CN113583162B - Polyhexene elastomer and preparation method thereof - Google Patents
Polyhexene elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polyhexene elastomer and a preparation method thereof, wherein the concentration of a crosslinking comonomer in the polyhexene elastomer is 1wt% -10 wt%; the number average molecular weight of the polyhexene elastomer is more than or equal to 20 ten thousand, the isotacticity is more than 90 percent, and the density is 0.850-0.900 g/cm 3 The glass transition temperature is less than or equal to-40 ℃. The preparation method comprises the following steps: under the protection of inert gas, mixing a solvent, a crosslinking comonomer and a cocatalyst, reacting for 5-20min, adding hexene-1 and a Ziegler-Natta main catalyst into the system, and carrying out polymerization reaction at-20-20 ℃ to obtain the polyhexene elastomer. The invention uses hexene-1 and crosslinking comonomer to react and prepare polyhexene elastomer, wherein the polymerization reaction adopts low-temperature polymerization, the catalyst does not need special treatment, the molecular weight of the obtained polymer is higher, the glass transition temperature is lower, the polymerization process of the solution method can reduce the content of oligomer, and can not block a reactor, thereby ensuring the polymerization reaction to be carried out smoothly.
Description
Technical Field
The invention relates to a preparation method for synthesizing a polyhexene elastomer by catalyzing 1-hexene by adopting a Ziegler-Natta catalyst, and the prepared polyhexene elastomer.
Background
Polyhexene (PHe) is a new elastomeric material formed by homopolymerization of hexene-1. PHe is a polyolefin elastomer between rubber and plastic, because of the presence of four carbon branches in its side chains, which promote the polymer chains to slide over each other, giving it an elastic behavior. Among many isotactic polymers of α -olefins, butene-1 and its lower homopolymers are crystalline thermoplastics, octene-1 and its higher homopolymers are crystalline, and only polyhexene (PHe) is a completely amorphous elastomer. The POE has low-temperature impact resistance which cannot be achieved by the traditional POE, can be applied to high-end customized medical industries (such as artificial heart valves and artificial finger joints), can also be applied to toughening modification directions of automobile tires and wire and cable industries, and has good application prospect. Only american Goodyear (Goodyear) and lode (Lord) companies have production technologies of polyhexene for sidewall materials of high-grade tires and substitute materials for artificial lumbar intervertebral discs, respectively, in the world.
In 1976, goodyear corporation invented polyolefin rubber for medical polymer applications. Patents US3933769 and US3991262 report the synthesis of Hexsyn series polyolefin rubbers using Ziegler-Natta catalysts to catalyze hexene-1. It has the features of high yield strength, long term hydrolysis and oxidation resistance, no toxicity, easy manufacture, low cost, etc.
In 1991, mitsubishi, japan polymerized hexene-1 and 4-methyl-1-pentene to prepare a rubber vibration damper. Patent US4990585 reports that 65% to 90% of hexene-1 and 35% to 10% of 4-methyl-1-pentene can be adjusted between 20000 and 500000 in molecular weight using Ziegler-Natta catalysts, but the glass transition temperature is low, only around-20 ℃.
In 1993, constrained geometry metallocene catalysts (CGC) were introduced by Dow chemical company in U.S. for the preparation of ethylene-octene copolymer elastomers. Patent US5064802 reports elastomers synthesized using metallocene catalysts by high temperature solution polymerization process, but the process pressure is high, above 10MPa, which is not good for operation.
No polyhexene production technology exists in China at present, and research and development efforts on high-performance elastomer materials are increased by large petrochemical companies and research institutes in China at present. Therefore, if the PHe can be successfully researched and developed, on one hand, the blank of the production technology of the domestic polyolefin elastomer can be filled, and the POE market with increasing domestic requirements is seized; on the other hand, the development of the PHe elastomer material can also widen the application field of hexene-1 products, promote the development of hexene-1 industry, and has important significance in breaking foreign technology monopoly, optimizing polyolefin product structure, enhancing downstream independent innovation capability, improving core competitiveness and the like.
Disclosure of Invention
The invention mainly aims to provide a polyhexene elastomer and a preparation method thereof, and the polyhexene elastomer prepared by the preparation method has higher molecular weight and lower glass transition temperature and is suitable for being used as a modifier of plastic rubber.
In order to achieve the above object, the present invention provides a polyhexene elastomer, which is a polyhexene elastomerThe number average molecular weight of the product is more than or equal to 20 ten thousand, the isotacticity is more than 90 percent, and the density is 0.850-0.900 g/cm 3 The glass transition temperature is less than or equal to-40 ℃.
The polyhexene elastomer of the invention, wherein the crosslinking comonomer is butadiene, pentadiene, hexadiene, heptadiene, octadiene or isomers thereof; the concentration of the crosslinking comonomer in the polyhexene elastomer is 1 to 10 weight percent; .
In order to achieve the above object, the present invention further provides a method for preparing a polyhexene elastomer, comprising the steps of:
under the protection of inert gas, mixing a solvent and a cocatalyst, reacting for 5-20min, adding hexene-1 and a Ziegler-Natta main catalyst into the system, and carrying out polymerization reaction at-20-20 ℃ to obtain the polyhexene elastomer.
The preparation method of the polyhexene elastomer, wherein, the Ziegler-Natta main catalyst comprises a Ziegler-Natta catalyst loaded by metallic titanium, wherein, the carrier is selected from spherical magnesium chloride or silica gel; the cocatalyst is an alkyl aluminum compound; the molar ratio of Al in the cocatalyst to Ti in the Ziegler-Natta main catalyst is 50-300.
The preparation method of the polyhexene elastomer comprises the step of selecting one or more of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, diethyl aluminum monochloride, diisopropyl aluminum monochloride, diisobutyl aluminum monochloride and di-n-butyl aluminum monochloride as the cocatalyst.
The preparation method of the polyhexene elastomer comprises the step of adding a crosslinking comonomer into the mixture of the solvent and the cocatalyst, wherein the crosslinking comonomer is butadiene, pentadiene, hexadiene, heptadiene, octadiene or isomers thereof.
The preparation method of the polyhexene elastomer comprises the step of selecting one or more solvents from n-hexane, cyclohexane, perfluorocyclohexane, n-heptane, cycloheptane, perfluorocycloheptane, n-octane, cyclooctane and perfluorocyclooctane.
The preparation method of the polyhexene elastomer, provided by the invention, has the advantages that the polymerization reaction temperature is-20-0 ℃, and the polymerization reaction time is 60-180min.
The preparation method of the polyhexene elastomer comprises the steps of quenching by using a terminator after polymerization reaction, washing and filtering to obtain the polyhexene elastomer.
The invention relates to a preparation method of a polyhexene elastomer, wherein, the terminator is selected from one of acidified ethanol, acidified octanol and acidified ethylene glycol.
The invention has the beneficial effects that:
the polyhexene elastomer of the invention has a number average molecular weight of more than or equal to 20 ten thousand, an isotacticity of more than 90 percent and a density of 0.850-0.900 g/cm 3 The glass transition temperature is less than or equal to-40 ℃, and the concentration of the crosslinking comonomer is 1-10 wt%, so that the rubber is suitable for being used as a modifier of plastic rubber.
In addition, the preparation method is simple, the device is not required to be modified, and the polyhexene elastomer product can be produced only by using the existing solution polymerization device; the requirement on the catalyst is not high, and the prior titanium-magnesium series Ziegler-Natta catalyst is only needed; the invention can also produce the polyhexene elastomer with different molecular weights by process regulation.
Drawings
FIG. 1 is a schematic view of an apparatus for producing a polyhexene elastomer according to an embodiment of the present invention;
FIG. 2 is an infrared spectrum of a polyhexene elastomer obtained in example 1;
FIG. 3 is a nuclear magnetic spectrum of a polyhexene elastomer obtained in example 1;
FIG. 4 shows a DSC spectrum of the polyhexene elastomer obtained in example 1.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are carried out on the premise of the technical solution of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are generally carried out under conventional conditions for the experimental methods not given specific conditions.
The invention provides a preparation method of a polyhexene elastomer, which comprises the following steps:
under the protection of nitrogen, mixing a solvent and a cocatalyst, reacting for 5-20min, adding hexene-1 and a Ziegler-Natta main catalyst into the system, and carrying out polymerization reaction at-20-20 ℃ to obtain the polyhexene elastomer.
In one embodiment, a crosslinking comonomer is also added to the solvent and cocatalyst combination. The invention firstly mixes the solvent, the cross-linking comonomer and the cocatalyst for a certain time, and then adds the hexene-1 and the Ziegler-Natta main catalyst, thus improving the catalytic activity of the main catalyst and leading the polymerization product to be purer.
In addition, in the polyhexene elastomer generated by the co-reaction of hexene-1 and a crosslinking comonomer, the copolymerization can enable a polymer structure to have double bonds, so that the crosslinking between polymer chains is realized, and the addition of the comonomer is less, so that the performance of the polyethylene elastomer is not influenced, and the performance of the elastomer can be further enhanced due to the existence of the double bonds.
Moreover, the temperature of the hexene-1 and the crosslinking comonomer for polymerization reaction is-20 to 20 ℃, namely the polymerization reaction process is completed at low temperature, and the low-temperature polymerization can remove the reaction heat in time, so that the reaction is carried out stably, and unexpected side reactions are reduced; meanwhile, the polymerization degree of the polymer can be increased through low-temperature polymerization, and the obtained polymer has higher molecular weight. Therefore, the copolymerization polymerization reaction of the invention can still obtain the polymer with higher isotacticity without adding an external electron donor, thereby simplifying the reaction process and saving the cost.
In one embodiment, the solvent of the present invention is an organic solvent, such as a hydrocarbon solvent or a halogen-substituted hydrocarbon solvent; in another embodiment, the solvent of the present invention is selected from one or more of n-hexane, cyclohexane, perfluorocyclohexane, n-heptane, cycloheptane, perfluorocycloheptane, n-octane, cyclooctane, perfluorocyclooctane. The amount of the solvent to be added is not particularly limited in the present invention, and generally, the solvent should be kept at a level of 10% to 90%, preferably 40% to 60%, of the reaction vessel.
In one embodiment, the crosslinking comonomer of the present invention is a diene or an isomer of a diene, such as butadiene, pentadiene, hexadiene, heptadiene, octadiene or an isomer thereof. In one embodiment, the crosslinking comonomer is added in an amount such that the crosslinking comonomer comprises from 1wt% to 10wt%, preferably from 1wt% to 5wt% of the total mass of the polyhexene elastomer produced.
The Ziegler-Natta procatalyst of the present invention is not particularly limited as long as it comprises a metal titanium supported Ziegler-Natta catalyst. In one embodiment, wherein the carrier is selected from spherical magnesium chloride or silica gel, the active component is titanium.
In the present invention, the cocatalyst is generally selected from alkylaluminum compounds, such as one or more selected from triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride and di-n-butylaluminum monochloride.
In one embodiment, the molar ratio of 1-hexene to Ti in the Ziegler-Natta procatalyst is from 1000 to 1500, and the molar ratio of Al in the cocatalyst to Ti in the Ziegler-Natta procatalyst is from 50 to 300, preferably from 50 to 150.
Under the protection of inert gas, mixing a solvent, a crosslinking comonomer and a cocatalyst, reacting for a period of time, such as 5-20min or 10-30min, adding hexene-1 and a Ziegler-Natta main catalyst into the system, carrying out polymerization reaction at-20-20 ℃, preferably-20-0 ℃, for 10-300min, preferably 30-180min, quenching by using a terminator, washing, and filtering to obtain the polyhexene elastomer. The terminator used in the present invention is not particularly limited as long as the purpose of terminating the reaction can be achieved, and in one embodiment, the terminator is one selected from the group consisting of acidified ethanol, acidified octanol, and acidified ethylene glycol.
In the present invention, the temperature control means in the production method is not particularly limited, and the temperature in the reaction apparatus may be controlled by, for example, a circulating medium such as a low-temperature flowable medium selected from silicone oil, ethylene glycol and the like. The inert gas in the present invention is not particularly limited, and examples thereof include nitrogen gas and argon gas.
Referring to fig. 1 as a specific embodiment, fig. 1 is a schematic view of an apparatus for preparing a polyhexene elastomer according to an embodiment of the present invention, and a method for preparing a polyhexene elastomer according to the present invention includes the following steps:
step 2, controlling the temperature in the kettle through a circulating medium, adding hexene-1 and a Ziegler-Natta main catalyst into the system in the step 1 after the preset temperature is reached, and starting to carry out polymerization reaction;
(3) Discharging materials after the reaction, quenching the catalyst by using a terminator, washing and filtering to obtain the polyhexene elastomer.
The concentration of the crosslinking comonomer in the polyhexene elastomer obtained by the method is 1 to 10 weight percent; the number average molecular weight of the polyhexene elastomer is more than or equal to 20 ten thousand, the isotacticity is more than 90 percent, and the density is 0.850-0.900 g/cm 3 The glass transition temperature is less than or equal to-40 ℃, and the modifier is suitable for plastic rubber.
The invention uses hexene-1 and crosslinking comonomer to react and prepare polyhexene elastomer, wherein the polymerization reaction adopts low-temperature polymerization, the catalyst does not need special treatment, the molecular weight of the obtained polymer is higher, the glass transition temperature is lower, the polymerization process of the solution method can reduce the content of oligomer, and can not block a reactor, thereby ensuring the polymerization reaction to be carried out smoothly.
The present invention will be described in detail below with reference to specific examples.
The Ziegler-Natta procatalyst used in the present application is a titanium supported Ziegler-Natta catalyst, which is available from Basell company, Z-N118 series.
Example 1
Under the protection of nitrogen, 2L of cyclohexane solvent is added into a 5L tank reactor, the liquid level is controlled at 40%, 1.54ml of triisobutylaluminum cocatalyst (Al/Ti = 50), after 5min of reaction, 0.5g of hexene 2L and Ziegler-Natta main catalyst are added into the system, polymerization reaction is carried out for 60min at-20 ℃, acidified ethanol with the mass concentration of 5% is used for terminating the reaction, and then washing is carried out for three times and filtering are carried out, so as to obtain the polyhexene elastomer.
The infrared spectrum, nuclear magnetic spectrum and DSC spectrum of the polyhexene elastomer obtained in the example are respectively shown in FIG. 2, 3 and 4.
In FIG. 2, the wave number is 2856-2955cm -1 The absorption peaks of methyl and methylene C-H stretching vibration appear in the range, and the wave number is 1377cm -1 And 1456cm -1 The C-H in-plane bending vibration absorption peaks of methyl and methylene are respectively positioned. Wave number of 725cm -1 The absorption peak of the in-plane vibration of methylene on the butyl branched chain appears. At the same time, the wave number is 3000-3010cm -1 The C-H stretching vibration absorption peak and wave number in vinyl in the range of 1640cm -1 The disappearance of C = C strong stretching vibration absorption peak indicates the disappearance of 1-hexene, forming a polyhexene-1 elastomer.
In FIG. 3, the C signal on the methyl group is observed in the range of chemical shifts 13.00-17.00 ppm. -CH with methyl group in branch 2 The signal peak of carbon atom(s) of (a) appears in the range of chemical shifts 22.70-23.18 ppm. The presence of 1,3 and 1,6 paired methyl branches can be confirmed by resonances occurring at approximately 28ppm and 40ppm carbon atoms.
As can be seen from FIG. 4, the glass transition temperature of the resulting product was-41.39 ℃.
In summary, PHe prepared by the process of the present invention is an amorphous elastomer.
Example 2
Under the protection of nitrogen, 2L of solvent perfluorocyclohexane is added into a 5L tank reactor, the liquid level is controlled at 40%, a crosslinking comonomer 1, 3-hexadiene 80ml and a cocatalyst triethylaluminum 3.08ml (Al/Ti = 100) are added, after 5min of reaction, hexene 1.5L and a Ziegler-Natta main catalyst 0.5g are added into the system, polymerization reaction is carried out at-10 ℃ for 120min, acidified ethanol with the mass concentration of 5% is used for terminating the reaction, and then washing is carried out for three times and filtering, thus obtaining the polyhexene elastomer.
Example 3
Under the protection of nitrogen, 2L of solvent n-heptane is added into a 5L tank reactor, the liquid level is controlled at 40%, 100ml of crosslinking comonomer 1, 3-pentadiene and 4.62ml of cocatalyst diethylaluminum chloride (Al/Ti = 150) are added, after 5min of reaction, 1L of hexene, 0.5g of Ziegler-Natta main catalyst are added into the system, polymerization reaction is carried out for 180min at 0 ℃, acidified ethanol with the mass concentration of 5% is used for terminating the reaction, and then washing is carried out for three times and filtering, thus obtaining the polyhexene elastomer.
Example 4
Under the protection of nitrogen, adding 2.5L of cyclohexane solvent into a 5L tank reactor, controlling the liquid level to be 50%, adding 60ml of crosslinking comonomer 1, 6-heptadiene and 1.54ml of tri-n-hexylaluminum (Al/Ti = 50) serving as a cocatalyst, reacting for 5min, then adding 1L of hexene, 0.5g of Ziegler-Natta procatalyst into the system, polymerizing for 180min at-10 ℃, terminating the reaction by using acidified ethanol with the mass concentration of 5%, washing for three times, and filtering to obtain the polyhexene elastomer.
Example 5
Under the protection of nitrogen, adding 2.5L of solvent n-heptane into a 5L tank reactor, controlling the liquid level at 50%, adding 80ml of crosslinking comonomer 1, 3-octadiene and 3.08ml of cocatalyst tri-n-butylaluminum (Al/Ti = 100), after 5min of reaction, adding 0.5g of hexene 2L and a Ziegler-Natta main catalyst into the system, carrying out polymerization reaction for 60min at 0 ℃, terminating the reaction by using acidified methanol with the mass concentration of 5%, then washing for three times, and filtering to obtain the polyhexene elastomer.
Example 6
Under the protection of nitrogen, adding 2.5L of solvent cycloheptane into a 5L tank reactor, controlling the liquid level at 50%, adding 100ml of crosslinking comonomer 1, 5-hexadiene and 4.62ml of cocatalyst namely chlorodi-n-butylaluminum (Al/Ti = 150), after reacting for 5min, adding 1.5L of hexene and 0.5g of Ziegler-Natta main catalyst into the system, carrying out polymerization reaction for 120min at-20 ℃, terminating the reaction by using acidified ethanol with the mass concentration of 5%, washing for three times, and filtering to obtain the polyhexene elastomer.
Example 7
Under the protection of nitrogen, 3L of solvent cyclooctane is added into a 5L tank reactor, the liquid level is controlled at 60%, 1, 2-pentadiene of crosslinking comonomer is added at 60%, 3.08ml of triethyl aluminum of cocatalyst (Al/Ti = 100), after 5min of reaction, 1L of hexene and 0.5g of Ziegler-Natta main catalyst are added into the system, polymerization reaction is carried out for 120min at 0 ℃, acidified ethanol with the mass concentration of 5% is used for stopping the reaction, and then washing is carried out for three times and filtering are carried out, thus obtaining the polyhexene elastomer.
Example 8
Under the protection of nitrogen, 3L of solvent cyclohexane is added into a 5L tank reactor, the liquid level is controlled at 60%, 80ml of crosslinking comonomer 1, 6-heptadiene and 4.62ml of cocatalyst triisobutylaluminum (Al/Ti = 150) are added, after 5min of reaction, 0.5g of hexene 2L and a Ziegler-Natta main catalyst are added into the system, polymerization is carried out for 180min at-20 ℃, acidified octanol with the mass concentration of 5% is used for stopping the reaction, and then washing is carried out for three times and filtering are carried out, so that the polyhexene elastomer is obtained.
Example 9
Under the protection of nitrogen, 3L of solvent n-octane is added into a 5L tank reactor, the liquid level is controlled at 60%, 100ml of crosslinking comonomer 1, 5-heptadiene and 1.54ml of cocatalyst monochlorodin-butyl aluminum (Al/Ti = 50) are added, after 5min of reaction, 1.5L of hexene and 0.5g of Ziegler-Natta main catalyst are added into the system, polymerization reaction is carried out for 60min at minus 10 ℃, acidified ethanol with the mass concentration of 5% is used for terminating the reaction, and then washing is carried out for three times and filtering, thus obtaining the polyhexene elastomer.
Example 10
Under the protection of nitrogen, 2L of solvent n-hexane is added into a 5L tank reactor, the liquid level is controlled at 40%, 60ml of crosslinking comonomer 1, 3-hexadiene and 4.62ml of tri-n-hexylaluminum as a cocatalyst (Al/Ti = 150) are added, after 5min of reaction, 0.5g of hexene 2L and a Ziegler-Natta main catalyst are added into the system, the polymerization reaction is carried out for 120min at the temperature of minus 10 ℃, acidified butanol with the mass concentration of 5% is used for terminating the reaction, and then washing is carried out for three times and filtering, so that the polyhexene elastomer is obtained.
Example 11
Under the protection of nitrogen, 2L of solvent n-heptane is added into a 5L tank reactor, the liquid level is controlled at 40%, 80ml of crosslinking comonomer 1, 5-hexadiene and 1.54ml of cocatalyst triisobutylaluminum (Al/Ti = 50) are added, after 5min of reaction, 1.5L of hexene, 0.5g of Ziegler-Natta main catalyst are added into the system, polymerization is carried out for 180min at 0 ℃, the reaction is terminated by using acidified ethanol with the mass concentration of 5%, and then washing is carried out for three times and filtering, thus obtaining the polyhexene elastomer.
Example 12
Under the protection of nitrogen, adding 2L of solvent n-hexane into a 5L tank reactor, controlling the liquid level to be 40%, adding 100ml of crosslinking comonomer 1, 6-heptadiene and 3.08ml of cocatalyst diethyl aluminum chloride (Al/Ti = 100), after reacting for 5min, adding 1L of hexene, 0.5g of Ziegler-Natta main catalyst into the system, polymerizing at-20 ℃ for 60min, terminating the reaction by using acidified methanol with the mass concentration of 5%, washing for three times, and filtering to obtain the polyhexene elastomer.
Example 13
Under the protection of nitrogen, 2.5L of solvent perfluorocyclohexane is added into a 5L tank reactor, the liquid level is controlled at 50%, 60ml of crosslinking comonomer 1, 3-hexadiene and 3.08ml of cocatalyst monochlorobibutyl aluminum (Al/Ti = 100) are added, after 5min of reaction, 1.5L of hexene and 0.5g of Ziegler-Natta main catalyst are added into the system, polymerization is carried out at-20 ℃ for 180min, the reaction is terminated by using 5 mass percent acidified ethanol, and then washing is carried out for three times and filtering, thus obtaining the polyhexene elastomer.
Example 14
Under the protection of nitrogen, 2.5L of solvent perfluoro-n-heptane is added into a 5L tank reactor, the liquid level is controlled at 50%, 80ml of crosslinking comonomer 1, 5-heptadiene and 4.62ml of cocatalyst triethylaluminum (Al/Ti = 150) are added, after 5min of reaction, 0.5g of hexene 1L and Ziegler-Natta procatalyst are added into the system, polymerization is carried out for 60min at minus 10 ℃, acidified ethanol with the mass concentration of 5% is used for terminating the reaction, and then washing is carried out for three times and filtering, thus obtaining the polyhexene elastomer.
Example 15
Under the protection of nitrogen, 2.5L of solvent n-hexane is added into a 5L tank reactor, the liquid level is controlled at 50%, 100ml of crosslinking comonomer 1, 3-hexadiene and 1.54ml of cocatalyst triisobutylaluminum (Al/Ti = 50) are added, after 5min of reaction, 0.5g of hexene 2L and a Ziegler-Natta main catalyst are added into the system, the polymerization reaction is carried out for 120min at 0 ℃, the reaction is terminated by using acidified methanol with the mass concentration of 5%, and then washing is carried out for three times and filtering, so as to obtain the polyhexene elastomer.
Example 16
Under the protection of nitrogen, 3L of solvent n-heptane is added into a 5L tank reactor, the liquid level is controlled at 60%, 60ml of crosslinking comonomer 1, 6-octadiene and 4.62ml of cocatalyst tri-n-hexyl aluminum (Al/Ti = 150) are added, after 5min of reaction, 1.5L of hexene and 0.5g of Ziegler-Natta main catalyst are added into the system, polymerization reaction is carried out for 60min at 0 ℃, acidified ethanol with the mass concentration of 5% is used for terminating the reaction, and then washing is carried out for three times and filtering, thus obtaining the polyhexene elastomer.
Example 17
Under the protection of nitrogen, adding 3L of solvent cycloheptane into a 5L tank reactor, controlling the liquid level at 60%, adding 80ml of crosslinking comonomer 1, 3-hexadiene and 1.54ml of cocatalyst monochloro-diisopropylaluminum (Al/Ti = 50), after reacting for 5min, adding 1L of hexene, 0.5g of Ziegler-Natta main catalyst into the system, carrying out polymerization reaction at-20 ℃ for 120min, terminating the reaction by using acidified methanol with the mass concentration of 5%, washing for three times, and filtering to obtain the polyhexene elastomer.
Example 18
Under the protection of nitrogen, 3L of solvent cyclohexane is added into a 5L tank reactor, the liquid level is controlled at 60%, 100ml of crosslinking comonomer 1, 5-octadiene and 3.08ml of cocatalyst triisobutyl aluminum (Al/Ti = 100) are added, after 5min of reaction, 0.5g of hexene 2L and a Ziegler-Natta main catalyst are added into the system, polymerization reaction is carried out for 180min at minus 10 ℃, acidified ethanol with the mass concentration of 5% is used for stopping the reaction, and then washing is carried out for three times and filtering are carried out, thus obtaining the polyhexene elastomer.
The results of the polymerization experiments of examples 1 to 18 are shown in Table 1, wherein "conversion" means the conversion of 1-hexene, "activity" is the catalytic activity of the catalyst, and "density", "isotacticity", "Tg" and "molecular weight" are the density, isotacticity, glass transition temperature and molecular weight, respectively, of the polymer obtained by polymerization.
TABLE 1 results of polymerization experiments in examples 1 to 18
As can be seen from the polymerization result data obtained in the above examples, the number average molecular weight of the polyhexene elastomer of the present invention is not less than 20 ten thousand, the isotacticity is more than 90%, and the density is 0.850-0.900 g/cm 3 The glass transition temperature is less than or equal to-40 ℃, and the concentration of the crosslinking comonomer is 1-10 wt%, so that the rubber is suitable for being used as a modifier of plastic rubber.
In addition, the preparation method is simple, the device is not required to be modified, and the polyhexene elastomer product can be produced only by using the existing solution polymerization device; the requirement on the catalyst is not high, and the prior titanium-magnesium series Ziegler-Natta catalyst is only needed; the invention can also produce polyhexene elastomer with different molecular weight through process control.
The polyhexene elastomer obtained by the invention is added into LDPE for modification, and the mechanical property data of the obtained modified PHe/LDPE blend is shown in the following table 2.
TABLE 2 mechanical Properties of modified Low Density polyethylene
Wherein PHe (wt%) refers to the weight percentage of the polyhexene elastomer in the modified low density polyethylene.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. The polyhexene elastomer is characterized in that the number average molecular weight of the polyhexene elastomer is not less than 20 ten thousand, the isotacticity is more than 90 percent, and the density is 0.850 to 0.900g/cm 3 The glass transition temperature is less than or equal to-40 ℃; the polyhexene elastomer comprises a crosslinking comonomer, wherein the crosslinking comonomer is butadiene, pentadiene, hexadiene, heptadiene, octadiene or isomers thereof, and the concentration of the crosslinking comonomer in the polyhexene elastomer is 1-10 wt%.
2. The method of producing a polyhexene elastomer according to claim 1, wherein the method comprises the steps of:
under the protection of inert gas, mixing a solvent and a cocatalyst, reacting for 5-20min, adding hexene-1 and a Ziegler-Natta main catalyst into the system, and carrying out polymerization reaction at-20-20 ℃ to obtain a polyhexene elastomer;
wherein a crosslinking comonomer is also added to the mixture of the solvent and the cocatalyst.
3. The process for the preparation of a polyhexene elastomer according to claim 2 wherein the Ziegler-Natta procatalyst is a Ziegler-Natta catalyst comprising a metallic titanium support, wherein the support is selected from the group consisting of spherical magnesium chloride or silica gel; the cocatalyst is an alkyl aluminum compound; the molar ratio of Al in the cocatalyst to Ti in the Ziegler-Natta main catalyst is 50-300.
4. The method of claim 3, wherein the cocatalyst is selected from one or more of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride and di-n-butylaluminum monochloride.
5. The method of producing a polyhexene elastomer according to claim 2 wherein the solvent is one or more selected from the group consisting of n-hexane, cyclohexane, perfluorocyclohexane, n-heptane, cycloheptane, perfluorocycloheptane, n-octane, cyclooctane, and perfluorocyclooctane.
6. The method of producing a polyhexene elastomer according to claim 2 wherein the polymerization temperature is-20 to 0 ℃ and the polymerization time is 60 to 180min.
7. The method of producing a polyhexene elastomer according to claim 2 wherein the polymerization is followed by quenching with a terminator, washing and filtering to obtain a polyhexene elastomer.
8. The method of producing a polyhexene elastomer according to claim 7 wherein the terminator is selected from the group consisting of acidified ethanol, acidified octanol, and acidified ethylene glycol.
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| JPH0249008A (en) * | 1988-05-25 | 1990-02-19 | Japan Synthetic Rubber Co Ltd | Olefin based random copolymer |
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| CN110922512A (en) * | 2018-09-19 | 2020-03-27 | 杭州双安科技有限公司 | Catalyst component for olefin polymerization, preparation method and application thereof |
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| JPH0249008A (en) * | 1988-05-25 | 1990-02-19 | Japan Synthetic Rubber Co Ltd | Olefin based random copolymer |
| CN104379679A (en) * | 2012-08-03 | 2015-02-25 | 埃克森美孚化学专利公司 | Polyalphaolefins prepared using modified salan catalyst compounds |
| CN110922512A (en) * | 2018-09-19 | 2020-03-27 | 杭州双安科技有限公司 | Catalyst component for olefin polymerization, preparation method and application thereof |
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