david studied the copolymerization of myrcene and styrene/methyl methacrylate by emulsion polymerization using AIBN as an initiator, wherein the copolymer has a high molecular weight (20000 g/mol) but a low conversion (5% -13%). Compared with cationic polymerization, the free radical polymerization has long reaction time, uncontrollable microstructure and unsatisfactory conversion rate. Compared with the method, the anionic polymerization has high speed, high conversion rate, narrow molecular weight distribution and controllable molecular weight and molecular structure, and the myrton and the Quirk successfully obtain the myrcene-styrene copolymer with narrow molecular weight distribution (PDI=1.09) by using the anionic polymerization method. However, the severe conditions of the anionic polymerization reaction and the sensitivity to water and oxygen make the industrial production difficult.
In recent years, many scientists have developed coordination polymerization to study the copolymerization of myrcene. In 2015, the Cui Dongmei subject group realized copolymerization of isoprene and myrcene by a rare earth lanthanide series catalytic system. In 2020, the Dirong subject group successfully realized the copolymerization of myrcene and isoprene, and myrcene and butadiene using a neodymium rare earth catalyst. 2021, kotohiro Nomura et al successfully achieved the copolymerization of myrcene with ethylene by half-titanocene catalysts. Beta-farnesene is relatively less studied at present due to its lower monomer productivity. With the development of industrial preparation technology and biological preparation technology in recent years, research on bio-based monomers is expanded to beta-farnesene. Under the action of a novel lanthanide catalyst, eval L researches the copolymerization reaction of myrcene and farnesene with styrene. The blend amount of myrcene and farnesene in the copolymer is 5.6-30.8% and 2.5-9.8% respectively. However, because rare earth metals are expensive, titanium metals have toxicity, free radical polymerization can generate gel, monomer conversion rate is low and the like, so that industrial production of bio-based rubber still faces a plurality of problems, and therefore, how to realize green and environment-friendly industrial preparation of bio-based rubber with better performance is important.
Disclosure of Invention
The invention aims to solve the technical problems of low molecular weight, high glass transition temperature, high cost and low efficiency of the existing preparation method of the existing bio-based rubber, and provides a high molecular weight iron-based bio-based rubber, a preparation method and application thereof, and a rubber composition based on the high molecular weight iron-based bio-based rubber.
The high molecular weight iron-based biobased rubber is prepared by catalyzing and copolymerizing a petroleum-based monomer and a biobased monomer through an iron-based catalyst, and the number average molecular weight of the high molecular weight iron-based biobased rubber is 5.0 multiplied by 10 5 g/mol～20.0×10 5 g/mol, molecular weight distribution is 1.5-3.0, and glass transition temperature Tg is minus 100 ℃ to minus 20 ℃.
Further defined, the petroleum-based monomer is isoprene or butadiene and the bio-based monomer is myrcene or farnesene.
Further defined, the molar ratio of petroleum-based monomer to bio-based monomer is (1:19) - (19:1).
Further, the molar ratio of the sum of the molar amounts of the petroleum-based monomer and the bio-based monomer to the iron element in the iron-based catalyst is (500 to 20000): 1. The sum of the molar amounts of the petroleum-based monomer and the bio-based monomer refers to the sum of the amounts of the materials of the petroleum-based monomer and the bio-based monomer.
Further defined, the structure of the iron-based catalyst is any one of the following:
the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
under the anhydrous and anaerobic condition, the bio-based monomer, the petroleum-based monomer, the iron-based catalyst, the solvent and the cocatalyst are added into a reactor, and the reaction is quenched for 10min to 240min at the temperature of 0 ℃ to 100 ℃ under the condition of stirring, and the reaction is repeatedly washed by ethanol and dried in vacuum, thus obtaining the high molecular weight iron-based bio-based rubber.
Further defined, the cocatalyst is one of MAO, MMAO, DMAO, or a mixture of an aluminum alkyl and a dealkylating agent, the aluminum alkyl being Al i Bu 3 、AlEt 3 、AlMe 3 One of the dealkylating agents is [ Ph ] 3 C] + [B(CF 5 ) 4 ] - Or B (C) 6 F 5 ) 3 。
Further defined, when the promoter is one of MAO, MMAO, DMAO, the molar ratio of the aluminum element in the promoter to the iron element in the iron-based catalyst is (10 to 1000): 1, when the cocatalyst is a mixture of aluminum alkyl and dealkylating agent, the mol ratio of aluminum element in aluminum alkyl to iron element in iron catalyst is (10-100): 1, and the mol ratio of boron element in dealkylating agent to iron element in iron catalyst is (1-10): 1.
Further defined, when the promoter is one of MAO, MMAO, DMAO, the molar ratio of aluminum element in the promoter to iron element in the iron-based catalyst is 500:1, when the cocatalyst is a mixture of aluminum alkyl and a dealkylation reagent, the molar ratio of aluminum element in the aluminum alkyl to iron element in the iron-based catalyst is 40:1, and the molar ratio of boron element in the dealkylation reagent to iron element in the iron-based catalyst is 1:1.
Further limited, the solvent is one or two of toluene, xylene, petroleum ether, n-hexane, cyclohexane, n-heptane, n-octane, methylene dichloride and hydrogenated gasoline, and the ratio of the solvent to the total volume of the bio-based monomer and the petroleum-based monomer is (1-50): 1.
Further defined, the reaction is carried out at 25℃for 60min.
The invention relates to a high molecular weight iron-based bio-based rubber for manufacturing chemical protective clothing, tires or soles.
The rubber composition based on the high molecular weight iron-based bio-based rubber is prepared from 100 parts by weight of the high molecular weight iron-based bio-based rubber, 10-75 parts by weight of carbon black, 1-3 parts by weight of a vulcanization accelerator, 0.1-15 parts by weight of a vulcanizing agent, 1-10 parts by weight of zinc oxide and 1-9 parts by weight of hard butter.
Further limited, the tensile strength of the rubber composition is more than or equal to 18MPa, the elongation at break is more than or equal to 350%, the tearing strength is more than or equal to 40N/mm, and the 100% stretching stress is more than or equal to 3MPa.
Further defined, the carbon black is one or a mixture of several of N330, N220 and N660 according to any ratio.
Further defined, the vulcanization accelerator is one or more of CZ, NA-22, DCBS, MBT, TT, DZ and TMTD.
Further defined, the vulcanizing agent is sulfur, including powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur.
Compared with the prior art, the invention has the remarkable effects that:
1) The iron-based bio-based rubber prepared by the invention has high molecular weight, low glass transition temperature, good physical and mechanical properties and good processability. The storage stability of the alloy can be improved while ensuring better mechanical strength. The application field of the synthetic rubber is further expanded.
2) The main catalyst adopted by the invention is an iron catalyst, and is green, environment-friendly, good in biocompatibility and simple to prepare.
3) The catalyst system provided by the invention has higher copolymerization activity on petroleum-based monomers such as butadiene and isoprene and biological-based monomers such as myrcene and farnesene, and can obtain more environment-friendly and sustainable biological-based rubber through the introduction of the biological-based monomers, thereby relieving the dependence on the petrochemical industry field and having important industrial application value.
Drawings
FIG. 1 is GPC of the iron-based bio-based rubber of example 1;
FIG. 2 is a DSC of the iron-based bio-based rubber of example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The terms "comprising," "including," "having," "containing," or any other variation thereof, as used in the following embodiments, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range. In the present specification and claims, the range limitations may be combined and/or interchanged, such ranges including all the sub-ranges contained therein if not expressly stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" is to be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the plural reference is obvious that there is a singular reference
Example 1: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 10:10), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield is>99%. Polymer M n (number average molecular weight, g/mol) 106.6 ten thousand, PDI (molecular weight distribution) 2.3, glass transition temperature-63.6 ℃.
The molecular weight information table of the high molecular weight iron-based biobased rubber of this example is shown in table 1.
TABLE 1 molecular weight information Table
| Peak | Mp(g/mol) | Mn(g/mol) | Mw(g/mol) | Mz(g/mol) | Mz+1(g/mol) | Mv(g/mol) | PD |
| Peak1 | 2154548 | 1066144 | 2414918 | 4037159 | 5471657 | 3817224 | 2.265 |
The rubber composition based on the high molecular weight iron-based bio-based rubber of example 1 was prepared from 100 parts by mass of the high molecular weight iron-based bio-based rubber of example 1, 30 parts by mass of N220, 2 parts by mass of a vulcanization accelerator CZ, 3 parts by mass of sulfur, 3 parts by mass of zinc oxide, 2 parts by mass of hard butter.
The properties of the obtained rubber composition were found to be 18.03MPa in tensile strength, 456.81% in elongation at break, 42.30N/mm in tear strength and 4.45MPa in 100% elongation stress.
Example 2: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 4:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 89%. Polymer M n (number average molecular weight, g/mol) 71.4 ten thousand, PDI (molecular weight distribution) 3.0, glass transition temperature-70.1 ℃.
Example 3: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:3), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield is>99%. Polymer M n (number average molecular weight, g/mol) 169.6 ten thousand, PDI (molecular weight distribution) 2.0, glass transition temperature-42.6 ℃.
The rubber composition based on the high molecular weight iron-based bio-based rubber of example 3 was prepared from 100 parts by mass of the high molecular weight iron-based bio-based rubber of example 3, 20 parts by mass of N220, 2 parts by mass of a vulcanization accelerator CZ, 3 parts by mass of sulfur, 2 parts by mass of zinc oxide, 2 parts by mass of hard butter.
The properties of the obtained rubber composition were found to be 18.78MPa in tensile strength, 374.5% in elongation at break, 41.70N/mm in tear strength and 4.89MPa in 100% elongation stress.
Example 4: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:9), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield is>99%. Polymer M n (number average molecular weight, g/mol) was 139.6 ten thousand, PDI (molecular weight distribution) was 2.2, and glass transition temperature was-45.7 ℃.
Example 5: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:19), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield is>99%. Polymer M n (number average molecular weight, g/mol) 121.6 ten thousand, PDI (molecular weight distribution) 1.9, glass transition temperature-28.7 ℃.
Example 6: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 50 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 87%. Polymer M n (number average molecular weight, g/mol) 74.9 ten thousand, PDI (molecular weight distribution) 2.5, glass transition temperature-53.7 ℃.
Example 7: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst E (20 mu mol,1equiv.,4.24 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 95%. Polymer M n (number average molecular weight, g/mol) was 127.3 ten thousand, PDI (molecular weight distribution) was 2.4, and glass transition temperature was-59.6 ℃.
The rubber composition based on the high molecular weight iron-based bio-based rubber of example 7 was prepared from 100 parts by mass of the high molecular weight iron-based bio-based rubber of example 7, 30 parts by mass of N220, 2 parts by mass of a vulcanization accelerator CZ, 3 parts by mass of sulfur, 3 parts by mass of zinc oxide, 2 parts by mass of hard butter.
The properties of the obtained rubber composition were found to be 18.65MPa in tensile strength, 432.79% in elongation at break, 43.57N/mm in tear strength and 4.27MPa in 100% elongation stress.
Example 8: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst H (20 mu mol,1equiv.,4.72 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 99%. Polymer M n (number average molecular weight, g/mol) was 115.5 ten thousand, PDI (molecular weight distribution) was 2.1, and glass transition temperature was-61.7 ℃.
Example 9: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst I (20 mu mol,1equiv.,6.76 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 94%. Polymer M n (number average molecular weight, g/mol) was 83.5 ten thousand, PDI (molecular weight distribution) was 2.3, and glass transition temperature was-65.2 ℃.
Example 10: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst N (20 mu mol,1equiv.,18.3 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
Yield rate>99%. Polymer M n The (number average molecular weight, g/mol) was 95.6 ten thousand, the PDI (molecular weight distribution) was 2.6, and the glass transition temperature was-66.3 ℃.
Example 11: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of myrcene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000equiv., and the molar ratio of the myrcene to the isoprene is 1:1) and a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of anhydrous and anaerobic argon, carrying out polymerization reaction for 60min at 25 ℃ under the condition of stirring, adding 1mL of an anti-aging agent, carrying out ethanol quenching reaction, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
Yield rate>99%. M of polymer n The (number average molecular weight, g/mol) was 93.5 ten thousand, the PDI (molecular weight distribution) was 2.2, and the glass transition temperature was-45.1 ℃.
The rubber composition based on the high molecular weight iron-based bio-based rubber of example 11 was prepared from 100 parts by mass of the high molecular weight iron-based bio-based rubber of example 11, 20 parts by mass of N220, 2 parts by mass of a vulcanization accelerator CZ, 3 parts by mass of sulfur, 3 parts by mass of zinc oxide, and 4 parts by mass of hard butter.
The properties of the obtained rubber composition were found to be 20.14MPa in tensile strength, 398.5% in elongation at break, 43.7N/mm in tear strength and 4.83MPa in 100% elongation stress.
Example 12: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and butadiene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the butadiene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of no water and no oxygen argon, carrying out polymerization at 25 ℃ for 60min under the condition of stirring, adding 1mL of an anti-aging agent, quenching the mixture by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
Yield rate>99%. M of polymer n (number average molecular weight, g/mol) 90.8 ten thousand, PDI (molecular weight distribution) 2.1, glass transition temperature-55.7 ℃.
Example 13: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of myrcene and butadiene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the myrcene to the butadiene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of anhydrous and anaerobic argon, carrying out polymerization at 25 ℃ for 60min under the condition of stirring, adding 1mL of an anti-aging agent, carrying out ethanol quenching reaction, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield thereof was found to be 99%. M of polymer n (number average molecular weight, g/mol) 86.1 tens of thousands, PDI (molecular weight distribution) 2.4, glass transition temperature-40.2 ℃.
Example 14: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MMAO (10 mmol,500equiv.,5.34 mL) under the condition of no water and no oxygen argon, carrying out polymerization reaction at 25 ℃ for 60min under the condition of stirring, adding 1mL of an anti-aging agent, carrying out ethanol quenching reaction, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 95%. Polymer M n The (number average molecular weight, g/mol) was 120 ten thousand, the PDI (molecular weight distribution) was 2.2, and the glass transition temperature was-66.1 ℃.
Example 15: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 3000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of no water and no oxygen argon, carrying out polymerization at 25 ℃ for 240min under the condition of stirring, adding 1mL of an anti-aging agent, quenching by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 98%. Micro M of polymer n (number average molecular weight, g/mol) 130.1 tens of thousands, PDI (molecular weight distribution) 2.3, glass transition temperature-62.8 ℃.
Example 16: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (6 mmol,300equiv.,4.0 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield thereof was found to be 93%. M of polymer n (number average molecular weight, g/mol) 133.5 ten thousand, PDI (molecular weight distribution) 2.3, glass transition temperature-64.1 ℃.
Example 17: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst J (20 mu mol,1equiv.,7.06 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of no water and no oxygen argon, carrying out polymerization reaction at 25 ℃ for 60min under the condition of stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield thereof was found to be 99%. M of polymer n (number average molecular weight, g/mol) was 89.1 ten thousand, PDI (molecular weight distribution) was 2.3, and glass transition temperature was-62.8 ℃.
Example 18: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst O (20 mu mol,1equiv.,17.72 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL), carrying out polymerization reaction at 25 ℃ for 60min under stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield thereof was found to be 99%. M of polymer n (number average molecular weight, g/mol) 113.4 ten thousand, PDI (molecular weight distribution) 2.3, glass transition temperature-60.8 ℃.
Example 19: the preparation method of the high molecular weight iron-based bio-based rubber comprises the following steps:
taking a Schlenk bottle, sequentially adding an iron-based catalyst A (20 mu mol,1equiv.,7.56 mg), 8mL of toluene, a mixed monomer of farnesene and isoprene (the molar ratio of the mixed monomer to the main catalyst is 2000, the molar ratio of the farnesene to the isoprene is 1:1), a cocatalyst MAO (10 mmol,500equiv.,6.66 mL) under the condition of no water and no oxygen argon, carrying out polymerization reaction at 25 ℃ for 30min under the condition of stirring, adding 1mL of an anti-aging agent, quenching the reaction by ethanol, pouring out clear liquid, washing the polymer with ethanol for 3 times again, and vacuum drying the obtained polymer to constant weight at 40 ℃ to obtain the high molecular weight iron-based bio-based rubber.
The yield was 90%. M of polymer n (number average molecular weight, g/mol) 98.1 tens of thousands, PDI (molecular weight distribution) 2.4, glass transition temperature-63.3 ℃.
Claims (8)
1. A method for preparing high molecular weight iron-based bio-based rubber, characterized in that the iron-based bio-based rubber is formed by catalyzing and copolymerizing petroleum-based monomers and bio-based monomers through an iron-based catalyst, and the number average molecular weight of the high molecular weight iron-based bio-based rubber is 5.0x10 5 g/mol～20.0×10 5 g/mol, molecular weight distribution of 1.5-3.0, glass transition temperature Tg of minus 100 ℃ to minus 20 ℃, petroleum-based monomer of isoprene or butadiene, biological-based monomer of myrcene or farnesene, molar ratio of petroleum-based monomer to biological-based monomer of (1:19) - (19:1), molar ratio of sum of petroleum-based monomer and biological-based monomer to iron element in iron-based catalyst of (500-20000): 1, the structure of iron-based catalyst is any one of the following:
the preparation method comprises the following steps:
under the anhydrous and anaerobic condition, the bio-based monomer, the petroleum-based monomer, the iron-based catalyst, the solvent and the cocatalyst are added into a reactor, and the reaction is quenched for 60min at 25 ℃ under the condition of stirring, and the reaction is repeatedly washed by ethanol and dried in vacuum, thus obtaining the high molecular weight iron-based bio-based rubber.
2. The method of claim 1, wherein the cocatalyst is one of MAO, MMAO, DMAO, or a mixture of an aluminum alkyl and a dealkylating agent, and the aluminum alkyl is Al i Bu 3 、AlEt 3 、AlMe 3 One of the dealkylating agents is [ Ph ] 3 C] + [B(CF 5 ) 4 ] - Or B (C) 6 F 5 ) 3 When the cocatalyst is one of MAO, MMAO, DMAO, the molar ratio of the aluminum element in the cocatalyst to the iron element in the iron-based catalyst is (10-1000): 1, when the cocatalyst is a mixture of aluminum alkyl and dealkylating agent, the mol ratio of aluminum element in aluminum alkyl to iron element in iron catalyst is (10-100): 1, and the mol ratio of boron element in dealkylating agent to iron element in iron catalyst is (1-10): 1.
3. The method according to claim 2, wherein when the cocatalyst is one of MAO, MMAO, DMAO, the molar ratio of aluminum element in the cocatalyst to iron element in the iron-based catalyst is 500:1, when the cocatalyst is a mixture of aluminum alkyl and a dealkylation reagent, the molar ratio of aluminum element in the aluminum alkyl to iron element in the iron-based catalyst is 40:1, and the molar ratio of boron element in the dealkylation reagent to iron element in the iron-based catalyst is 1:1.
4. The method according to claim 1, wherein the solvent is one or two of toluene, xylene, petroleum ether, n-hexane, cyclohexane, n-heptane, n-octane, methylene chloride and hydrogenated gasoline, and the ratio of the solvent to the total volume of the bio-based monomer and petroleum-based monomer is (1-50): 1.
5. the high molecular weight iron-based biobased rubber produced by the method of any one of claims 1 to 4 for use in the manufacture of chemical protective clothing, tires or shoe soles.
6. The rubber composition based on the high molecular weight iron-based bio-based rubber prepared by the method according to any one of claims 1 to 4, wherein the rubber composition is prepared from 100 parts by mass of the high molecular weight iron-based bio-based rubber, 10 to 75 parts by mass of carbon black, 1 to 3 parts by mass of a vulcanization accelerator, 0.1 to 15 parts by mass of a vulcanizing agent, 1 to 10 parts by mass of zinc oxide and 1 to 9 parts by mass of hard butter.
7. The rubber composition according to claim 6, wherein the tensile strength of the rubber composition is not less than 18MPa, the elongation at break is not less than 350%, the tear strength is not less than 40N/mm, and the 100% tensile stress is not less than 3MPa.
8. The rubber composition according to claim 6, wherein the carbon black is one or a mixture of several of N330, N220 and N660, the vulcanization accelerator is one or a mixture of several of CZ, NA-22, DCBS, MBT, TT, DZ and TMTD, and the vulcanizing agent is sulfur.
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