CN114524894B - Preparation method of poly4-methyl-1-pentene - Google Patents
Preparation method of poly4-methyl-1-pentene Download PDFInfo
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- CN114524894B CN114524894B CN202210161397.7A CN202210161397A CN114524894B CN 114524894 B CN114524894 B CN 114524894B CN 202210161397 A CN202210161397 A CN 202210161397A CN 114524894 B CN114524894 B CN 114524894B
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
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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
- C08F6/00—Post-polymerisation treatments
- C08F6/26—Treatment of polymers prepared in bulk also solid polymers or polymer melts
- C08F6/28—Purification
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a preparation method of poly-4-methyl-1-pentene, which is characterized by comprising the following steps: (1) bulk polymerization of 4-methyl-1-pentene: under anhydrous and anaerobic conditions, adding 4-methyl-1-pentene, a catalyst system and an optional molecular weight regulator into a reactor, and carrying out homopolymerization to obtain poly 4-methyl-1-pentene; (2) washing the polymer: adding an aqueous phase detergent into the poly4-methyl-1-pentene obtained in the step (1), and washing to obtain poly4-methyl-1-pentene polymer slurry; (3) solid-liquid separation: respectively obtaining a polymer and filtrate from the poly4-methyl-1-pentene polymer slurry obtained in the step (2) through a solid-liquid separation means; (4) oil-water separation: and (3) obtaining recovered monomers from the filtrate obtained in the step (3) through an oil-water separation means. Compared with the prior art, the preparation method has the advantages of high production efficiency, low ash content of the polymer and easy recovery of unreacted monomers.
Description
Technical Field
The invention relates to the technical field of polyolefin synthesis, in particular to a preparation method of poly-4-methyl-1-pentene.
Background
Isotactic poly4-methyl-1-pentene (PMP) is a polymer having bulky side groups (-CH) 2 -CH(CH 3 ) 2 ) The semi-crystalline polyolefin of (C) enables PMP to have unique properties of high transparency, low density, high chemical stability, high melting point, low dielectric constant, high permeability, etc. PMP has been widely used in many industrial and medical fields such as automobile parts, separation membranes, aseptic containers, etc. In the third generation of lung membrane materials, PMP is used as a polyolefin material with excellent performance, has the characteristics of good oxygen flux, nitrogen-oxygen selectivity, low dissolution, biological safety and the like, increases the separation degree of blood phase and gas phase, overcomes the problem of plasma leakage, and is recognized as the optimal membrane material for external membrane pulmonary oxygenation (ECMO).
The current industrial PMP production process is slurry polymerization (US 3347838), which requires separation of solvent and monomer in a recovery unit, which process is energy-intensive; on the other hand, PMP is used in large quantities in the food and medical fields, which requires low ash content of the polymer, preferably below 30ppm. The PMP ash mainly includes residual catalyst, co-catalyst, additives and mechanical impurities, and mainly contains Ti, cl, si, etc. There are two main methods currently in industry for reducing polymer ash: enhancing refining of raw materials, reducing the content of impurities such as water and oxygen, increasing the activity of the catalyst and reducing the consumption of the cocatalyst; another approach is to increase the catalyst activity by increasing the residence time, which is required to produce a particular brand.
The method has the advantages that the post-treatment of the bulk polymerization is simple, the polymer can be directly separated, the energy consumption is saved, the method is a very economical polymerization method, meanwhile, the concentration of the bulk polymerization monomer is high, the polymerization rate of the catalyst is faster, the residence time can be reduced, the production efficiency is improved, and the catalyst and the cocatalyst residues are not easy to remove in the bulk polymerization.
Disclosure of Invention
Aiming at the current state of the art, the invention provides a preparation method of poly4-methyl-1-pentene which has high production efficiency, low polymer ash content and easy recovery of unreacted monomers.
The technical scheme adopted for solving the technical problems is as follows: the preparation method of the poly4-methyl-1-pentene is characterized by comprising the following steps:
(1) Bulk polymerization of 4-methyl-1-pentene: under anhydrous and anaerobic conditions, adding 4-methyl-1-pentene, a catalyst system and an optional molecular weight regulator into a reactor, and carrying out homopolymerization to obtain poly 4-methyl-1-pentene;
(2) Polymer washing: adding an aqueous phase detergent into the poly4-methyl-1-pentene obtained in the step (1), and washing to obtain poly4-methyl-1-pentene polymer slurry;
(3) Solid-liquid separation: respectively obtaining a polymer and filtrate from the poly4-methyl-1-pentene polymer slurry obtained in the step (2) through a solid-liquid separation means;
(4) Oil-water separation: and (3) obtaining recovered monomers from the filtrate obtained in the step (3) through an oil-water separation means.
Wherein, the molecular weight regulator can be added optionally, and can be added or not.
Preferably, in step (1), the catalyst system comprises a main catalyst and a cocatalyst;
the main catalyst is at least one of a metallocene catalyst, a Ziegler-Natta catalyst, a post-metallocene catalyst, a supported metallocene catalyst and a supported post-metallocene catalyst;
the cocatalyst is at least one of methylaluminoxane compound (MAO), modified methylaluminoxane compound (MMAO), a tris (pentafluorophenyl) boron compound, a triphenylcarbenium tetrakis (pentafluorophenyl) boron compound, an N, N-dimethylanilinium tetrakis (pentafluorophenyl) boron compound, triisobutylaluminum, trimethylaluminum and triethylaluminum.
The carrier can be silica gel, magnesium chloride, various polymer carriers and the like, and silica gel and magnesium chloride are preferred.
Preferably, in the step (1), the molecular weight regulator is at least one of hydrogen and diethyl zinc.
Preferably, the reactor used in step (1) is a tubular reactor or a tank reactor, and the polymerization mode used is batch polymerization, semi-continuous polymerization or continuous polymerization.
Preferably, the polymerization temperature employed in step (1) is from 0 to 120℃and preferably from 20 to 80 ℃.
Preferably, the isotacticity of the poly-4-methyl-1-pentene obtained in step (1) is controlled to be 60% or more, preferably 80% or more, more preferably 90% or more; a weight average molecular weight of 10000 ～ 1000000, preferably 100000 to 800000; the molecular weight distribution index is 1.0 to 8.0, and the conversion is controlled to 50% or less, preferably 20% or less.
Preferably, in the step (2), the aqueous phase detergent is at least one of alcohol, acid and alkali. Specifically, hydrochloric acid, sodium hydroxide, potassium hydroxide, methanol, ethanol, etc. are mentioned.
Further, the aqueous phase detergent is sodium hydroxide aqueous solution.
Preferably, the solid-liquid separation means used in step (3) is filtration or centrifugation.
Preferably, the oil-water separation means used in step (4) is direct delamination by standing.
Compared with the prior art, the invention has the advantages that:
(1) The activity of the catalyst using bulk polymerization is greatly improved because: the concentration of the bulk polymerization monomer is high, and the polymerization rate of the catalyst is faster, so that the residence time can be reduced, and the production efficiency can be improved;
(2) By sequentially washing, solid-liquid separation and oil-water separation of the polymer obtained by bulk polymerization, most of the ash remaining in the polymer can be removed.
Detailed Description
The present invention is described in further detail below with reference to examples.
Example 1:
the batch polymerization is carried out under the normal pressure of a 100mL glass bottle, the system is firstly repeatedly vacuumized and replaced by nitrogen at 90 ℃ for 1 hour, so that the whole reaction system reaches the requirements of sealing, no water and no oxygen, the temperature of the system is set to 60 ℃, 30mL of 4-methyl-1-pentene, 10mg of supported metallocene catalyst, MMAO and 20mL of hydrogen are added into the system, the molar ratio of titanium to aluminum is 1:100, the pressure of the system is constantly under the normal pressure through nitrogen supplementation, and ethanol is injected into the system to terminate the reaction after 30 minutes of reaction; then adding 30mL of aqueous solution containing 10wt% NaOH, stirring thoroughly, washing, and filtering to obtain polymer and filtrate; 4-methyl-1-pentene in the filtrate is directly layered by standing, recovered and reused, and the polymer is dried in vacuum at 60 ℃ for more than 8 hours.
Example 2:
the reaction time was shortened to 10min, and the other conditions were the same as in example 1.
Example 3:
the 10wt% aqueous NaOH solution was replaced with 10wt% aqueous HCl solution, and the other conditions were the same as in example 2.
Comparative example 1:
intermittent polymerization is adopted, the batch polymerization is carried out under the normal pressure of a 100mL glass bottle, the system is firstly subjected to repeated vacuumizing-nitrogen replacement at 90 ℃ for 1 hour, so that the whole reaction system achieves the requirements of sealing and no water and oxygen, the system temperature is set to 60 ℃, then 100mL of n-hexane, 30mL of 4-methyl-1-pentene, 10mg of supported metallocene catalyst, MMAO and 20mL of hydrogen are added into the system, the molar ratio of titanium to aluminum is 1:100, the system pressure is constantly under the normal pressure through nitrogen supplementation, and ethanol is injected into the system to terminate the reaction after 3 hours of reaction; then adding 30mL of aqueous solution containing 10wt% NaOH, stirring thoroughly, washing, and filtering to obtain polymer and filtrate; 4-methyl-1-pentene in the filtrate is directly layered by standing, recovered, reprocessed and used, and the polymer is washed with ethanol for a plurality of times and then dried in vacuum at 60 ℃ for more than 8 hours.
Comparative example 2:
the reaction time was 1h, and the other conditions were the same as in comparative example 1.
Comparative example 3:
the polymerization conditions were the same as in example 2, and after the polymerization, ethanol was injected to terminate the reaction, and ethanol was added to stir for 8 hours, and then the polymer was obtained by filtration, washing and drying.
Comparative example 4:
the polymerization conditions were the same as in comparative example 2, and after the polymerization, ethanol was injected to terminate the reaction, and ethanol was added to stir for 8 hours, and then the polymer was obtained by filtration, washing and drying.
The polymerization test results of all the above examples and comparative examples are shown in Table 1.
The testing method comprises the following steps:
(1) The molecular weights (Mw and Mn) and the distribution index (PDI) of the polymers were determined by high temperature gel permeation chromatography (Polymer Char IR-5), equipped with an infrared detector and a viscosity detector; 1,2, 4-trichlorobenzene is used as solvent to prepare 0.1-0.3 wt% polymer solution at 150 ℃ with the flow rate of the solvent being 1.0ml/min;
(2) The melting point (Tm) of the polymer is measured by TA Instruments DSC25, 5.0-7.0 mg of polymer sample is taken to heat up to 260 ℃ at 30 ℃/min, the temperature is kept for 5min to eliminate the heat history, then the temperature is reduced to 20 ℃ at 10 ℃/min, the temperature is kept for 3min, the temperature is increased to 260 ℃ at the speed of 10 ℃/min, and the thermal performance of the polymer is obtained from the second heating curve;
(3) The polymer composition uses carbon spectrum nuclear magnetism% 13 C NMR) at 125 ℃, instrument model Bruker AC 400; preparing a deuterated o-dichlorobenzene solution with the mass fraction of 10% from the polymer at 150 ℃, and dissolving in advance for 3 to 4 hours to make the sample solution uniform; the instrument parameters are optimized to be pulse angle 90 degrees, reverse proton decoupling,Pulse delay time 8s, collection time 1.3s and spectrum width 8000Hz, and average scanning times are not less than 5000 times;
(4) The metal residual amount of the polymer was tested by ICP; firstly, carrying out digestion on a polymer at 220 ℃ by an M6 microwave digestion instrument; ICP testing employed Spectro ICP-OES ARCOSII SOP;
(5) The monomer conversion and catalyst activity were calculated from the mass of the polymer.
Table 1:
as can be seen from table 1:
(1) Comparative examples 1,2 and 4 used slurry polymerization, comparative example 3 and all examples used bulk polymerization, and the comparison revealed that the catalyst activity using bulk polymerization was greatly improved because: the concentration of the bulk polymerization monomer is high, and the polymerization rate of the catalyst is faster, so that the residence time can be reduced, and the production efficiency can be improved;
(2) In the comparative example 3, the polymer is not subjected to post-treatment, and in all the examples, the obtained polymer is sequentially subjected to washing, solid-liquid separation and oil-water separation, so that most of ash remained in the polymer can be removed, and meanwhile, the process is not used for introducing a solvent, and unreacted monomers can be conveniently recycled;
in conclusion, compared with the existing polymerization process, the process has the advantages of high activity, convenience in separation, low metal residue and the like.
Claims (10)
1. The preparation method of the poly4-methyl-1-pentene is characterized by comprising the following steps:
(1) Bulk polymerization of 4-methyl-1-pentene: under anhydrous and anaerobic conditions, adding 4-methyl-1-pentene, a catalyst system and an optional molecular weight regulator into a reactor, and carrying out homopolymerization to obtain poly 4-methyl-1-pentene;
(2) Polymer washing: adding an aqueous phase detergent into the poly4-methyl-1-pentene obtained in the step (1), and washing to obtain poly4-methyl-1-pentene polymer slurry;
(3) Solid-liquid separation: respectively obtaining a polymer and filtrate from the poly4-methyl-1-pentene polymer slurry obtained in the step (2) through a solid-liquid separation means;
(4) Oil-water separation: and (3) obtaining recovered monomers from the filtrate obtained in the step (3) through an oil-water separation means.
2. The method for producing poly-4-methyl-1-pentene according to claim 1, wherein: in the step (1), the catalyst system comprises a main catalyst and a cocatalyst;
the main catalyst is at least one of a metallocene catalyst, a Ziegler-Natta catalyst, a post-metallocene catalyst, a supported metallocene catalyst and a supported post-metallocene catalyst;
the cocatalyst is at least one of methylaluminoxane compound, modified methylaluminoxane compound, tri (pentafluorophenyl) boron compound, triphenylcarbonium tetra (pentafluorophenyl) boron compound, N-dimethylanilinium tetra (pentafluorophenyl) boron compound, triisobutylaluminum, trimethylaluminum and triethylaluminum.
3. The method for producing poly-4-methyl-1-pentene according to claim 1, wherein: in the step (1), the molecular weight regulator is at least one of hydrogen and diethyl zinc.
4. The method for producing poly-4-methyl-1-pentene according to claim 1, wherein: the reactor adopted in the step (1) is a tubular reactor or a kettle reactor, and the adopted polymerization mode is batch polymerization, semi-continuous polymerization or continuous polymerization.
5. The method for producing poly-4-methyl-1-pentene according to claim 1, wherein: the polymerization temperature adopted in the step (1) is 0-120 ℃.
6. The method for producing poly-4-methyl-1-pentene according to claim 1, wherein: the isotacticity of the poly-4-methyl-1-pentene obtained in the step (1) is controlled to be more than 60%, the weight average molecular weight is 10000 ～ 1000000, the molecular weight distribution index is 1.0-8.0, and the conversion rate is controlled to be less than 50%.
7. The method for producing poly-4-methyl-1-pentene according to claim 1, wherein: in the step (2), the water phase detergent is at least one of alcohol, acid and alkali.
8. The method for producing poly-4-methyl-1-pentene according to claim 7, wherein: the water phase detergent is sodium hydroxide water solution.
9. The method for producing poly-4-methyl-1-pentene according to claim 1, wherein: the solid-liquid separation means adopted in the step (3) is filtration or centrifugation.
10. The process for preparing poly-4-methyl-1-pentene according to any one of claims 1 to 9, wherein: the oil-water separation means adopted in the step (4) is standing and direct layering.
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| EP3305839A1 (en) * | 2016-10-10 | 2018-04-11 | Fraunhofer Gesellschaft zur Förderung der Angewand | Method for recycling polyolefin containing waste |
| CN111954685B (en) * | 2018-04-11 | 2023-08-08 | 三井化学株式会社 | Process for producing 4-methyl-1-pentene polymer particles and 4-methyl-1-pentene resin |
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